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US20070197393A1 - Tricyclic benzoylpyrazole derivatives - Google Patents

Tricyclic benzoylpyrazole derivatives Download PDF

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US20070197393A1
US20070197393A1 US11/461,491 US46149106A US2007197393A1 US 20070197393 A1 US20070197393 A1 US 20070197393A1 US 46149106 A US46149106 A US 46149106A US 2007197393 A1 US2007197393 A1 US 2007197393A1
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Matthias Witschel
Steffen Kudis
Klaus Langemann
Ernst Baumann
Wolfgang Von Deyn
Guido Mayer
Ulf Misslitz
Ulf Neidlein
Martina Otten
Karl-Otto Westphalen
Helmut Walter
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the present invention relates to novel tricyclic benzoylpyrazole derivatives of the formula I where:
  • the invention relates to processes and intermediates for preparing compounds of the formula I, to compositions comprising them, and to the use of these derivatives or of the compositions comprising them for controlling harmful plants.
  • WO 97/19087 and EP-A 860 441 disclose tricyclic compounds which are characterized in that the respective benzoyl unit that they contain is fused via positions 3 and 4 with a bicycle.
  • the herbicidal properties of the prior-art compounds and their compatibility with crop plants are not entirely satisfactory. It is an object of the present invention to provide novel, biologically, in particular herbicidally, active compounds having improved properties.
  • the compounds of the formula I can contain one or more chiral centers, in which case they are present as enantiomers or diastereomer mixtures.
  • the invention provides both the pure enantiomers or diastereomers and their mixtures.
  • the compounds of the formula I can also be present in the form of their agriculturally useful salts, the type of salt generally being immaterial. Generally suitable are the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not negatively affect the herbicidal action of the compounds I.
  • Suitable cations are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, where, if desired, one to four hydrogen atoms may be replaced by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzy
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
  • IIa also represents the tautomeric forms IIa′ and IIa′′
  • IIb also represents the tautomeric forms IIb′ and IIb′′
  • organic molecular moieties mentioned for the substitutents R 1 -R 17 or as radicals on phenyl and heterocyclyl radicals are collective terms for individual enumerations of the individual group members.
  • All hydrocarbon chains i.e. all alkyl, haloalkyl, hydroxyalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, N-alkylaminosulfonyl, N,N-dialkylaminosulfonyl, N-alkylamino, N,N-dialkylamino, N-haloalkylamino, N,N-dihaloalkylamino, N-alkylsulfonylamino, N-haloalkylsulfonylamino, N
  • Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated heterocycle which contains one to three identical or different heteroatoms selected from the following group: oxygen, sulfur and nitrogen” denotes, for example, 5-membered rings having one heteroatom such as:
  • the sulfur of the abovementioned heterocycles may be oxidized to S ⁇ O or S( ⁇ O) 2 ;
  • the variables preferably have the following meanings, in each case alone or in combination:
  • Y together with the two carbons to which it is attached forms the following heterocycles:
  • the tricyclic benzoylpyrazole derivatives of the formula I can be obtained by various routes, for example by one of the following processes:
  • L 3 is a nucleophilically replaceable leaving group, such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoroacetate, etc.
  • halogen for example bromine or chlorine
  • hetaryl for example imidazolyl or pyridyl
  • carboxylate for example acetate or trifluoroacetate, etc.
  • the activated tricyclic benzoic acid VI ⁇ can be employed directly, such as in the case of the tricyclic benzoyl halides, or be generated in situ, for example using dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic ester, 2-pyridine disulfide/triphenylphosphine, carbonyldiimidazole, etc.
  • auxiliary base it may be advantageous to carry out the acylation reaction in the presence of a base.
  • the reactants and the auxiliary base are advantageously employed in equimolar amounts.
  • a slight excess of auxiliary base for example from 1.2 to 1.5 molar equivalents, based on VI, may be advantageous in certain cases.
  • Suitable auxiliary bases are tertiary alkylamines, pyridine, or alkali metal carbonates.
  • Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene or chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxide, or esters, such as ethyl acetate, or mixtures of these.
  • tricyclic benzoyl halides are employed as activated carboxylic acid components, it may be advantageous to cool the reaction mixture to 0-10° C. when adding this reaction partner.
  • the mixture is subsequently stirred at 20-100° C., preferably at 25-50° C., until the reaction has gone to completion.
  • Work-up is carried out in a customary manner, for example by pouring the reaction mixture into water and extracting the product of value.
  • Solvents which are suitable for this purpose are, in particular, methylene chloride, diethyl ether and ethyl acetate.
  • the organic phase is dried and the solvent removed, and the crude ester can then be employed for the rearrangement without further purification.
  • esters VIII to give the compounds of the formula I ⁇ is advantageously carried out at from 20 to 100° C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as catalyst.
  • Solvents which may be used are, for example, acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures of these. Preferred solvents are acetonitrile and dioxane.
  • Suitable bases are tertiary amines, such as triethylamine, aromatic amines, such as pyridine, or alkali metal carbonates, such as sodium carbonate or potassium carbonate, which are preferably employed in equimolar amounts or in an up to four-fold excess, based on the ester. Preference is given to using triethylamine or alkali metal carbonate, preferably in double the equimolar ratio, based on the ester.
  • Suitable cyano compounds are inorganic cyanides, such as sodium cyanide or potassium cyanide, and organic cyano compounds, such as acetone cyanohydrin or trimethylsilyl cyanide. They are employed in an amount of from 1 to 50 mol percent, based on the ester. Preference is given to using acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of from 5 to 15, preferably 10, mol percent, based on the ester.
  • the reaction mixture is, for example, acidified using dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, for example methylene chloride or ethyl acetate.
  • the organic extract can be extracted with 5-10% strength alkali metal carbonate solution, for example sodium carbonate or potassium carbonate solution.
  • the aqueous phase is acidified and the resulting precipitate is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, the extract being dried and concentrated.
  • ester VIII in situ by reacting a pyrazole of the formula VII, or an alkali metal salt thereof, with a tricyclic benzene derivative of the formula IX in the presence of carbon monoxide, a catalyst and a base.
  • L 4 is a leaving group, such as halogen, for example chlorine, bromine or iodine, or sulfonate such as mesylate or triflate; preference is given to bromine or triflate.
  • halogen for example chlorine, bromine or iodine
  • sulfonate such as mesylate or triflate
  • ester VIII reacts directly to give the tricyclic benzoylpyrazole derivative of the formula I ⁇ .
  • Suitable catalysts are palladium ligand complexes in which the palladium is present in oxidation state 0, metallic palladium, if appropriate applied to a support, and preferably palladium(II) salts.
  • the reaction with palladium(II) salts and metallic palladium is preferably carried out in the presence of complex ligands.
  • a suitable palladium(0) ligand complex is, for example, tetrakis(triphenylphosphane)palladium.
  • Metallic palladium is preferably applied to an inert carrier, such as, for example, activated carbon, silica, alumina, barium sulfate or calcium carbonate.
  • an inert carrier such as, for example, activated carbon, silica, alumina, barium sulfate or calcium carbonate.
  • the reaction is preferably carried out in the presence of complex ligands, such as, for example, triphenylphosphane.
  • Suitable palladium(II) salts are, for example, palladium acetate and palladium chloride. Preference is given to carrying out the reaction in the presence of complex ligands such as, for example, triphenylphosphane.
  • Suitable complex ligands for the palladium ligand complexes, or complex ligands in whose presence the reaction with metallic palladium or palladium(II) salts is preferably carried out are tertiary phosphanes whose structure is represented by the following formulae: where n is a number from 1 to 4 and the radicals R a to R g are C 1 -C 6 -alkyl, aryl-C 1 -C 2 -alkyl or preferably aryl.
  • Aryl is, for example, naphthyl and unsubstituted or substituted phenyl such as, for example, 2-tolyl and in particular unsubstituted phenyl.
  • the complex palladium salts can be prepared in a manner known per se starting from commercially available palladium salts, such as palladium chloride or palladium acetate, and the corresponding phosphanes, such as, for example, triphenylphosphane or 1,2-bis(diphenylphosphano)ethane.
  • palladium salts such as palladium chloride or palladium acetate
  • phosphanes such as, for example, triphenylphosphane or 1,2-bis(diphenylphosphano)ethane.
  • a large number of complexed palladium salts is also commercially available.
  • Preferred palladium salts are [(R)-(+)-2,2′-bis(diphenylphosphano)-1,1′-binaphthyl]palladium(II) chloride, bis(triphenylphosphane)palladium(II) acetate and in particular bis(triphenylphosphane)palladium(II) chloride.
  • the palladium catalyst is generally employed in a concentration of from 0.05 to 5 mol %, and preferably of 1-3 mol %.
  • Suitable bases are tertiary amines, such as, for example, N-methylpiperidine, ethyldiisopropylamine, 1,8-bisdimethylaminonaphthalene and in particular triethylamine.
  • alkali metal carbonates such as sodium carbonate or potassium carbonate.
  • mixtures of potassium carbonate and triethylamine are also suitable.
  • Suitable solvents are nitrites, such as benzonitrile and acetonitrile, amides, such as dimethylformamide, dimethylacetamide, tetra-C 1 -C 4 -alkylureas or N-methylpyrrolidone, and preferably ethers, such as tetrahydrofuran, methyl tert-butyl ether. Particular preference is given to using, as solvents, ethers such as 1,4-dioxane and dimethoxyethane.
  • halogenating agents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride and oxalyl bromide.
  • the tricyclic benzoic acids of the formula VI ⁇ ( ⁇ VIb) can be prepared by acidic or basic hydrolysis from the corresponding esters VIc.
  • radicals which can be removed by hydrolysis are alkoxy, phenoxy, alkylthio and phenylthio radicals which can be unsubstituted or substituted, halides, heteroaryl radicals which are attached via nitrogen, amino and imino radicals which may be unsubstituted or substituted, etc.
  • the particularly preferred embodiments of the tricyclic benzoic acid derivatives of the formulae VI, VIa, VIb and VIc correspond to those of the tricyclic benzoylpyrazole derivatives of the formula I.
  • the tricyclic benzoic esters VIc can be obtained in different ways.
  • benzoic esters of the formula X which are prepared in a manner known per se (cf., for example, Chem. Pharm. Bull. 1985, 33 (8), 3336; Helv. Chim. Acta 1987, 70, 1326; J. Chem. Soc. Perkin Trans. 1972, 2019; J. Chem. Soc. Perkin Trans. 1991, 2763; Tetrahydron Asymmetry 1998, 9, 1137), can be cyclized to cyclic ketones of the formula XI (cf., for example, Chem. Ber. 1923, 56, 1819; J. Chem. Soc. Perkin 11991, 2763; J. Med. Chem.
  • a Lewis acid such as boron trifluoride
  • a hydrazine cf. A. R. Katritzky et al., Comprehensive Heterocycl
  • diketone XII can be reacted with hydroxylamine or equivalents thereof (cf. A. R. Katritzky et al., Comprehensive Heterocyclic Chemistry, Vol. 6, p. 61-64, 118 (1984), Pergamon Press; Chem. Ber. 1967, 100, 3326). This gives the corresponding isoxazole derivatives which can be modified further by customary processes.
  • aldehydes of the formula XIV which can be prepared in a manner known per se, analogously to processes known from the literature by reaction with a hydrazine or hydroxylamine (or equivalents of these) into the corresponding hydrazones or oximes (cf., for example, Synth. Commun. 1990, 20, 1373; J. Org. Chem. 1980, 45, 3756).
  • a hydrazine or hydroxylamine or equivalents of these
  • oximes cf., for example, Synth. Commun. 1990, 20, 1373; J. Org. Chem. 1980, 45, 3756.
  • pyrazoles or pyrazolines and isoxazoles or isoxazolines can be modified further by customary processes.
  • the resulting heterocycles can, if desired, be modified further by processes known per se.
  • the abovementioned substitutents R 3a are hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, hydroxyl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy; furthermore, the abovementioned radicals R 3b are hydrogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl.
  • the tricyclic benzoic esters of the formula VIc or the tricyclic benzoic acids of the formula VIb can be obtained by reacting a tricyclic benzene derivative of the formula IX with a C 1 -C 6 -alcohol or water in the presence of carbon monoxide, a catalyst and a base.
  • a tricyclic benzene derivative of the formula IX with a C 1 -C 6 -alcohol or water in the presence of carbon monoxide, a catalyst and a base.
  • the conditions mentioned under process F apply.
  • L 4 is a leaving group, such as halogen, for example chlorine, bromine or iodine, or sulfate, such as mesylate or triflate; preference is given to bromine or triflate.
  • halogen for example chlorine, bromine or iodine
  • sulfate such as mesylate or triflate
  • the tricyclic benzoic acids of the formula VIb can be obtained by converting a tricyclic benzene derivative of the formula IX where L 4 is halogen, such as chlorine or bromine, in particular bromine, by reaction with, for example, n-butyllithium or magnesium into the metalated derivative, followed by quenching with carbon dioxide (cf., for example, J. Org. Chem. 1990, 55, 773; Angew. Chem. Int. Ed. 1969, 8, 68).
  • L 4 is halogen, such as chlorine or bromine, in particular bromine
  • the compounds of the formula IX can be obtained in different ways, the fused system, for example, can be constructed analogously to the processes described for the compounds of the formula VIc.
  • the compounds of the formula XV can be obtained in different ways; for example, the fused system can be constructed analogously to the processes described for the compounds of the formula VIc.
  • the selection of the protective groups depends both on the reaction conditions and on the structure of the molecule.
  • the protective groups, their introduction and their removal are generally known from the literature (cf., for example, T. W. Greene et al., “Protective Groups in Organic Synthesis”, 2 nd edition, Wiley, New York, 1991), and they can be employed analogously to processes known from the literature.
  • a carbon monoxide pressure of 20 bar was applied, the mixture was stirred for 5 minutes and the autoclave was vented. This procedure was repeated 3 times.
  • the autoclave was subsequently heated to 130° C., a carbon monoxide pressure of 20 bar was applied once more and the mixture was stirred for 24 hours. After cooling and venting, the solvent was removed, and the residue was taken up in water, adjusted to pH 11 and washed with methylene chloride.
  • the mixture was subsequently acidified to pH 4 using 10 percent strength hydrochloric acid and extracted with methylene chloride. The combined organic phases were washed with saturated ammonium chloride solution and dried, and the solvent was removed.
  • the diazonium salt described above was subsequently added at from 10 to 15° C., and the mixture was slowly heated to 50° C. A further 54 g (0.84 mol) of sulfur dioxide were then introduced, and stirring was continued at 50° C. for another 30 minutes. After cooling, 7.4 g (0.1 mol) of chlorine gas were then introduced at room temperature, stirring was continued for 15 minutes and the phases which had formed were then separated. The organic phase was dried and the solvent was removed. This gave 207 g of methyl 2-chlorosulfonyl-4-chlorobenzoate.
  • This oxime was reacted further without any further purification by dissolving it in 40 ml of methylene chloride, followed by dropwise addition of 15.0 ml (25.0 mmol) of sodium hypochlorite solution (12.5% of active chlorine). A spatula tip of sodium acetate was added and the mixture was stirred at room temperature for 12 hours. The organic phase was separated off, the aqueous phase was extracted with methylene chloride, the combined organic phases were washed with water and dried, and the solvent was removed.
  • the solution was dried, and the solvent was distilled off.
  • the solution was extracted with methylene chloride, the combined organic phases were dried, and the solvent was subsequently removed.
  • the compounds of the formula I and their agriculturally useful salts are suitable, both in the form of isomer mixtures and in the form of the pure isomers, as herbicides.
  • the herbicidal compositions comprising compounds of the formula I control vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.
  • the compounds of the formula I, or herbicidal compositions comprising them can additionally be employed in a further number of crop plants for eliminating undesirable plants.
  • suitable crops are the following:
  • the compounds of the formula I may also be used in crops which tolerate the action of herbicides owing to breeding, including genetic engineering methods.
  • the compounds of the formula I, or the herbicidal compositions comprising them can be used for example in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, spreading or watering.
  • the use forms depend on the intended purpose; in any case, they should guarantee the finest possible distribution of the active compounds according to the invention.
  • the herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries which are customarily used for formulating crop protection agents.
  • Suitable for use as inert auxiliaries are essentially the following:
  • mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal-tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, for example amines such as N-methylpyrrolidone, and water.
  • paraffin tetrahydronaphthalene
  • alkylated naphthalenes and their derivatives alkylated benzenes or their derivatives
  • alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol
  • ketones such as cyclohexanone
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the tricyclic benzoylpyrazole derivatives of the formula I can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier.
  • concentrates comprising active compound, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.
  • Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, e.g. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooc
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active compounds together with a solid carrier.
  • Granules e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
  • Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
  • the concentrations of the compounds of the formula I in the ready-to-use preparations can be varied within wide ranges.
  • the formulations comprise approximately from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active compound.
  • the active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • the compounds of the formula I or the herbicidal compositions can be applied pre- or post-emergence. If the active compounds are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).
  • the rates of application of the compound of the formula I are from 0.001 to 3.0, preferably 0.01 to 1.0, kg/ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage.
  • the tricyclic benzylpyrazole derivatives of the formula I may be mixed with a large number of representatives of other herbicidal or growth-regulating active compound groups and applied concomitantly.
  • Suitable components for mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy-/heteroaryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF 3 -phenyl derivatives, carbamates, quinoline carboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their
  • the culture containers used were plastic pots containing loamy sand with approximately 3.0% of humus as the substrate.
  • the seeds of the test plants were sown separately for each species.
  • the active compounds which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles.
  • the containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover causes uniform germination of the test plants, unless this was adversely affected by the active compounds.
  • test plants were first grown to a plant height of from 3 to 15 cm, depending on the plant habit, and only then treated with the active compounds which had been suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to the treatment.
  • the application rate for the post-emergence treatment was 0.5 or 0.25 kg of a.s./ha.
  • the plants were kept at 10-25° C. or 20-35° C.
  • the test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
  • Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the above-ground parts, and 0 means no damage, or normal course of growth.
  • the plants used in the greenhouse trials were of the following species: Scientific Name Common Name Chenopodium album lambsquarters (goosefoot) Echinochloa crusgalli barnyardgrass Setaria viridis green foxtail Solanum nigrum black nightshade Veronica ssp. speadwell
  • the compound 2.2 shows very good activity against the abovementioned undesired broad-leaved weeds and weed grasses when applied by the post-emergence method.

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Abstract

Tricyclic benzoylpyrazole derivatives of the formula I
Figure US20070197393A1-20070823-C00001
 where:
  • X is oxygen, sulfur, S═O, S(═O)2, CR6R7, NR8 or a bond; Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated 5- or 6-membered heterocycle;
  • R1, R2, R6, R7 are hydrogen, alkyl, haloalkyl, alkoxy or haloalkoxy;
  • R3 is halogen, alkyl, haloalkyl, alkoxy or haloalkoxy;
  • R4 is hydrogen, nitro, halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, unsubstituted or substituted aminosulfonyl or unsubstituted or substituted sulfonylamino;
  • R5 is hydrogen, alkyl or halogen; l is 0, 1 or 2;
  • R8 is hydrogen, alkyl, haloalkyl, alkylcarbonyl, formyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylsulfonyl or haloalkylsulfonyl;
  • R9 is substituted pyrazol-4-ylcarbonyl or substituted 5-oxopyrazolin-4-ylmethylidene; and their agriculturally useful salts; processes and intermediates for preparing the tricyclic benzoylpyrazole derivatives; compositions comprising them and the use of these derivatives or of the compositions comprising them for controlling undesirable plants are described.

Description

  • The present invention relates to novel tricyclic benzoylpyrazole derivatives of the formula I
    Figure US20070197393A1-20070823-C00002
    where:
      • X is oxygen, sulfur, S═O, S(═O)2, CR6R7, NR8 or a bond;
      • Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated 5- or 6-membered heterocycle which contains one to three identical or different heteroatoms selected from the following group: oxygen, sulfur or nitrogen;
      • R1, R2, R6, R7 are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
      • R3 is halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
      • R4 is hydrogen, nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl) amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino;
      • R5 is hydrogen, C1-C6-alkyl or halogen;
      • R8 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, formyl, C1-C6-alkoxycarbonyl, C1-C6-haloalkoxycarbonyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
      • l is 0, 1 or 2;
      • R9 is a radical IIa or IIb
        Figure US20070197393A1-20070823-C00003
        where
      • R10 is hydroxyl, mercapto, halogen, OR13, SR13, SO2R14, NR15R16 or N-bonded heterocyclyl, where the heterocyclyl radical may be partially or fully halogenated and/or may carry one to three of the following radicals:
        • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
      • R11 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, hydroxyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
      • R12 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl, hydroxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio or C1-C6-haloalkylthio;
      • R13 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl, C1-C20-alkylcarbonyl, C2-C20-alkenylcarbonyl, C2-C6-alkynylcarbonyl, C3-C6-cycloalkylcarbonyl, C1-C6-alkoxycarbonyl, C3-C6-alkenyloxycarbonyl, C3-C6-alkynyloxycarbonyl, C1-C6-alkylthiocarbonyl, C1-C6-alkylaminocarbonyl, C3-C6-alkenylaminocarbonyl, C3-C6-alkynylaminocarbonyl, N,N-di(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkyl) aminocarbonyl, N—(C3-C6-alkynyl)-N—(C1-C6-alkyl)aminocarbonyl, N—(C1-C6-alkoxy)-N—(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkoxy)aminocarbonyl, N—(C3-C6-alkynyl)-N—(C1-C6-alkoxy)aminocarbonyl, di(C1-C6-alkyl)aminothiocarbonyl, C1-C6-alkylcarbonyl-C1-C6-alkyl, C1-C6-alkoxyimino-C1-C6-alkyl, N—(C1-C6-alkylamino)imino-C1-C6-alkyl or N,N-di(C1-C6-alkylamino)imino-C1-C6-alkyl, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three of the following groups:
        • cyano, C1-C4-alkoxy, C1-C4-alkylthio, di(C1-C4-alkyl)amino, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkoxy-C1-C4-alkoxycarbonyl, di(C1-C4-alkyl)amino-C1-C4-alkoxycarbonyl, hydroxycarbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, aminocarbonyl, C1-C4-alkylcarbonyloxy or C3-C6-cycloalkyl;
        • is phenyl, heterocyclyl, phenyl-C1-C6-alkyl, heterocyclyl-C1-C6-alkyl, phenylcarbonyl-C1-C6-alkyl, heterocyclylcarbonyl-C1-C6-alkyl, phenylcarbonyl, heterocyclylcarbonyl, phenoxycarbonyl, phenyloxythiocarbonyl, heterocyclyloxycarbonyl, heterocyclyloxythiocarbonyl, phenylaminocarbonyl, N—(C1-C6-alkyl)-N-(phenyl)aminocarbonyl, heterocyclylaminocarbonyl, N—(C1-C6-alkyl)-N-(heterocyclyl)aminocarbonyl, phenyl-C2-C6-alkenylcarbonyl or heterocyclyl-C2-C6-alkenylcarbonyl, where the phenyl and the heterocyclyl radical of the 18 lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:
        • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, heterocyclyl or N-bonded heterocyclyl, where the two lastmentioned substitutents for their part may be partially or fully halogenated and/or may carry one to three of the following radicals:
        • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
      • R14 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, di(C1-C6-alkyl)amino or di(C1-C6-haloalkyl)amino, where the above-mentioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three of the following groups:
        • cyano, C1-C4-alkoxy, C1-C4-alkylthio, di(C1-C4-alkyl)amino, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkoxy-C1-C4-alkoxycarbonyl, di(C1-C4-alkyl)amino-C1-C4-alkoxycarbonyl, hydroxycarbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, aminocarbonyl, C1-C4-alkylcarbonyloxy or C3-C6-cycloalkyl;
        • is phenyl, heterocyclyl, phenyl-C1-C6-alkyl, heterocyclyl-C1-C6-alkyl, phenoxy, heterocyclyloxy, where the phenyl and the heterocyclyl radical of the lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:
        • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
      • R15 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, di(C1-C6-alkyl)amino or C1-C6-alkylcarbonylamino, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three radicals of the following group:
        • cyano, C1-C4-alkoxy, C1-C4-alkylthio, di(C1-C4-alkyl)amino, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkoxy-C1-C4-alkoxycarbonyl, di(C1-C4-alkyl)amino-C1-C4-alkoxycarbonyl, hydroxycarbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, aminocarbonyl, C1-C4-alkylcarbonyloxy or C3-C6-cycloalkyl;
        • is phenyl, heterocyclyl, phenyl-C1-C6-alkyl or heterocyclyl-C1-C6-alkyl, where the phenyl or heterocyclyl radical of the four lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:
        • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
      • R16 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl or C1-C6-alkylcarbonyl;
        and their agriculturally useful salts.
  • Moreover, the invention relates to processes and intermediates for preparing compounds of the formula I, to compositions comprising them, and to the use of these derivatives or of the compositions comprising them for controlling harmful plants.
  • WO 97/19087 and EP-A 860 441 disclose tricyclic compounds which are characterized in that the respective benzoyl unit that they contain is fused via positions 3 and 4 with a bicycle. However, the herbicidal properties of the prior-art compounds and their compatibility with crop plants are not entirely satisfactory. It is an object of the present invention to provide novel, biologically, in particular herbicidally, active compounds having improved properties.
  • We have found that this object is achieved by the tricyclic benzoylpyrazole derivatives of the formula I and their herbicidal action.
  • Furthermore, we have found processes and intermediates for synthesizing the compounds of the formula I. Likewise, we have found herbicidal compositions which comprise the compounds I and have very good herbicidal action. Moreover, we have found processes for preparing these compositions and methods for controlling undesirable vegetation using the compounds I.
  • Depending on the substitution pattern, the compounds of the formula I can contain one or more chiral centers, in which case they are present as enantiomers or diastereomer mixtures. The invention provides both the pure enantiomers or diastereomers and their mixtures.
  • The compounds of the formula I can also be present in the form of their agriculturally useful salts, the type of salt generally being immaterial. Generally suitable are the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not negatively affect the herbicidal action of the compounds I.
  • Suitable cations are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, where, if desired, one to four hydrogen atoms may be replaced by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
  • In the case of R10=hydroxyl or mercapto, IIa also represents the tautomeric forms IIa′ and IIa″
    Figure US20070197393A1-20070823-C00004
  • Likewise, in the case of R10=hydroxyl or mercapto, IIb also represents the tautomeric forms IIb′ and IIb″
    Figure US20070197393A1-20070823-C00005
  • The organic molecular moieties mentioned for the substitutents R1-R17 or as radicals on phenyl and heterocyclyl radicals are collective terms for individual enumerations of the individual group members. All hydrocarbon chains, i.e. all alkyl, haloalkyl, hydroxyalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, N-alkylaminosulfonyl, N,N-dialkylaminosulfonyl, N-alkylamino, N,N-dialkylamino, N-haloalkylamino, N,N-dihaloalkylamino, N-alkylsulfonylamino, N-haloalkylsulfonylamino, N-alkyl-N-alkylsulfonylamino, N-alkyl-N-haloalkylsulfonylamino, alkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylthiocarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, dialkylaminothiocarbonyl, alkoxyalkyl, hydroxyalkoxyalkyl, alkylcarbonylalkyl, alkoxyiminoalkyl, N-(alkylamino)iminoalkyl, N-(dialkylamino)iminoalkyl, phenylalkenylcarbonyl, heterocyclylalkenylcarbonyl, N-alkoxy-N-alkylaminocarbonyl, N-alkyl-N-phenylaminocarbonyl, N-alkyl-N-heterocyclylaminocarbonyl, phenylalkyl, heterocyclylalkyl, phenylcarbonylalkyl, heterocyclylcarbonylalkyl, dialkylaminoalkoxycarbonyl, alkoxyalkoxycarbonyl, alkenylcarbonyl, alkenyloxycarbonyl, alkenylaminocarbonyl, N-alkenyl-N-alkylaminocarbonyl, N-alkenyl-N-alkoxyaminocarbonyl, alkynylcarbonyl, alkynyloxycarbonyl, alkynylaminocarbonyl, N-alkynyl-N-alkylaminocarbonyl, N-alkynyl-N-alkoxyaminocarbonyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, alkenyloxy and alkynyloxy moieties, may be straight-chain or branched. Unless indicated otherwise, halogenated substitutents preferably carry one to five identical or different halogen atoms. The term halogen denotes in each case fluorine, chlorine, bromine or iodine.
  • Examples of other meanings are:
      • C1-C4-alkyl and the alkyl moieties of hydroxy-C1-C4-alkyl: for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;
      • C1-C6-alkyl, and the alkyl moieties of C1-C6-alkylcarbonyl-C1-C6-alkyl, C1-C6-alkoxyimino-C1-C6-alkyl, N—(C1-C6-alkylamino)imino-C1-C6-alkyl, N-(di-C1-C6-alkylamino)imino-C1-C6-alkyl, N—(C1-C6-alkoxy)-N—(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkynyl)-N—(C1-C6-alkyl)aminocarbonyl, N—(C1-C6-alkyl)-N-phenylaminocarbonyl, N—(C1-C6-alkyl)-N-heterocyclylaminocarbonyl, phenyl-C1-C6-alkyl, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl) amino, N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino, heterocyclyl-C1-C6-alkyl, phenylcarbonyl-C1-C6-alkyl, heterocyclylcarbonyl-C1-C6-alkyl: C1-C4-alkyl as mentioned above, and also, for example, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-3-methylpropyl;
      • C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;
      • C1-C6-haloalkyl, and the haloalkyl moieties of N—C1-C6-haloalkylamino and N,N-(di-C1-C6-haloalkyl)amino: C1-C4-haloalkyl as mentioned above, and also, for example, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl or dodecafluorohexyl;
      • C1-C4-alkoxy: for example methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy;
      • C1-C6-alkoxy, and the alkoxy moieties of C1-C6-alkoxyimino-C1-C6-alkyl, N—(C1-C6-alkoxy)-N—(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkoxy)aminocarbonyl and N—(C3-C6-alkynyl)-N—(C1-C6-alkoxy)aminocarbonyl: C1-C4-alkoxy as mentioned above, and also, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy;
      • C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy;
      • C1-C6-haloalkoxy: C1-C4-haloalkoxy as mentioned above, and also, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;
      • C1-C4-alkylthio: for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio or 1,1-dimethylethylthio;
      • C1-C6-alkylthio, and the alkylthio moieties of C1-C6-alkylthiocarbonyl: C1-C4-alkylthio as mentioned above and also, for example, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio;
      • C1-C6-haloalkylthio: a C1-C6-alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2,3-dichloropropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio, nonafluorobutylthio, 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio or dodecafluorohexylthio;
      • C1-C6-alkylsulfinyl (C1-C6-alkyl-S(═O)—): for example methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl or 1-ethyl-2-methylpropylsulfinyl;
      • C1-C6-haloalkylsulfinyl: a C1-C6-alkylsulfinyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2-difluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2,2,2-trichloroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro-2,2-difluoroethylsulfinyl, 2,2-dichloro-2-fluoroethylsulfinyl, pentafluoroethylsulfinyl, 2-fluoropropylsulfinyl, 3-fluoropropylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2-bromopropylsulfinyl, 3-bromopropylsulfinyl, 2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl, 2,3-dichloropropylsulfinyl, 3,3,3-trifluoropropylsulfinyl, 3,3,3-trichloropropylsulfinyl, 2,2,3,3,3-pentafluoropropylsulfinyl, heptafluoropropylsulfinyl, 1-(fluoromethyl)-2-fluoroethylsulfinyl, 1-(chloromethyl)-2-chloroethylsulfinyl, 1-(bromomethyl)-2-bromoethylsulfinyl, 4-fluorobutylsulfinyl, 4-chlorobutylsulfinyl, 4-bromobutylsulfinyl, nonafluorobutylsulfinyl, 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-bromopentylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl or dodecafluorohexylsulfinyl;
      • C1-C6-alkylsulfonyl (C1-C6-alkyl-S(═O)2—), and the alkylsulfonyl radicals of N—(C1-C6-alkylsulfonyl)amino and N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino: for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl or 1-ethyl-2-methylpropylsulfonyl;
      • C1-C6-haloalkylsulfonyl, and the haloalkylsulfonyl radicals of N—(C1-C6-haloalkylsulfonyl)amino and N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino: a C1-C6-alkylsulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2,3-dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(chloromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl, nonafluorobutylsulfonyl, 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorohexylsulfonyl, 6-bromohexylsulfonyl, 6-iodohexylsulfonyl or dodecafluorohexylsulfonyl;
      • C1-C6-alkylamino, and the alkylamino radicals of N—(C1-C6-alkylamino)imino-C1-C6-alkyl: for example methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1,1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1,1-dimethylpropylamino, 1,2-dimethylpropylamino, 1-methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1,1-dimethylbutylamino, 1,2-dimethylbutylamino, 1,3-dimethylbutylamino, 2,2-dimethylbutylamino, 2,3-dimethylbutylamino, 3,3-dimethylbutylamino, 1-ethylbutylamino, 2-ethylbutylamino, 1,1,2-trimethylpropylamino, 1,2,2-trimethylpropylamino, 1-ethyl-1-methylpropylamino or 1-ethyl-2-methylpropylamino;
      • (C1-C6-alkylamino)sulfonyl: for example methylaminosulfonyl, ethylaminosulfonyl, propylaminosulfonyl, 1-methylethylaminosulfonyl, butylaminosulfonyl, 1-methylpropylaminosulfonyl, 2-methylpropylaminosulfonyl, 1,1-dimethylethylaminosulfonyl, pentylaminosulfonyl, 1-methylbutylaminosulfonyl, 2-methylbutylaminosulfonyl, 3-methylbutylaminosulfonyl, 2,2-dimethylpropylaminosulfonyl, 1-ethylpropylaminosulfonyl, hexylaminosulfonyl, 1,1-dimethylpropylaminosulfonyl, 1,2-dimethylpropylaminosulfonyl, 1-methylpentylaminosulfonyl, 2-methylpentylaminosulfonyl, 3-methylpentylaminosulfonyl, 4-methylpentylaminosulfonyl, 1,1-dimethylbutylaminosulfonyl, 1,2-dimethylbutylaminosulfonyl, 1,3-dimethylbutylaminosulfonyl, 2,2-dimethylbutylaminosulfonyl, 2,3-dimethylbutylaminosulfonyl, 3,3-dimethylbutylaminosulfonyl, 1-ethylbutylaminosulfonyl, 2-ethylbutylaminosulfonyl, 1,1,2-trimethylpropylaminosulfonyl, 1,2,2-trimethylpropylaminosulfonyl, 1-ethyl-1-methylpropylaminosulfonyl or 1-ethyl-2-methylpropylaminosulfonyl;
      • di(C1-C6-alkyl)aminosulfonyl: for example N,N-dimethylaminosulfonyl, N,N-diethylaminosulfonyl, N,N-di(1-methylethyl)aminosulfonyl, N,N-dipropylaminosulfonyl, N,N-dibutylaminosulfonyl, N,N-di(1-methylpropyl)aminosulfonyl, N,N-di(2-methylpropyl)aminosulfonyl, N,N-di(1,1-dimethylethyl)aminosulfonyl, N-ethyl-N-methylaminosulfonyl, N-methyl-N-propylaminosulfonyl, N-methyl-N-(1-methylethyl)aminosulfonyl, N-butyl-N-methylaminosulfonyl, N-methyl-N-(1-methylpropyl)aminosulfonyl, N-methyl-N-(2-methylpropyl)aminosulfonyl, N-(1,1-dimethylethyl)-N-methylaminosulfonyl, N-ethyl-N-propylaminosulfonyl, N-ethyl-N-(1-methylethyl)aminosulfonyl, N-butyl-N-ethylaminosulfonyl, N-ethyl-N-(1-methylpropyl)aminosulfonyl, N-ethyl-N-(2-methylpropyl)aminosulfonyl, N-ethyl-N-(1,1-dimethylethyl)aminosulfonyl, N-(1-methylethyl)-N-propylaminosulfonyl, N-butyl-N-propylaminosulfonyl, N-(1-methylpropyl)-N-propylaminosulfonyl, N-(2-methylpropyl)-N-propylaminosulfonyl, N-(1,1-dimethylethyl)-N-propylaminosulfonyl, N-butyl-N-(1-methylethyl)aminosulfonyl, N-(1-methylethyl)-N-(1-methylpropyl)aminosulfonyl, N-(1-methylethyl)-N-(2-methylpropyl)aminosulfonyl, N-(1,1-dimethylethyl)-N-(1-methylethyl)aminosulfonyl, N-butyl-N-(1-methylpropyl)aminosulfonyl, N-butyl-N-(2-methylpropyl)aminosulfonyl, N-butyl-N-(1,1-dimethylethyl)aminosulfonyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminosulfonyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)aminosulfonyl, N-(1,1-dimethylethyl)-N-(2-methylpropyl)aminosulfonyl, N-methyl-N-pentylaminosulfonyl, N-methyl-N-(1-methylbutyl)aminosulfonyl, N-methyl-N-(2-methylbutyl)aminosulfonyl, N-methyl-N-(3-methylbutyl)aminosulfonyl, N-methyl-N-(2,2-dimethylpropyl)aminosulfonyl, N-methyl-N-(1-ethylpropyl)aminosulfonyl, N-methyl-N-hexylaminosulfonyl, N-methyl-N-(1,1-dimethylpropyl)aminosulfonyl, N-methyl-N-(1,2-dimethylpropyl)aminosulfonyl, N-methyl-N-(1-methylpentyl)aminosulfonyl, N-methyl-N-(2-methylpentyl)aminosulfonyl, N-methyl-N-(3-methylpentyl)aminosulfonyl, N-methyl-N-(4-methylpentyl)aminosulfonyl, N-methyl-N-(1,1-dimethylbutyl)aminosulfonyl, N-methyl-N-(1,2-dimethylbutyl)aminosulfonyl, N-methyl-N-(1,3-dimethylbutyl)aminosulfonyl, N-methyl-N-(2,2-dimethylbutyl)aminosulfonyl, N-methyl-N-(2,3-dimethylbutyl)aminosulfonyl, N-methyl-N-(3,3-dimethylbutyl)aminosulfonyl, N-methyl-N-(1-ethylbutyl)aminosulfonyl, N-methyl-N-(2-ethylbutyl)aminosulfonyl, N-methyl-N-(1,1,2-trimethylpropyl)aminosulfonyl, N-methyl-N-(1,2,2-trimethylpropyl)aminosulfonyl, N-methyl-N-(1-ethyl-1-methylpropyl)aminosulfonyl, N-methyl-N-(1-ethyl-2-methylpropyl)aminosulfonyl, N-ethyl-N-pentylaminosulfonyl, N-ethyl-N-(1-methylbutyl)aminosulfonyl, N-ethyl-N-(2-methylbutyl)aminosulfonyl, N-ethyl-N-(3-methylbutyl)aminosulfonyl, N-ethyl-N-(2,2-dimethylpropyl)aminosulfonyl, N-ethyl-N-(1-ethylpropyl)aminosulfonyl, N-ethyl-N-hexylaminosulfonyl, N-ethyl-N-(1,1-dimethylpropyl)aminosulfonyl, N-ethyl-N-(1,2-dimethylpropyl)aminosulfonyl, N-ethyl-N-(1-methylpentyl)aminosulfonyl, N-ethyl-N-(2-methylpentyl)aminosulfonyl, N-ethyl-N-(3-methylpentyl)aminosulfonyl, N-ethyl-N-(4-methylpentyl)aminosulfonyl, N-ethyl-N-(1,1-dimethylbutyl)aminosulfonyl, N-ethyl-N-(1,2-dimethylbutyl)aminosulfonyl, N-ethyl-N-(1,3-dimethylbutyl)aminosulfonyl, N-ethyl-N-(2,2-dimethylbutyl)aminosulfonyl, N-ethyl-N-(2,3-dimethylbutyl)aminosulfonyl, N-ethyl-N-(3,3-dimethylbutyl)aminosulfonyl, N-ethyl-N-(1-ethylbutyl)aminosulfonyl, N-ethyl-N-(2-ethylbutyl)aminosulfonyl, N-ethyl-N-(1,1,2-trimethylpropyl)aminosulfonyl, N-ethyl-N-(1,2,2-trimethylpropyl)aminosulfonyl, N-ethyl-N-(1-ethyl-1-methylpropyl)aminosulfonyl, N-ethyl-N-(1-ethyl-2-methylpropyl)aminosulfonyl, N-propyl-N-pentylaminosulfonyl, N-butyl-N-pentylaminosulfonyl, N,N-dipentylaminosulfonyl, N-propyl-N-hexylaminosulfonyl, N-butyl-N-hexylaminosulfonyl, N-pentyl-N-hexylaminosulfonyl or N,N-dihexylaminosulfonyl;
      • di(C1-C4-alkyl)amino, and the dialkylamino radicals of di(C1-C4-alkyl)amino-C1-C4-alkoxycarbonyl and N-(di-C1-C4-alkylamino)imino-C1-C6-alkyl: for example N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-di(1-methylethyl)amino, N,N-dibutylamino, N,N-di(1-methylpropyl)amino, N,N-di(2-methylpropyl)amino, N,N-di(1,1-dimethylethyl)amino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-methyl-N-(1-methylethyl)amino, N-butyl-N-methylamino, N-methyl-N-(1-methylpropyl)amino, N-methyl-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)amino, N-butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)amino, N-ethyl-N-(2-methylpropyl)amino, N-ethyl-N-(1,1-dimethylethyl)amino, N-(1-methylethyl)-N-propylamino, N-butyl-N-propylamino, N-(1-methylpropyl)-N-propylamino, N-(2-methylpropyl)-N-propylamino, N-(1,1-dimethylethyl)-N-propylamino, N-butyl-N-(1-methylethyl)amino, N-(1-methylethyl)-N-(1-methylpropyl)amino, N-(1-methylethyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylethyl)amino, N-butyl-N-(1-methylpropyl)amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(1,1-dimethylethyl)amino, N-(1-methylpropyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylpropyl)amino or N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino;
      • di(C1-C6-alkyl)amino, and the dialkylamino radicals of di(C1-C6-alkyl)aminoimino-C1-C6-alkyl: di(C1-C4-alkyl)amino as mentioned above, and also N,N-dipentylamino, N,N-dihexylamino, N-methyl-N-pentylamino, N-ethyl-N-pentylamino, N-methyl-N-hexylamino or N-ethyl-N-hexylamino;
      • C1-C4-alkylcarbonyl: for example methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl or 1,1-dimethylethylcarbonyl;
      • C1-C6-alkylcarbonyl, and the alkylcarbonyl radicals of C1-C6-alkylcarbonyl-C1-C6-alkyl: C1-C4-alkylcarbonyl as mentioned above, and also, for example, pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, hexylcarbonyl, 1,1-dimethylpropylcarbonyl, 1,2-dimethylpropylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1,1-dimethylbutylcarbonyl, 1,2-dimethylbutylcarbonyl, 1,3-dimethylbutylcarbonyl, 2,2-dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1,1,2-trimethylpropylcarbonyl, 1,2,2-trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl or 1-ethyl-2-methylpropylcarbonyl;
      • C1-C20-alkylcarbonyl: C1-C6-alkylcarbonyl as mentioned above, and also heptylcarbonyl, octylcarbonyl, pentadecylcarbonyl or heptadecylcarbonyl;
      • C1-C4-alkoxycarbonyl, and the alkoxycarbonyl moieties of di(C1-C4-alkyl)amino-C1-C4-alkoxycarbonyl: for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1,1-dimethylethoxycarbonyl;
      • (C1-C6-alkoxy)carbonyl: (C1-C4-alkoxy)carbonyl as mentioned above, and also, for example, pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, hexoxycarbonyl, 1,1-dimethylpropoxycarbonyl, 1,2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1,1-dimethylbutoxycarbonyl, 1,2-dimethylbutoxycarbonyl, 1,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1,1,2-trimethylpropoxycarbonyl, 1,2,2-trimethylpropoxycarbonyl, 1-ethyl-1-methyl-propoxycarbonyl or 1-ethyl-2-methyl-propoxycarbonyl;
      • C1-C6-haloalkoxycarbonyl: a C1-C6-alkoxycarbonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, chlorodifluoromethoxycarbonyl, bromodifluoromethoxycarbonyl, 2-fluoroethoxycarbonyl, 2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl, 2-iodoethoxycarbonyl, 2,2-difluoroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 2-chloro-2-fluoroethoxycarbonyl, 2-chloro-2,2-difluoroethoxycarbonyl, 2,2-dichloro-2-fluoroethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, pentafluoroethoxycarbonyl, 2-fluoropropoxycarbonyl, 3-fluoropropoxycarbonyl, 2-chloropropoxycarbonyl, 3-chloropropoxycarbonyl, 2-bromopropoxycarbonyl, 3-bromopropoxycarbonyl, 2,2-difluoropropoxycarbonyl, 2,3-difluoropropoxycarbonyl, 2,3-dichloropropoxycarbonyl, 3,3,3-trifluoropropoxycarbonyl, 3,3,3-trichloropropoxycarbonyl, 2,2,3,3,3-pentafluoropropoxycarbonyl, heptafluoropropoxycarbonyl, 1-(fluoromethyl)-2-fluoroethoxycarbonyl, 1-(chloromethyl)-2-chloroethoxycarbonyl, 1-(bromomethyl)-2-bromoethoxycarbonyl, 4-fluorobutoxycarbonyl, 4-chlorobutoxycarbonyl, 4-bromobutoxycarbonyl, nonafluorobutoxycarbonyl, 5-fluoropentoxycarbonyl, 5-chloropentoxycarbonyl, 5-bromopentoxycarbonyl, 5-iodopentoxycarbonyl, 6-fluorohexoxycarbonyl, 6-bromohexoxycarbonyl, 6-iodohexoxycarbonyl or dodecafluorohexoxycarbonyl;
      • (C1-C4-alkyl)carbonyloxy: acetyloxy, ethylcarbonyloxy, propylcarbonyloxy, 1-methylethylcarbonyloxy, butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy or 1,1-dimethylethylcarbonyloxy;
      • (C1-C4-alkylamino)carbonyl: for example methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, 1-methylethylaminocarbonyl, butylaminocarbonyl, 1-methylpropylaminocarbonyl, 2-methylpropylaminocarbonyl or 1,1-dimethylethylaminocarbonyl;
      • (C1-C6-alkylamino)carbonyl: (C1-C4-alkylamino)carbonyl as mentioned above, and also, for example, pentylaminocarbonyl, 1-methylbutylaminocarbonyl, 2-methylbutylaminocarbonyl, 3-methylbutylaminocarbonyl, 2,2-dimethylpropylaminocarbonyl, 1-ethylpropylaminocarbonyl, hexylaminocarbonyl, 1,1-dimethylpropylaminocarbonyl, 1,2-dimethylpropylaminocarbonyl, 1-methylpentylaminocarbonyl, 2-methylpentylaminocarbonyl, 3-methylpentylaminocarbonyl, 4-methylpentylaminocarbonyl, 1,1-dimethylbutylaminocarbonyl, 1,2-dimethylbutylaminocarbonyl, 1,3-dimethylbutylaminocarbonyl, 2,2-dimethylbutylaminocarbonyl, 2,3-dimethylbutylaminocarbonyl, 3,3-dimethylbutylaminocarbonyl, 1-ethylbutylaminocarbonyl, 2-ethylbutylaminocarbonyl, 1,1,2-trimethylpropylaminocarbonyl, 1,2,2-trimethylpropylaminocarbonyl, 1-ethyl-1-methylpropylaminocarbonyl or 1-ethyl-2-methylpropylaminocarbonyl;
      • di(C1-C4-alkyl)aminocarbonyl: for example N,N-dimethylaminocarbonyl, N,N-diethylaminocarbonyl, N,N-di(1-methylethyl)aminocarbonyl, N,N-dipropylaminocarbonyl, N,N-dibutylaminocarbonyl, N,N-di(1-methylpropyl)aminocarbonyl, N,N-di(2-methylpropyl)aminocarbonyl, N,N-di(1,1-dimethylethyl)aminocarbonyl, N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N-(1-methylethyl)aminocarbonyl, N-butyl-N-methylaminocarbonyl, N-methyl-N-(1-methylpropyl)aminocarbonyl, N-methyl-N-(2-methylpropyl)aminocarbonyl, N-(1,1-dimethylethyl)-N-methylaminocarbonyl, N-ethyl-N-propylaminocarbonyl, N-ethyl-N-(1-methylethyl)aminocarbonyl, N-butyl-N-ethylaminocarbonyl, N-ethyl-N-(1-methylpropyl)aminocarbonyl, N-ethyl-N-(2-methylpropyl)aminocarbonyl, N-ethyl-N-(1,1-dimethylethyl)aminocarbonyl, N-(1-methylethyl)-N-propylaminocarbonyl, N-butyl-N-propylaminocarbonyl, N-(1-methylpropyl)-N-propylaminocarbonyl, N-(2-methylpropyl)-N-propylaminocarbonyl, N-(1,1-dimethylethyl)-N-propylaminocarbonyl, N-butyl-N-(1-methylethyl)aminocarbonyl, N-(1-methylethyl)-N-(1-methylpropyl)aminocarbonyl, N-(1-methylethyl)-N-(2-methylpropyl)aminocarbonyl, N-(1,1-dimethylethyl)-N-(1-methylethyl)aminocarbonyl, N-butyl-N-(1-methylpropyl)aminocarbonyl, N-butyl-N-(2-methylpropyl)aminocarbonyl, N-butyl-N-(1,1-dimethylethyl)aminocarbonyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminocarbonyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)aminocarbonyl or N-(1,1-dimethylethyl)-N-(2-methylpropyl)aminocarbonyl;
      • di(C1-C6-alkyl)aminocarbonyl: di(C1-C4-alkyl)aminocarbonyl as mentioned above, and also, for example, N-methyl-N-pentylaminocarbonyl, N-methyl-N-(1-methylbutyl)aminocarbonyl, N-Methyl-N-(2-methylbutyl)aminocarbonyl, N-methyl-N-(3-methylbutyl)aminocarbonyl, N-methyl-N-(2,2-dimethylpropyl)aminocarbonyl, N-methyl-N-(1-ethylpropyl)aminocarbonyl, N-methyl-N-hexylaminocarbonyl, N-methyl-N-(1,1-dimethylpropyl)aminocarbonyl, N-methyl-N-(1,2-dimethylpropyl)aminocarbonyl, N-methyl-N-(1-methylpentyl)aminocarbonyl, N-methyl-N-(2-methylpentyl)aminocarbonyl, N-methyl-N-(3-methylpentyl)aminocarbonyl, N-methyl-N-(4-methylpentyl)aminocarbonyl, N-methyl-N-(1,1-dimethylbutyl)aminocarbonyl, N-methyl-N-(1,2-dimethylbutyl)aminocarbonyl, N-methyl-N-(1,3-dimethylbutyl)aminocarbonyl, N-methyl-N-(2,2-dimethylbutyl)aminocarbonyl, N-methyl-N-(2,3-dimethylbutyl)aminocarbonyl, N-methyl-N-(3,3-dimethylbutyl)aminocarbonyl, N-methyl-N-(1-ethylbutyl)aminocarbonyl, N-methyl-N-(2-ethylbutyl)aminocarbonyl, N-methyl-N-(1,1,2-trimethylpropyl)aminocarbonyl, N-methyl-N-(1,2,2-trimethylpropyl)aminocarbonyl, N-methyl-N-(1-ethyl-1-methylpropyl)aminocarbonyl, N-methyl-N-(1-ethyl-2-methylpropyl)aminocarbonyl, N-ethyl-N-pentylaminocarbonyl, N-ethyl-N-(1-methylbutyl)aminocarbonyl, N-ethyl-N-(2-methylbutyl)aminocarbonyl, N-ethyl-N-(3-methylbutyl)aminocarbonyl, N-ethyl-N-(2,2-dimethylpropyl)aminocarbonyl, N-ethyl-N-(1-ethylpropyl)aminocarbonyl, N-ethyl-N-hexylaminocarbonyl, N-ethyl-N-(1,1-dimethylpropyl)aminocarbonyl, N-ethyl-N-(1,2-dimethylpropyl)aminocarbonyl, N-ethyl-N-(1-methylpentyl)aminocarbonyl, N-ethyl-N-(2-methylpentyl)aminocarbonyl, N-ethyl-N-(3-methylpentyl)aminocarbonyl, N-ethyl-N-(4-methylpentyl)aminocarbonyl, N-ethyl-N-(1,1-dimethylbutyl)aminocarbonyl, N-ethyl-N-(1,2-dimethylbutyl)aminocarbonyl, N-ethyl-N-(1,3-dimethylbutyl)aminocarbonyl, N-ethyl-N-(2,2-dimethylbutyl)aminocarbonyl, N-ethyl-N-(2,3-dimethylbutyl)aminocarbonyl, N-ethyl-N-(3,3-dimethylbutyl)aminocarbonyl, N-ethyl-N-(1-ethylbutyl)aminocarbonyl, N-ethyl-N-(2-ethylbutyl)aminocarbonyl, N-ethyl-N-(1,1,2-trimethylpropyl)aminocarbonyl, N-ethyl-N-(1,2,2-trimethylpropyl)aminocarbonyl, N-ethyl-N-(1-ethyl-1-methylpropyl)aminocarbonyl, N-ethyl-N-(1-ethyl-2-methylpropyl)aminocarbonyl, N-propyl-N-pentylaminocarbonyl, N-butyl-N-pentylaminocarbonyl, N,N-dipentylaminocarbonyl, N-propyl-N-hexylaminocarbonyl, N-butyl-N-hexylaminocarbonyl, N-pentyl-N-hexylaminocarbonyl or N,N-dihexylaminocarbonyl;
      • di(C1-C6-alkyl)aminothiocarbonyl: for example N,N-dimethylaminothiocarbonyl, N,N-diethylaminothiocarbonyl, N,N-di(1-methylethyl)aminothiocarbonyl, N,N-dipropylaminothiocarbonyl, N,N-dibutylaminothiocarbonyl, N,N-di(1-methylpropyl)aminothiocarbonyl, N,N-di(2-methylpropyl)aminothiocarbonyl, N,N-di(1,1-dimethylethyl)aminothiocarbonyl, N-ethyl-N-methylaminothiocarbonyl, N-methyl-N-propylaminothiocarbonyl, N-methyl-N-(1-methylethyl)aminothiocarbonyl, N-butyl-N-methylaminothiocarbonyl, N-methyl-N-(1-methylpropyl)aminothiocarbonyl, N-methyl-N-(2-methylpropyl)aminothiocarbonyl, N-(1,1-dimethylethyl)-N-methylaminothiocarbonyl, N-ethyl-N-propylaminothiocarbonyl, N-ethyl-N-(1-methylethyl)aminothiocarbonyl, N-butyl-N-ethylaminothiocarbonyl, N-ethyl-N-(1-methylpropyl)aminothiocarbonyl, N-ethyl-N-(2-methylpropyl)aminothiocarbonyl, N-ethyl-N-(1,1-dimethylethyl)aminothiocarbonyl, N-(1-methylethyl)-N-propylaminothiocarbonyl, N-butyl-N-propylaminothiocarbonyl, N-(1-methylpropyl)-N-propylaminothiocarbonyl, N-(2-methylpropyl)-N-propylaminothiocarbonyl, N-(1,1-dimethylethyl)-N-propylaminothiocarbonyl, N-butyl-N-(1-methylethyl)aminothiocarbonyl, N-(1-methylethyl)-N-(1-methylpropyl)aminothiocarbonyl, N-(1-methylethyl)-N-(2-methylpropyl)aminothiocarbonyl, N-(1,1-dimethylethyl)-N-(1-methylethyl)aminothiocarbonyl, N-butyl-N-(1-methylpropyl)aminothiocarbonyl, N-butyl-N-(2-methylpropyl)aminothiocarbonyl, N-butyl-N-(1,1-dimethylethyl)aminothiocarbonyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminothiocarbonyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)aminothiocarbonyl, N-(1,1-dimethylethyl)-N-(2-methylpropyl)aminothiocarbonyl, N-methyl-N-pentylaminothiocarbonyl, N-methyl-N-(1-methylbutyl)aminothiocarbonyl, N-methyl-N-(2-methylbutyl)aminothiocarbonyl, N-methyl-N-(3-methylbutyl)aminothiocarbonyl, N-methyl-N-(2,2-dimethylpropyl)aminothiocarbonyl, N-methyl-N-(1-ethylpropyl)aminothiocarbonyl, N-methyl-N-hexylaminothiocarbonyl, N-methyl-N-(1,1-dimethylpropyl)aminothiocarbonyl, N-methyl-N-(1,2-dimethylpropyl)aminothiocarbonyl, N-methyl-N-(1-methylpentyl)aminothiocarbonyl, N-methyl-N-(2-methylpentyl)aminothiocarbonyl, N-methyl-N-(3-methylpentyl)aminothiocarbonyl, N-methyl-N-(4-methylpentyl)aminothiocarbonyl, N-methyl-N-(1,1-dimethylbutyl)aminothiocarbonyl, N-methyl-N-(1,2-dimethylbutyl)aminothiocarbonyl, N-methyl-N-(1,3-dimethylbutyl)aminothiocarbonyl, N-methyl-N-(2,2-dimethylbutyl)aminothiocarbonyl, N-methyl-N-(2,3-dimethylbutyl)aminothiocarbonyl, N-methyl-N-(3,3-dimethylbutyl)aminothiocarbonyl, N-methyl-N-(1-ethylbutyl)aminothiocarbonyl, N-methyl-N-(2-ethylbutyl)aminothiocarbonyl, N-methyl-N-ethyl-N-(1,1,2-trimethylpropyl)aminothiocarbonyl, N-methyl-N-(1,2,2-trimethylpropyl)aminothiocarbonyl, N-methyl-N-(1-ethyl-1-methylpropyl)aminothiocarbonyl, N-methyl-N-(1-ethyl-2-methylpropyl)aminothiocarbonyl, N-ethyl-N-pentylaminothiocarbonyl, N-ethyl-N-(1-methylbutyl)aminothiocarbonyl, N-ethyl-N-(2-methylbutyl)aminothiocarbonyl, N-ethyl-N-(3-methylbutyl)aminothiocarbonyl, N-ethyl-N-(2,2-dimethylpropyl)aminothiocarbonyl, N-ethyl-N-(1-ethylpropyl)aminothiocarbonyl, N-ethyl-N-hexylaminothiocarbonyl, N-ethyl-N-(1,1-dimethylpropyl)aminothiocarbonyl, N-ethyl-N-(1,2-dimethylpropyl)aminothiocarbonyl, N-ethyl-N-(1-methylpentyl)aminothiocarbonyl, N-ethyl-N-(2-methylpentyl)aminothiocarbonyl, N-ethyl-N-(3-methylpentyl)aminothiocarbonyl, N-ethyl-N-(4-methylpentyl)aminothiocarbonyl, N-ethyl-N-(1,1-dimethylbutyl)aminothiocarbonyl, N-ethyl-N-(1,2-dimethylbutyl)aminothiocarbonyl, N-ethyl-N-(1,3-dimethylbutyl)aminothiocarbonyl, N-ethyl-N-(2,2-dimethylbutyl)aminothiocarbonyl, N-ethyl-N-(2,3-dimethylbutyl)aminothiocarbonyl, N-ethyl-N-(3,3-dimethylbutyl)aminothiocarbonyl, N-ethyl-N-(1-ethylbutyl)aminothiocarbonyl, N-ethyl-N-(2-ethylbutyl)aminothiocarbonyl, N-ethyl-N-(1,1,2-trimethylpropyl)aminothiocarbonyl, N-ethyl-N-(1,2,2-trimethylpropyl)aminothiocarbonyl, N-ethyl-N-(1-ethyl-1-methylpropyl)aminothiocarbonyl, N-ethyl-N-(1-ethyl-2-methylpropyl)aminothiocarbonyl, N-propyl-N-pentylaminothiocarbonyl, N-butyl-N-pentylaminothiocarbonyl, N,N-dipentylaminothiocarbonyl, N-propyl-N-hexylaminothiocarbonyl, N-butyl-N-hexylaminothiocarbonyl, N-pentyl-N-hexylaminothiocarbonyl or N,N-dihexylaminothiocarbonyl;
      • C1-C4-alkoxy-C1-C4-alkyl and the alkoxyalkyl moieties of hydroxy-C1-C4-alkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkoxy as mentioned above, i.e., for example, methoxymethyl, ethoxymethyl, propoxymethyl, (1-methylethoxy)methyl, butoxymethyl, (1-methylpropoxy)methyl, (2-methylpropoxy)methyl, (1,1-dimethylethoxy)methyl, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(butoxy)ethyl, 2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl, 2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)propyl, 2-(ethoxy)propyl, 2-(propoxy)propyl, 2-(1-methylethoxy)propyl, 2-(butoxy)propyl, 2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)propyl, 3-(propoxy)propyl, 3-(1-methylethoxy)propyl, 3-(butoxy)propyl, 3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl, 3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl, 2-(propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(butoxy)butyl, 2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl, 3-(propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(butoxy)butyl, 3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl, 3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl, 4-(propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or 4-(1,1-dimethylethoxy)butyl;
      • C1-C4-alkoxy-C1-C4-alkoxy as alkoxyalkoxy moieties of C1-C4-alkoxy-C1-C4-alkoxycarbonyl: C1-C4-alkoxy which is substituted by C1-C4-alkoxy as mentioned above, i.e., for example, methoxymethoxy, ethoxymethoxy, propoxymethoxy, (1-methylethoxy)methoxy, butoxymethoxy, (1-methylpropoxy)methoxy, (2-methylpropoxy)methoxy, (1,1-dimethylethoxy)methoxy, 2-(methoxy)ethoxy, 2-(ethoxy)ethoxy, 2-(propoxy)ethoxy, 2-(1-methylethoxy)ethoxy, 2-(butoxy)ethoxy, 2-(1-methylpropoxy)ethoxy, 2-(2-methylpropoxy)ethoxy, 2-(1,1-dimethylethoxy)ethoxy, 2-(methoxy)propoxy, 2-(ethoxy)propoxy, 2-(propoxy)propoxy, 2-(1-methylethoxy)propoxy, 2-(butoxy)propoxy, 2-(1-methylpropoxy)propoxy, 2-(2-methylpropoxy)propoxy, 2-(1,1-dimethylethoxy)propoxy, 3-(methoxy)propoxy, 3-(ethoxy)propoxy, 3-(propoxy)propoxy, 3-(1-methylethoxy)propoxy, 3-(butoxy)propoxy, 3-(1-methylpropoxy)propoxy, 3-(2-methylpropoxy)propoxy, 3-(1,1-dimethylethoxy)propoxy, 2-(methoxy)butoxy, 2-(ethoxy)butoxy, 2-(propoxy)butoxy, 2-(1-methylethoxy)butoxy, 2-(butoxy)butoxy, 2-(1-methylpropoxy)butoxy, 2-(2-methylpropoxy)butoxy, 2-(1,1-dimethylethoxy)butoxy, 3-(methoxy)butoxy, 3-(ethoxy)butoxy, 3-(propoxy)butoxy, 3-(1-methylethoxy)butoxy, 3-(butoxy)butoxy, 3-(1-methylpropoxy)butoxy, 3-(2-methylpropoxy)butoxy, 3-(1,1-dimethylethoxy)butoxy, 4-(methoxy)butoxy, 4-(ethoxy)butoxy, 4-(propoxy)butoxy, 4-(1-methylethoxy)butoxy, 4-(butoxy)butoxy, 4-(1-methylpropoxy)butoxy, 4-(2-methylpropoxy)butoxy or 4-(1,1-dimethylethoxy)butoxy;
      • C3-C6-alkenyl, and the alkenyl moieties of C3-C6-alkenylcarbonyl, C3-C6-alkenyloxy, C3-C6-alkenyloxycarbonyl, C3-C6-alkenylaminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkoxy)aminocarbonyl: for example prop-2-en-1-yl, but-1-en-4-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, 2-buten-1-yl, 1-penten-3-yl, 1-penten-4-yl, 2-penten-4-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl or 1-ethyl-2-methylprop-2-en-1-yl;
      • C2-C6-alkenyl, and the alkenyl moieties of C2-C6-alkenylcarbonyl, phenyl-C2-C6-alkenylcarbonyl and heterocyclyl-C2-C6-alkenylcarbonyl: C3-C6-alkenyl as mentioned above, and also ethenyl;
      • C2-C20-alkenyl as alkenyl moiety of C2-C20-alkenylcarbonyl: C2-C6-alkenyl as mentioned above, and also pentadecenyl or heptadecenyl;
      • C3-C6-haloalkenyl: a C3-C6-alkenyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, 2-chloroallyl, 3-chloroallyl, 2,3-dichloroallyl, 3,3-dichloroallyl, 2,3,3-trichloroallyl, 2,3-dichlorobut-2-phenyl, 2-bromoallyl, 3-bromoallyl, 2,3-dibromoallyl, 3,3-dibromoallyl, 2,3,3-tribromoallyl or 2,3-dibromobut-2-enyl;
      • C3-C6-alkynyl, and the alkynyl moieties of C3-C6-alkynylcarbonyl, C3-C6-alkynyloxy, C3-C6-alkynyloxycarbonyl, C3-C6-alkynylaminocarbonyl, N—(C3-C6-alkynyl)-N—(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkynyl)-N—(C1-C6-alkoxyamino)carbonyl: for example propargyl, but-1-yn-3-yl, but-1-yn-4-yl, but-2-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-3-yl, hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4-yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl, hex-3-yn-2-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-2-yn-4-yl or 4-methylpent-2-yn-5-yl;
      • C2-C6-alkynyl, and the alkynyl moieties of C2-C6-alkynylcarbonyl: C3-C6-alkynyl as mentioned above, and also ethynyl;
      • C3-C6-haloalkynyl: a C3-C6-alkynyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, 1,1-difluoroprop-2-yn-1-yl, 3-iodoprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl, 4-iodobut-3-yn-1-yl, 5-fluoropent-3-yn-1-yl, 5-iodopent-4-yn-1-yl, 6-fluorohex-4-yn-1-yl or 6-iodohex-5-yn-1-yl;
      • C3-C6-cycloalkyl, and the cycloalkyl moieties of C3-C6-cycloalkylcarbonyl: for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
      • heterocyclyl, and the heterocyclyl moieties of heterocyclyloxy, heterocyclylcarbonyl, heterocyclyl-C1-C6-alkyl, heterocyclyloxycarbonyl, heterocyclyloxythiocarbonyl, heterocyclyl-C2-C6-alkenylcarbonyl, heterocyclylcarbonyl-C1-C6-alkyl, N—(C1-C6-alkyl)-N-(heterocyclyl)aminocarbonyl, heterocyclylaminocarbonyl: a saturated, partially saturated or unsaturated 5- or 6-membered heterocyclic ring which is attached via carbon and contains one to four identical or different heteroatoms selected from the following group: oxygen, sulfur and nitrogen, i.e., for example, 5-membered rings having, for example, one heteroatom, having two heteroatoms, having three heteroatoms or having four heteroatoms or, for example, 6-membered rings having, for example, one heteroatom, having two heteroatoms, having three heteroatoms or having four heteroatoms, i.e. 5-membered rings having one heteroatom, such as:
        • tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, tetrahydropyrrol-2-yl, tetrahydropyrrol-3-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 4,5-dihydrofuran-2-yl, 4,5-dihydrofuran-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 4,5-dihydrothien-2-yl, 4,5-dihydrothien-3-yl, 2,3-dihydro-1H-pyrrol-2-yl, 2,3-dihydro-1H-pyrrol-3-yl, 2,5-dihydro-1H-pyrrol-2-yl, 2,5-dihydro-1H-pyrrol-3-yl, 4,5-dihydro-1H-pyrrol-2-yl, 4,5-dihydro-1H-pyrrol-3-yl, 3,4-dihydro-2H-pyrrol-2-yl, 3,4-dihydro-2H-pyrrol-3-yl, 3,4-dihydro-5H-pyrrol-2-yl, 3,4-dihydro-5H-pyrrol-3-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrrol-2-yl or pyrrol-3-yl;
        • 5-membered rings having two heteroatoms such as: tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydroisoxazol-3-yl, tetrahydroisoxazol-4-yl, tetrahydroisoxazol-5-yl, 1,2-oxathiolan-3-yl, 1,2-oxathiolan-4-yl, 1,2-oxathiolan-5-yl, tetrahydroisothiazol-3-yl, tetrahydroisothiazol-4-yl, tetrahydroisothiazol-5-yl, 1,2-dithiolan-3-yl, 1,2-dithiolan-4-yl, tetrahydroimidazol-2-yl, tetrahydroimidazol-4-yl, tetrahydrooxazol-2-yl, tetrahydrooxazol-4-yl, tetrahydrooxazol-5-yl, tetrahydrothiazol-2-yl, tetrahydrothiazol-4-yl, tetrahydrothiazol-5-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, 4,5-dihydro-1H-pyrazol-3-yl, 4,5-dihydro-1H-pyrazol-4-yl, 4,5-dihydro-1H-pyrazol-5-yl, 2,5-dihydro-1H-pyrazol-3-yl, 2,5-dihydro-1H-pyrazol-4-yl, 2,5-dihydro-1H-pyrazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-3-yl, 2,5-dihydroisoxazol-4-yl, 2,5-dihydroisoxazol-5-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisothiazol-3-yl, 4,5-dihydroisothiazol-4-yl, 4,5-dihydroisothiazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydroisothiazol-3-yl, 2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl, Δ3-1,2-dithiol-3-yl, Δ3-1,2-dithiol-4-yl, Δ3-1,2-dithiol-5-yl, 4,5-dihydro-1H-imidazol-2-yl, 4,5-dihydro-1H-imidazol-4-yl, 4,5-dihydro-1H-imidazol-5-yl, 2,5-dihydro-1H-imidazol-2-yl, 2,5-dihydro-1H-imidazol-4-yl, 2,5-dihydro-1H-imidazol-5-yl, 2,3-dihydro-1H-imidazol-2-yl, 2,3-dihydro-1H-imidazol-4-yl, 4,5-dihydrooxazol-2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 1,3-dioxol-2-yl, 1,3-dioxol-4-yl, 1,3-dithiol-2-yl, 1,3-dithiol-4-yl, 1,3-oxathiol-2-yl, 1,3-oxathiol-4-yl, 1,3-oxathiol-5-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl or thiazol-5-yl;
        • 5-membered rings having three heteroatoms such as: 1,2,3-Δ2-oxadiazolin-4-yl, 1,2,3-Δ2-oxadiazolin-5-yl, 1,2,4-Δ4-oxadiazolin-3-yl, 1,2,4-Δ4-oxadiazolin-5-yl, 1,2,4-Δ2-oxadiazolin-3-yl, 1,2,4-Δ2-oxadiazolin-5-yl, 1,2,4-Δ3-oxadiazolin-3-yl, 1,2,4-Δ3-oxadiazolin-5-yl, 1,3,4-Δ2-oxadiazolin-2-yl, 1,3,4-Δ2-oxadiazolin-5-yl, 1,3,4-Δ3-oxadiazolin-2-yl, 1,3,4-oxadiazolin-2-yl, 1,2,3-Δ2-thiadiazolin-4-yl, 1,2,3-Δ2-thiadiazolin-5-yl, 1,2,4-Δ4-thiadiazolin-3-yl, 1,2,4-Δ4-thiadiazolin-5-yl, 1,2,4-Δ3-thiadiazolin-3-yl, 1,2,4-Δ3-thiadiazolin-5-yl, 1,2,4-Δ2-thiadiazolin-3-yl, 1,2,4-Δ2-thiadiazolin-5-yl, 1,3,4-Δ2-thiadiazolin-2-yl, 1,3,4-Δ2-thiadiazolin-5-yl, 1,3,4-Δ3-thiadiazolin-2-yl, 1,3,4-thiadiazolin-2-yl, 1,3,2-dioxathiolan-4-yl, 1,2,3-Δ2-triazolin-4-yl, 1,2,3-Δ2-triazolin-5-yl, 1,2,4-Δ2-triazolin-3-yl, 1,2,4-Δ2-triazolin-5-yl, 1,2,4-Δ3-triazolin-3-yl, 1,2,4-Δ3-triazolin-5-yl, 1,2,4-Δ1-triazolin-2-yl, 1,2,4-triazolin-3-yl, 3H-1,2,4-dithiazol-5-yl, 2H-1,3,4-dithiazol-5-yl, 2H-1,3,4-oxathiazol-5-yl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,4-oxadiazol-3-yl, 1,2,4,-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazolyl-2-yl, 1,2,3-triazol-4-yl or 1,2,4-triazol-3-yl;
        • 5-membered rings having four heteroatoms such as: tetrazol-5-yl;
        • 6-membered rings having one heteroatom such as: tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 2H-3,4-dihydropyran-6-yl, 2H-3,4-dihydropyran-5-yl, 2H-3,4-dihydropyran-4-yl, 2H-3,4-dihydropyran-3-yl, 2H-3,4-dihydropyran-2-yl, 2H-3,4-dihydropyran-6-yl, 2H-3,4-dihydrothiopyran-5-yl, 2H-3,4-dihydrothiopyran-4-yl, 2H-3,4-dihydropyran-3-yl, 2H-3,4-dihydropyran-2-yl, 1,2,3,4-tetrahydropyridin-6-yl, 1,2,3,4-tetrahydropyridin-5-yl, 1,2,3,4-tetrahydropyridin-4-yl, 1,2,3,4-tetrahydropyridin-3-yl, 1,2,3,4-tetrahydropyridin-2-yl, 2H-5,6-dihydropyran-2-yl, 2H-5,6-dihydropyran-3-yl, 2H-5,6-dihydropyran-4-yl, 2H-5,6-dihydropyran-5-yl, 2H-5,6-dihydropyran-6-yl, 2H-5,6-dihydrothiopyran-2-yl, 2H-5,6-dihydrothiopyran-3-yl, 2H-5,6-dihydrothiopyran-4-yl, 2H-5,6-dihydrothiopyran-5-yl, 2H-5,6-dihydrothiopyran-6-yl, 1,2,5,6-tetrahydropyridin-2-yl, 1,2,5,6-tetrahydropyridin-3-yl, 1,2,5,6-tetrahydropyridin-4-yl, 1,2,5,6-tetrahydropyridin-5-yl, 1,2,5,6-tetrahydropyridin-6-yl, 2,3,4,5-tetrahydropyridin-2-yl, 2,3,4,5-tetrahydropyridin-3-yl, 2,3,4,5-tetrahydropyridin-4-yl, 2,3,4,5-tetrahydropyridin-5-yl, 2,3,4,5-tetrahydropyridin-6-yl, 4H-pyran-2-yl, 4H-pyran-3-yl, 4H-pyran-4-yl, 4H-thiopyran-2-yl, 4H-thiopyran-3-yl, 4H-thiopyran-4-yl, 1,4-dihydropyridin-2-yl, 1,4-dihydropyridin-3-yl, 1,4-dihydropyridin-4-yl, 2H-pyran-2-yl, 2H-pyran-3-yl, 2H-pyran-4-yl, 2H-pyran-5-yl, 2H-pyran-6-yl, 2H-thiopyran-2-yl, 2H-thiopyran-3-yl, 2H-thiopyran-4-yl, 2H-thiopyran-5-yl, 2H-thiopyran-6-yl, 1,2-dihydropyridin-2-yl, 1,2-dihydropyridin-3-yl, 1,2-dihydropyridin-4-yl, 1,2-dihydropyridin-5-yl, 1,2-dihydropyridin-6-yl, 3,4-dihydropyridin-2-yl, 3,4-dihydropyridin-3-yl, 3,4-dihydropyridin-4-yl, 3,4-dihydropyridin-5-yl, 3,4-dihydropyridin-6-yl, 2,5-dihydropyridin-2-yl, 2,5-dihydropyridin-3-yl, 2,5-dihydropyridin-4-yl, 2,5-dihydropyridin-5-yl, 2,5-dihydropyridin-6-yl, 2,3-dihydropyridin-2-yl, 2,3-dihydropyridin-3-yl, 2,3-dihydropyridin-4-yl, 2,3-dihydropyridin-5-yl, 2,3-dihydropyridin-6-yl, pyridin-2-yl, pyridin-3-yl or pyridin-4-yl;
        • 6-membered rings having two heteroatoms such as: 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1,3-dithian-2-yl, 1,3-dithian-4-yl, 1,3-dithian-5-yl, 1,4-dithian-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-yl, 1,3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, 1,2-dithian-3-yl, 1,2-dithian-4-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, hexahydropyrazin-2-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, tetrahydro-1,3-oxazin-2-yl, tetrahydro-1,3-oxazin-4-yl, tetrahydro-1,3-oxazin-5-yl, tetrahydro-1,3-oxazin-6-yl, tetrahydro-1,3-thiazin-2-yl, tetrahydro-1,3-thiazin-4-yl, tetrahydro-1,3-thiazin-5-yl, tetrahydro-1,3-thiazin-6-yl, tetrahydro-1,4-thiazin-2-yl, tetrahydro-1,4-thiazin-3-yl, tetrahydro-1,4-oxazin-2-yl, tetrahydro-1,4-oxazin-3-yl, tetrahydro-1,2-oxazin-3-yl, tetrahydro-1,2-oxazin-4-yl, tetrahydro-1,2-oxazin-5-yl, tetrahydro-1,2-oxazin-6-yl, 2H-5,6-dihydro-1,2-oxazin-3-yl, 2H-5,6-dihydro-1,2-oxazin-4-yl, 2H-5,6-dihydro-1,2-oxazin-5-yl, 2H-5,6-dihydro-1,2-oxazin-6-yl, 2H-5,6-dihydro-1,2-thiazin-3-yl, 2H-5,6-dihydro-1,2-thiazin-4-yl, 2H-5,6-dihydro-1,2-thiazin-5-yl, 2H-5,6-dihydro-1,2-thiazin-6-yl, 4H-5,6-dihydro-1,2-oxazin-3-yl, 4H-5,6-dihydro-1,2-oxazin-4-yl, 4H-5,6-dihydro-1,2-oxazin-5-yl, 4H-5,6-dihydro-1,2-oxazin-6-yl, 4H-5,6-dihydro-1,2-thiazin-3-yl, 4H-5,6-dihydro-1,2-thiazin-4-yl, 4H-5,6-dihydro-1,2-thiazin-5-yl, 4H-5,6-dihydro-1,2-thiazin-6-yl, 2H-3,6-dihydro-1,2-oxazin-3-yl, 2H-3,6-dihydro-1,2-oxazin-4-yl, 2H-3,6-dihydro-1,2-oxazin-5-yl, 2H-3,6-dihydro-1,2-oxazin-6-yl, 2H-3,6-dihydro-1,2-thiazin-3-yl, 2H-3,6-dihydro-1,2-thiazin-4-yl, 2H-3,6-dihydro-1,2-thiazin-5-yl, 2H-3,6-dihydro-1,2-thiazin-6-yl, 2H-3,4-dihydro-1,2-oxazin-3-yl, 2H-3,4-dihydro-1,2-oxazin-4-yl, 2H-3,4-dihydro-1,2-oxazin-5-yl, 2H-3,4-dihydro-1,2-oxazin-6-yl, 2H-3,4-dihydro-1,2-thiazin-3-yl, 2H-3,4-dihydro-1,2-thiazin-4-yl, 2H-3,4-dihydro-1,2-thiazin-5-yl, 2H-3,4-dihydro-1,2-thiazin-6-yl, 2,3,4,5-tetrahydropyridazin-3-yl, 2,3,4,5-tetrahydropyridazin-4-yl, 2,3,4,5-tetrahydropyridazin-5-yl, 2,3,4,5-tetrahydropyridazin-6-yl, 3,4,5,6-tetrahydropyridazin-3-yl, 3,4,5,6-tetrahydropyridazin-4-yl, 1,2,5,6-tetrahydropyridazin-3-yl, 1,2,5,6-tetrahydropyridazin-4-yl, 1,2,5,6-tetrahydropyridazin-5-yl, 1,2,5,6-tetrahydropyridazin-6-yl, 1,2,3,6-tetrahydropyridazin-3-yl, 1,2,3,6-tetrahydropyridazin-4-yl, 4H-5,6-dihydro-1,3-oxazin-2-yl, 4H-5,6-dihydro-1,3-oxazin-4-yl, 4H-5,6-dihydro-1,3-oxazin-5-yl, 4H-5,6-dihydro-1,3-oxazin-6-yl, 4H-5,6-dihydro-1,3-thiazin-2-yl, 4H-5,6-dihydro-1,3-thiazin-4-yl, 4H-5,6-dihydro-1,3-thiazin-5-yl, 4H-5,6-dihydro-1,3-thiazin-6-yl, 3,4,5,6-tetrahydropyrimidin-2-yl, 3,4,5,6-tetrahydropyrimidin-4-yl, 3,4,5,6-tetrahydropyrimidin-5-yl, 3,4,5,6-tetrahydropyrimidin-6-yl, 1,2,3,4-tetrahydropyrazin-2-yl, 1,2,3,4-tetrahydropyrazin-5-yl, 1,2,3,4-tetrahydropyrimidin-2-yl, 1,2,3,4-tetrahydropyrimidin-4-yl, 1,2,3,4-tetrahydropyrimidin-5-yl, 1,2,3,4-tetrahydropyrimidin-6-yl, 2,3-dihydro-1,4-thiazin-2-yl, 2,3-dihydro-1,4-thiazin-3-yl, 2,3-dihydro-1,4-thiazin-5-yl, 2,3-dihydro-1,4-thiazin-6-yl, 2H-1,2-oxazin-3-yl, 2H-1,2-oxazin-4-yl, 2H-1,2-oxazin-5-yl, 2H-1,2-oxazin-6-yl, 2H-1,2-thiazin-3-yl, 2H-1,2-thiazin-4-yl, 2H-1,2-thiazin-5-yl, 2H-1,2-thiazin-6-yl, 4H-1,2-oxazin-3-yl, 4H-1,2-oxazin-4-yl, 4H-1,2-oxazin-5-yl, 4H-1,2-oxazin-6-yl, 4H-1,2-thiazin-3-yl, 4H-1,2-thiazin-4-yl, 4H-1,2-thiazin-5-yl, 4H-1,2-thiazin-6-yl, 6H-1,2-oxazin-3-yl, 6H-1,2-oxazin-4-yl, 6H-1,2-oxazin-5-yl, 6H-1,2-oxazin-6-yl, 6H-1,2-thiazin-3-yl, 6H-1,2-thiazin-4-yl, 6H-1,2-thiazin-5-yl, 6H-1,2-thiazin-6-yl, 2H-1,3-oxazin-2-yl, 2H-1,3-oxazin-4-yl, 2H-1,3-oxazin-5-yl, 2H-1,3-oxazin-6-yl, 2H-1,3-thiazin-2-yl, 2H-1,3-thiazin-4-yl, 2H-1,3-thiazin-5-yl, 2H-1,3-thiazin-6-yl, 4H-1,3-oxazin-2-yl, 4H-1,3-oxazin-4-yl, 4H-1,3-oxazin-5-yl, 4H-1,3-oxazin-6-yl, 4H-1,3-thiazin-2-yl, 4H-1,3-thiazin-4-yl, 4H-1,3-thiazin-5-yl, 4H-1,3-thiazin-6-yl, 6H-1,3-oxazin-2-yl, 6H-1,3-oxazin-4-yl, 6H-1,3-oxazin-5-yl, 6H-1,3-oxazin-6-yl, 6H-1,3-thiazin-2-yl, 6H-1,3-oxazin-4-yl, 6H-1,3-oxazin-5-yl, 6H-1,3-thiazin-6-yl, 2H-1,4-oxazin-2-yl, 2H-1,4-oxazin-3-yl, 2H-1,4-oxazin-5-yl, 2H-1,4-oxazin-6-yl, 2H-1,4-thiazin-2-yl, 2H-1,4-thiazin-3-yl, 2H-1,4-thiazin-5-yl, 2H-1,4-thiazin-6-yl, 4H-1,4-oxazin-2-yl, 4H-1,4-oxazin-3-yl, 4H-1,4-thiazin-2-yl, 4H-1,4-thiazin-3-yl, 1,4-dihydropyridazin-3-yl, 1,4-dihydropyridazin-4-yl, 1,4-dihydropyridazin-5-yl, 1,4-dihydropyridazin-6-yl, 1,4-dihydropyrazin-2-yl, 1,2-dihydropyrazin-2-yl, 1,2-dihydropyrazin-3-yl, 1,2-dihydropyrazin-5-yl, 1,2-dihydropyrazin-6-yl, 1,4-dihydropyrimidin-2-yl, 1,4-dihydropyrimidin-4-yl, 1,4-dihydropyrimidin-5-yl, 1,4-dihydropyrimidin-6-yl, 3,4-dihydropyrimidin-2-yl, 3,4-dihydropyrimidin-4-yl, 3,4-dihydropyrimidin-5-yl or 3,4-dihydropyrimidin-6-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl or pyrazin-2-yl;
        • 6-membered rings having three heteroatoms such as: 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl;
        • 6-membered rings having four heteroatoms such as: 1,2,4,5-tetrazin-3-yl;
        • where, if appropriate, the sulfur of the above-mentioned heterocycles may be oxidized to S═O or S(═O)2
        • and where a bicyclic ring system may be formed with a fused-on phenyl ring or with a C3-C6-carbocycle or with a further 5- to 6-membered heterocycle.
      • N-bonded heterocyclyl: a saturated, partially saturated or unsaturated 5- or 6-membered heterocyclic ring which is attached via nitrogen and contains at least one nitrogen and, if appropriate, one to three identical or different heteroatoms selected from the following group: oxygen, sulfur and nitrogen, i.e., for example,
        • N-bonded 5-membered rings such as: tetrahydropyrrol-1-yl, 2,3-dihydro-1H-pyrrol-1-yl, 2,5-dihydro-1H-pyrrol-1-yl, pyrrol-1-yl, tetrahydropyrazol-1-yl, tetrahydroisoxazol-2-yl, tetrahydroisothiazol-2-yl, tetrahydroimidazol-1-yl, tetrahydrooxazol-3-yl, tetrahydrothiazol-3-yl, 4,5-dihydro-1H-pyrazol-1-yl, 2,5-dihydro-1H-pyrazol-1-yl, 2,3-dihydro-1H-pyrazol-1-yl, 2,5-dihydroisoxazol-2-yl, 2,3-dihydroisoxazol-2-yl, 2,5-dihydroisothiazol-2-yl, 2,3-dihydroisoxazol-2-yl, 4,5-dihydro-1H-imidazol-1-yl, 2,5-dihydro-1H-imidazol-1-yl, 2,3-dihydro-1H-imidazol-1-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrothiazol-3-yl, pyrazol-1-yl, imidazol-1-yl, 1,2,4-Δ4-oxadiazolin-2-yl, 1,2,4-Δ2-oxadiazolin-4-yl, 1,2,4-Δ3-oxadiazolin-2-yl, 1,3,4-Δ2-oxadiazolin-4-yl, 1,2,4-Δ5-thiadiazolin-2-yl, 1,2,4-Δ3-thiadiazolin-2-yl, 1,2,4-Δ2-thiadiazolin-4-yl, 1,3,4-Δ2-thiadiazolin-4-yl, 1,2,3-Δ2-triazolin-1-yl, 1,2,4-Δ2-triazolin-1-yl, 1,2,4-Δ2-triazolin-4-yl, 1,2,4-Δ3-triazolin-1-yl, 1,2,4-Δ1-triazolin-4-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, tetrazol-1-yl;
        • and also N-bonded 6-membered rings such as: piperidin-1-yl, 1,2,3,4-tetrahydropyridin-1-yl, 1,2,5,6-tetrahydropyridin-1-yl, 1,4-dihydropyridin-1-yl, 1,2-dihydropyridin-1-yl, hexahydropyrimidin-1-yl, hexahydropyrazin-1-yl, hexahydropyridazin-1-yl, tetrahydro-1,3-oxazin-3-yl, tetrahydro-1,3-thiazin-3-yl, tetrahydro-1,4-thiazin-4-yl, tetrahydro-1,4-oxazin-4-yl, tetrahydro-1,2-oxazin-2-yl, 2H-5,6-dihydro-1,2-oxazin-2-yl, 2H-5,6-dihydro-1,2-thiazin-2-yl, 2H-3,6-dihydro-1,2-oxazin-2-yl, 2H-3,6-dihydro-1,2-thiazin-2-yl, 2H-3,4-dihydro-1,2-oxazin-2-yl, 2H-3,4-dihydro-1,2-thiazin-2-yl, 2,3,4,5-tetrahydropyridazin-2-yl, 1,2,5,6-tetrahydropyridazin-1-yl, 1,2,5,6-tetrahydropyridazin-2-yl, 1,2,3,6-tetrahydropyridazin-1-yl, 3,4,5,6-tetrahydropyrimidin-3-yl, 1,2,3,4-tetrahydropyrazin-1-yl, 1,2,3,4-tetrahydropyrimidin-1-yl, 1,2,3,4-tetrahydropyrimidin-3-yl, 2,3-dihydro-1,4-thiazin-4-yl, 2H-1,2-oxazin-2-yl, 2H-1,2-thiazin-2-yl, 4H-1,4-oxazin-4-yl, 4H-1,4-thiazin-4-yl, 1,4-dihydropyridazin-1-yl, 1,4-dihydropyrazin-1-yl, 1,2-dihydropyrazin-1-yl, 1,4-dihydropyrimidin-1-yl or 3,4-dihydropyrimidin-3-yl;
        • and also N-bonded cyclic imides such as:
        • phthalimide, tetrahydrophthalimide, succinimide, maleimide, glutarimide, 5-oxotriazolin-1-yl, 5-oxo-1,3,4-oxadiazolin-4-yl or 2,4-dioxo-(1H,3H)-pyrimidin-3-yl;
        • where a bicyclic ring system may be formed with a fused-on phenyl ring or with a C3-C6-carbocycle or a further 5- to 6-membered heterocycle.
  • All phenyl rings, heterocyclyl or N-heterocyclyl radicals and all phenyl components in phenoxy, phenyl-C1-C6-alkyl, phenylcarbonyl-C1-C6-alkyl, phenylcarbonyl, phenylalkenylcarbonyl, phenoxycarbonyl, phenyloxythiocarbonyl, phenylaminocarbonyl and N—(C1-C6-alkyl)-N-phenylaminocarbonyl or heterocyclyl components in heterocyclyloxy, heterocyclyl-C1-C6-alkyl, heterocyclylcarbonyl-C1-C6-alkyl, heterocyclylcarbonyl, heterocyclyloxythiocarbonyl, heterocyclylalkenylcarbonyl, heterocyclyloxycarbonyl, heterocyclylaminocarbonyl and N—(C1-C6-alkyl)-N-heterocyclylaminocarbonyl are, unless stated otherwise, preferably unsubstituted, or they carry one to three halogen atoms and/or one nitro group, one cyano radical and/or one or two methyl, trifluoromethyl, methoxy or trifluoromethoxy substitutents.
  • Furthermore, the expression “Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated heterocycle which contains one to three identical or different heteroatoms selected from the following group: oxygen, sulfur and nitrogen” denotes, for example, 5-membered rings having one heteroatom such as:
  • tetrahydrofurandiyl, tetrahydrothienediyl, tetrahydropyrrolediyl, dihydrofurandiyl, dihydrothienediyl, dihydropyrrolediyl, furandiyl, thienediyl or pyrrolediyl;
  • or 5-membered rings having two heteroatoms such as:
  • tetrahydropyrazolediyl, tetrahydroisoxazolediyl, 1,2-oxathiolanediyl, tetrahydroisothiazolediyl, 1,2-dithiolanediyl, tetrahydroimidazolediyl, tetrahydrooxazolediyl, tetrahydrothiazolediyl, 1,3-dioxolanediyl, 1,3-oxathiolanediyl, dihydropyrazolediyl, dihydroisoxazolediyl, dihydroisothiazolediyl, 1,2-dithiolediyl, dihydroimidazolediyl, dihydrooxazolediyl, dihydrothiazolediyl, dioxolediyl, oxathiolediyl, pyrazolediyl, isoxazolediyl, isothiazolediyl, imidazolediyl, oxazolediyl or thiazolediyl;
  • or 5-membered rings having three heteroatoms such as:
  • 1,2,3-oxadiazolinediyl, 1,2,3-thiadiazolinediyl, 1,2,3-triazolinediyl, 1,2,3-oxadiazolediyl, 1,2,3-thiadiazolediyl or 1,2,3-triazolediyl;
  • or 6-membered rings having one heteroatom such as:
  • tetrahydropyrandiyl, piperidinediyl, tetrahydrothiopyrandiyl, dihydropyrandiyl, dihydrothiopyrandiyl, tetrahydropyridinediyl, pyrandiyl, thiopyrandiyl, dihydropyrinediyl or pyridinediyl;
  • or 6-membered rings having two heteroatoms such as:
  • 1,3-dioxanediyl, 1,4-dioxanediyl, 1,3-dithianediyl, 1,4-dithianediyl, 1,3-oxathianediyl, 1,4-oxathianediyl, 1,2-dithianediyl, hexahydropyrimidinediyl, hexahydropyrazinediyl, hexahydropyridazinediyl, tetrahydro-1,3-oxazinediyl, tetrahydro-1,3-thiazinediyl, tetrahydro-1,4-oxazinediyl, tetrahydro-1,2-oxazinediyl, dihydro-1,2-oxazinediyl, dihydro-1,2-thiazinediyl, tetrahydropyridazinediyl, dihydro-1,3-oxazinediyl, dihydro-1,3-oxazinediyl, dihydro-1,3-thiazinediyl, tetrahydropyrimidinediyl, tetrahydropyrazinediyl, dihydro-1,4-thiazinediyl, dihydro-1,4-oxazinediyl, dihydro-1,4-dioxinediyl, dihydro-1,4-dithiinediyl, 1,2-oxazinediyl, 1,2-thiazinediyl, 1,3-oxazinediyl, 1,3-thiazinediyl, 1,4-oxazinediyl, 1,4-thiazinediyl, dihydropyridazinediyl, dihydropyrazinediyl, dihydropyrimidinediyl, pyridazinediyl, pyrimidinediyl or pyrazinediyl;
  • or 6-membered rings having 3 heteroatoms such as:
  • 1,2,4-triazinediyl;
  • where, if appropriate, the sulfur of the abovementioned heterocycles may be oxidized to S═O or S(═O)2;
  • and where the moiety is fused to the skeleton via two adjacent carbon atoms.
  • The compounds of the formula I according to the invention where R9=IIa are referred to as compounds of the formula Ia, and compounds of the formula I where R9=IIb are referred to as Ib.
  • Preference is given to the compounds of the formula I, where
    • R11 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, hydroxyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
  • Preference is likewise given to the compounds of the formula Ia.
  • With respect to the use of the compounds of the formula I according to the invention as herbicides, the variables preferably have the following meanings, in each case alone or in combination:
    • X is oxygen, sulfur, S═O, S(═O)2, CR6R7, NR8 or a bond;
    • Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated 5- or 6-membered heterocycle which contains one or two identical or different heteroatoms selected from the following group: oxygen, sulfur or nitrogen;
    • R1, R2 are hydrogen or C1-C6-alkyl;
    • R3 is halogen, C1-C6-alkyl or C1-C6-alkoxy;
    • R4 is nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl)amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino;
      • in particular nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
    • R5 is hydrogen;
    • R6, R7 are hydrogen or C1-C6-alkyl;
    • R8 is C1-C6-alkyl, C1-C6-alkylcarbonyl or C1-C6-alkylsulfonyl;
    • l is 0, 1 or 2;
    • R9 is a radical IIa
      Figure US20070197393A1-20070823-C00006
      where
    • R10 is hydroxyl, mercapto, halogen, OR13, SR13, SO2R14 or N-bonded heterocyclyl, where the heterocyclyl radical may be partially or fully halogenated and/or may carry one to three of the following radicals:
      • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
    • R11 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C3-C6-cycloalkyl;
    • R12 is hydrogen, C1-C6-alkyl or C1-C6-haloalkyl;
    • R13 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, C1-C6-alkylcarbonyl, C2-C6-alkenylcarbonyl, C3-C6-cycloalkylcarbonyl, C1-C6-alkoxycarbonyl, C3-C6-alkenyloxycarbonyl, C3-C6-alkynyloxycarbonyl, C1-C6-alkylthiocarbonyl, C1-C6-alkylaminocarbonyl, C3-C6-alkenylaminocarbonyl, C3-C6-alkynylaminocarbonyl, N,N-di(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkynyl)-N—(C1-C6-alkyl)aminocarbonyl, N—(C1-C6-alkoxy)-N—(C1-C6-alkyl) aminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkoxy)aminocarbonyl N—(C3-C6-alkynyl)-N—(C1-C6-alkoxy)aminocarbonyl, di(C1-C6-alkyl)aminothiocarbonyl, C1-C6-alkylcarbonyl-C1-C6-alkyl, C1-C6-alkoxyimino-C1-C6-alkyl, N—(C1-C6-alkylamino)imino-C1-C6-alkyl or N,N-di(C1-C6-alkylamino)imino-C1-C6-alkyl, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three of the following groups:
      • cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, hydroxycarbonyl, di(C1-C4-alkyl)aminocarbonyl, C1-C4-alkylcarbonyloxy or C3-C6-cycloalkyl;
      • is phenyl, heterocyclyl, phenyl-C1-C6-alkyl, heterocyclyl-C1-C6-alkyl, phenylcarbonyl-C1-C6-alkyl, heterocyclylcarbonyl-C1-C6-alkyl, phenylcarbonyl, heterocyclylcarbonyl, phenoxycarbonyl, phenyloxythiocarbonyl, heterocyclyloxycarbonyl, heterocyclyloxythiocarbonyl, phenyl-C2-C6-alkenylcarbonyl or heterocyclyl-C2-C6-alkenylcarbonyl, where the phenyl and the heterocyclyl radical of the 14 lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:
      • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, heterocyclyl or N-bonded heterocyclyl, where the two lastmentioned substitutents for their part may be partially or fully halogenated and/or may carry one to three of the following radicals: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
    • R14 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-cycloalkyl, C1-C6-alkoxy or di(C1-C6-haloalkyl)amino, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three of the following groups:
      • cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, hydroxycarbonyl, di(C1-C4-alkyl)aminocarbonyl, C1-C4-alkylcarbonyloxy or C3-C6-cycloalkyl;
      • is phenyl, heterocyclyl, phenyl-C1-C6-alkyl, heterocyclyl-C1-C6-alkyl, phenoxy, heterocyclyloxy, where the phenyl and the heterocyclyl radical of the lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:
      • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
  • Particular preference is given to compounds of the formula I where the variables have the following meanings, either alone or in combination:
    • X is oxygen, sulfur, S═O, S(═O)2, CR6R7 or a bond;
    • Y together with the two carbons to which it is attached forms the following heterocycles:
      • (in the embodiments of the heterocycles below, the upper undulating line represents in each case the link to the hydrocarbon which carries the radicals R1 and R2, and the lower undulating line represents the link to the meta-carbon of the benzoyl moiety).
        Figure US20070197393A1-20070823-C00007
        Figure US20070197393A1-20070823-C00008
        where the sulfur of the abovementioned heterocycles may be oxidized to S═O or S(═O)2;
        in particular, Y together with the two carbons to which it is attached forms the following heterocycles:
        Figure US20070197393A1-20070823-C00009
        Figure US20070197393A1-20070823-C00010
    • R1, R2 are hydrogen;
    • R3 is C1-C6-alkyl, such as methyl, ethyl or n-propyl; in particular methyl;
    • R4 is nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio or C1-C6-alkylsulfonyl; in particular nitro, halogen, such as fluorine, chlorine or bromine, C1-C6-haloalkyl such as trifluoromethyl, C1-C6-alkylthio, such as methylthio or ethylthio, or C1-C6-alkylsulfonyl, such as methylsulfonyl or ethylsulfonyl;
      • particularly preferably nitro, chlorine, trifluoromethyl, methylthio or methylsulfonyl;
    • R5 is hydrogen;
    • R6, R7 are hydrogen or C1-C6-alkyl, such as methyl or ethyl;
      • in particular hydrogen or methyl;
    • l is 0, 1 or 2;
      • in particular 0 or 1;
    • R9 is a radical IIa
      Figure US20070197393A1-20070823-C00011
      where
    • R10 is hydroxyl;
    • R11 is C1-C6-alkyl, such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 2-methylpropyl or 1,1-dimethylethyl or cyclopropyl;
      • in particular methyl or ethyl;
      • likewise particularly preferred cyclopropyl;
    • R12 is hydrogen or C1-C6-alkyl, such as methyl, ethyl, n-propyl or 1-methylethyl;
      • in particular hydrogen or methyl.
  • Very particular preference is given to the compounds 1a where
    • X is oxygen, sulfur, S(═O)2, CH2 or a bond;
    • Y together with the two carbons to which it is attached forms the following heterocycles:
      Figure US20070197393A1-20070823-C00012
    • R1, R2 are hydrogen;
    • R3 is C1-C4-alkyl;
    • R4 is nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio or C1-C6-alkylsulfonyl;
    • R5 is hydrogen or C1-C6-alkyl;
    • l is 0, 1 or 2;
    • R9 is a radical IIa;
    • R10 is hydroxyl;
    • R11 is hydrogen, C1-C6-alkyl or cyclopropyl;
      • in particular C1-C6-alkyl;
    • R12 is hydrogen, C1-C6-alkyl or C1-C6-haloalkyl.
  • Very particular preference is also given to the compounds Ia where X is oxygen, sulfur or a bond.
  • Very particular preference is also given to the compounds 1a where
    • Y together with the two carbons to which it is attached forms a heterocycle selected from the following group: dihydropyrazolediyl, dihydroisoxazolediyl, pyrazolediyl, isoxazolediyl or pyrimidinediyl.
  • Most preferably, Y together with the two carbons to which it is attached forms the following heterocycles:
    Figure US20070197393A1-20070823-C00013
  • Very particular preference is also given to the compounds of the formula I where
    • R1, R2 are hydrogen;
    • R3 is C1-C6-alkyl;
    • R4 is nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio or C1-C6-alkylsulfonyl;
      • in particular halogen, C1-C6-alkoxy, C1-C6-alkylthio or C1-C6-alkylsulfonyl;
    • R5 is hydrogen;
    • l is 0 oder 1.
  • Very particular preference is also given to the compounds of the formula I where
    • R10 is hydroxyl or phenylcarbonyloxy which may be unsubstituted or partially or fully halogenated and/or may carry one to three of the following radicals: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
      • in particular hydroxyl;
    • R11 is C1-C6-alkyl or C3-C6-cycloalkyl;
      • in particular C1-C6-alkyl or
      • also in particular cyclopropyl;
    • R12 is hydrogen or C1-C6-alkyl;
      • in particular hydrogen.
  • Very particular preference is also given to the compounds of the formula Ia1 (≡Ia where R1, R2, R5 and R12=H, l=0, meaning of the heterocycle according to structural formula), most particularly to compounds Ia1.n where the variables X, R4, R10 and R11 are as defined in Table 1.
  • The radical definitions of R1 to R12, X, Y and l given above and the meaning of the fused heterocycle are of particular importance for the compounds according to the invention, not only in combination with one another, but also taken on their own. (For reasons of clarity, in the formulae Ia1, Ia2 . . . , the meaning of the fused heterocycle is in each case as given in the corresponding structural formula.)
    TABLE 1
    Ia1
    Figure US20070197393A1-20070823-C00014
    n X R4 R10 R11
      1 bond F OH CH3
      2 bond Cl OH CH3
      3 bond Br OH CH3
      4 bond NO2 OH CH3
      5 bond SCH3 OH CH3
      6 bond SO2CH3 OH CH3
      7 bond SO2CH2CH3 OH CH3
      8 bond CH3 OH CH3
      9 bond CF3 OH CH3
     10 bond OCHF2 OH CH3
     11 CH2 F OH CH3
     12 CH2 Cl OH CH3
     13 CH2 Br OH CH3
     14 CH2 NO2 OH CH3
     15 CH2 SCH3 OH CH3
     16 CH2 SO2CH3 OH CH3
     17 CH2 SO2CH2CH3 OH CH3
     18 CH2 CH3 OH CH3
     19 CH2 CF3 OH CH3
     20 CH2 OCHF2 OH CH3
     21 O F OH CH3
     22 O Cl OH CH3
     23 O Br OH CH3
     24 O NO2 OH CH3
     25 O SCH3 OH CH3
     26 O SO2CH3 OH CH3
     27 O SO2CH2CH3 OH CH3
     28 O CH3 OH CH3
     29 O CF3 OH CH3
     30 O OCHF2 OH CH3
     31 S F OH CH3
     32 S Cl OH CH3
     33 S Br OH CH3
     34 S NO2 OH CH3
     35 S SCH3 OH CH3
     36 S SO2CH3 OH CH3
     37 S SO2CH2CH3 OH CH3
     38 S CH3 OH CH3
     39 S CF3 OH CH3
     40 S OCHF2 OH CH3
     41 SO2 F OH CH3
     42 SO2 Cl OH CH3
     43 SO2 Br OH CH3
     44 SO2 NO2 OH CH3
     45 SO2 SCH3 OH CH3
     46 SO2 SO2CH3 OH CH3
     47 SO2 SO2CH2CH3 OH CH3
     48 SO2 CH3 OH CH3
     49 SO2 CF3 OH CH3
     50 SO2 OCHF2 OH CH3
     51 bond F OH CH2CH3
     52 bond Cl OH CH2CH3
     53 bond Br OH CH2CH3
     54 bond NO2 OH CH2CH3
     55 bond SCH3 OH CH2CH3
     56 bond SO2CH3 OH CH2CH3
     57 bond SO2CH2CH3 OH CH2CH3
     58 bond CH3 OH CH2CH3
     59 bond CF3 OH CH2CH3
     60 bond OCHF2 OH CH2CH3
     61 CH2 F OH CH2CH3
     62 CH2 Cl OH CH2CH3
     63 CH2 Br OH CH2CH3
     64 CH2 NO2 OH CH2CH3
     65 CH2 SCH3 OH CH2CH3
     66 CH2 SO2CH3 OH CH2CH3
     67 CH2 SO2CH2CH3 OH CH2CH3
     68 CH2 CH3 OH CH2CH3
     69 CH2 CF3 OH CH2CH3
     70 CH2 OCHF2 OH CH2CH3
     71 O F OH CH2CH3
     72 O Cl OH CH2CH3
     73 O Br OH CH2CH3
     74 O NO2 OH CH2CH3
     75 O SCH3 OH CH2CH3
     76 O SO2CH3 OH CH2CH3
     77 O SO2CH2CH3 OH CH2CH3
     78 O CH3 OH CH2CH3
     79 O CF3 OH CH2CH3
     80 O OCHF2 OH CH2CH3
     81 S F OH CH2CH3
     82 S Cl OH CH2CH3
     83 S Br OH CH2CH3
     84 S NO2 OH CH2CH3
     85 S SCH3 OH CH2CH3
     86 S SO2CH3 OH CH2CH3
     87 S SO2CH2CH3 OH CH2CH3
     88 S CH3 OH CH2CH3
     89 S CF3 OH CH2CH3
     90 S OCHF2 OH CH2CH3
     91 SO2 F OH CH2CH3
     92 SO2 Cl OH CH2CH3
     93 SO2 Br OH CH2CH3
     94 SO2 NO2 OH CH2CH3
     95 SO2 SCH3 OH CH2CH3
     96 SO2 SO2CH3 OH CH2CH3
     97 SO2 SO2CH2CH3 OH CH2CH3
     98 SO2 CH3 OH CH2CH3
     99 SO2 CF3 OH CH2CH3
     100 SO2 OCHF2 OH CH2CH3
     101 bond F OCOC6H5 CH3
     102 bond Cl OCOC6H5 CH3
     103 bond Br OCOC6H5 CH3
     104 bond NO2 OCOC6H5 CH3
     105 bond SCH3 OCOC6H5 CH3
     106 bond SO2CH3 OCOC6H5 CH3
     107 bond SO2CH2CH3 OCOC6H5 CH3
     108 bond CH3 OCOC6H5 CH3
     109 bond CF3 OCOC6H5 CH3
     110 bond OCHF2 OCOC6H5 CH3
     111 CH2 F OCOC6H5 CH3
     112 CH2 Cl OCOC6H5 CH3
     113 CH2 Br OCOC6H5 CH3
     114 CH2 NO2 OCOC6H5 CH3
     115 CH2 SCH3 OCOC6H5 CH3
     116 CH2 SO2CH3 OCOC6H5 CH3
     117 CH2 SO2CH2CH3 OCOC6H5 CH3
     118 CH2 CH3 OCOC6H5 CH3
     119 CH2 CF3 OCOC6H5 CH3
     120 CH2 OCHF2 OCOC6H5 CH3
     121 O F OCOC6H5 CH3
     122 O Cl OCOC6H5 CH3
     123 O Br OCOC6H5 CH3
     124 O NO2 OCOC6H5 CH3
     125 O SCH3 OCOC6H5 CH3
     126 O SO2CH3 OCOC6H5 CH3
     127 O SO2CH2CH3 OCOC6H5 CH3
     128 O CH3 OCOC6H5 CH3
     129 O CF3 OCOC6H5 CH3
     130 O OCHF2 OCOC6H5 CH3
     131 S F OCOC6H5 CH3
     132 S Cl OCOC6H5 CH3
     133 S Br OCOC6H5 CH3
     134 S NO2 OCOC6H5 CH3
     135 S SCH3 OCOC6H5 CH3
     136 S SO2CH3 OCOC6H5 CH3
     137 S SO2CH2CH3 OCOC6H5 CH3
     138 S CH3 OCOC6H5 CH3
     139 S CF3 OCOC6H5 CH3
     140 S OCHF2 OCOC6H5 CH3
     141 SO2 F OCOC6H5 CH3
     142 SO2 Cl OCOC6H5 CH3
     143 SO2 Br OCOC6H5 CH3
     144 SO2 NO2 OCOC6H5 CH3
     145 SO2 SCH3 OCOC6H5 CH3
     146 SO2 SO2CH3 OCOC6H5 CH3
     147 SO2 SO2CH2CH3 OCOC6H5 CH3
     148 SO2 CH3 OCOC6H5 CH3
     149 SO2 CF3 OCOC6H5 CH3
     150 SO2 OCHF2 OCOC6H5 CH3
     151 bond F OCOC6H5 CH2CH3
     152 bond Cl OCOC6H5 CH2CH3
     153 bond Br OCOC6H5 CH2CH3
     154 bond NO2 OCOC6H5 CH2CH3
     155 bond SCH3 OCOC6H5 CH2CH3
     156 bond SO2CH3 OCOC6H5 CH2CH3
     157 bond SO2CH2CH3 OCOC6H5 CH2CH3
     158 bond CH3 OCOC6H5 CH2CH3
     159 bond CF3 OCOC6H5 CH2CH3
     160 bond OCHF2 OCOC6H5 CH2CH3
     161 CH2 F OCOC6H5 CH2CH3
     162 CH2 Cl OCOC6H5 CH2CH3
     163 CH2 Br OCOC6H5 CH2CH3
     164 CH2 NO2 OCOC6H5 CH2CH3
     165 CH2 SCH3 OCOC6H5 CH2CH3
     166 CH2 SO2CH3 OCOC6H5 CH2CH3
     167 CH2 SO2CH2CH3 OCOC6H5 CH2CH3
     168 CH2 CH3 OCOC6H5 CH2CH3
     169 CH2 CF3 OCOC6H5 CH2CH3
     170 CH2 OCHF2 OCOC6H5 CH2CH3
     171 O F OCOC6H5 CH2CH3
     172 O Cl OCOC6H5 CH2CH3
     173 O Br OCOC6H5 CH2CH3
     174 O NO2 OCOC6H5 CH2CH3
     175 O SCH3 OCOC6H5 CH2CH3
     176 O SO2CH3 OCOC6H5 CH2CH3
     177 O SO2CH2CH3 OCOC6H5 CH2CH3
     178 O CH3 OCOC6H5 CH2CH3
     179 O CF3 OCOC6H5 CH2CH3
     180 O OCHF2 OCOC6H5 CH2CH3
     181 S F OCOC6H5 CH2CH3
     182 S Cl OCOC6H5 CH2CH3
     183 S Br OCOC6H5 CH2CH3
     184 S NO2 OCOC6H5 CH2CH3
     185 S SCH3 OCOC6H5 CH2CH3
     186 S SO2CH3 OCOC6H5 CH2CH3
     187 S SO2CH2CH3 OCOC6H5 CH2CH3
     188 S CH3 OCOC6H5 CH2CH3
     189 S CF3 OCOC6H5 CH2CH3
     190 S OCHF2 OCOC6H5 CH2CH3
     191 SO2 F OCOC6H5 CH2CH3
     192 SO2 Cl OCOC6H5 CH2CH3
     193 SO2 Br OCOC6H5 CH2CH3
     194 SO2 NO2 OCOC6H5 CH2CH3
     195 SO2 SCH3 OCOC6H5 CH2CH3
     196 SO2 SO2CH3 OCOC6H5 CH2CH3
     197 SO2 SO2CH2CH3 OCOC6H5 CH2CH3
     198 SO2 CH3 OCOC6H5 CH2CH3
     199 SO2 CF3 OCOC6H5 CH2CH3
     200 SO2 OCHF2 OCOC6H5 CH2CH3
     201 bond F OCOC(CH3)3 CH3
     202 bond Cl OCOC(CH3)3 CH3
     203 bond Br OCOC(CH3)3 CH3
     204 bond NO2 OCOC(CH3)3 CH3
     205 bond SCH3 OCOC(CH3)3 CH3
     206 bond SO2CH3 OCOC(CH3)3 CH3
     207 bond SO2CH2CH3 OCOC(CH3)3 CH3
     208 bond CH3 OCOC(CH3)3 CH3
     209 bond CF3 OCOC(CH3)3 CH3
     210 bond OCHF2 OCOC(CH3)3 CH3
     211 CH2 F OCOC(CH3)3 CH3
     212 CH2 Cl OCOC(CH3)3 CH3
     213 CH2 Br OCOC(CH3)3 CH3
     214 CH2 NO2 OCOC(CH3)3 CH3
     215 CH2 SCH3 OCOC(CH3)3 CH3
     216 CH2 SO2CH3 OCOC(CH3)3 CH3
     217 CH2 SO2CH2CH3 OCOC(CH3)3 CH3
     218 CH2 CH3 OCOC(CH3)3 CH3
     219 CH2 CF3 OCOC(CH3)3 CH3
     220 CH2 OCHF2 OCOC(CH3)3 CH3
     221 O F OCOC(CH3)3 CH3
     222 O Cl OCOC(CH3)3 CH3
     223 O Br OCOC(CH3)3 CH3
     224 O NO2 OCOC(CH3)3 CH3
     225 O SCH3 OCOC(CH3)3 CH3
     226 O SO2CH3 OCOC(CH3)3 CH3
     227 O SO2CH2CH3 OCOC(CH3)3 CH3
     228 O CH3 OCOC(CH3)3 CH3
     229 O CF3 OCOC(CH3)3 CH3
     230 O OCHF2 OCOC(CH3)3 CH3
     231 S F OCOC(CH3)3 CH3
     232 S Cl OCOC(CH3)3 CH3
     233 S Br OCOC(CH3)3 CH3
     234 S NO2 OCOC(CH3)3 CH3
     235 S SCH3 OCOC(CH3)3 CH3
     236 S SO2CH3 OCOC(CH3)3 CH3
     237 S SO2CH2CH3 OCOC(CH3)3 CH3
     238 S CH3 OCOC(CH3)3 CH3
     239 S CF3 OCOC(CH3)3 CH3
     240 S OCHF2 OCOC(CH3)3 CH3
     241 SO2 F OCOC(CH3)3 CH3
     242 SO2 Cl OCOC(CH3)3 CH3
     243 SO2 Br OCOC(CH3)3 CH3
     244 SO2 NO2 OCOC(CH3)3 CH3
     245 SO2 SCH3 OCOC(CH3)3 CH3
     246 SO2 SO2CH3 OCOC(CH3)3 CH3
     247 SO2 SO2CH2CH3 OCOC(CH3)3 CH3
     248 SO2 CH3 OCOC(CH3)3 CH3
     249 SO2 CF3 OCOC(CH3)3 CH3
     250 SO2 OCHF2 OCOC(CH3)3 CH3
     251 bond F OCOC(CH3)3 CH2CH3
     252 bond Cl OCOC(CH3)3 CH2CH3
     253 bond Br OCOC(CH3)3 CH2CH3
     254 bond NO2 OCOC(CH3)3 CH2CH3
     255 bond SCH3 OCOC(CH3)3 CH2CH3
     256 bond SO2CH3 OCOC(CH3)3 CH2CH3
     257 bond SO2CH2CH3 OCOC(CH3)3 CH2CH3
     258 bond CH3 OCOC(CH3)3 CH2CH3
     259 bond CF3 OCOC(CH3)3 CH2CH3
     260 bond OCHF2 OCOC(CH3)3 CH2CH3
     261 CH2 F OCOC(CH3)3 CH2CH3
     262 CH2 Cl OCOC(CH3)3 CH2CH3
     263 CH2 Br OCOC(CH3)3 CH2CH3
     264 CH2 NO2 OCOC(CH3)3 CH2CH3
     265 CH2 SCH3 OCOC(CH3)3 CH2CH3
     266 CH2 SO2CH3 OCOC(CH3)3 CH2CH3
     267 CH2 SO2CH2CH3 OCOC(CH3)3 CH2CH3
     268 CH2 CH3 OCOC(CH3)3 CH2CH3
     269 CH2 CF3 OCOC(CH3)3 CH2CH3
     270 CH2 OCHF2 OCOC(CH3)3 CH2CH3
     271 O F OCOC(CH3)3 CH2CH3
     272 O Cl OCOC(CH3)3 CH2CH3
     273 O Br OCOC(CH3)3 CH2CH3
     274 O NO2 OCOC(CH3)3 CH2CH3
     275 O SCH3 OCOC(CH3)3 CH2CH3
     276 O SO2CH3 OCOC(CH3)3 CH2CH3
     277 O SO2CH2CH3 OCOC(CH3)3 CH2CH3
     278 O CH3 OCOC(CH3)3 CH2CH3
     279 O CF3 OCOC(CH3)3 CH2CH3
     280 O OCHF2 OCOC(CH3)3 CH2CH3
     281 S F OCOC(CH3)3 CH2CH3
     282 S Cl OCOC(CH3)3 CH2CH3
     283 S Br OCOC(CH3)3 CH2CH3
     284 S NO2 OCOC(CH3)3 CH2CH3
     285 S SCH3 OCOC(CH3)3 CH2CH3
     286 S SO2CH3 OCOC(CH3)3 CH2CH3
     287 S SO2CH2CH3 OCOC(CH3)3 CH2CH3
     288 S CH3 OCOC(CH3)3 CH2CH3
     289 S CF3 OCOC(CH3)3 CH2CH3
     290 S OCHF2 OCOC(CH3)3 CH2CH3
     291 SO2 F OCOC(CH3)3 CH2CH3
     292 SO2 Cl OCOC(CH3)3 CH2CH3
     293 SO2 Br OCOC(CH3)3 CH2CH3
     294 SO2 NO2 OCOC(CH3)3 CH2CH3
     295 SO2 SCH3 OCOC(CH3)3 CH2CH3
     296 SO2 SO2CH3 OCOC(CH3)3 CH2CH3
     297 SO2 SO2CH2CH3 OCOC(CH3)3 CH2CH3
     298 SO2 CH3 OCOC(CH3)3 CH2CH3
     299 SO2 CF3 OCOC(CH3)3 CH2CH3
     300 SO2 OCHF2 OCOC(CH3)3 CH2CH3
     301 bond F OCOSCH3 CH3
     302 bond Cl OCOSCH3 CH3
     303 bond Br OCOSCH3 CH3
     304 bond NO2 OCOSCH3 CH3
     305 bond SCH3 OCOSCH3 CH3
     306 bond SO2CH3 OCOSCH3 CH3
     307 bond SO2CH2CH3 OCOSCH3 CH3
     308 bond CH3 OCOSCH3 CH3
     309 bond CF3 OCOSCH3 CH3
     310 bond OCHF2 OCOSCH3 CH3
     311 CH2 F OCOSCH3 CH3
     312 CH2 Cl OCOSCH3 CH3
     313 CH2 Br OCOSCH3 CH3
     314 CH2 NO2 OCOSCH3 CH3
     315 CH2 SCH3 OCOSCH3 CH3
     316 CH2 SO2CH3 OCOSCH3 CH3
     317 CH2 SO2CH2CH3 OCOSCH3 CH3
     318 CH2 CH3 OCOSCH3 CH3
     319 CH2 CF3 OCOSCH3 CH3
     320 CH2 OCHF2 OCOSCH3 CH3
     321 O F OCOSCH3 CH3
     322 O Cl OCOSCH3 CH3
     323 O Br OCOSCH3 CH3
     324 O NO2 OCOSCH3 CH3
     325 O SCH3 OCOSCH3 CH3
     326 O SO2CH3 OCOSCH3 CH3
     327 O SO2CH2CH3 OCOSCH3 CH3
     328 O CH3 OCOSCH3 CH3
     329 O CF3 OCOSCH3 CH3
     330 O OCHF2 OCOSCH3 CH3
     331 S F OCOSCH3 CH3
     332 S Cl OCOSCH3 CH3
     333 S Br OCOSCH3 CH3
     334 S NO2 OCOSCH3 CH3
     335 S SCH3 OCOSCH3 CH3
     336 S SO2CH3 OCOSCH3 CH3
     337 S SO2CH2CH3 OCOSCH3 CH3
     338 S CH3 OCOSCH3 CH3
     339 S CF3 OCOSCH3 CH3
     340 S OCHF2 OCOSCH3 CH3
     341 SO2 F OCOSCH3 CH3
     342 SO2 Cl OCOSCH3 CH3
     343 SO2 Br OCOSCH3 CH3
     344 SO2 NO2 OCOSCH3 CH3
     345 SO2 SCH3 OCOSCH3 CH3
     346 SO2 SO2CH3 OCOSCH3 CH3
     347 SO2 SO2CH2CH3 OCOSCH3 CH3
     348 SO2 CH3 OCOSCH3 CH3
     349 SO2 CF3 OCOSCH3 CH3
     350 SO2 OCHF2 OCOSCH3 CH3
     351 bond F OCOSCH3 CH2CH3
     352 bond Cl OCOSCH3 CH2CH3
     353 bond Br OCOSCH3 CH2CH3
     354 bond NO2 OCOSCH3 CH2CH3
     355 bond SCH3 OCOSCH3 CH2CH3
     356 bond SO2CH3 OCOSCH3 CH2CH3
     357 bond SO2CH2CH3 OCOSCH3 CH2CH3
     358 bond CH3 OCOSCH3 CH2CH3
     359 bond CF3 OCOSCH3 CH2CH3
     360 bond OCHF2 OCOSCH3 CH2CH3
     361 CH2 F OCOSCH3 CH2CH3
     362 CH2 Cl OCOSCH3 CH2CH3
     363 CH2 Br OCOSCH3 CH2CH3
     364 CH2 NO2 OCOSCH3 CH2CH3
     365 CH2 SCH3 OCOSCH3 CH2CH3
     366 CH2 SO2CH3 OCOSCH3 CH2CH3
     367 CH2 SO2CH2CH3 OCOSCH3 CH2CH3
     368 CH2 CH3 OCOSCH3 CH2CH3
     369 CH2 CF3 OCOSCH3 CH2CH3
     370 CH2 OCHF2 OCOSCH3 CH2CH3
     371 O F OCOSCH3 CH2CH3
     372 O Cl OCOSCH3 CH2CH3
     373 O Br OCOSCH3 CH2CH3
     374 O NO2 OCOSCH3 CH2CH3
     375 O SCH3 OCOSCH3 CH2CH3
     376 O SO2CH3 OCOSCH3 CH2CH3
     377 O SO2CH2CH3 OCOSCH3 CH2CH3
     378 O CH3 OCOSCH3 CH2CH3
     379 O CF3 OCOSCH3 CH2CH3
     380 O OCHF2 OCOSCH3 CH2CH3
     381 S F OCOSCH3 CH2CH3
     382 S Cl OCOSCH3 CH2CH3
     383 S Br OCOSCH3 CH2CH3
     384 S NO2 OCOSCH3 CH2CH3
     385 S SCH3 OCOSCH3 CH2CH3
     386 S SO2CH3 OCOSCH3 CH2CH3
     387 S SO2CH2CH3 OCOSCH3 CH2CH3
     388 S CH3 OCOSCH3 CH2CH3
     389 S CF3 OCOSCH3 CH2CH3
     390 S OCHF2 OCOSCH3 CH2CH3
     391 SO2 F OCOSCH3 CH2CH3
     392 SO2 Cl OCOSCH3 CH2CH3
     393 SO2 Br OCOSCH3 CH2CH3
     394 SO2 NO2 OCOSCH3 CH2CH3
     395 SO2 SCH3 OCOSCH3 CH2CH3
     396 SO2 SO2CH3 OCOSCH3 CH2CH3
     397 SO2 SO2CH2CH3 OCOSCH3 CH2CH3
     398 SO2 CH3 OCOSCH3 CH2CH3
     399 SO2 CF3 OCOSCH3 CH2CH3
     400 SO2 OCHF2 OCOSCH3 CH2CH3
     401 bond F OCH3 CH3
     402 bond Cl OCH3 CH3
     403 bond Br OCH3 CH3
     404 bond NO2 OCH3 CH3
     405 bond SCH3 OCH3 CH3
     406 bond SO2CH3 OCH3 CH3
     407 bond SO2CH2CH3 OCH3 CH3
     408 bond CH3 OCH3 CH3
     409 bond CF3 OCH3 CH3
     410 bond OCHF2 OCH3 CH3
     411 CH2 F OCH3 CH3
     412 CH2 Cl OCH3 CH3
     413 CH2 Br OCH3 CH3
     414 CH2 NO2 OCH3 CH3
     415 CH2 SCH3 OCH3 CH3
     416 CH2 SO2CH3 OCH3 CH3
     417 CH2 SO2CH2CH3 OCH3 CH3
     418 CH2 CH3 OCH3 CH3
     419 CH2 CF3 OCH3 CH3
     420 CH2 OCHF2 OCH3 CH3
     421 O F OCH3 CH3
     422 O Cl OCH3 CH3
     423 O Br OCH3 CH3
     424 O NO2 OCH3 CH3
     425 O SCH3 OCH3 CH3
     426 O SO2CH3 OCH3 CH3
     427 O SO2CH2CH3 OCH3 CH3
     428 O CH3 OCH3 CH3
     429 O CF3 OCH3 CH3
     430 O OCHF2 OCH3 CH3
     431 S F OCH3 CH3
     432 S Cl OCH3 CH3
     433 S Br OCH3 CH3
     434 S NO2 OCH3 CH3
     435 S SCH3 OCH3 CH3
     436 S SO2CH3 OCH3 CH3
     437 S SO2CH2CH3 OCH3 CH3
     438 S CH3 OCH3 CH3
     439 S CF3 OCH3 CH3
     440 S OCHF2 OCH3 CH3
     441 SO2 F OCH3 CH3
     442 SO2 Cl OCH3 CH3
     443 SO2 Br OCH3 CH3
     444 SO2 NO2 OCH3 CH3
     445 SO2 SCH3 OCH3 CH3
     446 SO2 SO2CH3 OCH3 CH3
     447 SO2 SO2CH2CH3 OCH3 CH3
     448 SO2 CH3 OCH3 CH3
     449 SO2 CF3 OCH3 CH3
     450 SO2 OCHF2 OCH3 CH3
     451 bond F OCH3 CH2CH3
     452 bond Cl OCH3 CH2CH3
     453 bond Br OCH3 CH2CH3
     454 bond NO2 OCH3 CH2CH3
     455 bond SCH3 OCH3 CH2CH3
     456 bond SO2CH3 OCH3 CH2CH3
     457 bond SO2CH2CH3 OCH3 CH2CH3
     458 bond CH3 OCH3 CH2CH3
     459 bond CF3 OCH3 CH2CH3
     460 bond OCHF2 OCH3 CH2CH3
     461 CH2 F OCH3 CH2CH3
     462 CH2 Cl OCH3 CH2CH3
     463 CH2 Br OCH3 CH2CH3
     464 CH2 NO2 OCH3 CH2CH3
     465 CH2 SCH3 OCH3 CH2CH3
     466 CH2 SO2CH3 OCH3 CH2CH3
     467 CH2 SO2CH2CH3 OCH3 CH2CH3
     468 CH2 CH3 OCH3 CH2CH3
     469 CH2 CF3 OCH3 CH2CH3
     470 CH2 OCHF2 OCH3 CH2CH3
     471 O F OCH3 CH2CH3
     472 O Cl OCH3 CH2CH3
     473 O Br OCH3 CH2CH3
     474 O NO2 OCH3 CH2CH3
     475 O SCH3 OCH3 CH2CH3
     476 O SO2CH3 OCH3 CH2CH3
     477 O SO2CH2CH3 OCH3 CH2CH3
     478 O CH3 OCH3 CH2CH3
     479 O CF3 OCH3 CH2CH3
     480 O OCHF2 OCH3 CH2CH3
     481 S F OCH3 CH2CH3
     482 S Cl OCH3 CH2CH3
     483 S Br OCH3 CH2CH3
     484 S NO2 OCH3 CH2CH3
     485 S SCH3 OCH3 CH2CH3
     486 S SO2CH3 OCH3 CH2CH3
     487 S SO2CH2CH3 OCH3 CH2CH3
     488 S CH3 OCH3 CH2CH3
     489 S CF3 OCH3 CH2CH3
     490 S OCHF2 OCH3 CH2CH3
     491 SO2 F OCH3 CH2CH3
     492 SO2 Cl OCH3 CH2CH3
     493 SO2 Br OCH3 CH2CH3
     494 SO2 NO2 OCH3 CH2CH3
     495 SO2 SCH3 OCH3 CH2CH3
     496 SO2 SO2CH3 OCH3 CH2CH3
     497 SO2 SO2CH2CH3 OCH3 CH2CH3
     498 SO2 CH3 OCH3 CH2CH3
     499 SO2 CF3 OCH3 CH2CH3
     500 SO2 OCHF2 OCH3 CH2CH3
     501 bond F OCH(CH3)2 CH3
     502 bond Cl OCH(CH3)2 CH3
     503 bond Br OCH(CH3)2 CH3
     504 bond NO2 OCH(CH3)2 CH3
     505 bond SCH3 OCH(CH3)2 CH3
     506 bond SO2CH3 OCH(CH3)2 CH3
     507 bond SO2CH2CH3 OCH(CH3)2 CH3
     508 bond CH3 OCH(CH3)2 CH3
     509 bond CF3 OCH(CH3)2 CH3
     510 bond OCHF2 OCH(CH3)2 CH3
     511 CH2 F OCH(CH3)2 CH3
     512 CH2 Cl OCH(CH3)2 CH3
     513 CH2 Br OCH(CH3)2 CH3
     514 CH2 NO2 OCH(CH3)2 CH3
     515 CH2 SCH3 OCH(CH3)2 CH3
     516 CH2 SO2CH3 OCH(CH3)2 CH3
     517 CH2 SO2CH2CH3 OCH(CH3)2 CH3
     518 CH2 CH3 OCH(CH3)2 CH3
     519 CH2 CF3 OCH(CH3)2 CH3
     520 CH2 OCHF2 OCH(CH3)2 CH3
     521 O F OCH(CH3)2 CH3
     522 O Cl OCH(CH3)2 CH3
     523 O Br OCH(CH3)2 CH3
     524 O NO2 OCH(CH3)2 CH3
     525 O SCH3 OCH(CH3)2 CH3
     526 O SO2CH3 OCH(CH3)2 CH3
     527 O SO2CH2CH3 OCH(CH3)2 CH3
     528 O CH3 OCH(CH3)2 CH3
     529 O CF3 OCH(CH3)2 CH3
     530 O OCHF2 OCH(CH3)2 CH3
     531 S F OCH(CH3)2 CH3
     532 S Cl OCH(CH3)2 CH3
     533 S Br OCH(CH3)2 CH3
     534 S NO2 OCH(CH3)2 CH3
     535 S SCH3 OCH(CH3)2 CH3
     536 S SO2CH3 OCH(CH3)2 CH3
     537 S SO2CH2CH3 OCH(CH3)2 CH3
     538 S CH3 OCH(CH3)2 CH3
     539 S CF3 OCH(CH3)2 CH3
     540 S OCHF2 OCH(CH3)2 CH3
     541 SO2 F OCH(CH3)2 CH3
     542 SO2 Cl OCH(CH3)2 CH3
     543 SO2 Br OCH(CH3)2 CH3
     544 SO2 NO2 OCH(CH3)2 CH3
     545 SO2 SCH3 OCH(CH3)2 CH3
     546 SO2 SO2CH3 OCH(CH3)2 CH3
     547 SO2 SO2CH2CH3 OCH(CH3)2 CH3
     548 SO2 CH3 OCH(CH3)2 CH3
     549 SO2 CF3 OCH(CH3)2 CH3
     550 SO2 OCHF2 OCH(CH3)2 CH3
     551 bond F OCH(CH3)2 CH2CH3
     552 bond Cl OCH(CH3)2 CH2CH3
     553 bond Br OCH(CH3)2 CH2CH3
     554 bond NO2 OCH(CH3)2 CH2CH3
     555 bond SCH3 OCH(CH3)2 CH2CH3
     556 bond SO2CH3 OCH(CH3)2 CH2CH3
     557 bond SO2CH2CH3 OCH(CH3)2 CH2CH3
     558 bond CH3 OCH(CH3)2 CH2CH3
     559 bond CF3 OCH(CH3)2 CH2CH3
     560 bond OCHF2 OCH(CH3)2 CH2CH3
     561 CH2 F OCH(CH3)2 CH2CH3
     562 CH2 Cl OCH(CH3)2 CH2CH3
     563 CH2 Br OCH(CH3)2 CH2CH3
     564 CH2 NO2 OCH(CH3)2 CH2CH3
     565 CH2 SCH3 OCH(CH3)2 CH2CH3
     566 CH2 SO2CH3 OCH(CH3)2 CH2CH3
     567 CH2 SO2CH2CH3 OCH(CH3)2 CH2CH3
     568 CH2 CH3 OCH(CH3)2 CH2CH3
     569 CH2 CF3 OCH(CH3)2 CH2CH3
     570 CH2 OCHF2 OCH(CH3)2 CH2CH3
     571 O F OCH(CH3)2 CH2CH3
     572 O Cl OCH(CH3)2 CH2CH3
     573 O Br OCH(CH3)2 CH2CH3
     574 O NO2 OCH(CH3)2 CH2CH3
     575 O SCH3 OCH(CH3)2 CH2CH3
     576 O SO2CH3 OCH(CH3)2 CH2CH3
     577 O SO2CH2CH3 OCH(CH3)2 CH2CH3
     578 O CH3 OCH(CH3)2 CH2CH3
     579 O CF3 OCH(CH3)2 CH2CH3
     580 O OCHF2 OCH(CH3)2 CH2CH3
     581 S F OCH(CH3)2 CH2CH3
     582 S Cl OCH(CH3)2 CH2CH3
     583 S Br OCH(CH3)2 CH2CH3
     584 S NO2 OCH(CH3)2 CH2CH3
     585 S SCH3 OCH(CH3)2 CH2CH3
     586 S SO2CH3 OCH(CH3)2 CH2CH3
     587 S SO2CH2CH3 OCH(CH3)2 CH2CH3
     588 S CH3 OCH(CH3)2 CH2CH3
     589 S CF3 OCH(CH3)2 CH2CH3
     590 S OCHF2 OCH(CH3)2 CH2CH3
     591 SO2 F OCH(CH3)2 CH2CH3
     592 SO2 Cl OCH(CH3)2 CH2CH3
     593 SO2 Br OCH(CH3)2 CH2CH3
     594 SO2 NO2 OCH(CH3)2 CH2CH3
     595 SO2 SCH3 OCH(CH3)2 CH2CH3
     596 SO2 SO2CH3 OCH(CH3)2 CH2CH3
     597 SO2 SO2CH2CH3 OCH(CH3)2 CH2CH3
     598 SO2 CH3 OCH(CH3)2 CH2CH3
     599 SO2 CF3 OCH(CH3)2 CH2CH3
     600 SO2 OCHF2 OCH(CH3)2 CH2CH3
     601 bond F OCH2C6H5 CH3
     602 bond Cl OCH2C6H5 CH3
     603 bond Br OCH2C6H5 CH3
     604 bond NO2 OCH2C6H5 CH3
     605 bond SCH3 OCH2C6H5 CH3
     606 bond SO2CH3 OCH2C6H5 CH3
     607 bond SO2CH2CH3 OCH2C6H5 CH3
     608 bond CH3 OCH2C6H5 CH3
     609 bond CF3 OCH2C6H5 CH3
     610 bond OCHF2 OCH2C6H5 CH3
     611 CH2 F OCH2C6H5 CH3
     612 CH2 Cl OCH2C6H5 CH3
     613 CH2 Br OCH2C6H5 CH3
     614 CH2 NO2 OCH2C6H5 CH3
     615 CH2 SCH3 OCH2C6H5 CH3
     616 CH2 SO2CH3 OCH2C6H5 CH3
     617 CH2 SO2CH2CH3 OCH2C6H5 CH3
     618 CH2 CH3 OCH2C6H5 CH3
     619 CH2 CF3 OCH2C6H5 CH3
     620 CH2 OCHF2 OCH2C6H5 CH3
     621 O F OCH2C6H5 CH3
     622 O Cl OCH2C6H5 CH3
     623 O Br OCH2C6H5 CH3
     624 O NO2 OCH2C6H5 CH3
     625 O SCH3 OCH2C6H5 CH3
     626 O SO2CH3 OCH2C6H5 CH3
     627 O SO2CH2CH3 OCH2C6H5 CH3
     628 O CH3 OCH2C6H5 CH3
     629 O CF3 OCH2C6H5 CH3
     630 O OCHF2 OCH2C6H5 CH3
     631 S F OCH2C6H5 CH3
     632 S Cl OCH2C6H5 CH3
     633 S Br OCH2C6H5 CH3
     634 S NO2 OCH2C6H5 CH3
     635 S SCH3 OCH2C6H5 CH3
     636 S SO2CH3 OCH2C6H5 CH3
     637 S SO2CH2CH3 OCH2C6H5 CH3
     638 S CH3 OCH2C6H5 CH3
     639 S CF3 OCH2C6H5 CH3
     640 S OCHF2 OCH2C6H5 CH3
     641 SO2 F OCH2C6H5 CH3
     642 SO2 Cl OCH2C6H5 CH3
     643 SO2 Br OCH2C6H5 CH3
     644 SO2 NO2 OCH2C6H5 CH3
     645 SO2 SCH3 OCH2C6H5 CH3
     646 SO2 SO2CH3 OCH2C6H5 CH3
     647 SO2 SO2CH2CH3 OCH2C6H5 CH3
     648 SO2 CH3 OCH2C6H5 CH3
     649 SO2 CF3 OCH2C6H5 CH3
     650 SO2 OCHF2 OCH2C6H5 CH3
     651 bond F OCH2C6H5 CH2CH3
     652 bond Cl OCH2C6H5 CH2CH3
     653 bond Br OCH2C6H5 CH2CH3
     654 bond NO2 OCH2C6H5 CH2CH3
     655 bond SCH3 OCH2C6H5 CH2CH3
     656 bond SO2CH3 OCH2C6H5 CH2CH3
     657 bond SO2CH2CH3 OCH2C6H5 CH2CH3
     658 bond CH3 OCH2C6H5 CH2CH3
     659 bond CF3 OCH2C6H5 CH2CH3
     660 bond OCHF2 OCH2C6H5 CH2CH3
     661 CH2 F OCH2C6H5 CH2CH3
     662 CH2 Cl OCH2C6H5 CH2CH3
     663 CH2 Br OCH2C6H5 CH2CH3
     664 CH2 NO2 OCH2C6H5 CH2CH3
     665 CH2 SCH3 OCH2C6H5 CH2CH3
     666 CH2 SO2CH3 OCH2C6H5 CH2CH3
     667 CH2 SO2CH2CH3 OCH2C6H5 CH2CH3
     668 CH2 CH3 OCH2C6H5 CH2CH3
     669 CH2 CF3 OCH2C6H5 CH2CH3
     670 CH2 OCHF2 OCH2C6H5 CH2CH3
     671 O F OCH2C6H5 CH2CH3
     672 O Cl OCH2C6H5 CH2CH3
     673 O Br OCH2C6H5 CH2CH3
     674 O NO2 OCH2C6H5 CH2CH3
     675 O SCH3 OCH2C6H5 CH2CH3
     676 O SO2CH3 OCH2C6H5 CH2CH3
     677 O SO2CH2CH3 OCH2C6H5 CH2CH3
     678 O CH3 OCH2C6H5 CH2CH3
     679 O CF3 OCH2C6H5 CH2CH3
     680 O OCHF2 OCH2C6H5 CH2CH3
     681 S F OCH2C6H5 CH2CH3
     682 S Cl OCH2C6H5 CH2CH3
     683 S Br OCH2C6H5 CH2CH3
     684 S NO2 OCH2C6H5 CH2CH3
     685 S SCH3 OCH2C6H5 CH2CH3
     686 S SO2CH3 OCH2C6H5 CH2CH3
     687 S SO2CH2CH3 OCH2C6H5 CH2CH3
     688 S CH3 OCH2C6H5 CH2CH3
     689 S CF3 OCH2C6H5 CH2CH3
     690 S OCHF2 OCH2C6H5 CH2CH3
     691 SO2 F OCH2C6H5 CH2CH3
     692 SO2 Cl OCH2C6H5 CH2CH3
     693 SO2 Br OCH2C6H5 CH2CH3
     694 SO2 NO2 OCH2C6H5 CH2CH3
     695 SO2 SCH3 OCH2C6H5 CH2CH3
     696 SO2 SO2CH3 OCH2C6H5 CH2CH3
     697 SO2 SO2CH2CH3 OCH2C6H5 CH2CH3
     698 SO2 CH3 OCH2C6H5 CH2CH3
     699 SO2 CF3 OCH2C6H5 CH2CH3
     700 SO2 OCHF2 OCH2C6H5 CH2CH3
     701 bond F OSO2(4-CH3—C6H4) CH3
     702 bond Cl OSO2(4-CH3—C6H4) CH3
     703 bond Br OSO2(4-CH3—C6H4) CH3
     704 bond NO2 OSO2(4-CH3—C6H4) CH3
     705 bond SCH3 OSO2(4-CH3—C6H4) CH3
     706 bond SO2CH3 OSO2(4-CH3—C6H4) CH3
     707 bond SO2CH2CH3 OSO2(4-CH3—C6H4) CH3
     708 bond CH3 OSO2(4-CH3—C6H4) CH3
     709 bond CF3 OSO2(4-CH3—C6H4) CH3
     710 bond OCHF2 OSO2(4-CH3—C6H4) CH3
     711 CH2 F OSO2(4-CH3—C6H4) CH3
     712 CH2 Cl OSO2(4-CH3—C6H4) CH3
     713 CH2 Br OSO2(4-CH3—C6H4) CH3
     714 CH2 NO2 OSO2(4-CH3—C6H4) CH3
     715 CH2 SCH3 OSO2(4-CH3—C6H4) CH3
     716 CH2 SO2CH3 OSO2(4-CH3—C6H4) CH3
     717 CH2 SO2CH2CH3 OSO2(4-CH3—C6H4) CH3
     718 CH2 CH3 OSO2(4-CH3—C6H4) CH3
     719 CH2 CF3 OSO2(4-CH3—C6H4) CH3
     720 CH2 OCHF2 OSO2(4-CH3—C6H4) CH3
     721 O F OSO2(4-CH3—C6H4) CH3
     722 O Cl OSO2(4-CH3—C6H4) CH3
     723 O Br OSO2(4-CH3—C6H4) CH3
     724 O NO2 OSO2(4-CH3—C6H4) CH3
     725 O SCH3 OSO2(4-CH3—C6H4) CH3
     726 O SO2CH3 OSO2(4-CH3—C6H4) CH3
     727 O SO2CH2CH3 OSO2(4-CH3—C6H4) CH3
     728 O CH3 OSO2(4-CH3—C6H4) CH3
     729 O CF3 OSO2(4-CH3—C6H4) CH3
     730 O OCHF2 OSO2(4-CH3—C6H4) CH3
     731 S F OSO2(4-CH3—C6H4) CH3
     732 S Cl OSO2(4-CH3—C6H4) CH3
     733 S Br OSO2(4-CH3—C6H4) CH3
     734 S NO2 OSO2(4-CH3—C6H4) CH3
     735 S SCH3 OSO2(4-CH3—C6H4) CH3
     736 S SO2CH3 OSO2(4-CH3—C6H4) CH3
     737 S SO2CH2CH3 OSO2(4-CH3—C6H4) CH3
     738 S CH3 OSO2(4-CH3—C6H4) CH3
     739 S CF3 OSO2(4-CH3—C6H4) CH3
     740 S OCHF2 OSO2(4-CH3—C6H4) CH3
     741 SO2 F OSO2(4-CH3—C6H4) CH3
     742 SO2 Cl OSO2(4-CH3—C6H4) CH3
     743 SO2 Br OSO2(4-CH3—C6H4) CH3
     744 SO2 NO2 OSO2(4-CH3—C6H4) CH3
     745 SO2 SCH3 OSO2(4-CH3—C6H4) CH3
     746 SO2 SO2CH3 OSO2(4-CH3—C6H4) CH3
     747 SO2 SO2CH2CH3 OSO2(4-CH3—C6H4) CH3
     748 SO2 CH3 OSO2(4-CH3—C6H4) CH3
     749 SO2 CF3 OSO2(4-CH3—C6H4) CH3
     750 SO2 OCHF2 OSO2(4-CH3—C6H4) CH3
     751 bond F OSO2(4-CH3—C6H4) CH2CH3
     752 bond Cl OSO2(4-CH3—C6H4) CH2CH3
     753 bond Br OSO2(4-CH3—C6H4) CH2CH3
     754 bond NO2 OSO2(4-CH3—C6H4) CH2CH3
     755 bond SCH3 OSO2(4-CH3—C6H4) CH2CH3
     756 bond SO2CH3 OSO2(4-CH3—C6H4) CH2CH3
     757 bond SO2CH2CH3 OSO2(4-CH3—C6H4) CH2CH3
     758 bond CH3 OSO2(4-CH3—C6H4) CH2CH3
     759 bond CF3 OSO2(4-CH3—C6H4) CH2CH3
     760 bond OCHF2 OSO2(4-CH3—C6H4) CH2CH3
     761 CH2 F OSO2(4-CH3—C6H4) CH2CH3
     762 CH2 Cl OSO2(4-CH3—C6H4) CH2CH3
     763 CH2 Br OSO2(4-CH3—C6H4) CH2CH3
     764 CH2 NO2 OSO2(4-CH3—C6H4) CH2CH3
     765 CH2 SCH3 OSO2(4-CH3—C6H4) CH2CH3
     766 CH2 SO2CH3 OSO2(4-CH3—C6H4) CH2CH3
     767 CH2 SO2CH2CH3 OSO2(4-CH3—C6H4) CH2CH3
     768 CH2 CH3 OSO2(4-CH3—C6H4) CH2CH3
     769 CH2 CF3 OSO2(4-CH3—C6H4) CH2CH3
     770 CH2 OCHF2 OSO2(4-CH3—C6H4) CH2CH3
     771 O F OSO2(4-CH3—C6H4) CH2CH3
     772 O Cl OSO2(4-CH3—C6H4) CH2CH3
     773 O Br OSO2(4-CH3—C6H4) CH2CH3
     774 O NO2 OSO2(4-CH3—C6H4) CH2CH3
     775 O SCH3 OSO2(4-CH3—C6H4) CH2CH3
     776 O SO2CH3 OSO2(4-CH3—C6H4) CH2CH3
     777 O SO2CH2CH3 OSO2(4-CH3—C6H4) CH2CH3
     778 O CH3 OSO2(4-CH3—C6H4) CH2CH3
     779 O CF3 OSO2(4-CH3—C6H4) CH2CH3
     780 O OCHF2 OSO2(4-CH3—C6H4) CH2CH3
     781 S F OSO2(4-CH3—C6H4) CH2CH3
     782 S Cl OSO2(4-CH3—C6H4) CH2CH3
     783 S Br OSO2(4-CH3—C6H4) CH2CH3
     784 S NO2 OSO2(4-CH3—C6H4) CH2CH3
     785 S SCH3 OSO2(4-CH3—C6H4) CH2CH3
     786 S SO2CH3 OSO2(4-CH3—C6H4) CH2CH3
     787 S SO2CH2CH3 OSO2(4-CH3—C6H4) CH2CH3
     788 S CH3 OSO2(4-CH3—C6H4) CH2CH3
     789 S CF3 OSO2(4-CH3—C6H4) CH2CH3
     790 S OCHF2 OSO2(4-CH3—C6H4) CH2CH3
     791 SO2 F OSO2(4-CH3—C6H4) CH2CH3
     792 SO2 Cl OSO2(4-CH3—C6H4) CH2CH3
     793 SO2 Br OSO2(4-CH3—C6H4) CH2CH3
     794 SO2 NO2 OSO2(4-CH3—C6H4) CH2CH3
     795 SO2 SCH3 OSO2(4-CH3—C6H4) CH2CH3
     796 SO2 SO2CH3 OSO2(4-CH3—C6H4) CH2CH3
     797 SO2 SO2CH2CH3 OSO2(4-CH3—C6H4) CH2CH3
     798 SO2 CH3 OSO2(4-CH3—C6H4) CH2CH3
     799 SO2 CF3 OSO2(4-CH3—C6H4) CH2CH3
     800 SO2 OCHF2 OSO2(4-CH3—C6H4) CH2CH3
     801 bond F SCH3 CH3
     802 bond Cl SCH3 CH3
     803 bond Br SCH3 CH3
     804 bond NO2 SCH3 CH3
     805 bond SCH3 SCH3 CH3
     806 bond SO2CH3 SCH3 CH3
     807 bond SO2CH2CH3 SCH3 CH3
     808 bond CH3 SCH3 CH3
     809 bond CF3 SCH3 CH3
     810 bond OCHF2 SCH3 CH3
     811 CH2 F SCH3 CH3
     812 CH2 Cl SCH3 CH3
     813 CH2 Br SCH3 CH3
     814 CH2 NO2 SCH3 CH3
     815 CH2 SCH3 SCH3 CH3
     816 CH2 SO2CH3 SCH3 CH3
     817 CH2 SO2CH2CH3 SCH3 CH3
     818 CH2 CH3 SCH3 CH3
     819 CH2 CF3 SCH3 CH3
     820 CH2 OCHF2 SCH3 CH3
     821 O F SCH3 CH3
     822 O Cl SCH3 CH3
     823 O Br SCH3 CH3
     824 O NO2 SCH3 CH3
     825 O SCH3 SCH3 CH3
     826 O SO2CH3 SCH3 CH3
     827 O SO2CH2CH3 SCH3 CH3
     828 O CH3 SCH3 CH3
     829 O CF3 SCH3 CH3
     830 O OCHF2 SCH3 CH3
     831 S F SCH3 CH3
     832 S Cl SCH3 CH3
     833 S Br SCH3 CH3
     834 S NO2 SCH3 CH3
     835 S SCH3 SCH3 CH3
     836 S SO2CH3 SCH3 CH3
     837 S SO2CH2CH3 SCH3 CH3
     838 S CH3 SCH3 CH3
     839 S CF3 SCH3 CH3
     840 S OCHF2 SCH3 CH3
     841 SO2 F SCH3 CH3
     842 SO2 Cl SCH3 CH3
     843 SO2 Br SCH3 CH3
     844 SO2 NO2 SCH3 CH3
     845 SO2 SCH3 SCH3 CH3
     846 SO2 SO2CH3 SCH3 CH3
     847 SO2 SO2CH2CH3 SCH3 CH3
     848 SO2 CH3 SCH3 CH3
     849 SO2 CF3 SCH3 CH3
     850 SO2 OCHF2 SCH3 CH3
     851 bond F SCH3 CH2CH3
     852 bond Cl SCH3 CH2CH3
     853 bond Br SCH3 CH2CH3
     854 bond NO2 SCH3 CH2CH3
     855 bond SCH3 SCH3 CH2CH3
     856 bond SO2CH3 SCH3 CH2CH3
     857 bond SO2CH2CH3 SCH3 CH2CH3
     858 bond CH3 SCH3 CH2CH3
     859 bond CF3 SCH3 CH2CH3
     860 bond OCHF2 SCH3 CH2CH3
     861 CH2 F SCH3 CH2CH3
     862 CH2 Cl SCH3 CH2CH3
     863 CH2 Br SCH3 CH2CH3
     864 CH2 NO2 SCH3 CH2CH3
     865 CH2 SCH3 SCH3 CH2CH3
     866 CH2 SO2CH3 SCH3 CH2CH3
     867 CH2 SO2CH2CH3 SCH3 CH2CH3
     868 CH2 CH3 SCH3 CH2CH3
     869 CH2 CF3 SCH3 CH2CH3
     870 CH2 OCHF2 SCH3 CH2CH3
     871 O F SCH3 CH2CH3
     872 O Cl SCH3 CH2CH3
     873 O Br SCH3 CH2CH3
     874 O NO2 SCH3 CH2CH3
     875 O SCH3 SCH3 CH2CH3
     876 O SO2CH3 SCH3 CH2CH3
     877 O SO2CH2CH3 SCH3 CH2CH3
     878 O CH3 SCH3 CH2CH3
     879 O CF3 SCH3 CH2CH3
     880 O OCHF2 SCH3 CH2CH3
     881 S F SCH3 CH2CH3
     882 S Cl SCH3 CH2CH3
     883 S Br SCH3 CH2CH3
     884 S NO2 SCH3 CH2CH3
     885 S SCH3 SCH3 CH2CH3
     886 S SO2CH3 SCH3 CH2CH3
     887 S SO2CH2CH3 SCH3 CH2CH3
     888 S CH3 SCH3 CH2CH3
     889 S CF3 SCH3 CH2CH3
     890 S OCHF2 SCH3 CH2CH3
     891 SO2 F SCH3 CH2CH3
     892 SO2 Cl SCH3 CH2CH3
     893 SO2 Br SCH3 CH2CH3
     894 SO2 NO2 SCH3 CH2CH3
     895 SO2 SCH3 SCH3 CH2CH3
     896 SO2 SO2CH3 SCH3 CH2CH3
     897 SO2 SO2CH2CH3 SCH3 CH2CH3
     898 SO2 CH3 SCH3 CH2CH3
     899 SO2 CF3 SCH3 CH2CH3
     900 SO2 OCHF2 SCH3 CH2CH3
     901 bond F Cl CH3
     902 bond Cl Cl CH3
     903 bond Br Cl CH3
     904 bond NO2 Cl CH3
     905 bond SCH3 Cl CH3
     906 bond SO2CH3 Cl CH3
     907 bond SO2CH2CH3 Cl CH3
     908 bond CH3 Cl CH3
     909 bond CF3 Cl CH3
     910 bond OCHF2 Cl CH3
     911 CH2 F Cl CH3
     912 CH2 Cl Cl CH3
     913 CH2 Br Cl CH3
     914 CH2 NO2 Cl CH3
     915 CH2 SCH3 Cl CH3
     916 CH2 SO2CH3 Cl CH3
     917 CH2 SO2CH2CH3 Cl CH3
     918 CH2 CH3 Cl CH3
     919 CH2 CF3 Cl CH3
     920 CH2 OCHF2 Cl CH3
     921 O F Cl CH3
     922 O Cl Cl CH3
     923 O Br Cl CH3
     924 O NO2 Cl CH3
     925 O SCH3 Cl CH3
     926 O SO2CH3 Cl CH3
     927 O SO2CH2CH3 Cl CH3
     928 O CH3 Cl CH3
     929 O CF3 Cl CH3
     930 O OCHF2 Cl CH3
     931 S F Cl CH3
     932 S Cl Cl CH3
     933 S Br Cl CH3
     934 S NO2 Cl CH3
     935 S SCH3 Cl CH3
     936 S SO2CH3 Cl CH3
     937 S SO2CH2CH3 Cl CH3
     938 S CH3 Cl CH3
     939 S CF3 Cl CH3
     940 S OCHF2 Cl CH3
     941 SO2 F Cl CH3
     942 SO2 Cl Cl CH3
     943 SO2 Br Cl CH3
     944 SO2 NO2 Cl CH3
     945 SO2 SCH3 Cl CH3
     946 SO2 SO2CH3 Cl CH3
     947 SO2 SO2CH2CH3 Cl CH3
     948 SO2 CH3 Cl CH3
     949 SO2 CF3 Cl CH3
     950 SO2 OCHF2 Cl CH3
     951 bond F Cl CH2CH3
     952 bond Cl Cl CH2CH3
     953 bond Br Cl CH2CH3
     954 bond NO2 Cl CH2CH3
     955 bond SCH3 Cl CH2CH3
     956 bond SO2CH3 Cl CH2CH3
     957 bond SO2CH2CH3 Cl CH2CH3
     958 bond CH3 Cl CH2CH3
     959 bond CF3 Cl CH2CH3
     960 bond OCHF2 Cl CH2CH3
     961 CH2 F Cl CH2CH3
     962 CH2 Cl Cl CH2CH3
     963 CH2 Br Cl CH2CH3
     964 CH2 NO2 Cl CH2CH3
     965 CH2 SCH3 Cl CH2CH3
     966 CH2 SO2CH3 Cl CH2CH3
     967 CH2 SO2CH2CH3 Cl CH2CH3
     968 CH2 CH3 Cl CH2CH3
     969 CH2 CF3 Cl CH2CH3
     970 CH2 OCHF2 Cl CH2CH3
     971 O F Cl CH2CH3
     972 O Cl Cl CH2CH3
     973 O Br Cl CH2CH3
     974 O NO2 Cl CH2CH3
     975 O SCH3 Cl CH2CH3
     976 O SO2CH3 Cl CH2CH3
     977 O SO2CH2CH3 Cl CH2CH3
     978 O CH3 Cl CH2CH3
     979 O CF3 Cl CH2CH3
     980 O OCHF2 Cl CH2CH3
     981 S F Cl CH2CH3
     982 S Cl Cl CH2CH3
     983 S Br Cl CH2CH3
     984 S NO2 Cl CH2CH3
     985 S SCH3 Cl CH2CH3
     986 S SO2CH3 Cl CH2CH3
     987 S SO2CH2CH3 Cl CH2CH3
     988 S CH3 Cl CH2CH3
     989 S CF3 Cl CH2CH3
     990 S OCHF2 Cl CH2CH3
     991 SO2 F Cl CH2CH3
     992 SO2 Cl Cl CH2CH3
     993 SO2 Br Cl CH2CH3
     994 SO2 NO2 Cl CH2CH3
     995 SO2 SCH3 Cl CH2CH3
     996 SO2 SO2CH3 Cl CH2CH3
     997 SO2 SO2CH2CH3 Cl CH2CH3
     998 SO2 CH3 Cl CH2CH3
     999 SO2 CF3 Cl CH2CH3
    1000 SO2 OCHF2 Cl CH2CH3
    1001 bond F OH CH(CH3)2
    1002 bond Cl OH CH(CH3)2
    1003 bond Br OH CH(CH3)2
    1004 bond NO2 OH CH(CH3)2
    1005 bond SCH3 OH CH(CH3)2
    1006 bond SO2CH3 OH CH(CH3)2
    1007 bond SO2CH2CH3 OH CH(CH3)2
    1008 bond CH3 OH CH(CH3)2
    1009 bond CF3 OH CH(CH3)2
    1010 bond OCHF2 OH CH(CH3)2
    1011 CH2 F OH CH(CH3)2
    1012 CH2 Cl OH CH(CH3)2
    1013 CH2 Br OH CH(CH3)2
    1014 CH2 NO2 OH CH(CH3)2
    1015 CH2 SCH3 OH CH(CH3)2
    1016 CH2 SO2CH3 OH CH(CH3)2
    1017 CH2 SO2CH2CH3 OH CH(CH3)2
    1018 CH2 CH3 OH CH(CH3)2
    1019 CH2 CF3 OH CH(CH3)2
    1020 CH2 OCHF2 OH CH(CH3)2
    1021 O F OH CH(CH3)2
    1022 O Cl OH CH(CH3)2
    1023 O Br OH CH(CH3)2
    1024 O NO2 OH CH(CH3)2
    1025 O SCH3 OH CH(CH3)2
    1026 O SO2CH3 OH CH(CH3)2
    1027 O SO2CH2CH3 OH CH(CH3)2
    1028 O CH3 OH CH(CH3)2
    1029 O CF3 OH CH(CH3)2
    1030 O OCHF2 OH CH(CH3)2
    1031 S F OH CH(CH3)2
    1032 S Cl OH CH(CH3)2
    1033 S Br OH CH(CH3)2
    1034 S NO2 OH CH(CH3)2
    1035 S SCH3 OH CH(CH3)2
    1036 S SO2CH3 OH CH(CH3)2
    1037 S SO2CH2CH3 OH CH(CH3)2
    1038 S CH3 OH CH(CH3)2
    1039 S CF3 OH CH(CH3)2
    1040 S OCHF2 OH CH(CH3)2
    1041 SO2 F OH CH(CH3)2
    1042 SO2 Cl OH CH(CH3)2
    1043 SO2 Br OH CH(CH3)2
    1044 SO2 NO2 OH CH(CH3)2
    1045 SO2 SCH3 OH CH(CH3)2
    1046 SO2 SO2CH3 OH CH(CH3)2
    1047 SO2 SO2CH2CH3 OH CH(CH3)2
    1048 SO2 CH3 OH CH(CH3)2
    1049 SO2 CF3 OH CH(CH3)2
    1050 SO2 OCHF2 OH CH(CH3)2
    1051 bond F OH C(CH3)3
    1052 bond Cl OH C(CH3)3
    1053 bond Br OH C(CH3)3
    1054 bond NO2 OH C(CH3)3
    1055 bond SCH3 OH C(CH3)3
    1056 bond SO2CH3 OH C(CH3)3
    1057 bond SO2CH2CH3 OH C(CH3)3
    1058 bond CH3 OH C(CH3)3
    1059 bond CF3 OH C(CH3)3
    1060 bond OCHF2 OH C(CH3)3
    1061 CH2 F OH C(CH3)3
    1062 CH2 Cl OH C(CH3)3
    1063 CH2 Br OH C(CH3)3
    1064 CH2 NO2 OH C(CH3)3
    1065 CH2 SCH3 OH C(CH3)3
    1066 CH2 SO2CH3 OH C(CH3)3
    1067 CH2 SO2CH2CH3 OH C(CH3)3
    1068 CH2 CH3 OH C(CH3)3
    1069 CH2 CF3 OH C(CH3)3
    1070 CH2 OCHF2 OH C(CH3)3
    1071 O F OH C(CH3)3
    1072 O Cl OH C(CH3)3
    1073 O Br OH C(CH3)3
    1074 O NO2 OH C(CH3)3
    1075 O SCH3 OH C(CH3)3
    1076 O SO2CH3 OH C(CH3)3
    1077 O SO2CH2CH3 OH C(CH3)3
    1078 O CH3 OH C(CH3)3
    1079 O CF3 OH C(CH3)3
    1080 O OCHF2 OH C(CH3)3
    1081 S F OH C(CH3)3
    1082 S Cl OH C(CH3)3
    1083 S Br OH C(CH3)3
    1084 S NO2 OH C(CH3)3
    1085 S SCH3 OH C(CH3)3
    1086 S SO2CH3 OH C(CH3)3
    1087 S SO2CH2CH3 OH C(CH3)3
    1088 S CH3 OH C(CH3)3
    1089 S CF3 OH C(CH3)3
    1090 S OCHF2 OH C(CH3)3
    1091 SO2 F OH C(CH3)3
    1092 SO2 Cl OH C(CH3)3
    1093 SO2 Br OH C(CH3)3
    1094 SO2 NO2 OH C(CH3)3
    1095 SO2 SCH3 OH C(CH3)3
    1096 SO2 SO2CH3 OH C(CH3)3
    1097 SO2 SO2CH2CH3 OH C(CH3)3
    1098 SO2 CH3 OH C(CH3)3
    1099 SO2 CF3 OH C(CH3)3
    1100 SO2 OCHF2 OH C(CH3)3
    1101 bond F OCOC6H5 CH(CH3)2
    1102 bond Cl OCOC6H5 CH(CH3)2
    1103 bond Br OCOC6H5 CH(CH3)2
    1104 bond NO2 OCOC6H5 CH(CH3)2
    1105 bond SCH3 OCOC6H5 CH(CH3)2
    1106 bond SO2CH3 OCOC6H5 CH(CH3)2
    1107 bond SO2CH2CH3 OCOC6H5 CH(CH3)2
    1108 bond CH3 OCOC6H5 CH(CH3)2
    1109 bond CF3 OCOC6H5 CH(CH3)2
    1110 bond OCHF2 OCOC6H5 CH(CH3)2
    1111 CH2 F OCOC6H5 CH(CH3)2
    1112 CH2 Cl OCOC6H5 CH(CH3)2
    1113 CH2 Br OCOC6H5 CH(CH3)2
    1114 CH2 NO2 OCOC6H5 CH(CH3)2
    1115 CH2 SCH3 OCOC6H5 CH(CH3)2
    1116 CH2 SO2CH3 OCOC6H5 CH(CH3)2
    1117 CH2 SO2CH2CH3 OCOC6H5 CH(CH3)2
    1118 CH2 CH3 OCOC6H5 CH(CH3)2
    1119 CH2 CF3 OCOC6H5 CH(CH3)2
    1120 CH2 OCHF2 OCOC6H5 CH(CH3)2
    1121 O F OCOC6H5 CH(CH3)2
    1122 O Cl OCOC6H5 CH(CH3)2
    1123 O Br OCOC6H5 CH(CH3)2
    1124 O NO2 OCOC6H5 CH(CH3)2
    1125 O SCH3 OCOC6H5 CH(CH3)2
    1126 O SO2CH3 OCOC6H5 CH(CH3)2
    1127 O SO2CH2CH3 OCOC6H5 CH(CH3)2
    1128 O CH3 OCOC6H5 CH(CH3)2
    1129 O CF3 OCOC6H5 CH(CH3)2
    1130 O OCHF2 OCOC6H5 CH(CH3)2
    1131 S F OCOC6H5 CH(CH3)2
    1132 S Cl OCOC6H5 CH(CH3)2
    1133 S Br OCOC6H5 CH(CH3)2
    1134 S NO2 OCOC6H5 CH(CH3)2
    1135 S SCH3 OCOC6H5 CH(CH3)2
    1136 S SO2CH3 OCOC6H5 CH(CH3)2
    1137 S SO2CH2CH3 OCOC6H5 CH(CH3)2
    1138 S CH3 OCOC6H5 CH(CH3)2
    1139 S CF3 OCOC6H5 CH(CH3)2
    1140 S OCHF2 OCOC6H5 CH(CH3)2
    1141 SO2 F OCOC6H5 CH(CH3)2
    1142 SO2 Cl OCOC6H5 CH(CH3)2
    1143 SO2 Br OCOC6H5 CH(CH3)2
    1144 SO2 NO2 OCOC6H5 CH(CH3)2
    1145 SO2 SCH3 OCOC6H5 CH(CH3)2
    1146 SO2 SO2CH3 OCOC6H5 CH(CH3)2
    1147 SO2 SO2CH2CH3 OCOC6H5 CH(CH3)2
    1148 SO2 CH3 OCOC6H5 CH(CH3)2
    1149 SO2 CF3 OCOC6H5 CH(CH3)2
    1150 SO2 OCHF2 OCOC6H5 CH(CH3)2
    1151 bond F OCOC6H5 C(CH3)3
    1152 bond Cl OCOC6H5 C(CH3)3
    1153 bond Br OCOC6H5 C(CH3)3
    1154 bond NO2 OCOC6H5 C(CH3)3
    1155 bond SCH3 OCOC6H5 C(CH3)3
    1156 bond SO2CH3 OCOC6H5 C(CH3)3
    1157 bond SO2CH2CH3 OCOC6H5 C(CH3)3
    1158 bond CH3 OCOC6H5 C(CH3)3
    1159 bond CF3 OCOC6H5 C(CH3)3
    1160 bond OCHF2 OCOC6H5 C(CH3)3
    1161 CH2 F OCOC6H5 C(CH3)3
    1162 CH2 Cl OCOC6H5 C(CH3)3
    1163 CH2 Br OCOC6H5 C(CH3)3
    1164 CH2 NO2 OCOC6H5 C(CH3)3
    1165 CH2 SCH3 OCOC6H5 C(CH3)3
    1166 CH2 SO2CH3 OCOC6H5 C(CH3)3
    1167 CH2 SO2CH2CH3 OCOC6H5 C(CH3)3
    1168 CH2 CH3 OCOC6H5 C(CH3)3
    1169 CH2 CF3 OCOC6H5 C(CH3)3
    1170 CH2 OCHF2 OCOC6H5 C(CH3)3
    1171 O F OCOC6H5 C(CH3)3
    1172 O Cl OCOC6H5 C(CH3)3
    1173 O Br OCOC6H5 C(CH3)3
    1174 O NO2 OCOC6H5 C(CH3)3
    1175 O SCH3 OCOC6H5 C(CH3)3
    1176 O SO2CH3 OCOC6H5 C(CH3)3
    1177 O SO2CH2CH3 OCOC6H5 C(CH3)3
    1178 O CH3 OCOC6H5 C(CH3)3
    1179 O CF3 OCOC6H5 C(CH3)3
    1180 O OCHF2 OCOC6H5 C(CH3)3
    1181 S F OCOC6H5 C(CH3)3
    1182 S Cl OCOC6H5 C(CH3)3
    1183 S Br OCOC6H5 C(CH3)3
    1184 S NO2 OCOC6H5 C(CH3)3
    1185 S SCH3 OCOC6H5 C(CH3)3
    1186 S SO2CH3 OCOC6H5 C(CH3)3
    1187 S SO2CH2CH3 OCOC6H5 C(CH3)3
    1188 S CH3 OCOC6H5 C(CH3)3
    1189 S CF3 OCOC6H5 C(CH3)3
    1190 S OCHF2 OCOC6H5 C(CH3)3
    1191 SO2 F OCOC6H5 C(CH3)3
    1192 SO2 Cl OCOC6H5 C(CH3)3
    1193 SO2 Br OCOC6H5 C(CH3)3
    1194 SO2 NO2 OCOC6H5 C(CH3)3
    1195 SO2 SCH3 OCOC6H5 C(CH3)3
    1196 SO2 SO2CH3 OCOC6H5 C(CH3)3
    1197 SO2 SO2CH2CH3 OCOC6H5 C(CH3)3
    1198 SO2 CH3 OCOC6H5 C(CH3)3
    1199 SO2 CF3 OCOC6H5 C(CH3)3
    1200 SO2 OCHF2 OCOC6H5 C(CH3)3
    1201 bond F OCOC(CH3)3 CH(CH3)2
    1202 bond Cl OCOC(CH3)3 CH(CH3)2
    1203 bond Br OCOC(CH3)3 CH(CH3)2
    1204 bond NO2 OCOC(CH3)3 CH(CH3)2
    1205 bond SCH3 OCOC(CH3)3 CH(CH3)2
    1206 bond SO2CH3 OCOC(CH3)3 CH(CH3)2
    1207 bond SO2CH2CH3 OCOC(CH3)3 CH(CH3)2
    1208 bond CH3 OCOC(CH3)3 CH(CH3)2
    1209 bond CF3 OCOC(CH3)3 CH(CH3)2
    1210 bond OCHF2 OCOC(CH3)3 CH(CH3)2
    1211 CH2 F OCOC(CH3)3 CH(CH3)2
    1212 CH2 Cl OCOC(CH3)3 CH(CH3)2
    1213 CH2 Br OCOC(CH3)3 CH(CH3)2
    1214 CH2 NO2 OCOC(CH3)3 CH(CH3)2
    1215 CH2 SCH3 OCOC(CH3)3 CH(CH3)2
    1216 CH2 SO2CH3 OCOC(CH3)3 CH(CH3)2
    1217 CH2 SO2CH2CH3 OCOC(CH3)3 CH(CH3)2
    1218 CH2 CH3 OCOC(CH3)3 CH(CH3)2
    1219 CH2 CF3 OCOC(CH3)3 CH(CH3)2
    1220 CH2 OCHF2 OCOC(CH3)3 CH(CH3)2
    1221 O F OCOC(CH3)3 CH(CH3)2
    1222 O Cl OCOC(CH3)3 CH(CH3)2
    1223 O Br OCOC(CH3)3 CH(CH3)2
    1224 O NO2 OCOC(CH3)3 CH(CH3)2
    1225 O SCH3 OCOC(CH3)3 CH(CH3)2
    1226 O SO2CH3 OCOC(CH3)3 CH(CH3)2
    1227 O SO2CH2CH3 OCOC(CH3)3 CH(CH3)2
    1228 O CH3 OCOC(CH3)3 CH(CH3)2
    1229 O CF3 OCOC(CH3)3 CH(CH3)2
    1230 O OCHF2 OCOC(CH3)3 CH(CH3)2
    1231 S F OCOC(CH3)3 CH(CH3)2
    1232 S Cl OCOC(CH3)3 CH(CH3)2
    1233 S Br OCOC(CH3)3 CH(CH3)2
    1234 S NO2 OCOC(CH3)3 CH(CH3)2
    1235 S SCH3 OCOC(CH3)3 CH(CH3)2
    1236 S SO2CH3 OCOC(CH3)3 CH(CH3)2
    1237 S SO2CH2CH3 OCOC(CH3)3 CH(CH3)2
    1238 S CH3 OCOC(CH3)3 CH(CH3)2
    1239 S CF3 OCOC(CH3)3 CH(CH3)2
    1240 S OCHF2 OCOC(CH3)3 CH(CH3)2
    1241 SO2 F OCOC(CH3)3 CH(CH3)2
    1242 SO2 Cl OCOC(CH3)3 CH(CH3)2
    1243 SO2 Br OCOC(CH3)3 CH(CH3)2
    1244 SO2 NO2 OCOC(CH3)3 CH(CH3)2
    1245 SO2 SCH3 OCOC(CH3)3 CH(CH3)2
    1246 SO2 SO2CH3 OCOC(CH3)3 CH(CH3)2
    1247 SO2 SO2CH2CH3 OCOC(CH3)3 CH(CH3)2
    1248 SO2 CH3 OCOC(CH3)3 CH(CH3)2
    1249 SO2 CF3 OCOC(CH3)3 CH(CH3)2
    1250 SO2 OCHF2 OCOC(CH3)3 CH(CH3)2
    1251 bond F OCOC(CH3)3 C(CH3)3
    1252 bond Cl OCOC(CH3)3 C(CH3)3
    1253 bond Br OCOC(CH3)3 C(CH3)3
    1254 bond NO2 OCOC(CH3)3 C(CH3)3
    1255 bond SCH3 OCOC(CH3)3 C(CH3)3
    1256 bond SO2CH3 OCOC(CH3)3 C(CH3)3
    1257 bond SO2CH2CH3 OCOC(CH3)3 C(CH3)3
    1258 bond CH3 OCOC(CH3)3 C(CH3)3
    1259 bond CF3 OCOC(CH3)3 C(CH3)3
    1260 bond OCHF2 OCOC(CH3)3 C(CH3)3
    1261 CH2 F OCOC(CH3)3 C(CH3)3
    1262 CH2 Cl OCOC(CH3)3 C(CH3)3
    1263 CH2 Br OCOC(CH3)3 C(CH3)3
    1264 CH2 NO2 OCOC(CH3)3 C(CH3)3
    1265 CH2 SCH3 OCOC(CH3)3 C(CH3)3
    1266 CH2 SO2CH3 OCOC(CH3)3 C(CH3)3
    1267 CH2 SO2CH2CH3 OCOC(CH3)3 C(CH3)3
    1268 CH2 CH3 OCOC(CH3)3 C(CH3)3
    1269 CH2 CF3 OCOC(CH3)3 C(CH3)3
    1270 CH2 OCHF2 OCOC(CH3)3 C(CH3)3
    1271 O F OCOC(CH3)3 C(CH3)3
    1272 O Cl OCOC(CH3)3 C(CH3)3
    1273 O Br OCOC(CH3)3 C(CH3)3
    1274 O NO2 OCOC(CH3)3 C(CH3)3
    1275 O SCH3 OCOC(CH3)3 C(CH3)3
    1276 O SO2CH3 OCOC(CH3)3 C(CH3)3
    1277 O SO2CH2CH3 OCOC(CH3)3 C(CH3)3
    1278 O CH3 OCOC(CH3)3 C(CH3)3
    1279 O CF3 OCOC(CH3)3 C(CH3)3
    1280 O OCHF2 OCOC(CH3)3 C(CH3)3
    1281 S F OCOC(CH3)3 C(CH3)3
    1282 S Cl OCOC(CH3)3 C(CH3)3
    1283 S Br OCOC(CH3)3 C(CH3)3
    1284 S NO2 OCOC(CH3)3 C(CH3)3
    1285 S SCH3 OCOC(CH3)3 C(CH3)3
    1286 S SO2CH3 OCOC(CH3)3 C(CH3)3
    1287 S SO2CH2CH3 OCOC(CH3)3 C(CH3)3
    1288 S CH3 OCOC(CH3)3 C(CH3)3
    1289 S CF3 OCOC(CH3)3 C(CH3)3
    1290 S OCHF2 OCOC(CH3)3 C(CH3)3
    1291 SO2 F OCOC(CH3)3 C(CH3)3
    1292 SO2 Cl OCOC(CH3)3 C(CH3)3
    1293 SO2 Br OCOC(CH3)3 C(CH3)3
    1294 SO2 NO2 OCOC(CH3)3 C(CH3)3
    1295 SO2 SCH3 OCOC(CH3)3 C(CH3)3
    1296 SO2 SO2CH3 OCOC(CH3)3 C(CH3)3
    1297 SO2 SO2CH2CH3 OCOC(CH3)3 C(CH3)3
    1298 SO2 CH3 OCOC(CH3)3 C(CH3)3
    1299 SO2 CF3 OCOC(CH3)3 C(CH3)3
    1300 SO2 OCHF2 OCOC(CH3)3 C(CH3)3
    1301 bond F OCOSCH3 CH(CH3)2
    1302 bond Cl OCOSCH3 CH(CH3)2
    1303 bond Br OCOSCH3 CH(CH3)2
    1304 bond NO2 OCOSCH3 CH(CH3)2
    1305 bond SCH3 OCOSCH3 CH(CH3)2
    1306 bond SO2CH3 OCOSCH3 CH(CH3)2
    1307 bond SO2CH2CH3 OCOSCH3 CH(CH3)2
    1308 bond CH3 OCOSCH3 CH(CH3)2
    1309 bond CF3 OCOSCH3 CH(CH3)2
    1310 bond OCHF2 OCOSCH3 CH(CH3)2
    1311 CH2 F OCOSCH3 CH(CH3)2
    1312 CH2 Cl OCOSCH3 CH(CH3)2
    1313 CH2 Br OCOSCH3 CH(CH3)2
    1314 CH2 NO2 OCOSCH3 CH(CH3)2
    1315 CH2 SCH3 OCOSCH3 CH(CH3)2
    1316 CH2 SO2CH3 OCOSCH3 CH(CH3)2
    1317 CH2 SO2CH2CH3 OCOSCH3 CH(CH3)2
    1318 CH2 CH3 OCOSCH3 CH(CH3)2
    1319 CH2 CF3 OCOSCH3 CH(CH3)2
    1320 CH2 OCHF2 OCOSCH3 CH(CH3)2
    1321 O F OCOSCH3 CH(CH3)2
    1322 O Cl OCOSCH3 CH(CH3)2
    1323 O Br OCOSCH3 CH(CH3)2
    1324 O NO2 OCOSCH3 CH(CH3)2
    1325 O SCH3 OCOSCH3 CH(CH3)2
    1326 O SO2CH3 OCOSCH3 CH(CH3)2
    1327 O SO2CH2CH3 OCOSCH3 CH(CH3)2
    1328 O CH3 OCOSCH3 CH(CH3)2
    1329 O CF3 OCOSCH3 CH(CH3)2
    1330 O OCHF2 OCOSCH3 CH(CH3)2
    1331 S F OCOSCH3 CH(CH3)2
    1332 S Cl OCOSCH3 CH(CH3)2
    1333 S Br OCOSCH3 CH(CH3)2
    1334 S NO2 OCOSCH3 CH(CH3)2
    1335 S SCH3 OCOSCH3 CH(CH3)2
    1336 S SO2CH3 OCOSCH3 CH(CH3)2
    1337 S SO2CH2CH3 OCOSCH3 CH(CH3)2
    1338 S CH3 OCOSCH3 CH(CH3)2
    1339 S CF3 OCOSCH3 CH(CH3)2
    1340 S OCHF2 OCOSCH3 CH(CH3)2
    1341 SO2 F OCOSCH3 CH(CH3)2
    1342 SO2 Cl OCOSCH3 CH(CH3)2
    1343 SO2 Br OCOSCH3 CH(CH3)2
    1344 SO2 NO2 OCOSCH3 CH(CH3)2
    1345 SO2 SCH3 OCOSCH3 CH(CH3)2
    1346 SO2 SO2CH3 OCOSCH3 CH(CH3)2
    1347 SO2 SO2CH2CH3 OCOSCH3 CH(CH3)2
    1348 SO2 CH3 OCOSCH3 CH(CH3)2
    1349 SO2 CF3 OCOSCH3 CH(CH3)2
    1350 SO2 OCHF2 OCOSCH3 CH(CH3)2
    1351 bond F OCOSCH3 C(CH3)3
    1352 bond Cl OCOSCH3 C(CH3)3
    1353 bond Br OCOSCH3 C(CH3)3
    1354 bond NO2 OCOSCH3 C(CH3)3
    1355 bond SCH3 OCOSCH3 C(CH3)3
    1356 bond SO2CH3 OCOSCH3 C(CH3)3
    1357 bond SO2CH2CH3 OCOSCH3 C(CH3)3
    1358 bond CH3 OCOSCH3 C(CH3)3
    1359 bond CF3 OCOSCH3 C(CH3)3
    1360 bond OCHF2 OCOSCH3 C(CH3)3
    1361 CH2 F OCOSCH3 C(CH3)3
    1362 CH2 Cl OCOSCH3 C(CH3)3
    1363 CH2 Br OCOSCH3 C(CH3)3
    1364 CH2 NO2 OCOSCH3 C(CH3)3
    1365 CH2 SCH3 OCOSCH3 C(CH3)3
    1366 CH2 SO2CH3 OCOSCH3 C(CH3)3
    1367 CH2 SO2CH2CH3 OCOSCH3 C(CH3)3
    1368 CH2 CH3 OCOSCH3 C(CH3)3
    1369 CH2 CF3 OCOSCH3 C(CH3)3
    1370 CH2 OCHF2 OCOSCH3 C(CH3)3
    1371 O F OCOSCH3 C(CH3)3
    1372 O Cl OCOSCH3 C(CH3)3
    1373 O Br OCOSCH3 C(CH3)3
    1374 O NO2 OCOSCH3 C(CH3)3
    1375 O SCH3 OCOSCH3 C(CH3)3
    1376 O SO2CH3 OCOSCH3 C(CH3)3
    1377 O SO2CH2CH3 OCOSCH3 C(CH3)3
    1378 O CH3 OCOSCH3 C(CH3)3
    1379 O CF3 OCOSCH3 C(CH3)3
    1380 O OCHF2 OCOSCH3 C(CH3)3
    1381 S F OCOSCH3 C(CH3)3
    1382 S Cl OCOSCH3 C(CH3)3
    1383 S Br OCOSCH3 C(CH3)3
    1384 S NO2 OCOSCH3 C(CH3)3
    1385 S SCH3 OCOSCH3 C(CH3)3
    1386 S SO2CH3 OCOSCH3 C(CH3)3
    1387 S SO2CH2CH3 OCOSCH3 C(CH3)3
    1388 S CH3 OCOSCH3 C(CH3)3
    1389 S CF3 OCOSCH3 C(CH3)3
    1390 S OCHF2 OCOSCH3 C(CH3)3
    1391 SO2 F OCOSCH3 C(CH3)3
    1392 SO2 Cl OCOSCH3 C(CH3)3
    1393 SO2 Br OCOSCH3 C(CH3)3
    1394 SO2 NO2 OCOSCH3 C(CH3)3
    1395 SO2 SCH3 OCOSCH3 C(CH3)3
    1396 SO2 SO2CH3 OCOSCH3 C(CH3)3
    1397 SO2 SO2CH2CH3 OCOSCH3 C(CH3)3
    1398 SO2 CH3 OCOSCH3 C(CH3)3
    1399 SO2 CF3 OCOSCH3 C(CH3)3
    1400 SO2 OCHF2 OCOSCH3 C(CH3)3
    1401 bond F OCH3 CH(CH3)2
    1402 bond Cl OCH3 CH(CH3)2
    1403 bond Br OCH3 CH(CH3)2
    1404 bond NO2 OCH3 CH(CH3)2
    1405 bond SCH3 OCH3 CH(CH3)2
    1406 bond SO2CH3 OCH3 CH(CH3)2
    1407 bond SO2CH2CH3 OCH3 CH(CH3)2
    1408 bond CH3 OCH3 CH(CH3)2
    1409 bond CF3 OCH3 CH(CH3)2
    1410 bond OCHF2 OCH3 CH(CH3)2
    1411 CH2 F OCH3 CH(CH3)2
    1412 CH2 Cl OCH3 CH(CH3)2
    1413 CH2 Br OCH3 CH(CH3)2
    1414 CH2 NO2 OCH3 CH(CH3)2
    1415 CH2 SCH3 OCH3 CH(CH3)2
    1416 CH2 SO2CH3 OCH3 CH(CH3)2
    1417 CH2 SO2CH2CH3 OCH3 CH(CH3)2
    1418 CH2 CH3 OCH3 CH(CH3)2
    1419 CH2 CF3 OCH3 CH(CH3)2
    1420 CH2 OCHF2 OCH3 CH(CH3)2
    1421 O F OCH3 CH(CH3)2
    1422 O Cl OCH3 CH(CH3)2
    1423 O Br OCH3 CH(CH3)2
    1424 O NO2 OCH3 CH(CH3)2
    1425 O SCH3 OCH3 CH(CH3)2
    1426 O SO2CH3 OCH3 CH(CH3)2
    1427 O SO2CH2CH3 OCH3 CH(CH3)2
    1428 O CH3 OCH3 CH(CH3)2
    1429 O CF3 OCH3 CH(CH3)2
    1430 O OCHF2 OCH3 CH(CH3)2
    1431 S F OCH3 CH(CH3)2
    1432 S Cl OCH3 CH(CH3)2
    1433 S Br OCH3 CH(CH3)2
    1434 S NO2 OCH3 CH(CH3)2
    1435 S SCH3 OCH3 CH(CH3)2
    1436 S SO2CH3 OCH3 CH(CH3)2
    1437 S SO2CH2CH3 OCH3 CH(CH3)2
    1438 S CH3 OCH3 CH(CH3)2
    1439 S CF3 OCH3 CH(CH3)2
    1440 S OCHF2 OCH3 CH(CH3)2
    1441 SO2 F OCH3 CH(CH3)2
    1442 SO2 Cl OCH3 CH(CH3)2
    1443 SO2 Br OCH3 CH(CH3)2
    1444 SO2 NO2 OCH3 CH(CH3)2
    1445 SO2 SCH3 OCH3 CH(CH3)2
    1446 SO2 SO2CH3 OCH3 CH(CH3)2
    1447 SO2 SO2CH2CH3 OCH3 CH(CH3)2
    1448 SO2 CH3 OCH3 CH(CH3)2
    1449 SO2 CF3 OCH3 CH(CH3)2
    1450 SO2 OCHF2 OCH3 CH(CH3)2
    1451 bond F OCH3 C(CH3)3
    1452 bond Cl OCH3 C(CH3)3
    1453 bond Br OCH3 C(CH3)3
    1454 bond NO2 OCH3 C(CH3)3
    1455 bond SCH3 OCH3 C(CH3)3
    1456 bond SO2CH3 OCH3 C(CH3)3
    1457 bond SO2CH2CH3 OCH3 C(CH3)3
    1458 bond CH3 OCH3 C(CH3)3
    1459 bond CF3 OCH3 C(CH3)3
    1460 bond OCHF2 OCH3 C(CH3)3
    1461 CH2 F OCH3 C(CH3)3
    1462 CH2 Cl OCH3 C(CH3)3
    1463 CH2 Br OCH3 C(CH3)3
    1464 CH2 NO2 OCH3 C(CH3)3
    1465 CH2 SCH3 OCH3 C(CH3)3
    1466 CH2 SO2CH3 OCH3 C(CH3)3
    1467 CH2 SO2CH2CH3 OCH3 C(CH3)3
    1468 CH2 CH3 OCH3 C(CH3)3
    1469 CH2 CF3 OCH3 C(CH3)3
    1470 CH2 OCHF2 OCH3 C(CH3)3
    1471 O F OCH3 C(CH3)3
    1472 O Cl OCH3 C(CH3)3
    1473 O Br OCH3 C(CH3)3
    1474 O NO2 OCH3 C(CH3)3
    1475 O SCH3 OCH3 C(CH3)3
    1476 O SO2CH3 OCH3 C(CH3)3
    1477 O SO2CH2CH3 OCH3 C(CH3)3
    1478 O CH3 OCH3 C(CH3)3
    1479 O CF3 OCH3 C(CH3)3
    1480 O OCHF2 OCH3 C(CH3)3
    1481 S F OCH3 C(CH3)3
    1482 S Cl OCH3 C(CH3)3
    1483 S Br OCH3 C(CH3)3
    1484 S NO2 OCH3 C(CH3)3
    1485 S SCH3 OCH3 C(CH3)3
    1486 S SO2CH3 OCH3 C(CH3)3
    1487 S SO2CH2CH3 OCH3 C(CH3)3
    1488 S CH3 OCH3 C(CH3)3
    1489 S CF3 OCH3 C(CH3)3
    1490 S OCHF2 OCH3 C(CH3)3
    1491 SO2 F OCH3 C(CH3)3
    1492 SO2 Cl OCH3 C(CH3)3
    1493 SO2 Br OCH3 C(CH3)3
    1494 SO2 NO2 OCH3 C(CH3)3
    1495 SO2 SCH3 OCH3 C(CH3)3
    1496 SO2 SO2CH3 OCH3 C(CH3)3
    1497 SO2 SO2CH2CH3 OCH3 C(CH3)3
    1498 SO2 CH3 OCH3 C(CH3)3
    1499 SO2 CF3 OCH3 C(CH3)3
    1500 SO2 OCHF2 OCH3 C(CH3)3
    1501 bond F OCH(CH3)2 CH(CH3)2
    1502 bond Cl OCH(CH3)2 CH(CH3)2
    1503 bond Br OCH(CH3)2 CH(CH3)2
    1504 bond NO2 OCH(CH3)2 CH(CH3)2
    1505 bond SCH3 OCH(CH3)2 CH(CH3)2
    1506 bond SO2CH3 OCH(CH3)2 CH(CH3)2
    1507 bond SO2CH2CH3 OCH(CH3)2 CH(CH3)2
    1508 bond CH3 OCH(CH3)2 CH(CH3)2
    1509 bond CF3 OCH(CH3)2 CH(CH3)2
    1510 bond OCHF2 OCH(CH3)2 CH(CH3)2
    1511 CH2 F OCH(CH3)2 CH(CH3)2
    1512 CH2 Cl OCH(CH3)2 CH(CH3)2
    1513 CH2 Br OCH(CH3)2 CH(CH3)2
    1514 CH2 NO2 OCH(CH3)2 CH(CH3)2
    1515 CH2 SCH3 OCH(CH3)2 CH(CH3)2
    1516 CH2 SO2CH3 OCH(CH3)2 CH(CH3)2
    1517 CH2 SO2CH2CH3 OCH(CH3)2 CH(CH3)2
    1518 CH2 CH3 OCH(CH3)2 CH(CH3)2
    1519 CH2 CF3 OCH(CH3)2 CH(CH3)2
    1520 CH2 OCHF2 OCH(CH3)2 CH(CH3)2
    1521 O F OCH(CH3)2 CH(CH3)2
    1522 O Cl OCH(CH3)2 CH(CH3)2
    1523 O Br OCH(CH3)2 CH(CH3)2
    1524 O NO2 OCH(CH3)2 CH(CH3)2
    1525 O SCH3 OCH(CH3)2 CH(CH3)2
    1526 O SO2CH3 OCH(CH3)2 CH(CH3)2
    1527 O SO2CH2CH3 OCH(CH3)2 CH(CH3)2
    1528 O CH3 OCH(CH3)2 CH(CH3)2
    1529 O CF3 OCH(CH3)2 CH(CH3)2
    1530 O OCHF2 OCH(CH3)2 CH(CH3)2
    1531 S F OCH(CH3)2 CH(CH3)2
    1532 S Cl OCH(CH3)2 CH(CH3)2
    1533 S Br OCH(CH3)2 CH(CH3)2
    1534 S NO2 OCH(CH3)2 CH(CH3)2
    1535 S SCH3 OCH(CH3)2 CH(CH3)2
    1536 S SO2CH3 OCH(CH3)2 CH(CH3)2
    1537 S SO2CH2CH3 OCH(CH3)2 CH(CH3)2
    1538 S CH3 OCH(CH3)2 CH(CH3)2
    1539 S CF3 OCH(CH3)2 CH(CH3)2
    1540 S OCHF2 OCH(CH3)2 CH(CH3)2
    1541 SO2 F OCH(CH3)2 CH(CH3)2
    1542 SO2 Cl OCH(CH3)2 CH(CH3)2
    1543 SO2 Br OCH(CH3)2 CH(CH3)2
    1544 SO2 NO2 OCH(CH3)2 CH(CH3)2
    1545 SO2 SCH3 OCH(CH3)2 CH(CH3)2
    1546 SO2 SO2CH3 OCH(CH3)2 CH(CH3)2
    1547 SO2 SO2CH2CH3 OCH(CH3)2 CH(CH3)2
    1548 SO2 CH3 OCH(CH3)2 CH(CH3)2
    1549 SO2 CF3 OCH(CH3)2 CH(CH3)2
    1550 SO2 OCHF2 OCH(CH3)2 CH(CH3)2
    1551 bond F OCH(CH3)2 C(CH3)3
    1552 bond Cl OCH(CH3)2 C(CH3)3
    1553 bond Br OCH(CH3)2 C(CH3)3
    1554 bond NO2 OCH(CH3)2 C(CH3)3
    1555 bond SCH3 OCH(CH3)2 C(CH3)3
    1556 bond SO2CH3 OCH(CH3)2 C(CH3)3
    1557 bond SO2CH2CH3 OCH(CH3)2 C(CH3)3
    1558 bond CH3 OCH(CH3)2 C(CH3)3
    1559 bond CF3 OCH(CH3)2 C(CH3)3
    1560 bond OCHF2 OCH(CH3)2 C(CH3)3
    1561 CH2 F OCH(CH3)2 C(CH3)3
    1562 CH2 Cl OCH(CH3)2 C(CH3)3
    1563 CH2 Br OCH(CH3)2 C(CH3)3
    1564 CH2 NO2 OCH(CH3)2 C(CH3)3
    1565 CH2 SCH3 OCH(CH3)2 C(CH3)3
    1566 CH2 SO2CH3 OCH(CH3)2 C(CH3)3
    1567 CH2 SO2CH2CH3 OCH(CH3)2 C(CH3)3
    1568 CH2 CH3 OCH(CH3)2 C(CH3)3
    1569 CH2 CF3 OCH(CH3)2 C(CH3)3
    1570 CH2 OCHF2 OCH(CH3)2 C(CH3)3
    1571 O F OCH(CH3)2 C(CH3)3
    1572 O Cl OCH(CH3)2 C(CH3)3
    1573 O Br OCH(CH3)2 C(CH3)3
    1574 O NO2 OCH(CH3)2 C(CH3)3
    1575 O SCH3 OCH(CH3)2 C(CH3)3
    1576 O SO2CH3 OCH(CH3)2 C(CH3)3
    1577 O SO2CH2CH3 OCH(CH3)2 C(CH3)3
    1578 O CH3 OCH(CH3)2 C(CH3)3
    1579 O CF3 OCH(CH3)2 C(CH3)3
    1580 O OCHF2 OCH(CH3)2 C(CH3)3
    1581 S F OCH(CH3)2 C(CH3)3
    1582 S Cl OCH(CH3)2 C(CH3)3
    1583 S Br OCH(CH3)2 C(CH3)3
    1584 S NO2 OCH(CH3)2 C(CH3)3
    1585 S SCH3 OCH(CH3)2 C(CH3)3
    1586 S SO2CH3 OCH(CH3)2 C(CH3)3
    1587 S SO2CH2CH3 OCH(CH3)2 C(CH3)3
    1588 S CH3 OCH(CH3)2 C(CH3)3
    1589 S CF3 OCH(CH3)2 C(CH3)3
    1590 S OCHF2 OCH(CH3)2 C(CH3)3
    1591 SO2 F OCH(CH3)2 C(CH3)3
    1592 SO2 Cl OCH(CH3)2 C(CH3)3
    1593 SO2 Br OCH(CH3)2 C(CH3)3
    1594 SO2 NO2 OCH(CH3)2 C(CH3)3
    1595 SO2 SCH3 OCH(CH3)2 C(CH3)3
    1596 SO2 SO2CH3 OCH(CH3)2 C(CH3)3
    1597 SO2 SO2CH2CH3 OCH(CH3)2 C(CH3)3
    1598 SO2 CH3 OCH(CH3)2 C(CH3)3
    1599 SO2 CF3 OCH(CH3)2 C(CH3)3
    1600 SO2 OCHF2 OCH(CH3)2 C(CH3)3
    1601 bond F OCH2C6H5 CH(CH3)2
    1602 bond Cl OCH2C6H5 CH(CH3)2
    1603 bond Br OCH2C6H5 CH(CH3)2
    1604 bond NO2 OCH2C6H5 CH(CH3)2
    1605 bond SCH3 OCH2C6H5 CH(CH3)2
    1606 bond SO2CH3 OCH2C6H5 CH(CH3)2
    1607 bond SO2CH2CH3 OCH2C6H5 CH(CH3)2
    1608 bond CH3 OCH2C6H5 CH(CH3)2
    1609 bond CF3 OCH2C6H5 CH(CH3)2
    1610 bond OCHF2 OCH2C6H5 CH(CH3)2
    1611 CH2 F OCH2C6H5 CH(CH3)2
    1612 CH2 Cl OCH2C6H5 CH(CH3)2
    1613 CH2 Br OCH2C6H5 CH(CH3)2
    1614 CH2 NO2 OCH2C6H5 CH(CH3)2
    1615 CH2 SCH3 OCH2C6H5 CH(CH3)2
    1616 CH2 SO2CH3 OCH2C6H5 CH(CH3)2
    1617 CH2 SO2CH2CH3 OCH2C6H5 CH(CH3)2
    1618 CH2 CH3 OCH2C6H5 CH(CH3)2
    1619 CH2 CF3 OCH2C6H5 CH(CH3)2
    1620 CH2 OCHF2 OCH2C6H5 CH(CH3)2
    1621 O F OCH2C6H5 CH(CH3)2
    1622 O Cl OCH2C6H5 CH(CH3)2
    1623 O Br OCH2C6H5 CH(CH3)2
    1624 O NO2 OCH2C6H5 CH(CH3)2
    1625 O SCH3 OCH2C6H5 CH(CH3)2
    1626 O SO2CH3 OCH2C6H5 CH(CH3)2
    1627 O SO2CH2CH3 OCH2C6H5 CH(CH3)2
    1628 O CH3 OCH2C6H5 CH(CH3)2
    1629 O CF3 OCH2C6H5 CH(CH3)2
    1630 O OCHF2 OCH2C6H5 CH(CH3)2
    1631 S F OCH2C6H5 CH(CH3)2
    1632 S Cl OCH2C6H5 CH(CH3)2
    1633 S Br OCH2C6H5 CH(CH3)2
    1634 S NO2 OCH2C6H5 CH(CH3)2
    1635 S SCH3 OCH2C6H5 CH(CH3)2
    1636 S SO2CH3 OCH2C6H5 CH(CH3)2
    1637 S SO2CH2CH3 OCH2C6H5 CH(CH3)2
    1638 S CH3 OCH2C6H5 CH(CH3)2
    1639 S CF3 OCH2C6H5 CH(CH3)2
    1640 S OCHF2 OCH2C6H5 CH(CH3)2
    1641 SO2 F OCH2C6H5 CH(CH3)2
    1642 SO2 Cl OCH2C6H5 CH(CH3)2
    1643 SO2 Br OCH2C6H5 CH(CH3)2
    1644 SO2 NO2 OCH2C6H5 CH(CH3)2
    1645 SO2 SCH3 OCH2C6H5 CH(CH3)2
    1646 SO2 SO2CH3 OCH2C6H5 CH(CH3)2
    1647 SO2 SO2CH2CH3 OCH2C6H5 CH(CH3)2
    1648 SO2 CH3 OCH2C6H5 CH(CH3)2
    1649 SO2 CF3 OCH2C6H5 CH(CH3)2
    1650 SO2 OCHF2 OCH2C6H5 CH(CH3)2
    1651 bond F OCH2C6H5 C(CH3)3
    1652 bond Cl OCH2C6H5 C(CH3)3
    1653 bond Br OCH2C6H5 C(CH3)3
    1654 bond NO2 OCH2C6H5 C(CH3)3
    1655 bond SCH3 OCH2C6H5 C(CH3)3
    1656 bond SO2CH3 OCH2C6H5 C(CH3)3
    1657 bond SO2CH2CH3 OCH2C6H5 C(CH3)3
    1658 bond CH3 OCH2C6H5 C(CH3)3
    1659 bond CF3 OCH2C6H5 C(CH3)3
    1660 bond OCHF2 OCH2C6H5 C(CH3)3
    1661 CH2 F OCH2C6H5 C(CH3)3
    1662 CH2 Cl OCH2C6H5 C(CH3)3
    1663 CH2 Br OCH2C6H5 C(CH3)3
    1664 CH2 NO2 OCH2C6H5 C(CH3)3
    1665 CH2 SCH3 OCH2C6H5 C(CH3)3
    1666 CH2 SO2CH3 OCH2C6H5 C(CH3)3
    1667 CH2 SO2CH2CH3 OCH2C6H5 C(CH3)3
    1668 CH2 CH3 OCH2C6H5 C(CH3)3
    1669 CH2 CF3 OCH2C6H5 C(CH3)3
    1670 CH2 OCHF2 OCH2C6H5 C(CH3)3
    1671 O F OCH2C6H5 C(CH3)3
    1672 O Cl OCH2C6H5 C(CH3)3
    1673 O Br OCH2C6H5 C(CH3)3
    1674 O NO2 OCH2C6H5 C(CH3)3
    1675 O SCH3 OCH2C6H5 C(CH3)3
    1676 O SO2CH3 OCH2C6H5 C(CH3)3
    1677 O SO2CH2CH3 OCH2C6H5 C(CH3)3
    1678 O CH3 OCH2C6H5 C(CH3)3
    1679 O CF3 OCH2C6H5 C(CH3)3
    1680 O OCHF2 OCH2C6H5 C(CH3)3
    1681 S F OCH2C6H5 C(CH3)3
    1682 S Cl OCH2C6H5 C(CH3)3
    1683 S Br OCH2C6H5 C(CH3)3
    1684 S NO2 OCH2C6H5 C(CH3)3
    1685 S SCH3 OCH2C6H5 C(CH3)3
    1686 S SO2CH3 OCH2C6H5 C(CH3)3
    1687 S SO2CH2CH3 OCH2C6H5 C(CH3)3
    1688 S CH3 OCH2C6H5 C(CH3)3
    1689 S CF3 OCH2C6H5 C(CH3)3
    1690 S OCHF2 OCH2C6H5 C(CH3)3
    1691 SO2 F OCH2C6H5 C(CH3)3
    1692 SO2 Cl OCH2C6H5 C(CH3)3
    1693 SO2 Br OCH2C6H5 C(CH3)3
    1694 SO2 NO2 OCH2C6H5 C(CH3)3
    1695 SO2 SCH3 OCH2C6H5 C(CH3)3
    1696 SO2 SO2CH3 OCH2C6H5 C(CH3)3
    1697 SO2 SO2CH2CH3 OCH2C6H5 C(CH3)3
    1698 SO2 CH3 OCH2C6H5 C(CH3)3
    1699 SO2 CF3 OCH2C6H5 C(CH3)3
    1700 SO2 OCHF2 OCH2C6H5 C(CH3)3
    1701 bond F OSO2(4-CH3—C6H4) CH(CH3)2
    1702 bond Cl OSO2(4-CH3—C6H4) CH(CH3)2
    1703 bond Br OSO2(4-CH3—C6H4) CH(CH3)2
    1704 bond NO2 OSO2(4-CH3—C6H4) CH(CH3)2
    1705 bond SCH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1706 bond SO2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1707 bond SO2CH2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1708 bond CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1709 bond CF3 OSO2(4-CH3—C6H4) CH(CH3)2
    1710 bond OCHF2 OSO2(4-CH3—C6H4) CH(CH3)2
    1711 CH2 F OSO2(4-CH3—C6H4) CH(CH3)2
    1712 CH2 Cl OSO2(4-CH3—C6H4) CH(CH3)2
    1713 CH2 Br OSO2(4-CH3—C6H4) CH(CH3)2
    1714 CH2 NO2 OSO2(4-CH3—C6H4) CH(CH3)2
    1715 CH2 SCH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1716 CH2 SO2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1717 CH2 SO2CH2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1718 CH2 CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1719 CH2 CF3 OSO2(4-CH3—C6H4) CH(CH3)2
    1720 CH2 OCHF2 OSO2(4-CH3—C6H4) CH(CH3)2
    1721 O F OSO2(4-CH3—C6H4) CH(CH3)2
    1722 O Cl OSO2(4-CH3—C6H4) CH(CH3)2
    1723 O Br OSO2(4-CH3—C6H4) CH(CH3)2
    1724 O NO2 OSO2(4-CH3—C6H4) CH(CH3)2
    1725 O SCH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1726 O SO2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1727 O SO2CH2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1728 O CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1729 O CF3 OSO2(4-CH3—C6H4) CH(CH3)2
    1730 O OCHF2 OSO2(4-CH3—C6H4) CH(CH3)2
    1731 S F OSO2(4-CH3—C6H4) CH(CH3)2
    1732 S Cl OSO2(4-CH3—C6H4) CH(CH3)2
    1733 S Br OSO2(4-CH3—C6H4) CH(CH3)2
    1734 S NO2 OSO2(4-CH3—C6H4) CH(CH3)2
    1735 S SCH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1736 S SO2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1737 S SO2CH2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1738 S CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1739 S CF3 OSO2(4-CH3—C6H4) CH(CH3)2
    1740 S OCHF2 OSO2(4-CH3—C6H4) CH(CH3)2
    1741 SO2 F OSO2(4-CH3—C6H4) CH(CH3)2
    1742 SO2 Cl OSO2(4-CH3—C6H4) CH(CH3)2
    1743 SO2 Br OSO2(4-CH3—C6H4) CH(CH3)2
    1744 SO2 NO2 OSO2(4-CH3—C6H4) CH(CH3)2
    1745 SO2 SCH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1746 SO2 SO2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1747 SO2 SO2CH2CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1748 SO2 CH3 OSO2(4-CH3—C6H4) CH(CH3)2
    1749 SO2 CF3 OSO2(4-CH3—C6H4) CH(CH3)2
    1750 SO2 OCHF2 OSO2(4-CH3—C6H4) CH(CH3)2
    1751 bond F OSO2(4-CH3—C6H4) C(CH3)3
    1752 bond Cl OSO2(4-CH3—C6H4) C(CH3)3
    1753 bond Br OSO2(4-CH3—C6H4) C(CH3)3
    1754 bond NO2 OSO2(4-CH3—C6H4) C(CH3)3
    1755 bond SCH3 OSO2(4-CH3—C6H4) C(CH3)3
    1756 bond SO2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1757 bond SO2CH2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1758 bond CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1759 bond CF3 OSO2(4-CH3—C6H4) C(CH3)3
    1760 bond OCHF2 OSO2(4-CH3—C6H4) C(CH3)3
    1761 CH2 F OSO2(4-CH3—C6H4) C(CH3)3
    1762 CH2 Cl OSO2(4-CH3—C6H4) C(CH3)3
    1763 CH2 Br OSO2(4-CH3—C6H4) C(CH3)3
    1764 CH2 NO2 OSO2(4-CH3—C6H4) C(CH3)3
    1765 CH2 SCH3 OSO2(4-CH3—C6H4) C(CH3)3
    1766 CH2 SO2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1767 CH2 SO2CH2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1768 CH2 CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1769 CH2 CF3 OSO2(4-CH3—C6H4) C(CH3)3
    1770 CH2 OCHF2 OSO2(4-CH3—C6H4) C(CH3)3
    1771 O F OSO2(4-CH3—C6H4) C(CH3)3
    1772 O Cl OSO2(4-CH3—C6H4) C(CH3)3
    1773 O Br OSO2(4-CH3—C6H4) C(CH3)3
    1774 O NO2 OSO2(4-CH3—C6H4) C(CH3)3
    1775 O SCH3 OSO2(4-CH3—C6H4) C(CH3)3
    1776 O SO2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1777 O SO2CH2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1778 O CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1779 O CF3 OSO2(4-CH3—C6H4) C(CH3)3
    1780 O OCHF2 OSO2(4-CH3—C6H4) C(CH3)3
    1781 S F OSO2(4-CH3—C6H4) C(CH3)3
    1782 S Cl OSO2(4-CH3—C6H4) C(CH3)3
    1783 S Br OSO2(4-CH3—C6H4) C(CH3)3
    1784 S NO2 OSO2(4-CH3—C6H4) C(CH3)3
    1785 S SCH3 OSO2(4-CH3—C6H4) C(CH3)3
    1786 S SO2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1787 S SO2CH2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1788 S CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1789 S CF3 OSO2(4-CH3—C6H4) C(CH3)3
    1790 S OCHF2 OSO2(4-CH3—C6H4) C(CH3)3
    1791 SO2 F OSO2(4-CH3—C6H4) C(CH3)3
    1792 SO2 Cl OSO2(4-CH3—C6H4) C(CH3)3
    1793 SO2 Br OSO2(4-CH3—C6H4) C(CH3)3
    1794 SO2 NO2 OSO2(4-CH3—C6H4) C(CH3)3
    1795 SO2 SCH3 OSO2(4-CH3—C6H4) C(CH3)3
    1796 SO2 SO2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1797 SO2 SO2CH2CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1798 SO2 CH3 OSO2(4-CH3—C6H4) C(CH3)3
    1799 SO2 CF3 OSO2(4-CH3—C6H4) C(CH3)3
    1800 SO2 OCHF2 OSO2(4-CH3—C6H4) C(CH3)3
    1801 bond F SCH3 CH(CH3)2
    1802 bond Cl SCH3 CH(CH3)2
    1803 bond Br SCH3 CH(CH3)2
    1804 bond NO2 SCH3 CH(CH3)2
    1805 bond SCH3 SCH3 CH(CH3)2
    1806 bond SO2CH3 SCH3 CH(CH3)2
    1807 bond SO2CH2CH3 SCH3 CH(CH3)2
    1808 bond CH3 SCH3 CH(CH3)2
    1809 bond CF3 SCH3 CH(CH3)2
    1810 bond OCHF2 SCH3 CH(CH3)2
    1811 CH2 F SCH3 CH(CH3)2
    1812 CH2 Cl SCH3 CH(CH3)2
    1813 CH2 Br SCH3 CH(CH3)2
    1814 CH2 NO2 SCH3 CH(CH3)2
    1815 CH2 SCH3 SCH3 CH(CH3)2
    1816 CH2 SO2CH3 SCH3 CH(CH3)2
    1817 CH2 SO2CH2CH3 SCH3 CH(CH3)2
    1818 CH2 CH3 SCH3 CH(CH3)2
    1819 CH2 CF3 SCH3 CH(CH3)2
    1820 CH2 OCHF2 SCH3 CH(CH3)2
    1821 O F SCH3 CH(CH3)2
    1822 O Cl SCH3 CH(CH3)2
    1823 O Br SCH3 CH(CH3)2
    1824 O NO2 SCH3 CH(CH3)2
    1825 O SCH3 SCH3 CH(CH3)2
    1826 O SO2CH3 SCH3 CH(CH3)2
    1827 O SO2CH2CH3 SCH3 CH(CH3)2
    1828 O CH3 SCH3 CH(CH3)2
    1829 O CF3 SCH3 CH(CH3)2
    1830 O OCHF2 SCH3 CH(CH3)2
    1831 S F SCH3 CH(CH3)2
    1832 S Cl SCH3 CH(CH3)2
    1833 S Br SCH3 CH(CH3)2
    1834 S NO2 SCH3 CH(CH3)2
    1835 S SCH3 SCH3 CH(CH3)2
    1836 S SO2CH3 SCH3 CH(CH3)2
    1837 S SO2CH2CH3 SCH3 CH(CH3)2
    1838 S CH3 SCH3 CH(CH3)2
    1839 S CF3 SCH3 CH(CH3)2
    1840 S OCHF2 SCH3 CH(CH3)2
    1841 SO2 F SCH3 CH(CH3)2
    1842 SO2 Cl SCH3 CH(CH3)2
    1843 SO2 Br SCH3 CH(CH3)2
    1844 SO2 NO2 SCH3 CH(CH3)2
    1845 SO2 SCH3 SCH3 CH(CH3)2
    1846 SO2 SO2CH3 SCH3 CH(CH3)2
    1847 SO2 SO2CH2CH3 SCH3 CH(CH3)2
    1848 SO2 CH3 SCH3 CH(CH3)2
    1849 SO2 CF3 SCH3 CH(CH3)2
    1850 SO2 OCHF2 SCH3 CH(CH3)2
    1851 bond F SCH3 C(CH3)3
    1852 bond Cl SCH3 C(CH3)3
    1853 bond Br SCH3 C(CH3)3
    1854 bond NO2 SCH3 C(CH3)3
    1855 bond SCH3 SCH3 C(CH3)3
    1856 bond SO2CH3 SCH3 C(CH3)3
    1857 bond SO2CH2CH3 SCH3 C(CH3)3
    1858 bond CH3 SCH3 C(CH3)3
    1859 bond CF3 SCH3 C(CH3)3
    1860 bond OCHF2 SCH3 C(CH3)3
    1861 CH2 F SCH3 C(CH3)3
    1862 CH2 Cl SCH3 C(CH3)3
    1863 CH2 Br SCH3 C(CH3)3
    1864 CH2 NO2 SCH3 C(CH3)3
    1865 CH2 SCH3 SCH3 C(CH3)3
    1866 CH2 SO2CH3 SCH3 C(CH3)3
    1867 CH2 SO2CH2CH3 SCH3 C(CH3)3
    1868 CH2 CH3 SCH3 C(CH3)3
    1869 CH2 CF3 SCH3 C(CH3)3
    1870 CH2 OCHF2 SCH3 C(CH3)3
    1871 O F SCH3 C(CH3)3
    1872 O Cl SCH3 C(CH3)3
    1873 O Br SCH3 C(CH3)3
    1874 O NO2 SCH3 C(CH3)3
    1875 O SCH3 SCH3 C(CH3)3
    1876 O SO2CH3 SCH3 C(CH3)3
    1877 O SO2CH2CH3 SCH3 C(CH3)3
    1878 O CH3 SCH3 C(CH3)3
    1879 O CF3 SCH3 C(CH3)3
    1880 O OCHF2 SCH3 C(CH3)3
    1881 S F SCH3 C(CH3)3
    1882 S Cl SCH3 C(CH3)3
    1883 S Br SCH3 C(CH3)3
    1884 S NO2 SCH3 C(CH3)3
    1885 S SCH3 SCH3 C(CH3)3
    1886 S SO2CH3 SCH3 C(CH3)3
    1887 S SO2CH2CH3 SCH3 C(CH3)3
    1888 S CH3 SCH3 C(CH3)3
    1889 S CF3 SCH3 C(CH3)3
    1890 S OCHF2 SCH3 C(CH3)3
    1891 SO2 F SCH3 C(CH3)3
    1892 SO2 Cl SCH3 C(CH3)3
    1893 SO2 Br SCH3 C(CH3)3
    1894 SO2 NO2 SCH3 C(CH3)3
    1895 SO2 SCH3 SCH3 C(CH3)3
    1896 SO2 SO2CH3 SCH3 C(CH3)3
    1897 SO2 SO2CH2CH3 SCH3 C(CH3)3
    1898 SO2 CH3 SCH3 C(CH3)3
    1899 SO2 CF3 SCH3 C(CH3)3
    1900 SO2 OCHF2 SCH3 C(CH3)3
    1901 bond F Cl CH(CH3)2
    1902 bond Cl Cl CH(CH3)2
    1903 bond Br Cl CH(CH3)2
    1904 bond NO2 Cl CH(CH3)2
    1905 bond SCH3 Cl CH(CH3)2
    1906 bond SO2CH3 Cl CH(CH3)2
    1907 bond SO2CH2CH3 Cl CH(CH3)2
    1908 bond CH3 Cl CH(CH3)2
    1909 bond CF3 Cl CH(CH3)2
    1910 bond OCHF2 Cl CH(CH3)2
    1911 CH2 F Cl CH(CH3)2
    1912 CH2 Cl Cl CH(CH3)2
    1913 CH2 Br Cl CH(CH3)2
    1914 CH2 NO2 Cl CH(CH3)2
    1915 CH2 SCH3 Cl CH(CH3)2
    1916 CH2 SO2CH3 Cl CH(CH3)2
    1917 CH2 SO2CH2CH3 Cl CH(CH3)2
    1918 CH2 CH3 Cl CH(CH3)2
    1919 CH2 CF3 Cl CH(CH3)2
    1920 CH2 OCHF2 Cl CH(CH3)2
    1921 O F Cl CH(CH3)2
    1922 O Cl Cl CH(CH3)2
    1923 O Br Cl CH(CH3)2
    1924 O NO2 Cl CH(CH3)2
    1925 O SCH3 Cl CH(CH3)2
    1926 O SO2CH3 Cl CH(CH3)2
    1927 O SO2CH2CH3 Cl CH(CH3)2
    1928 O CH3 Cl CH(CH3)2
    1929 O CF3 Cl CH(CH3)2
    1930 O OCHF2 Cl CH(CH3)2
    1931 S F Cl CH(CH3)2
    1932 S Cl Cl CH(CH3)2
    1933 S Br Cl CH(CH3)2
    1934 S NO2 Cl CH(CH3)2
    1935 S SCH3 Cl CH(CH3)2
    1936 S SO2CH3 Cl CH(CH3)2
    1937 S SO2CH2CH3 Cl CH(CH3)2
    1938 S CH3 Cl CH(CH3)2
    1939 S CF3 Cl CH(CH3)2
    1940 S OCHF2 Cl CH(CH3)2
    1941 SO2 F Cl CH(CH3)2
    1942 SO2 Cl Cl CH(CH3)2
    1943 SO2 Br Cl CH(CH3)2
    1944 SO2 NO2 Cl CH(CH3)2
    1945 SO2 SCH3 Cl CH(CH3)2
    1946 SO2 SO2CH3 Cl CH(CH3)2
    1947 SO2 SO2CH2CH3 Cl CH(CH3)2
    1948 SO2 CH3 Cl CH(CH3)2
    1949 SO2 CF3 Cl CH(CH3)2
    1950 SO2 OCHF2 Cl CH(CH3)2
    1951 bond F Cl C(CH3)3
    1952 bond Cl Cl C(CH3)3
    1953 bond Br Cl C(CH3)3
    1954 bond NO2 Cl C(CH3)3
    1955 bond SCH3 Cl C(CH3)3
    1956 bond SO2CH3 Cl C(CH3)3
    1957 bond SO2CH2CH3 Cl C(CH3)3
    1958 bond CH3 Cl C(CH3)3
    1959 bond CF3 Cl C(CH3)3
    1960 bond OCHF2 Cl C(CH3)3
    1961 CH2 F Cl C(CH3)3
    1962 CH2 Cl Cl C(CH3)3
    1963 CH2 Br Cl C(CH3)3
    1964 CH2 NO2 Cl C(CH3)3
    1965 CH2 SCH3 Cl C(CH3)3
    1966 CH2 SO2CH3 Cl C(CH3)3
    1967 CH2 SO2CH2CH3 Cl C(CH3)3
    1968 CH2 CH3 Cl C(CH3)3
    1969 CH2 CF3 Cl C(CH3)3
    1970 CH2 OCHF2 Cl C(CH3)3
    1971 O F Cl C(CH3)3
    1972 O Cl Cl C(CH3)3
    1973 O Br Cl C(CH3)3
    1974 O NO2 Cl C(CH3)3
    1975 O SCH3 Cl C(CH3)3
    1976 O SO2CH3 Cl C(CH3)3
    1977 O SO2CH2CH3 Cl C(CH3)3
    1978 O CH3 Cl C(CH3)3
    1979 O CF3 Cl C(CH3)3
    1980 O OCHF2 Cl C(CH3)3
    1981 S F Cl C(CH3)3
    1982 S Cl Cl C(CH3)3
    1983 S Br Cl C(CH3)3
    1984 S NO2 Cl C(CH3)3
    1985 S SCH3 Cl C(CH3)3
    1986 S SO2CH3 Cl C(CH3)3
    1987 S SO2CH2CH3 Cl C(CH3)3
    1988 S CH3 Cl C(CH3)3
    1989 S CF3 Cl C(CH3)3
    1990 S OCHF2 Cl C(CH3)3
    1991 SO2 F Cl C(CH3)3
    1992 SO2 Cl Cl C(CH3)3
    1993 SO2 Br Cl C(CH3)3
    1994 SO2 NO2 Cl C(CH3)3
    1995 SO2 SCH3 Cl C(CH3)3
    1996 SO2 SO2CH3 Cl C(CH3)3
    1997 SO2 SO2CH2CH3 Cl C(CH3)3
    1998 SO2 CH3 Cl C(CH3)3
    1999 SO2 CF3 Cl C(CH3)3
    2000 SO2 OCHF2 Cl C(CH3)3
  • Very particular preference is also given to the compounds of the formula Ia2 (≡Ia where R1, R2, R5 and R12=H, R3=CH3, l=1), in particular to the compounds Ia2.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00015
  • Very particular preference is also given to the compounds of the formula Ia3 (≡Ia where R1, R2, R5 and R12=H, R3═CH3, l=1), in particular to the compounds Ia3.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00016
  • Very particular preference is also given to the compounds of the formula Ia4 (≡Ia where R1, R2, R5 and R12=H, R3=CH3, l=2), in particular to the compounds Ia4.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00017
  • Very particular preference is also given to the compounds of the formula Ia5 (≡Ia where R1, R2, R5 and R12=H, R3=CH3, l=1), in particular to the compounds Ia5.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00018
  • Very particular preference is also given to the compounds of the formula Ia6 (≡Ia where R1, R2, R5 and R12=H, R3=CH3, l=2), in particular to the compounds Ia6.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00019
  • Very particular preference is also given to the compounds of the formula Ia7 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia7.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00020
  • Very particular preference is also given to the compounds of the formula Ia8 (≡Ia where R1, R2, R5 and R12=H, R3=CH3, l=1), in particular to the compounds Ia8.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00021
  • Very particular preference is also given to the compounds of the formula Ia9 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia9.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00022
  • Very particular preference is also given to the compounds of the formula Ia10 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia10.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00023
  • Very particular preference is also given to the compounds of the formula Ia11 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia11.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00024
  • Very particular preference is also given to the compounds of the formula Ia12 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia12.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00025
  • Very particular preference is also given to the compounds of the formula Ia13 (=Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia13.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00026
  • Very particular preference is also given to the compounds of the formula Ia14 (≡Ia where R1, R2, R5 and R12=H, R3=CH3, l=1), in particular to the compounds Ia14.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00027
  • Very particular preference is also given to the compounds of the formula Ia15 (≡Ia where R1, R2, R5 and R12=H, R3=CH3, l=1), in particular to the compounds Ia15.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00028
  • Very particular preference is also given to the compounds of the formula Ia16 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia16.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00029
  • Very particular preference is also given to the compounds of the formula Ia17 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia17.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00030
  • Very particular preference is also given to the compounds of the formula Ia18 (≡Ia where R1, R2, R5 and R12=H, R13=CH3, l=1), in particular to the compounds Ia18.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00031
  • Very particular preference is also given to the compounds of the formula Ia19 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia19.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00032
  • Very particular preference is also given to the compounds of the formula Ia20 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia20.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00033
  • Very particular preference is also given to the compounds of the formula Ia21 (≡Ia where R1, R2, R5 and R12=H, l=0), in particular to the compounds Ia21.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00034
  • Very particular preference is also given to the compounds of the formula Ia22 (≡Ia where R1, R2, R5 and R12=H, R3=CH3, l=1), in particular to the compounds Ia22.n, where the variables X, R4, R10 and R11 are as defined in Table 1.
    Figure US20070197393A1-20070823-C00035
  • The tricyclic benzoylpyrazole derivatives of the formula I can be obtained by various routes, for example by one of the following processes:
    • A. Preparation of compounds of the formula I where R10=halogen by reacting a tricyclic benzoylpyrazole derivative of the formula Iα (≡I where R10=hydroxyl) with a halogenating agent:
      Figure US20070197393A1-20070823-C00036
      • Suitable halogenating agents are, for example, phosgene, diphosgene, triphosgene, thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus pentachloride, mesyl chloride, chloromethylene-N,N-dimethylammonium chloride, oxalyl bromide, phosphorus oxybromide, etc.
      • The starting materials are generally employed in equimolar amounts. However, it may also be advantageous to employ an excess of one or the other component.
      • Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons, for example toluene, xylene or chlorobenzene, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxide, or mixtures of these. However, it is also possible to carry out the reaction in the absence of solvent.
      • The reaction temperature is generally in the range from 0° C. to the boiling point of the reaction mixture.
      • Work-up can be carried out in a manner known per se to afford the product.
    • B. Preparation of compounds of the formula I where R10=OR13, by reacting a tricyclic benzoylpyrazole derivative of the formula Iα (≡I where R10=hydroxyl) with an alkylating agent III.
      Figure US20070197393A1-20070823-C00037
      • L1 is a nucleophilically replaceable leaving group, such as halogen, for example chlorine or bromine, hetaryl, for example imidazolyl, carboxylate, for example acetate, or sulfonate, for example mesylate or triflate, etc.
      • The compounds of the formula III can be employed directly, such as, for example, in the case of the carbonyl halides, or be generated in situ, for example activated carboxylic acids (using carboxylic acid and dicyclohexylcarbodiimide etc.).
      • The starting materials are generally employed in equimolar amounts. However, it may also be advantageous to employ an excess of one or the other component.
      • If appropriate, it may also be advantageous to carry out the reaction in the presence of a base. Here, the reactants and the base are advantageously employed in equimolar amounts. In certain cases, an excess of base, for example from 1.5 to 3 molar equivalents, may be advantageous.
      • Suitable bases are tertiary alkylamines, such as triethylamine, aromatic amines, such as pyridine, alkali metal carbonates, for example sodium carbonate or potassium carbonate, alkali metal bicarbonates, for example sodium bicarbonate and potassium bicarbonate, alkali metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, or alkali metal hydrides, for example sodium hydride. Preference is given to using triethylamine or pyridine.
      • Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons, for example toluene, xylene or chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxide, or esters, such as ethyl acetate, or mixtures of these.
      • The reaction temperature is generally in the range from 0° C. to the boiling point of the reaction mixture.
      • Work-up can be carried out in a manner known per se to afford the product.
    • C. Preparation of compounds of the formula I where R10=OR13, SR13, NR15R16 or N-bonded heterocyclyl by reacting compounds of the formula Iβ (≡I where R10=halogen) with a compound of the formula IVα, IVβ, IVγ or IVδ, if appropriate in the presence of a base or with prior formation of salt.
      Figure US20070197393A1-20070823-C00038
      • The starting materials are generally employed in equimolar amounts. However, it may also be advantageous to employ an excess of one or the other component.
      • If appropriate, it may also be advantageous to carry out the reaction in the presence of a base. Here, the reactants and the base are advantageously employed in equimolar amounts. An excess of base, for example from 1.5 to 3 molar equivalents, based on Iβ (where R10=halogen), may be advantageous in certain cases.
      • Suitable bases are tertiary alkylamines, such as triethylamine, aromatic amines, such as pyridine, alkali metal carbonates, for example sodium carbonate or potassium carbonate, alkali metal bicarbonates, for example sodium bicarbonate and potassium bicarbonate, alkali metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, or alkali metal hydrides, for example sodium hydride. Preference is given to using sodium hydride or potassium tert-butoxide.
      • Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons, for example toluene, xylene or chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxide, or mixtures of these.
      • The reaction temperature is generally in the range from 0° C. to the boiling point of the reaction mixture.
      • Work-up can be carried out in a manner known per se to afford the product.
    • D. Preparation of compounds of the formula I where R10=SO2R14 by reacting compounds of the formula I where R10=SR10 (Iγ) with an oxidizing agent.
      Figure US20070197393A1-20070823-C00039
      • Suitable oxidizing agents are, for example, m-chloroperbenzoic acid, peroxyacetic acid, trifluoroperoxyacetic acid, hydrogen peroxide, if appropriate in the presence of a catalyst, such as tungstate.
      • The starting materials are generally employed in equimolar amounts. However, it may also be advantageous to employ an excess of one or the other component.
      • Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons, for example, toluene, xylene or chlorobenzene, ethers, such as diethyl ether, methyltert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents, such as acetonitrile or dimethylformamide, or esters, such as ethyl acetate, or mixtures of these.
      • The reaction temperature is generally in the range from 0° C. to the boiling point of the reaction mixture.
      • Work-up can be carried out in a manner known per se to afford the product.
    • E. Preparation of compounds of the formula I where R9=IIa (where R10+ hydroxyl or mercapto) by reacting a metalated pyrazole derivative of the formula V with a tricyclic benzoic acid derivative of the formula VIα:
      Figure US20070197393A1-20070823-C00040
      • Here, M is a metal, in particular an alkali metal, such as lithium or sodium, an alkaline earth metal, such as, for example, magnesium, or a transition metal, such as palladium, nickel, etc. and L2 is a nucleophilically replaceable leaving group, such as halogen, for example chlorine or bromine, alkylsulfonate, such as mesylate, haloalkylsulfonate, such as triflate, or cyanide.
      • The reaction is generally carried out at temperatures of from −100° C. to the reflux temperature of the reaction mixture. Suitable solvents are inert aprotic solvents, such as ethers, for example diethyl ether, tetrahydrofuran. The compounds of the formula VIα are generally employed in excess, but it may also be advantageous to employ them in equimolar amounts or in substoichiometric amounts. Work-up is carried out to afford the product.
      • The metalated pyrazole derivatives of the formula V can be formed in a manner known per se by reacting pyrazoles which are halogenated in the 4-position with metals, such as lithium, sodium, magnesium, etc., or with organometallic compounds, such as, for example, butyllithium. However, it is also possible to metalate pyrazoles which are linked in the 4 position to hydrogen directly, for example with the abovementioned metals or organometallic compounds. The reactions are generally carried out in an inert aprotic solvent, preferably in ether, such as diethyl ether, tetrahydrofuran, etc. The reaction temperature is in the range from −100° C. to the boiling point of the reaction mixture. The compounds of the formula V are generally directly reacted further or generated in situ.
    • F. Preparation of compounds of the formula Iα (≡I where R10=hydroxyl) by reacting an activated tricyclic benzoic acid of the formula VIβ or a tricyclic benzoic acid VIγ, preferably activated in situ, with a pyrazole of the formula VII to give the acylation product, followed by rearrangement.
      Figure US20070197393A1-20070823-C00041
  • L3 is a nucleophilically replaceable leaving group, such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoroacetate, etc.
  • The activated tricyclic benzoic acid VIβ can be employed directly, such as in the case of the tricyclic benzoyl halides, or be generated in situ, for example using dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic ester, 2-pyridine disulfide/triphenylphosphine, carbonyldiimidazole, etc.
  • If appropriate, it may be advantageous to carry out the acylation reaction in the presence of a base. Here, the reactants and the auxiliary base are advantageously employed in equimolar amounts. A slight excess of auxiliary base, for example from 1.2 to 1.5 molar equivalents, based on VI, may be advantageous in certain cases.
  • Suitable auxiliary bases are tertiary alkylamines, pyridine, or alkali metal carbonates. Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene or chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxide, or esters, such as ethyl acetate, or mixtures of these.
  • If tricyclic benzoyl halides are employed as activated carboxylic acid components, it may be advantageous to cool the reaction mixture to 0-10° C. when adding this reaction partner. The mixture is subsequently stirred at 20-100° C., preferably at 25-50° C., until the reaction has gone to completion. Work-up is carried out in a customary manner, for example by pouring the reaction mixture into water and extracting the product of value. Solvents which are suitable for this purpose are, in particular, methylene chloride, diethyl ether and ethyl acetate. The organic phase is dried and the solvent removed, and the crude ester can then be employed for the rearrangement without further purification.
  • The rearrangement of the esters VIII to give the compounds of the formula Iα is advantageously carried out at from 20 to 100° C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as catalyst.
  • Solvents which may be used are, for example, acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures of these. Preferred solvents are acetonitrile and dioxane.
  • Suitable bases are tertiary amines, such as triethylamine, aromatic amines, such as pyridine, or alkali metal carbonates, such as sodium carbonate or potassium carbonate, which are preferably employed in equimolar amounts or in an up to four-fold excess, based on the ester. Preference is given to using triethylamine or alkali metal carbonate, preferably in double the equimolar ratio, based on the ester.
  • Suitable cyano compounds are inorganic cyanides, such as sodium cyanide or potassium cyanide, and organic cyano compounds, such as acetone cyanohydrin or trimethylsilyl cyanide. They are employed in an amount of from 1 to 50 mol percent, based on the ester. Preference is given to using acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of from 5 to 15, preferably 10, mol percent, based on the ester.
  • Work-up may be carried out in a manner known per se. The reaction mixture is, for example, acidified using dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, for example methylene chloride or ethyl acetate. The organic extract can be extracted with 5-10% strength alkali metal carbonate solution, for example sodium carbonate or potassium carbonate solution. The aqueous phase is acidified and the resulting precipitate is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, the extract being dried and concentrated.
  • However, it is also possible to generate the ester VIII in situ by reacting a pyrazole of the formula VII, or an alkali metal salt thereof, with a tricyclic benzene derivative of the formula IX in the presence of carbon monoxide, a catalyst and a base.
    Figure US20070197393A1-20070823-C00042
  • L4 is a leaving group, such as halogen, for example chlorine, bromine or iodine, or sulfonate such as mesylate or triflate; preference is given to bromine or triflate.
  • If appropriate, the ester VIII reacts directly to give the tricyclic benzoylpyrazole derivative of the formula Iα.
  • Suitable catalysts are palladium ligand complexes in which the palladium is present in oxidation state 0, metallic palladium, if appropriate applied to a support, and preferably palladium(II) salts. The reaction with palladium(II) salts and metallic palladium is preferably carried out in the presence of complex ligands.
  • A suitable palladium(0) ligand complex is, for example, tetrakis(triphenylphosphane)palladium.
  • Metallic palladium is preferably applied to an inert carrier, such as, for example, activated carbon, silica, alumina, barium sulfate or calcium carbonate. The reaction is preferably carried out in the presence of complex ligands, such as, for example, triphenylphosphane.
  • Suitable palladium(II) salts are, for example, palladium acetate and palladium chloride. Preference is given to carrying out the reaction in the presence of complex ligands such as, for example, triphenylphosphane.
  • Suitable complex ligands for the palladium ligand complexes, or complex ligands in whose presence the reaction with metallic palladium or palladium(II) salts is preferably carried out are tertiary phosphanes whose structure is represented by the following formulae:
    Figure US20070197393A1-20070823-C00043
    where n is a number from 1 to 4 and the radicals Ra to Rg are C1-C6-alkyl, aryl-C1-C2-alkyl or preferably aryl. Aryl is, for example, naphthyl and unsubstituted or substituted phenyl such as, for example, 2-tolyl and in particular unsubstituted phenyl.
  • The complex palladium salts can be prepared in a manner known per se starting from commercially available palladium salts, such as palladium chloride or palladium acetate, and the corresponding phosphanes, such as, for example, triphenylphosphane or 1,2-bis(diphenylphosphano)ethane. A large number of complexed palladium salts is also commercially available. Preferred palladium salts are [(R)-(+)-2,2′-bis(diphenylphosphano)-1,1′-binaphthyl]palladium(II) chloride, bis(triphenylphosphane)palladium(II) acetate and in particular bis(triphenylphosphane)palladium(II) chloride.
  • The palladium catalyst is generally employed in a concentration of from 0.05 to 5 mol %, and preferably of 1-3 mol %.
  • Suitable bases are tertiary amines, such as, for example, N-methylpiperidine, ethyldiisopropylamine, 1,8-bisdimethylaminonaphthalene and in particular triethylamine. Also suitable are alkali metal carbonates, such as sodium carbonate or potassium carbonate. However, mixtures of potassium carbonate and triethylamine are also suitable.
  • In general, from 2 to 4 molar equivalents, in particular 2 molar equivalents, of the alkali metal carbonate, and from 1 to 4 molar equivalents, in particular 2 molar equivalents, of the tertiary amine are employed, based on the tricyclic benzene derivative of the formula IX.
  • Suitable solvents are nitrites, such as benzonitrile and acetonitrile, amides, such as dimethylformamide, dimethylacetamide, tetra-C1-C4-alkylureas or N-methylpyrrolidone, and preferably ethers, such as tetrahydrofuran, methyl tert-butyl ether. Particular preference is given to using, as solvents, ethers such as 1,4-dioxane and dimethoxyethane.
  • The tricyclic benzoyl halides of the formula VIβ where L3=Cl, Br can be prepared in a manner known per se by reacting the tricyclic benzoic acids of the formula VIγ (≡VIb) with halogenating agents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride and oxalyl bromide.
  • In a known manner, the tricyclic benzoic acids of the formula VIγ (≡VIb) can be prepared by acidic or basic hydrolysis from the corresponding esters VIc.
  • Tricyclic benzoic acid derivatives of the formula VI
    Figure US20070197393A1-20070823-C00044
    where:
      • X is oxygen, sulfur, S═O, S(═O)2, CR6R7, NR8 or a bond;
      • Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated 5- or 6-membered heterocycle which contains one to three identical or different heteroatoms selected from the following group: oxygen, sulfur or nitrogen;
      • R1, R2, R6, R7 are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
      • R3 is halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
      • R4 is nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)-aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl) amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino;
      • R5 is hydrogen, C1-C6-alkyl or halogen;
      • R8 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, formyl, C1-C6-alkoxycarbonyl, C1-C6-haloalkoxycarbonyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
      • l is 0, 1 or 2;
      • R17 is hydroxyl or a radical which can be removed by hydrolysis;
        are novel.
  • Examples of radicals which can be removed by hydrolysis are alkoxy, phenoxy, alkylthio and phenylthio radicals which can be unsubstituted or substituted, halides, heteroaryl radicals which are attached via nitrogen, amino and imino radicals which may be unsubstituted or substituted, etc.
  • Preference is given to tricyclic benzoyl halides VIa (VI where R17=halogen)
    Figure US20070197393A1-20070823-C00045
    where the variables X, Y, R1 to R5 and l are as defined under formula VI and
      • Hal is halogen, in particular chloride or bromide.
  • Preference is also given to tricyclic benzoic acids of the formula VIb (VI where R17=hydroxyl; ≡VIγ),
    Figure US20070197393A1-20070823-C00046
    where the variables X, Y, R1 to R5 and l are as defined under formula VI.
  • Preference is also given to tricyclic benzoic esters of the formula VIc (VI where R17=T=C1-C6-alkoxy),
    Figure US20070197393A1-20070823-C00047
    where the variables X, Y, R1 to R5 and l are as defined under formula VI and
      • T is C1-C6-alkoxy.
  • With respect to the variables X, Y, R1 to R5 and l, the particularly preferred embodiments of the tricyclic benzoic acid derivatives of the formulae VI, VIa, VIb and VIc correspond to those of the tricyclic benzoylpyrazole derivatives of the formula I.
  • Particular preference is given to the compounds VI, VIa, VIb and VIc where Y together with the two carbons to which it is attached forms the following heterocycles:
    Figure US20070197393A1-20070823-C00048
  • Here, extraordinary preference is given to the compounds VI, VIa, VIb and VIc where
      • R4 is nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio or C1-C6-alkylsulfonyl; in particular C1-C6-alkylsulfonyl.
  • The tricyclic benzoic esters VIc can be obtained in different ways.
  • For example, benzoic esters of the formula X, which are prepared in a manner known per se (cf., for example, Chem. Pharm. Bull. 1985, 33 (8), 3336; Helv. Chim. Acta 1987, 70, 1326; J. Chem. Soc. Perkin Trans. 1972, 2019; J. Chem. Soc. Perkin Trans. 1991, 2763; Tetrahydron Asymmetry 1998, 9, 1137), can be cyclized to cyclic ketones of the formula XI (cf., for example, Chem. Ber. 1923, 56, 1819; J. Chem. Soc. Perkin 11991, 2763; J. Med. Chem. 1988, 31, 230; Tetrahedron 1987, 43, 4549; Synlett 1991, 6, 443; Chem. Pharm. Bull. 1985, 33 (8), 3336). Analogously to known processes (cf., for example, J. Heterocyclic Chem. 1976, 13, 545; J. Heterocyclic Chem. 1972, 9, 1341; J. Org. Chem. 1978, 43, 3015; J. Chem. Soc. Perkin Trans. I 1978, 86; J. Org. Chem. 1986, 51, 2021), these can be converted into the tricyclic benzoic esters of the formula VIc.
    Figure US20070197393A1-20070823-C00049
  • Furthermore, it may be suitable to cyclize the cyclic ketone of the formula XI in a manner known per se (XII), for example using an anhydride or acid anhydride, if appropriate in the presence of catalytic amounts of a Lewis acid, such as boron trifluoride (cf., for example, Can. J. Chem. 1979, 57, 3292; J. Am. Chem. Soc. 1953, 75, 626), followed by reaction with a hydrazine (cf. A. R. Katritzky et al., Comprehensive Heterocyclic Chemistry, Vol. 5, p. 121, 277-280 (1984), Pergamon Press; J. Org. Chem. 1961, 26, 451; Org. Synth. 1949, 29, 54), where the resulting pyrazole radical can be modified further by customary processes.
  • Furthermore, the diketone XII can be reacted with hydroxylamine or equivalents thereof (cf. A. R. Katritzky et al., Comprehensive Heterocyclic Chemistry, Vol. 6, p. 61-64, 118 (1984), Pergamon Press; Chem. Ber. 1967, 100, 3326). This gives the corresponding isoxazole derivatives which can be modified further by customary processes.
  • It is also possible to react the diketone XII with amidines (cf., for example, A. R. Katritzky et al., Comprehensive Heterocyclic Chemistry, Vol. 3, p. 112-114 (1924), Pergamon Press; J. Chem. Soc. C 1967, 1922; Org. Synth. 1963, IV, 182). If required, the resulting pyrimidine derivatives can be modified further by customary processes.
    Figure US20070197393A1-20070823-C00050
  • In the reactA123ions mentioned above, it is also possible to employ, instead of the diketone XII, equivalents thereof, such as enol ethers or enamines, which can be prepared analogously to known processes.
  • It may also be possible to react the cyclic ketone of the formula XI analogously to known processes with an aldehyde or ketone to give (XIII) (cf., for example, Tetrahedron Lett. 1978, 2111; Tetrahedron Lett. 1981, 5251; Chem. Ber. 1960, 2294; J. Chem. Soc. Perkin Trans. 1, 1991, 1467; Tetrahedron Lett. 1992, 8091). The resulting unsaturated cyclic ketone of the formula XIII can be reacted with a hydrazine in a manner known per se (cf., for example, A. R. Katritzky et al. Comprehensive Heterocyclic Chemistry, Vol. 2, 6 (1984), Pergamon Press; J. Heterocyclic Chem. 1969, 533; J. Heterocyclic Chem. 1968, 853), where the resulting pyrazoline can be modified further by customary processes.
  • It is furthermore possible to react the unsaturated cyclic ketone of the formula XIII with hydroxylamine or equivalents thereof (Z. Chem. 1980, 20, 19). This gives the corresponding isoxazoline derivatives, which can be modified further by customary processes.
    Figure US20070197393A1-20070823-C00051
  • Furthermore, it is possible to convert aldehydes of the formula XIV, which can be prepared in a manner known per se, analogously to processes known from the literature by reaction with a hydrazine or hydroxylamine (or equivalents of these) into the corresponding hydrazones or oximes (cf., for example, Synth. Commun. 1990, 20, 1373; J. Org. Chem. 1980, 45, 3756). These in turn can be converted in a manner known per se into the corresponding 1,3-dipoles, which then react in a [3+2]-cycloaddition to give the compounds VIc (cf., for example, Synth. Commun. 1990, 20, 1373; EP-A 386 892; J. Org. Chem. 1980, 45, 3756; Tetrahedron Lett. 1981, 22, 1333.)
  • The resulting pyrazoles or pyrazolines and isoxazoles or isoxazolines can be modified further by customary processes.
    Figure US20070197393A1-20070823-C00052
  • It is also possible to react the cyclic ketone of the formula XI with a dithiol or a “mixed alcohol” analogously to processes known from the literature (cf., for example, T. W. Greene et al., Protective Groups in Organic Synthesis, John Wiley & Sons, 133-140), and to subject it subsequently to a rearrangement in the presence of bromine or a suitable Lewis acid, such as, for example, tellurium tetrachloride (cf. Tetrahedron 1991, 47, 4187; Synthesis 1991, 223; J. Chem. Soc. Chem. Commun. 1985, 1645).
    Figure US20070197393A1-20070823-C00053
  • The resulting heterocycles can, if desired, be modified further by processes known per se.
  • The abovementioned substitutents R3a are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, hydroxyl, C1-C6-alkoxy or C1-C6-haloalkoxy; furthermore, the abovementioned radicals R3b are hydrogen, C1-C6-alkyl or C1-C6-haloalkyl.
  • The tricyclic benzoic esters of the formula VIc or the tricyclic benzoic acids of the formula VIb can be obtained by reacting a tricyclic benzene derivative of the formula IX with a C1-C6-alcohol or water in the presence of carbon monoxide, a catalyst and a base. In general, the conditions mentioned under process F apply.
    Figure US20070197393A1-20070823-C00054
  • L4 is a leaving group, such as halogen, for example chlorine, bromine or iodine, or sulfate, such as mesylate or triflate; preference is given to bromine or triflate.
  • Furthermore, the tricyclic benzoic acids of the formula VIb can be obtained by converting a tricyclic benzene derivative of the formula IX where L4 is halogen, such as chlorine or bromine, in particular bromine, by reaction with, for example, n-butyllithium or magnesium into the metalated derivative, followed by quenching with carbon dioxide (cf., for example, J. Org. Chem. 1990, 55, 773; Angew. Chem. Int. Ed. 1969, 8, 68).
    Figure US20070197393A1-20070823-C00055
  • It is also possible to obtain the tricyclic benzoic acids VIb by hydrolyzing the corresponding nitrites, analogously to processes known from the literature. The nitriles for their part can be obtained by halogen/nitrile exchange or by Sandmeyer reaction from the corresponding anilines XV.
    Figure US20070197393A1-20070823-C00056
  • The compounds of the formula IX,
  • where:
      • X is oxygen, sulfur, S═O, S(═O)2, CR6R7, NR8 or a bond;
      • Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated 5- or 6-membered heterocycle which contains one to three identical or different heteroatoms selected from the following group: oxygen, sulfur or nitrogen;
      • R1, R2, R6, R7 are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
      • R3 is halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
      • R4 is nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl)amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl) amino;
      • R5 is hydrogen, C1-C6-alkyl or halogen;
      • R8 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, formyl, C1-C6-alkoxycarbonyl, C1-C6-haloalkoxycarbonyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
      • l is 0, 1 or 2;
      • L4 is halogen, C1-C6-alkylsulfonyloxy, C1-C6-haloalkylsulfonyloxy or phenylsulfonyloxy, where the phenyl ring of the lastmentioned radical may be unsubstituted or partially or fully halogenated and/or may carry one to three of the following radicals: nitro, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
        are novel.
  • Preference is given to compounds of the formula IX where L4 is halogen, in particular bromine.
  • The particularly preferred embodiments of the compounds of the formula IX with respect to the variables X, Y, R1 to R5 and l correspond to those of the tricyclic benzoylpyrazole derivatives of the formula I.
  • Particular preference is given to the compounds of the formula IX where
      • Y together with the two carbons to which it is attached forms the following heterocycles:
        Figure US20070197393A1-20070823-C00057
  • Here, extraordinary preference is given to the compounds IX where
      • R4 is nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio or C1-C6-alkylsulfonyl; in particular C1-C6-alkylsulfonyl.
  • The compounds of the formula IX can be obtained in different ways, the fused system, for example, can be constructed analogously to the processes described for the compounds of the formula VIc.
  • However, it is also possible to construct the fused system from a suitable parent compound (analogously to the processes described for compounds of the formula VIc) and to introduce L4=halogen subsequently by customary halogenating reactions.
  • The anilines of the formula XV and the nitriles of the formula XVI
    Figure US20070197393A1-20070823-C00058
    where:
      • X is oxygen, sulfur, S═O, S(═O)2, CR6R7, NR8 or a bond;
      • Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated 5- or 6-membered heterocycle which contains one to three identical or different heteroatoms selected from the following group: oxygen, sulfur or nitrogen;
      • R1, R2, R6, R7 are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
      • R3 is halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
      • R4 is nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl) amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino;
      • R5 is hydrogen, C1-C6-alkyl or halogen;
      • R8 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, formyl, C1-C6-alkoxycarbonyl, C1-C6-haloalkoxycarbonyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
      • l is 0, 1 or 2;
        are also novel.
  • The particularly preferred embodiments of the compounds of the formulae XV and XVI with respect to the variables X, Y, R1 to R5 and l correspond to those of the tricyclic benzoylpyrazole derivatives of the formula I.
  • Particular preference is given to the compounds of the formula XV or XVI where
      • Y together with the two carbons to which it is attached forms the following heterocycles:
        Figure US20070197393A1-20070823-C00059
  • Here, extraordinary preference is given to the compounds XV or XVI where
      • R4 is nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio or C1-C6-alkylsulfonyl; in particular C1-C6-alkylsulfonyl.
  • The compounds of the formula XV can be obtained in different ways; for example, the fused system can be constructed analogously to the processes described for the compounds of the formula VIc.
  • However, it is also possible to construct the fused system from a suitable parent compound (analogously to the processes described for the compounds of the formula VIc) and to introduce a nitro group subsequently by nitration para to R4, analogously to processes known from the literature, and to convert this group in a manner known per se by reduction into the amino group.
  • If appropriate, it may be advantageous in the synthesis variants described above to introduce protective groups for certain functionalities if the functionalities are not compatible with the reaction conditions required.
  • The selection of the protective groups depends both on the reaction conditions and on the structure of the molecule. The protective groups, their introduction and their removal are generally known from the literature (cf., for example, T. W. Greene et al., “Protective Groups in Organic Synthesis”, 2nd edition, Wiley, New York, 1991), and they can be employed analogously to processes known from the literature.
  • Furthermore, it may be necessary to carry out a combination of the synthesis variants described above.
  • It is also possible to introduce further substitutents or to modify the substitutents present by electrophilic, nucleophilic, free-radical or organometallic reactions and by oxidation or reduction reactions.
    • PREPARATION EXAMPLES 1. (5-Phenylcarbonyloxy-1-methyl-1H-pyrazol-4-yl)-(8-methyl-sulfonyl-3a,4-dihydro-3H-indeno[1,2-c]isoxazol-5-yl)methanone (compound 2.2) 2-Allyl-6-chlorobenzaldehyde
  • Under an atmosphere of protective gas, a solution of 10.89 g (0.107 mol) of trimethylethylenediamine in 50 ml of anhydrous tetrahydrofuran was cooled to −10° C. and admixed dropwise with 66.6 ml of a 1.6 molar solution of n-butyllithium in hexane (0.107 mol). After 10 minutes, 15 g (0.107 mol) of 6-chlorobenzaldehyde in 70 ml of tetrahydrofuran were added dropwise, and the mixture was admixed with a further 0.214 mol of n-butyllithium in hexane (146.8 ml) and stirred at 0° C. for 2.5 hours. The mixture was cooled to −20° C., 12.42 g (0.139 mol) of copper(I) cyanide were added, the mixture was stirred at −10° C. for 30 minutes, and 28.42 g of allyl bromide in 100 ml of tetrahydrofuran were then added dropwise. The mixture was stirred at 0° C. for another 2.5 hours, and 230 ml of saturated ammonium chloride solution were then added dropwise. The resulting solid was separated off and the aqueous phase was extracted with diethyl ether. The combined organic phases were then washed with saturated ammonium chloride solution and dried, and the solvent was removed under reduced pressure. This gave 17.0 g of 2-allyl-6-chlorobenzaldehyde (89%) in the form of a dark oil.
  • 1H NMR (CDCl3, δ in ppm): 3.73 (d, 2H); 5.05 (dd, 2H); 5.96 (m, 1H); 7.05-7.48 (m, 3H); 10.58 (s, 1H).
    • 2-Allyl-6-chlorobenzaldehyde oxime
  • 5.58 g of sodium bicarbonate were added to a solution of 4.62 g of hydroxylamine hydrochloride in 50 ml of water, and the mixture was cooled to 0° C. A solution of 9.7 g (44.32 mmol) of 2-allyl-6-chlorobenzaldehyde in 50 ml of methanol was then added dropwise, and the mixture was stirred at room temperature overnight. The methanol was subsequently removed under reduced pressure and the residue was stirred into 300 ml of water. The aqueous phase was extracted with diethyl ether and the combined organic phases were washed with saturated ammonium chloride solution and dried, and the solvent was removed. This gave 8.7 g (quantitative) of 2-allyl-6-chlorobenzaldehyde oxime in the form of a viscous oil.
  • 1H NMR (CDCl3, δ in ppm): 3.58 (d, 2H); 5.02 (2d, 2H); 5.95 (m, 1H); 7.08-7.36 (m, 3H); 8.49 (s, 1H).
    • 8-Chloro-3a,4-dihydro-3H-indeno[1,2-c]isoxazole
  • At room temperature, 37.0 ml of a sodium hypochlorite solution (12.5% of active chlorine) were added dropwise to a solution of 8.4 g (42.9 mmol) of 2-allyl-6-chlorobenzaldehyde oxime in 100 ml of methylene chloride, and a spatula tip of sodium acetate was added. The mixture was stirred at room temperature for 2 hours, the organic phase was separated off, the aqueous phase was extracted with methylene chloride and the combined organic phases were washed with saturated ammonium chloride solution. The organic phase was dried and the solvent was removed. This gave 7.0 g (94%) of 8-chloro-3a,4-dihydro-3H-indeno-[1,2-c]isoxazole in the form of a viscous oil.
  • 1H NMR (CDCl3, δ in ppm): 2.81 (dd, 1H); 3.24 (dd, 1H); 3.78-4.03 (s, 2H); 4.78 (t, 1H); 7.23-7.41 (m, 3H).
    • 8-Methylthio-3a,4-dihydro-3H-indeno[1,2c]isoxazole
  • At room temperature, 3.6 g (52.0 mmol) of sodium thiomethoxide were added to a solution of 5.0 g (25.8 mmol) of 8-chloro-3a,4-dihydro-3H-indeno-[1,2-c]isoxazole in 60 ml of N-methylpyrrolidone, and the mixture was stirred overnight. The mixture was subsequently stirred into 800 ml of water, the aqueous phase was extracted with diethyl ether, the combined organic phases were washed with saturated ammonium chloride solution and dried, and the solvent was removed. This gave 4.6 g (87%) of 8-methylthio-3a,4-dihydro-3H-indeno[1,2-c]isoxazole in the form of a dark brown solid.
  • 1H NMR (CDCl3, δ in ppm): 2.54 (s, 3H); 2.78 (dd, 1H); 3.21 (dd, 1H); 3.72-3.93 (s, 2H); 4.64 (t, 1H); 7.09-7.38 (m, 3H).
    • 5-Bromo-8-methylthio-3a,4-dihydro-3H-indeno[1,2-c]isoxazole
  • 120 ml of sulfuric acid (98 percent strength) were cooled to 0° C., and 11.2 g (54.8 mmol) of 8-methylthio-3a,4-dihydro-3H-indeno[1,2-c]isoxazole were added a little at a time. 9.2 g (57.5 mmol) of bromine were then added dropwise, and stirring was continued at 0° C. for another 2 hours. The resulting solution was poured into 2 l of a mixture of water and ice, this mixture was stirred for 1.5 hours and the precipitated solid was filtered off with suction and then washed and dried. This gave 11.4 g (73%) of 5-bromo-8-methylthio-3a,4-dihydro-3H-indeno[1,2-c]isoxazole of a brown solid having a m.p. of 127-135° C.
  • 1H NMR (CDCl3, δ in ppm): 2.53 (s, 3H); 2.71 (dd, 1H); 3.24 (dd, 1H); 3.81-4.02 (s, 2H); 4.71 (t, 1H); 7.01 (d, 1H); 7.47 (d, 1H).
    • 5-Bromo-8-methylsulfonyl-3a,4-dihydro-3H-indeno[1,2-c]-isoxazole
  • A solution of 11.2 g (39.4 mmol) of 5-bromo-8-methylthio-3a,4-dihydro-3H-indeno[1,2-c]isoxazole and 1.55 g of sodium tungstate in 250 ml of toluene and 50 ml of glacial acetic acid was heated to 70° C. and mixed dropwise with 10.73 g (39 percent strength, 86.8 mmol) of hydrogen peroxide. Stirring was continued at 70° C. for another 3 hours, and a solid precipitated out. The mixture was allowed to cool to room temperature and stirred into 1 l of water, and the white solid was filtered off with suction. The organic phase of the filtrate was separated off and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with water and dried, and the solvent was removed. This gave a viscous brown oil which was stirred with hexane/ethyl acetate (4:1). The resulting precipitate was filtered off with suction and combined with the solid obtained above. This gave 7.3 g (59%) of 5-bromo-8-methylsulfonyl-3a,4-dihydro-3H-indeno[1,2-c]-isoxazole.
  • 1H-NMR (d6-DMSO, δ in ppm): 2.93 (dd, 1H); 3.23 (dd, 1H); 3.41 (s, 3H); 3.94 (dd, 1H); 4.16 (m, 1H); 4.81 (t, 1H); 7.82 (d, 1H); 8.03 (d, 1H).
    • (5-Hydroxy-1-methyl-1H-pyrazol-4-yl)-(8-methylsulfonyl-3a,4-dihydro-3H-indeno[1,2-c]isoxazol-5-yl)methanone (compound 2.1)
  • 0.62 g (6.33 mmol) of 5-hydroxy-1-methylpyrazole, 1.75 g (12.66 mmol) of dry potassium carbonate, 1.28 g (12.67 mmol) of triethylamine and 0.22 g (0.30 mmol) of bis-(triphenylphosphane)palladium dichloride were added to a suspension of 2.0 g (6.33 mmol) of 5-bromo-8-methylsulfonyl-3a,4-dihydro-3H-indeno[1,2-c]-isoxazole in 100 ml of dioxane. In a miniautoclave, a carbon monoxide pressure of 20 bar was applied, the mixture was stirred for 5 minutes and the autoclave was vented. This procedure was repeated 3 times. The autoclave was subsequently heated to 130° C., a carbon monoxide pressure of 20 bar was applied once more and the mixture was stirred for 24 hours. After cooling and venting, the solvent was removed, and the residue was taken up in water, adjusted to pH 11 and washed with methylene chloride. The mixture was subsequently acidified to pH 4 using 10 percent strength hydrochloric acid and extracted with methylene chloride. The combined organic phases were washed with saturated ammonium chloride solution and dried, and the solvent was removed. This gave 0.58 g (25%) of (5-hydroxy-1-methyl-1H-pyrazol-4-yl)-(8-methylsulfonyl-3a,4-dihydro-3H-indeno[1,2-c]isoxazole)-methanone in the form of a dark oil.
  • 1H NMR (CDCl3, δ in ppm): 3.03 (dd, 1H); 3.42 (s, 3H); 3.40 (m, 1H); 3.51 (s, 3H); 4.05 (m, 2H); 4.85 (t, 1H); 7.57 (s, 1H); 7.92 (d, 1H); 8.22 (d, 1H).
    • (5-Phenylcarbonyloxy-1-methyl-1H-pyrazol-4-yl)-(8-methylsulfonyl-3a,4-dihydro-3H-indeno[1,2-c]isoxazol-5-yl)methanone (compound 2.2)
  • Under an atmosphere of protective gas, 0.18 g of triethylamine and 0.26 g (1.82 mmol) of benzoyl chloride in 10 ml of tetrahydrofuran were added at 0° C. to a suspension of 0.55 g (1.52 mmol) of (5-hydroxy-1-methyl-1H-pyrazol-4-yl)-(8-methylsulfonyl-3a,4-dihydro-3H-indeno[1,2-c]-isoxazol-5-yl)methanone in 10 ml of tetrahydrofuran. The mixture was stirred overnight at room temperature, the solvent was removed, the residue was taken up in ethyl acetate, washed with water and dried, and the solvent was removed. The crude product was purified by silica gel chromatography (mobile phase: ethyl acetate:hexane=1:1). This gave 0.22 g (31%) of (5-phenylcarbonyloxy-1-methyl-1H-pyrazol-4-yl)-(8-methylsulfonyl-3a,4-dihydro-3H-indeno[1,2-c]isoxazol-5-yl)methanone in the form of a yellow solid having a m.p. of 86-93° C.
  • 1H NMR (CDCl3, δ in ppm): 3.22 (s, 3H); 3.34 (m, 2H); 3.81 (s, 3H); 3.98 (m, 2H); 4.81 (t, 1H); 7.20-8.21 (m, 8H).
    • 2. 4-(2-Methyl-9-chloro-[1]-thiochromano[4,3-c]pyrazol-6-yl)carbonyl-5-hydroxy-1-methyl-1H-pyrazole (compound 3.1) Methyl 2-chlorosulfonyl-4-chlorobenzoate
  • At from 0 to 5° C., a solution of 60.9 g (0.88 mol) of sodium nitrite in 100 ml of water was added dropwise to a solution of 139 g (0.75 mol) of methyl 2-amino-4-chlorobenzoate in 400 ml of concentrated hydrochloric acid and the mixture was stirred at 0° C. for another hour.
  • In a second apparatus, 3 g of copper(II) chloride, 3 g of benzyltriethylammonium chloride, 10 ml of water and 400 ml of 1,2-dichloroethane were combined and 64 g (1 mol) of sulfur dioxide were introduced.
  • The diazonium salt described above was subsequently added at from 10 to 15° C., and the mixture was slowly heated to 50° C. A further 54 g (0.84 mol) of sulfur dioxide were then introduced, and stirring was continued at 50° C. for another 30 minutes. After cooling, 7.4 g (0.1 mol) of chlorine gas were then introduced at room temperature, stirring was continued for 15 minutes and the phases which had formed were then separated. The organic phase was dried and the solvent was removed. This gave 207 g of methyl 2-chlorosulfonyl-4-chlorobenzoate.
  • 1H NMR (CDCl3, δ in ppm): 4.00 (s, 3H); 7.75 (m, 2H); 8.18 (m, 1H)
    • Methyl 2-mercapto-4-chlorobenzoate
  • Over a period of 1.5 hours, 243.5 g (3.7 mol) of zinc powder were added a little at a time to a suspension of 205 g (0.75 mol) of methyl 2-chlorosulfonyl-4-chlorobenzoate in 1 l of concentrated hydrochloric acid and 375 g of ice. The mixture was stirred for another 3 hours and slowly heated to 70° C. After 2 hours at this temperature, the mixture was cooled. The reaction mixture was allowed to stand at room temperature for 12 hours and then extracted with ethyl acetate, the combined organic phases were dried and the solvent was removed. This gave 125.4 g (83%) of methyl 2-mercapto-4-chlorobenzoate.
  • 1H NMR (CDCl3, δ in ppm): 3.95 (s, 3H); 4.88 (s, 1H); 7.10 (m, 1H); 7.30 (m, 1H); 7.96 (d, 1H).
    • Methyl 2-(2-hydroxycarbonyleth-1-yl)thio-4-chlorobenzoate
  • 179.5 g (1.3 mol) of potassium carbonate and, a little at a time, 94.5 g (0.62 mol) of 3-bromopropionic acid were added to a solution of 125.4 g (0.62 mol) of methyl 2-mercapto-4-chlorobenzoate in 1.5 l of acetone, and the reaction mixture was stirred at room temperature for 12 hours. The solvent was distilled off, the residue was taken up in water and the mixture was extracted with diethyl ether. The aqueous phase was then made acidic using concentrated hydrochloric acid, and the resulting precipitate was filtered off with suction and dried. This gave 150 g (88%) of methyl 2-(2-hydroxycarbonyleth-1-yl)thio-4-chlorobenzoate.
  • M.p.: 133 to 136° C.
    • Methyl 5-chloro-4-oxothiochromane-8-carboxylate
  • At 70° C., 50 g (0.18 mol) of methyl 2-(2-hydroxycarbonyleth-1-yl)thio-4-chlorobenzoate were added to 500 g of polyphosphoric acid, and the mixture was stirred for a further 30 minutes. The reaction mixture was then stirred into water and the resulting precipitate was filtered off with suction and dried. This gave 41.1 g (88%) of methyl 5-chloro-4-oxothiochromane-8-carboxylate.
  • 1H NMR (CDCl3, δ in ppm): 3.08 (m, 4H); 3.96 (s, 3H); 7.14 (d, 1H); 7.95 (d, 1H).
    • Methyl 5-chloro-3-(N,N-dimethylaminomethylidene)-4-oxothiochromane-8-carboxylate
  • 30 g (0.078 mol) of methyl 5-chloro-4-oxothiochromane-8-carboxylate in 300 ml of N,N-dimethylformamide dimethyl acetal were refluxed for 6 hours. Volatile components were then distilled off, the residue was taken up in methylene chloride and the organic phase washed with water. Drying and removal of the solvent gave 35.3 g (97%) of methyl 5-chloro-3-(N,N-dimethylaminomethylidene)-4-oxothiochromane-8-carboxylate.
  • 1H NMR (CDCl3, δ in ppm): 3.18 (s, 6H); 3.80 (s, 2H); 3.95 (s, 3H); 7.24 (d, 1H); 7.64 (s, 1H); 7.82 (d, 1H).
    • 2-Methyl-6-methoxycarbonyl-9-chloro-[1]-thiochromano[4,3-c]-pyrazole
  • 1.3 g (29.2 mmol) of methylhydrazine were added dropwise to a solution of 7.0 g (22.5 mmol) of methyl 5-chloro-3-(N,N-dimethylaminomethylidene)-4-oxothiochromane-8-carboxylate in 700 ml of ethanol, and the mixture was refluxed for 2 hours. The solvent was removed and the residue was chromatographed over silica gel using ethyl acetate/cyclohexane (2:3) as mobile phase. This gave 4.0 g (60%) of 2-methyl-6-methoxycarbonyl-9-chloro-[1]-thiochromano[4,3-c]pyrazole.
  • 1H NMR (CDCl3, δ in ppm): 3.76 (s, 2H); 3.95 (s, 3H); 4.00 (s, 3H); 7.24 (s, 1H); 7.36 (d, 1H); 7.70 (d, 1H).
    • 2-Methyl-6-hydroxycarbonyl-9-chloro-[1]-thiochromano[4,3-c]pyrazole
  • 4.0 g (13.6 mmol) of 2-methyl-6-methoxycarbonyl-9-chloro-[1]-thiochromano[4,3-c]pyrazole in 100 ml of methanol/water (1:1) were refluxed with 0.8 g (20 mmol) of sodium hydroxide for 1 hour. The organic solvent was removed under reduced pressure and the residue was extracted with ethyl acetate. The aqueous phase was acidified using concentrated hydrochloric acid and the resulting precipitate was filtered off with suction and dried. This gave 3.5 g (92%) of 2-methyl-6-hydroxycarbonyl-9-chloro-[1]-thiochromano[4,3-c]-pyrazole
  • 1H NMR (CDCl3, δ in ppm): 3.80 (s, 2H); 3.96 (s, 3H); 7.40 (d, 1H); 7.65 (m, 2H).
    • 4-(2-Methyl-9-chloro-[1]-thiochromano[4,3-c]pyrazol-6-yl)-carbonyl-5-hydroxy-1-methyl-1H-pyrazole (compound 3.1)
  • A mixture of 0.60 g (2.1 mmol) of 2-methyl-6-hydroxycarbonyl-9-chloro-[1]-thiochromano[4,3-c]-pyrazole and 0.21 g (2.1 mmol) of N,N-dicyclohexylcarbodiimide in 20 ml of acetonitrile was stirred at room temperature overnight. The mixture was admixed with in each case 500 ml of ethyl acetate and 2% strength sodium carbonate solution, the resulting precipitate was filtered off, the organic phase was dried and the solvent was removed. The residue was then refluxed with 0.59 g (4.3 mmol) of potassium carbonate in 5 ml of 1,4-dioxane for 3 hours. After cooling, the mixture was extracted with diethyl ether and the aqueous phase was acidified to pH 3. The resulting precipitate was filtered off with suction and dried. This gave 0.14 g of 4-(2-methyl-9-chloro-[1]-thiochromano[4,3-c]pyrazol-6-yl)-carbonyl-5-hydroxy-1-methyl-1H-pyrazole.
  • M.p.: 168-171° C.
    • 3. (5-Hydroxy-1-methyl-1H-pyrazol-4-yl)-(6-methoxy-3a,4-dihydro-3H-chromeno[4,3-c]isoxazolin-9-yl)methanone (compound 2.3) Methyl 2-hydroxy-3-formyl-4-methoxybenzoate
  • At from 0 to 5° C., a solution of 209.0 g (1.1 mol) of titanium tetrachloride in 150 ml of methylene chloride was added dropwise to a solution of 50.1 g (0.275 mol) of methyl 2-hydroxy-4-methoxybenzoate and 88 g (0.725 mol) of dichloromethoxymethane in 400 ml of methylene chloride, and the mixture was stirred at room temperature overnight. The mixture was then stirred into ice-water and extracted with methylene chloride. The combined organic phases were washed with sodium bicarbonate solution, water and sodium chloride solution and dried, and the solvent was then removed. Silica gel chromatography using cyclohexane/ethyl acetate=1:1 gave 24.5 g (42%) of methyl 2-hydroxy-3-formyl-4-methoxybenzoate in the form of a colorless solid of m.p.: 123-124° C.
  • 1H NMR (CDCl3, δ in ppm): 3.92 (s, 3H); 3.98 (s, 3H); 6.49 (d, 1H); 8.19 (d, 1H); 10.39 (s, 1H).
    • Methyl 2-allyloxy-3-formyl-4-methoxybenzoate
  • At room temperature, 23.2 g (0.192 mol) of allyl bromide were added dropwise to a mixture of 21.0 g (0.375 mol) of potassium hydroxide and 20.2 g (0.096 mol) of methyl 2-hydroxy-3-formyl-4-methoxybenzoate in 500 ml of dimethyl sulfoxide, and the mixture was stirred at room temperature for 4 hours. The mixture was subsequently stirred into 1.5 l of 3% strength aqueous hydrochloric acid and extracted with ethyl acetate. The combined organic phases were washed with water and dried, and the solvent was removed. Silica gel chromatography using cyclohexane/ethyl acetate=1:2 gave 7.7 g (36%) of methyl 2-allyloxy-3-formyl-4-methoxybenzoate in the form of a yellowish oil.
  • 1H NMR (CDCl3, δ in ppm): 3.86 (s, 3H); 3.93 (s, 3H); 4.58 (d, 2H); 5.32 (d, 1H); 5.39 (d, 1H); 6.15 (m, 1H); 6.79 (d, 1H); 8.04 (d, 1H); 10.41 (s, 1H).
    • 6-Methoxy-9-methoxycarbonyl-3a,4-dihydro-3H-chromeno[4,3-c]isoxazoline
  • Step a)
  • At room temperature, 4.6 g (18.4 mmol) of methyl 2-allyloxy-3-formyl-4-methoxybenzoate in 70 ml of methanol were added dropwise to a solution of 2.25 g (32.3 mmol) of hydroxylammonium chloride and 2.7 g of pyridine in 70 ml of water. The mixture was stirred at room temperature overnight, 150 ml of water were added, the mixture was extracted with methylene chloride, the combined organic phases were washed with 3% strength aqueous hydrochloric acid and dried, and the solvent was removed. The resulting oxime has a melting point of 126-129° C.
  • Step b)
  • This oxime was reacted further without any further purification by dissolving it in 40 ml of methylene chloride, followed by dropwise addition of 15.0 ml (25.0 mmol) of sodium hypochlorite solution (12.5% of active chlorine). A spatula tip of sodium acetate was added and the mixture was stirred at room temperature for 12 hours. The organic phase was separated off, the aqueous phase was extracted with methylene chloride, the combined organic phases were washed with water and dried, and the solvent was removed. Silica gel chromatography using cyclohexane/ethyl acetate=1:1 gave 2.2 g (49%) of 6-methoxy-9-methoxycarbonyl-3a,4-dihydro-3H-chromeno[4,3-c]-isoxazoline in the form of a colorless solid of m.p: 199-203° C.
  • 1H NMR (CDCl3, δ in ppm): 3.84 (s, 3H); 3.98 (s, 3H); 3.8-4.0 (m, 2H); 4.16 (dt, 1H); 4.63 (t, 1H); 4.84 (dd, 1H); 6.61 (d, 1H); 7.93 (d, 1H).
    • 6-Methoxy-9-hydroxycarbonyl-3a,4-dihydro-3H-chromeno[4,3-c]isoxazoline
  • At room temperature, a solution of 0.8 g (20.0 mmol) of sodium hydroxide in 7 ml of water was added dropwise to a solution of 2.1 g (8.0 mmol) of 6-methoxy-9-methoxycarbonyl-3a,4-dihydro-3H-chromeno[4,3-c]isoxazoline in 40 ml of methanol, and the mixture was refluxed for 6 hours. After cooling, the solvent was removed and the residue was taken up in about 50 ml of water and washed with methylene chloride. The aqueous phase was subsequently acidified using 10% strength hydrochloric acid (pH=1-2), and the precipitate was filtered off with suction, washed with water and dried at 60° C. This gave 1.7 g (86%) of 6-methoxy-9-hydroxycarbonyl-3a,4-dihydro-3H-chromeno[4,3-c]-isoxazoline in the form of colorless crystals.
  • 1H NMR (CDCl3, δ in ppm): 3.73 (dd, 1H); 3.89 (s, 3H); 3.84-3.95 (m, 1H); 4.11 (dd, 1H); 4.54 (dd, 1H); 4.79 (dd, 1H); 6.61 (d, 1H); 7.81 (d, 1H).
    • (5-Hydroxy-1-methyl-1H-pyrazol-4-yl)-(6-methoxy-3a,4-dihydro-3H-chromeno[4,3-c]isoxazolin-9-yl)methanone (compound 2.3)
  • Step a)
  • At room temperature, 0.26 g (2.2 mmol) of thionyl chloride and a drop of dimethylformamide were added to a solution of 0.50 g (2.0 mmol) of 6-methoxy-9-hydroxycarbonyl-3a,4-dihydro-3H-chromeno[(4,3-c)]isoxazoline in 30 ml of carbon tetrachloride, and the mixture was stirred at 40-50° C. for 3 hours. The solvent was subsequently removed under reduced pressure. This gave, in quantitative yield, 6-methoxy-9-chloroformyl-3a,4-dihydro-3H-chromeno[4,3-c]isoxazoline (0.54 g) as a brownish oil.
  • Step b)
  • 0.54 g (2 mmol) of 6-methoxy-9-chloroformyl-3a,4-dihydro-3H-chromeno[4,3-c]isoxazoline was dissolved in 30 ml of acetonitrile and, at 0° C., added dropwise to a solution of 0.2 g (2.0 mmol) of 1-methyl-5-hydroxypyrazole and 0.6 g (6.0 mmol) of triethylamine in 20 ml of acetonitrile. The mixture was stirred at room temperature overnight, the solvent was removed, and the residue was taken up in methylene chloride and washed with water. The solution was dried and the solvent was distilled off. The residue was dissolved in 30 ml of dioxane and admixed with 0.42 g (3.0 mmol) of potassium carbonate, and the mixture was refluxed for 7 hours. After cooling, the solvent was distilled off under reduced pressure, the residue was taken up in water and the solution was adjusted to pH=1 using 10% strength hydrochloric acid. The solution was extracted with methylene chloride, the combined organic phases were dried and the solvent was subsequently removed. This gave 0.45 g (68%) of (5-hydroxy-1-methyl-1H-pyrazol-4-yl)-(6-methoxy-3a,4-dihydro-3H-chromeno[4,3-c]isoxazolin-9-yl)methanone of m.p. 236-238° C.
  • 1H NMR (CDCl3, δ in ppm): 3.66 (s, 3H); 3.84-4.2 (m, 2H); 4.02 (s, 3H); 4.12 (dd, 1H); 4.63-4.77 (m, 2H); 6.68 (d, 1H); 7.24 (s, 1H); 7.61 (d, 1H).
    • 4. [5-Hydroxy-1-(1,1-dimethyleth-1-yl)-1H-pyrazol-4-yl]-[6-methoxy-3a,4-dihydro-3H-chromeno[4,3-c]isoxazolin-9-yl]methanone (compound 2.4)
  • 0.54 g (2 mmol) of 6-methoxy-9-chloroformyl-3a,4-dihydro-3H-chromeno[4,3-c]-isoxazoline was dissolved in 30 ml of acetonitrile and, at 0° C., added dropwise to a solution of 0.28 g (2.0 mmol) of 1-(1,1-dimethyleth-1-yl)-5-hydroxy-1H-pyrazole and 0.6 g (6.0 mmol) of triethylamine in 20 ml of acetonitrile. The mixture was stirred at room temperature overnight, the solvent was removed, and the residue was taken up in methylene chloride and washed with water. The solution was dried, and the solvent was distilled off. The residue was dissolved in 30 ml of dioxane and admixed with 0.42 g (3.0 mmol) of potassium carbonate, and the mixture was refluxed for 7 hours. After cooling, the solvent was distilled off under reduced pressure, the residue was taken up in water and the solution was adjusted to pH=1 using 10% strength hydrochloric acid. The solution was extracted with methylene chloride, the combined organic phases were dried, and the solvent was subsequently removed. This gave 0.3 g (40%) of [5-hydroxy-1-(1,1-dimethyleth-1-yl)-1H-pyrazol-4-yl]-[6-methoxy-3a,4-dihydro-3H-chromeno[4,3-c]isoxazolin-9-yl]methanone having a melting point of 223° C.-225° C.
  • 1H NMR (CDCl3, δ in ppm): 1.64 (s, 9H); 3.8-4.2 (m, 6H); 4.6-4.8 (m, 2H); 6.68 (d, 1H); 7.44 (s, 1H); 7.62 (d, 1H).
  • In addition to the compounds above, other tricyclic benzoylpyrazole derivatives of the formula I which were prepared or are preparable in a similar manner are listed in Tables 2 to 5:
    TABLE 2
    Figure US20070197393A1-20070823-C00060
    physical data (m.p. [° C.];
    No. X R4 R10 R11 R12 1H NMR [ppm])
    2.1 Bond SO2CH3 OH CH3 H 3.03 (dd, 1H); 3.42 (s, 3H); 3.51 (s, 3H); 4.05 (m, 2H); 4.85 (t, 1H); 7.57 (s, 1H); 7.92 (d, 1H); 8.22 (d, 1H)
    2.2 Bond SO2CH3 OCOC6H5 CH3 H 3.22 (s, 3H); 3.34 (m, 2H); 3.81 (s, 3H); 3.98 (m, 2H); 4.81 (t, 1H); 7.20-8.21 (m, 8H);
    2.3 O OCH3 OH CH3 H 236-238
    2.4 O OCH3 OH C(CH3)3 H 223-225
    2.5 O OCH3 OCO (3-F—C6H4) CH3 H oil
  • TABLE 3
    Figure US20070197393A1-20070823-C00061
    No. X R4 R10 R11 R12 physical data (m.p.[° C])
    3.1 S Cl OH CH3 H 168-171
    3.2 S Cl OH CH2CH3 H 115
    3.3 S SCH3 OH CH3 H 245
    3.4 S SCH3 OH CH2CH3 H 222
  • TABLE 4
    Figure US20070197393A1-20070823-C00062
    physical data (m.p. [° C.];
    No. X R4 R10 R11 R12 1H NMR [ppm])
    4.1 S Cl OH CH3 H 180° C.
    4.2 S Cl OH CH2CH3 H 112° C.
  • TABLE 5
    Figure US20070197393A1-20070823-C00063
    physical data (m.p. [° C.];
    Nr. X R4 R10 R11 R12 1H NMR [ppm])
    5.1 O SCH3 OH CH3 H 201
  • The compounds of the formula I and their agriculturally useful salts are suitable, both in the form of isomer mixtures and in the form of the pure isomers, as herbicides. The herbicidal compositions comprising compounds of the formula I control vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.
  • Depending on the application method in question, the compounds of the formula I, or herbicidal compositions comprising them, can additionally be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:
  • Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
  • In addition, the compounds of the formula I may also be used in crops which tolerate the action of herbicides owing to breeding, including genetic engineering methods.
  • The compounds of the formula I, or the herbicidal compositions comprising them, can be used for example in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, spreading or watering. The use forms depend on the intended purpose; in any case, they should guarantee the finest possible distribution of the active compounds according to the invention.
  • The herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries which are customarily used for formulating crop protection agents.
  • Suitable for use as inert auxiliaries are essentially the following:
  • mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, furthermore coal-tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, for example amines such as N-methylpyrrolidone, and water.
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the tricyclic benzoylpyrazole derivatives of the formula I, either as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates comprising active compound, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.
  • Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, e.g. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active compounds together with a solid carrier.
  • Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
  • The concentrations of the compounds of the formula I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise approximately from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active compound. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • The following formulation examples illustrate the preparation of such formulations:
    • I. 20 parts by weight of the compound No. 2.2 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, parts by weight of the adduct of from 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active compound.
    • II. 20 parts by weight of the compound No. 3.1 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active compound.
    • III. 20 parts by weight of the compound No. 2.3 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280° C. and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active compound.
    • IV. 20 parts by weight of the compound No. 2.4 are mixed thoroughly with 3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active compound.
    • V. 3 parts by weight of the compound No. 2.3 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3% by weight of the active compound.
    • VI. 20 parts by weight of the compound No. 2.4 are mixed intimately with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.
    • VII. 1 part by weight of the compound No. 2.2 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.
    • VIII. 1 part by weight of the compound No. 3.1 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM 31 (=nonionic emulsifier based on ethoxylated castor oil). This gives a stable emulsion concentrate.
  • The compounds of the formula I or the herbicidal compositions can be applied pre- or post-emergence. If the active compounds are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).
  • The rates of application of the compound of the formula I are from 0.001 to 3.0, preferably 0.01 to 1.0, kg/ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage.
  • To widen the spectrum of action and to achieve synergistic effects, the tricyclic benzylpyrazole derivatives of the formula I may be mixed with a large number of representatives of other herbicidal or growth-regulating active compound groups and applied concomitantly. Suitable components for mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy-/heteroaryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinoline carboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionic esters, phenylactic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
  • It may furthermore be advantageous to apply the compounds of the formula I, alone or in combination with other herbicides, in the form of a mixture with other crop protection agents, for example together with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
    • USE EXAMPLES
  • The herbicidal activity of the tricyclic benzylpyrazole derivatives of the formula I was demonstrated by the following greenhouse experiments:
  • The culture containers used were plastic pots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.
  • For the pre-emergence treatment, the active compounds, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover causes uniform germination of the test plants, unless this was adversely affected by the active compounds.
  • For post-emergence treatment, the test plants were first grown to a plant height of from 3 to 15 cm, depending on the plant habit, and only then treated with the active compounds which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to the treatment. The application rate for the post-emergence treatment was 0.5 or 0.25 kg of a.s./ha.
  • Depending on the species, the plants were kept at 10-25° C. or 20-35° C. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
  • Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the above-ground parts, and 0 means no damage, or normal course of growth.
  • The plants used in the greenhouse trials were of the following species:
    Scientific Name Common Name
    Chenopodium album lambsquarters (goosefoot)
    Echinochloa crusgalli barnyardgrass
    Setaria viridis green foxtail
    Solanum nigrum black nightshade
    Veronica ssp. speadwell
  • At application rates of 0.5 or 0.25 kg/ha, the compound 2.2 shows very good activity against the abovementioned undesired broad-leaved weeds and weed grasses when applied by the post-emergence method.

Claims (23)

1.-20. (canceled)
21. A tricyclic benzoylpyrazole compound of formula I
Figure US20070197393A1-20070823-C00064
where:
X is oxygen, sulfur, S═O, S(═O)2, CR6R7, or NR8;
Y together with the two carbons to which it is attached forms a saturated, partially saturated or unsaturated 5- or 6-membered heterocycle which contains one to three identical or different heteroatoms selected from the following group: oxygen, sulfur and nitrogen;
R1, R2, R6, R7 are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
R3 is halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
R4 is hydrogen, nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl)amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino;
R5 is hydrogen, C1-C6-alkyl or halogen;
R8 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, formyl, C1-C6-alkoxycarbonyl, C1-C6-haloalkoxycarbonyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
l is 0, 1 or 2;
R9 is a radical IIa or IIb
Figure US20070197393A1-20070823-C00065
where
R10 is hydroxyl, mercapto, halogen, OR13, SR13, SO2R14, NR15R16 or N-bonded heterocyclyl, where the heterocyclyl radical may be partially or fully halogenated and/or may carry one to three of the following radicals:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R11 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, hydroxyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
R12 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl, hydroxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio or C1-C6-haloalkylthio;
R13 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl, C1-C20-alkylcarbonyl, C2-C20-alkenylcarbonyl, C2-C6-alkynylcarbonyl, C3-C6-cycloalkylcarbonyl, C1-C6-alkoxycarbonyl, C3-C6-alkenyloxycarbonyl, C3-C6-alkynyloxycarbonyl, C1-C6-alkylthiocarbonyl, C1-C6-alkylaminocarbonyl, C3-C6-alkenylaminocarbonyl, C3-C6-alkynylaminocarbonyl, N,N-di(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkynyl)-N—(C1-C6-alkyl)aminocarbonyl, N—(C1-C6-alkoxy)-N—(C1-C6-alkyl)aminocarbonyl, N—(C3-C6-alkenyl)-N—(C1-C6-alkoxy)aminocarbonyl, N—(C3-C6-alkynyl)-N—(C1-C6-alkoxy)aminocarbonyl, di(C1-C6-alkyl)aminothiocarbonyl, C1-C6-alkylcarbonyl-C1-C6-alkyl, C1-C6-alkoxyimino-C1-C6-alkyl, N—(C1-C6-alkylamino)imino-C1-C6-alkyl or N,N-di(C1-C6-alkylamino)imino-C1-C6-alkyl, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three of the following groups:
cyano, C1-C4-alkoxy, C1-C4-alkylthio, di(C1-C4-alkyl)amino, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkoxy-C1-C4-alkoxycarbonyl, di(C1-C4-alkyl)amino-C1-C4-alkoxycarbonyl, hydroxycarbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, aminocarbonyl, C1-C4-alkylcarbonyloxy or C3-C6-cycloalkyl;
is phenyl, heterocyclyl, phenyl-C1-C6-alkyl, heterocyclyl-C1-C6-alkyl, phenylcarbonyl-C1-C6-alkyl, heterocyclylcarbonyl-C1-C6-alkyl, phenylcarbonyl, heterocyclylcarbonyl, phenoxycarbonyl, phenyloxythiocarbonyl, heterocyclyloxycarbonyl, heterocyclyloxythiocarbonyl, phenylaminocarbonyl, N—(C1-C6-alkyl)-N-(phenyl)aminocarbonyl, heterocyclylaminocarbonyl, N—(C1-C6-alkyl)-N-(heterocyclyl)aminocarbonyl, phenyl-C2-C6-alkenylcarbonyl or heterocyclyl-C2-C6-alkenylcarbonyl, where the phenyl and the heterocyclyl radical of the 18 lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, heterocyclyl or N-bonded heterocyclyl, where the two lastmentioned substitutents for their part may be partially or fully halogenated and/or may carry one to three of the following radicals:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R14 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, di(C1-C6-alkyl)amino or di(C1-C6-haloalkyl)amino, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three of the following groups:
cyano, C1-C4-alkoxy, C1-C4-alkylthio, di(C1-C4-alkyl)amino, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkoxy-C1-C4-alkoxycarbonyl, di(C1-C4-alkyl)amino-C1-C4-alkoxycarbonyl, hydroxycarbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, aminocarbonyl, C1-C4-alkylcarbonyloxy or C3-C6-cycloalkyl;
is phenyl, heterocyclyl, phenyl-C1-C6-alkyl, heterocyclyl-C1-C6-alkyl, phenoxy, heterocyclyloxy, where the phenyl and the heterocyclyl radical of the lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R15 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, di(C1-C6-alkyl)amino or C1-C6-alkylcarbonylamino, where the abovementioned alkyl, cycloalkyl and alkoxy radicals may be partially or fully halogenated and/or may carry one to three radicals of the following group:
cyano, C1-C4-alkoxy, C1-C4-alkylthio, di(C1-C4-alkyl)amino, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkoxy-C1-C4-alkoxycarbonyl, di(C1-C4-alkyl)amino-C1-C4-alkoxycarbonyl, hydroxycarbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, aminocarbonyl, C1-C4-alkylcarbonyloxy or C3-C6-cycloalkyl;
is phenyl, heterocyclyl, phenyl-C1-C6-alkyl or heterocyclyl-C1-C6-alkyl, where the phenyl or heterocyclyl radical of the four lastmentioned substitutents may be partially or fully halogenated and/or may carry one to three of the following radicals:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R16 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl or C1-C6-alkylcarbonyl;
or an agriculturally useful salt thereof.
22. The tricyclic benzoylpyrazole compound of formula I defined in claim 21 where R9 is IIa.
23. The tricyclic benzoylpyrazole compound of formula I defined in claim 21 where X is oxygen, sulfur or CR6R7.
24. The tricyclic benzoylpyrazole compound of formula I defined in claim 21 where
Y together with the two carbons to which it is attached forms a heterocycle selected from the following group: dihydroisoxazolediyl, isoxazolediyl or tetrahydroisoxazolediyl.
25. The tricyclic benzoylpyrazole compound of formula I defined in claim 21 where
R1, R2 are hydrogen;
R3 is C1-C6-alkyl;
R4 is nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio or C1-C6-alkylsulfonyl;
R5 is hydrogen;
l is 0 oder 1.
26. The tricyclic benzoylpyrazole compound of formula I defined in claim 21 where
R10 is hydroxyl;
R11 is C1-C6-alkyl or C3-C6-cycloalkyl;
R12 is hydrogen or C1-C6-alkyl.
27. A process for preparing the compound of formula I where R10=halogen as claimed in claim 21, which comprises reacting a tricyclic benzoylpyrazole compound of formula Iα (=I where R10=hydroxyl),
Figure US20070197393A1-20070823-C00066
where the variables R1 to R5, R11 and R12, X, Y and l are as defined in claim 21, with a halogenating agent.
28. A process for preparing the compound of formula I where R10=OR13 as claimed in claim 21, which comprises reacting a tricyclic benzoylpyrazole compound of formula Iα (=I where R10=hydroxyl),
Figure US20070197393A1-20070823-C00067
where the variables R1 to R5, R11 and R12, X, Y and l are as defined in claim 21, with a compound of formula III

L1R13  III
where the variable R13 is as defined in claim 21 and L1 is a nucleophilically replaceable leaving group.
29. A process for preparing the compound of formula I where R10=OR13, SR13, NR15R16 or N-bonded heterocyclyl as claimed in claim 21, which comprises reacting a compound of formula Iβ (≡I where R10=halogen),
Figure US20070197393A1-20070823-C00068
where the variables R1 to R5, R11 and R12, X, Y and l are as defined in claim 21, with a compound of formula IVα, IVβ, IVγ or IVδ
Figure US20070197393A1-20070823-C00069
 HOR13HSR13NHR15R16H(N-bonded heterocyclyl) Ivo. IVp ivy IV8
where the variables R13 to R16 are as defined in claim 21, optionally in the presence of a base.
30. A process for preparing the compound of formula I where R10=SO2R14 as claimed in claim 21, which comprises reacting a compound of formula Iγ (≡I where R10=SR14),
Figure US20070197393A1-20070823-C00070
where the variables R1 to R5, R11 and R12, X, Y and l are as defined in claim 21, with an oxidizing agent.
31. A process for preparing the compound of formula I where R9=IIa as claimed in claim 21, which comprises reacting a metalated pyrazole compound of formula V where M is a metal and R10 to R12 are as defined in claim 21, except for R10=hydroxyl and mercapto, with a tricyclic benzoic acid compound of formula VIα where R1 to R5, X, Y and l are as defined in claim 21 and L2 is a nucleophilically replaceable leaving group.
Figure US20070197393A1-20070823-C00071
32. A process for preparing the compound of formula Iα (=I where R10=hydroxyl) as claimed in claim 21, which comprises acylating a pyrazole of formula VII in which the variables R11 and R12 are as defined in claim 21
Figure US20070197393A1-20070823-C00072
with an activated tricyclic benzoic acid of formula VIβ or with a tricyclic benzoic acid of formula VIγ,
Figure US20070197393A1-20070823-C00073
where the variables R1 to R5, X, Y and l are as defined in claim 21 and L3 is a nucleophilically replaceable leaving group, and rearranging the acylation product, optionally in the presence of a catalyst.
33. A process for preparing the compound of formula Iα (≡I where R10=hydroxyl) as claimed in claim 21, which comprises reacting a pyrazole of formula VII in which the variables R11 and R12 are as defined in claim 21, or an alkali metal salt thereof,
Figure US20070197393A1-20070823-C00074
with a tricyclic benzene compound of formula IX where L4 is a leaving group and the variables X, Y, R1 to R5 and l are as defined in claim 21
Figure US20070197393A1-20070823-C00075
in the presence of carbon monoxide, a catalyst and a base.
34. A composition, comprising a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt thereof as claimed in claim 21 and auxiliaries which are customary for formulating crop protection agents.
35. A process for preparing the composition defined in claim 34, which comprises mixing a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt thereof and auxiliaries which are customary for formulating crop protection agents.
36. A method for controlling undesirable vegetation, which comprises allowing a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt thereof as claimed in claim 21 to act on plants, their habitat or on seed.
37. A tricyclic benzoic acid compound of formula VI
Figure US20070197393A1-20070823-C00076
in which the variables X, Y, R1 to R3 and R5 and l are as defined in claim 21 and
R4 is nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl)amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino;
R17 is hydroxyl or a radical which can be removed by hydrolysis.
38. A tricyclic benzene compound of formula IX
Figure US20070197393A1-20070823-C00077
in which the variables X, Y, R1 to R3 and R5 and l are as defined in claim 21 and
R4 is nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl)amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino;
R5 is hydrogen or C1-C6-alkyl;
L4 is halogen, C1-C6-alkylsulfonyloxy, C1-C6-haloalkylsulfonyloxy or phenylsulfonyloxy, where the phenyl ring of the lastmentioned radical may be unsubstituted or partially or fully halogenated and/or may carry one to three of the following radicals:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
39. An aniline compound of formula XV
Figure US20070197393A1-20070823-C00078
in which the variables X, Y, R1 to R3 and R5 and 1 are in each case as defined in claim 21 and
R4 is nitro, halogen, cyano, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl)amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino.
40. A nitrile compound of formula XVI
Figure US20070197393A1-20070823-C00079
in which the variables X, Y, R1 to R3 and l are in each case as defined in claim 21 and
R4 is nitro, halogen, cyano, C1-C6-haloalkyl, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkinylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N—(C1-C6-alkyl)aminosulfonyl, N,N-di-(C1-C6-alkyl)aminosulfonyl, N—(C1-C6-alkylsulfonyl)amino, N—(C1-C6-haloalkylsulfonyl)amino, N—(C1-C6-alkyl)-N—(C1-C6-alkylsulfonyl)amino or N—(C1-C6-alkyl)-N—(C1-C6-haloalkylsulfonyl)amino;
R5 is hydrogen or C1-C6-alkyl.
41. The compound of formula I defined in claim 21, wherein
X is O or S;
Y together with the two carbons to which it is attached forms an isoxazole ring which is saturated, partially saturated or unsaturated; and
R9 is a radical IIa.
42. The compound of formula I defined in claim 41, wherein R10 is hydroxyl, mercapto, halogen, OR13, SR13, SO2R14 or NR15R16.
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EP2597089A1 (en) 2009-10-29 2013-05-29 Bristol-Myers Squibb Company Tricyclic heterocyclic compounds
WO2018045149A1 (en) 2016-09-02 2018-03-08 Bristol-Myers Squibb Company Substituted tricyclic heterocyclic compounds
US11046646B2 (en) 2017-08-09 2021-06-29 Bristol-Myers Squibb Company Alkylphenyl compounds
WO2019032631A1 (en) 2017-08-09 2019-02-14 Bristol-Myers Squibb Company OXIME ETHER COMPOUNDS

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Publication number Priority date Publication date Assignee Title
US10174221B2 (en) 2015-12-04 2019-01-08 The Board Of Trustees Of The University Of Illinois Autonomic damage indication in coatings
US10640674B2 (en) 2015-12-04 2020-05-05 The Board Of Trustees Of The University Of Illinois Autonomic damage indication in coatings

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EP1163240A1 (en) 2001-12-19
US7115545B1 (en) 2006-10-03
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CA2367672A1 (en) 2000-09-21

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