DE4234709A1 - New herbicidal substd. pyrazole derivs. - Google Patents

Abstract

Substd. pyrazole derivs. of formula (I) are new. R1=1-4C alkyl; R2=1-4C alkyl, 1-4C alkylthio or 1-4C alkoxy (all opt. substd.); or R1+R2=(CH2)m; R3=H or halo; R4=H or 1-4C alkyl; R5=H, NO2, CN, COOR7, C(X)NR7R8 or C(X)R10; R6=H, halo, CN, 1-4C alkyl (opt. substd.) 1-4C alkoxy, phenyl (opt. substd.) pyrrolyl, or 2-8C alkyl, 3-8C alkenyl, 3-8C alkynyl or 3-8C alkoxy (all interrupted by one or more O) NR13C(X)R14 N(C(X)R15)2, etc. R7, R8=H or 1-4C alkyl; or R10=H or 1-4C alkyl (opt. substd.), R13=H, 1-4C alkyl, 2-6C alkenyl or 3-6C alkynyl; or R13+R14=(CH2)p; R14, R15=1-4C alkyl, 2-6C alkenyl, 3-6C alkynyl or phenyl (all opt. substd.) H, 3-6C cycloalkyl, XR18 or NR19R20; R18=1-4C alkyl (opt. substd. by one or more halo); R19, R20=H or 1-4C alkyl; m=3 or 4; p=2 or 3; and X=O or S.

Description

The invention relates to new substituted pyrazole derivatives, their preparation and their Use as a herbicidal agent.

It is already known that 1-phenylpyrazoles have herbicidal properties (EP 154 115).

However, the herbicidal activity of the known compounds is frequently inadequate, or selectivity problems occur with a corresponding herbicide effect main agricultural crops.

The object of the present invention is to provide new substituted ones Pyrazole derivatives that do not have these disadvantages and that in their biological Properties are superior to previously known compounds.

It has now been found that substituted pyrazole derivatives of the general formula I

in the
R ¹ C ₁ -C ₄ alkyl,
R ^{2 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkoxy, mono- or poly-halogen-substituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio or C ₁ -C ₄ alkoxy,
R ¹ and R ² together form the group - (CH ₂ ) _m -,
R ^{3 is} hydrogen or halogen,
R ^{4 is} hydrogen or C ₁ -C ₄ alkyl,
R ^{5 is} hydrogen, nitro, cyano or the group -COOR ⁷

R ^{6 is} hydrogen, halogen, C ₁ -C ₄ alkyl or the group -NR ¹¹ R ¹² ,

R ⁷ , R ⁸ and R ⁹ independently of one another are hydrogen or C ₁ -C ₄ -alkyl,
R ⁸ and R ⁹ together with the adjacent nitrogen atom form a 5- or 6-membered saturated carbocyclic ring,
R ¹⁰ is hydrogen, C ₁ -C ₄ alkyl, mono- or polysubstituted by halogen-substituted C ₁ -C ₄ alkyl,
R ¹¹ and R ¹² independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₂ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, phenyl, C ₁ -C ₄ -alkyl mono- or polysubstituted by halogen, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or phenyl, where if R ⁵ = hydrogen, nitro, cyano or the group -COOR ⁷ or -C (O) NR ⁸ R ⁹ , R ¹¹ and R ¹² does not represent hydrogen,
R ¹¹ and R ¹² together with the nitrogen atom form a five- or six-membered saturated carbocyclic or aromatic ring,
R ^{13 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,
R ¹³ and R ¹⁴ together form the group - (CH ₂ ) p-,
R ¹⁴ and R ^{15 are} independently hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, phenyl, mono- or polysubstituted by halogen C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, phenyl or the group -XR ¹⁸ or -NR ¹⁹ R ²⁰ ,
R ^{16 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₁ -C ₄ alkyl carbonyl, cyano-C ₁ -C ₃ alkyl or C ₁ - C ₄ alkoxycarbonyl-C ₁ -C ₃ alkyl,
R ^{17 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, cyano-C ₁ -C ₃ alkyl or C ₁ -C ₄ alkoxycarbonyl-C ₁ -C ₃ -alkyl,
R ^{18 is} C ₁ -C ₄ alkyl or mono- or polysubstituted by halogen-substituted C ₁ -C ₄ alkyl,
R ¹⁹ and R ²⁰ independently of one another are hydrogen or C _1-4 -alkyl,
m = 3 or 4,
n = 0, 1 or 2,
p = 2 or 3 and
X is oxygen or sulfur, mean a better herbicidal activity than the known compounds.

Substituted pyrazole derivatives of the general formula I, in which
R ^{1 is} methyl,
R ² butyl, methoxy or difluoromethoxy,
R ¹ and R ² together form the group - (CH ₂ ) ₄ -,
R ^{3 is} hydrogen or chlorine,
R ^{4 is} hydrogen,
R ^{5 is} hydrogen, nitro, cyano or the group -C (X) R ¹⁰ ,
R ^{6 is} hydrogen, chlorine, bromine, C ₁ -C ₄ -alkyl or the group -NR ¹¹ R ¹² , -NR ¹³ C (X) R ¹⁴ , -OR ¹⁶ or -S (O) _n R ¹⁷ ,
R ^{10 is} methyl or trifluoromethyl,
R ¹¹ and R ^{12 are} independently hydrogen, methyl or ethyl, where if R ⁵ = hydrogen, nitro or cyano, R ¹¹ and R ^{12 are} not hydrogen,
R ¹¹ and R ¹² together with the nitrogen atom form a pyrrole ring,
R ^{13 is} hydrogen or methyl,
R ¹⁴ is hydrogen, C ₁ -C ₄ alkyl, cyclopropyl, mono- or polysubstituted by chlorine-substituted C ₁ -C ₄ alkyl, phenyl or the group -OR ¹⁸ or -NR ¹⁹ R ^20,
R ¹⁶ and R ¹⁷ independently of one another are methyl, ethyl, methoxycarbonyl-C ₁ -C ₃ -alkyl or ethoxycarbonyl-C ₁ -C ₃ -alkyl,
R ^{18 is} methyl, ethyl or chlorophenyl,
R ¹⁹ and R ²⁰ independently of one another are hydrogen, methyl or ethyl,
n = 0, 1 or 2 and
X is oxygen or sulfur.

The term "halogen" includes fluorine, chlorine, bromine and iodine. The designation "alkyl", "alkenyl" and "alkynyl" means that the carbon chain can be branched or unbranched.

The compounds of the general formula I according to the invention can be prepared by one

• A) a compound of general formula II in which R ¹ , R ² and R ^{3 have} the meanings given in the general formula I, with compounds of the general formula III in which R ⁴ and R ^{5 have} the meanings given in the general formula I and Y represents C ₁ -C ₆ -alkoxy, hydroxy or halogen, or if R ^{5 represents} hydrogen
• B) a compound of the general formula II in which R ¹ , R ² and R ^{3 have} the meanings given in the general formula I, with 2-haloacrylonitriles of the formula IIIa or with 2,3-dihalopropionitriles of the formula IIIb in which Hal represents halogen, or if R ^{3 represents} halogen.
• C) a compound of the general formula Ia in which R ¹ , R ² , R ⁵ , R ¹¹ and R ^{12 have} the meanings given in the general formula I, first with a halogenating agent to give a compound of the general formula Ib in which R ¹ , R ² , R ⁵ , R ¹¹ and R ^{12 have} the meanings given in the general formula I and Hal is halogen, can react and then react further to give the desired compounds, or if R ^{5 is} for the group - C (S) R ¹⁰ and R ^{6 represent} amino
• D) a compound of the general formula Ic in which R ¹ , R ² , R ³ , R ⁴ and R ^{10 have} the meanings given in the general formula I, reacted with Lawesson's reagent, or if R ^{6 represents} the group -OR ¹⁶
• E) a compound of the general formula Id in which R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings given in the general formula I, first by diazotization to give a compound of the general formula Ie in which R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings given in the general formula I, then by boiling to give compounds of the general formula If in which R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings given in the general formula I, can react further and then with a compound of the general formula IVXR¹⁶ (IV) in the R ¹⁶ those in the general formula I has the meaning given and X represents an escape group, or if R ^{5 is} nitro and R ^{6 is} the group -SR ¹⁷
• F) Compounds of the general formula Ig in which R ¹ , R ² , R ³ and R ^{4 have} the meanings given in general formula I and Hal represents halogen, with a nucleophilic compound of the general formula V⊖SR ¹⁷ (V) in R ¹⁷ which in general Formula I has the meaning given, or if R ^{6 is} the group S (O) _n R ¹⁷ , in which n = 1 or 2, is
• G) Compounds of the general formula Ih in which R ¹ , R ² , R ³ , R ⁴ and R ^{17 have} the meanings given in the general formula I, by stepwise oxidation with metachloroperbenzoic acid.

The compounds of the general formula I according to the invention in which R ^{5 is} nitro and R ^{6 is} halogen can also be prepared by the processes described in DE 35 01 323.

The compounds of general formula I according to the invention, in which R ^{5 represents} the group -C (O) R ¹⁰ and R ^{6 represents} amino, can be prepared according to the methods described in Collect. Czech. Chem. Commun. 55, 1038-48 (1990).

The compounds of the general formula I according to the invention, in which R ^{6 represents} the group —NR ¹¹ R ¹² , can be prepared according to those described in DE 37 07 686, DE 35 43 034, EP 224 831, DE 35 43 035, JP 5 7167 972 and DE 27 47 531 known processes.

The compounds of the general formula I according to the invention, in which R ^{14 represents} the group —OR ¹⁸ or NR ¹⁹ R ²⁰ , can be derived from the compounds of the general formula I in which R ^{6 represents} amino, according to the methods described in Chem. Soc. Rev. 4, 231-50 (1975) and J. March, Advanced Organic Chemistry, 1985, p. 370 known methods.

The compounds of general formula I according to the invention in which R ^{5 is} cyano or nitro and R ^{6 is} C ₁ -C ₄ alkyl can be prepared by processes known per se. (J. Heterocyclic Chem. 24, 1669 (1987), ibid. 24, 739 (1987).

The reactions are advantageously carried out in such a way that the compounds of the general formulas II and III in a suitable solvent at temperatures between -30 and 150 ° C, preferably at room temperature, brings to reaction.

As halogenating agents for process variant C, for example Sulforyl chloride, sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, bromine or Chlorine can be used.

Escape group according to process variant E are chlorine or bromine.

The preparation can be carried out with or without a solvent If necessary, such solvents or diluents are used, which are inert to the respective reactants. Examples of such solvents or diluents are aliphatic, alicyclic and aromatic Hydrocarbons, each of which can optionally be chlorinated, such as, for example Hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, Chloroform, carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene, Ethers, such as, for example, diethyl ether, methyl ethyl ether, methyl t-butyl ether, Diisopropyl ether, dibutyl ether, dioxane and tetrahydrofuran, ketones such as Acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles, such as for example acetonitrile and propiontril, alcohols such as methanol, ethanol, Isopropanol, butanol, tert-butanol, tert-amyl alcohol and ethylene glycol, esters, such as Example ethyl acetate and amyl acetate, acid amides, such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethyl sulfoxide and sulfones such as for example sulfolane, bases such as pyridine and triethylamine, carboxylic acids, such as acetic acid and mineral acids such as sulfuric acid and Hydrochloric acid.

The compounds according to the invention are worked up in the customary manner and Wise. Purification is carried out by crystallization or column chromatography.

The compounds according to the invention are generally colorless or slightly yellow colored crystalline or viscous substances, some of which are readily soluble in chlorinated Hydrocarbons such as methylene chloride or chloroform, ethers such as for example diethyl ether or tetrahydrofuran, alcohols such as methanol or ethanol, ketones such as acetone or butanone, amides such as Dimethylformamide, or also sulfoxides, such as dimethyl sulfoxide.  

The compounds of general formula II required as intermediates

in which R ¹ , R ² and R ^{3 have} the meanings given in general formula I, can be prepared analogously to processes known per se (for example: JP 62158260) from the compounds of general formula VI

in which R ¹ , R ² and R ^{3 have} the meanings given in the general formula I, produce.

The compounds of the general formula VI in which R ¹ and R ^{2 have} the meanings given in the general formula I and R ^{3 is} halogen can be prepared by using compounds of the general formula VI in which R ^{3 is} hydrogen reacted with a halogenating agent.

Those required for the preparation of the compounds of the general formula VI Starting materials of the general formula VII

in which R ¹ is as defined in the general formula I has, for example, can be prepared by appropriate R ² is C ₁ -C ₄ alkyl or mono- or poly-halogen-substituted C ₁ -C ₄ alkyl ,

• a) a compound of the general formulas VIII, VIIIa or IX in which R ^{2 is} C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyl which is mono- or polysubstituted by halogen, with compounds of the general formula XR ¹ - NHNH ₂ (X) in which R ¹ is in the general formula I has the meaning indicated, if appropriate in the presence of a solvent,
  or if R ^{2 is} C ₁ -C ₄ -alkylthio or C ₁ -C ₄ -alkylthio which is mono- or polysubstituted by halogen,
• b) a compound of the general formula XI in which R ^{21 is} C ₁ -C ₄ alkyl, with compounds of the general formula X, optionally in the presence of a solvent, first to give compounds of the general formula XII in which R1 has the meaning given in the general formula I and R ^{21 represents} C ₁ -C ₄ alkyl, and then reacted with compounds of the general formula XIIIR ²² X (XIII) in which R ^{22 represents} C ₁ -C ₄ - Alkyl or for mono- or polysubstituted by halogen C ₁ -C ₄ alkyl and X represents a leaving group, can react and the resulting compound of the general formula XIV according to methods known from the literature (e.g. Zeitschrift für Chemie 420, (1968) saponified and decarboxylated, or
• c) a compound of the general formula XV in which R ^{21 is} C ₁ -C ₄ alkyl and R ^{22 is} C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyl which is substituted one or more times by halogen, with compounds of the general formula X to give compounds of general formula XIV is reacted, or if R ² is C ₁ -C ₄ alkoxy or mono- or poly-halogen-substituted C ₁ -C ₄ alkoxy
• d) compounds of the general formula XVI in which R ^{1 has} the meaning given in the general formula I, with compounds of the general formula XIII in the presence of a base, or
• e) compounds of the general formula XVII in which R ^{1 has} the meaning given in the general formula I and Z represents C ₁ -C ₄ -alkyl, with a compound of the general formula XIIIR ²² X (XIII) in which R ^{22 is} C ₁ -C₄-alkyl or C ₁ -C ₄ alkyl substituted one or more times by halogen and X represents a leaving group, can react with the addition of a base and the resulting compound of the general formula XVIII in which R has the meaning given in general formula I ^1, R ²² is C ₁ -C ₄ - alkyl or mono- or poly-substituted by halogen C ₁ -C ₄ alkyl and Z is C ₁ -C ₄ alkyl stands, can react with ammonia and the compound of general formula XIX thus obtained in which R ¹ has the meaning given in general formula I and R ²² is C ₁ -C ₄ - alkyl or mono- or poly-substituted by halogen C ₁ -C ₄ -alkyl, is reacted with sodium hydroxide and bromine, or, if R ³ in the general formula I represents halogen
• f) compounds of the general formulas XVIII or XIX in which R ¹ has the meaning given in general formula I, R ²² is C ₁ -C ₄ - alkyl or mono- or polysubstituted by halogen-substituted C ₁ -C ₄ alkyl and Z is C ₁ -C ₄ alkyl stands, with a halogenating agent to compounds of general formulas XVIIIa and XIXb in which R ¹ , R ²² and Z have the meanings given in the general formulas XVIII and XIX, or
• g) a compound of the general formula XIXa in which R has the meaning indicated ¹ in the general formula I, R ²² is C ₁ -C ₄ - alkyl or mono- or polysubstituted by halogen, C ₁ -C ₄ alkyl and Hal represents halogen, with sodium hydroxide and bromine to Compounds of the general formula XX in which R ¹ , R ²² and Hal have the meanings given in the formula XIXa, or if R ¹ and R ² together form a tri- or tetramethyl group
• h) a compound of the general formula XXI in which n = 2 or 3, is reacted with hydrazine
  and the 3 (5) -amino-5 (3) -hydroxyalkylpyrazoles of the general formula XXII thus obtained in which n = 2 or 3, with hexane-2,5-dione, phthalic anhydride or tetrahydrophthalic anhydride in analogy to methods known from the literature (Bull.Chem.Soc.Jp., 44,2856-8 (1971), EP 305826) to give compounds of the general formula XXIII in which n = 2 or 3 and Q for an amino protecting group, such as. B. Q ₁ , Q ₂ or Q ₃ stands, implements and this according to the Mitsunobu variant (Synthesis, 1 (1981)) to compounds of the general formula XXIV in which n = 2 or 3, cyclized and then in the case of Q ₁ with hydroxylamine as described in J. Org. Chem., 49, 1224-1227 (1984) and in the case of Q ₂ or Q ₃ with hydrazine, according to methods known from the literature (Org. Synthesis, Coll. Vol. 3, 148 (1955).

The starting materials of the general formula XXI can be known per se Establish methods (Chem. Ber., 109 (1), 253-60, 1976).

The intermediate products can be prepared with or without a solvent are used, if necessary, the solvents mentioned above are used.

The starting materials mentioned are known or can be analogous to themselves produce known methods.

Escape groups according to process variants b and e are chlorine and bromine.

The compounds according to the invention show a good herbicidal activity broad-leaved weeds and grasses. A selective use of the invention Active substances are possible in different crops, for example in rapeseed, beets, Soybeans, cotton, rice, corn, barley, wheat and other cereals. Here are individual active substances as selective herbicides in beets, cotton, soybeans, maize and Cereals particularly suitable. Likewise, the compounds for weed control in Permanent crops, such as forest, ornamental wood, fruit, wine, citrus, nut, Banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plants be used.

The compounds of the present invention can include, for example, the following Plant genera are used:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Sonchus, Solanum, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.  

Monocotyledon weeds of the genera: Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus, Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera.

Depending on the type of application, the application rates fluctuate in pre- and post-emergence Limits between 0.001 to 5 kg / ha.

The active compounds according to the invention can also be used as defoliant, desiccant and Herbicides are used.

The compounds according to the invention can either be used alone or in a mixture with one another or with other active ingredients. If necessary, others can Plant protection or pesticide depending on the intended purpose be added. If it is intended to broaden the spectrum of activity, other herbicides can also be added. For example, are suitable as herbicides effective mixture partners are those active ingredients that are described in Weed Abstracts, Vol. 1, 1992 under the title "List of common names and abbreviations employed for currently used herbicides and plant growth regulators ".

A promotion of the intensity and speed of action can, for example through additives that increase the effectiveness, such as organic solvents, wetting agents and oils, be achieved. Such additives may therefore reduce the Active ingredient dosage too.

The active compounds according to the invention or mixtures thereof are expedient in the form of preparations such as powders, scattering agents, granules, solutions, emulsions or Suspensions, with the addition of liquid and / or solid carriers respectively Diluents and optionally adhesive, wetting, emulsifying and / or Dispersing aids applied.

Suitable liquid carriers are, for example, aliphatic and aromatic Hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, Dimethyl sulfoxide, dimethylformamide, mineral oil fractions and vegetable oils.

Minerals such as bentonite, silica gel, Talc, kaolin, attapulgite, limestone and vegetable products such as flour.  

Examples of surface-active substances include calcium lignin sulfonate, Polyethylene alkylphenyl ether, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted Benzenesulfonic acids and their salts.

The proportion of the active ingredient (s) in the different preparations can vary widely. For example, the agents contain about 10 to 90 Weight percent active ingredient, about 90 to 10 weight percent liquid or solid Carriers and optionally up to 20 percent by weight of surfactants.

The agents can be applied in the customary manner, for example using water as Carrier in spray liquor quantities from about 100 to 1000 liters / ha. An application of funds in the so-called low-volume and ultra-low process is just as possible as theirs Application in the form of so-called microgranules.

The preparation of these preparations can be carried out in a manner known per se Example can be carried out by grinding or mixing processes. If desired can preparations of the individual components only shortly before their use be mixed, as is the case, for example, in the so-called tank mix process is carried out.  

For example, the following are used to prepare the various preparations Components used:

• A) wettable powder
  20 percent by weight of active ingredient
  35% by weight of bleaching earth
  8 weight percent calcium salt of lignin sulfonic acid
  2 percent by weight sodium salt of N-methyl-N-oleyl-taurine
  35 weight percent silica
• B) paste
  45 percent by weight of active ingredient
  5% by weight sodium aluminum silicate
  15 percent by weight cetyl polyglycol ether with 8 mol ethylene oxide
  2% by weight spindle oil
  10% by weight polyethylene glycol
  23 weight percent water
• C) Emulsion concentrate
  20 percent by weight of active ingredient
  75 weight percent isophorone
  5 percent by weight of a mixture based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignin sulfonic acid.

The following examples illustrate the preparation of the compounds according to the invention:

Example 1.0 5-amino-1- (3-chloro-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridin-2-yl) -4-thioacetylpyrazole

0.28 g (1 mmol) of 4-acetyl-5-amino-1- (3-chloro-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridi-n-2-yl) pyrazole are dissolved in 5 ml of dimethoxyethane and mixed with 0.24 g (0.6 mmol) of Lawesson's reagent. After stirring under reflux for 2 hours, the reaction solution is poured into water and extracted with ethyl acetate. The organic phase is washed with saturated sodium chloride solution, dried over magnesium sulfate and concentrated. The residue is purified by column chromatography (SiO ₂ / hexane / ethyl acetate 1: 1).
Yield: 0.21 g = 71% of theory
Mp: 166-167 ° C

Example 1.1 4-acetyl-5-amino-1- (3-chloro-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridi-n-2-yl) pyrazole

0.56 g (3 mmol) 3-chloro-2-hydrazino-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridine are dissolved in 5 ml ethanol and with 0.42 g (3 mmol) 2 -Ethoxymethylene-3-oxo-butyronitrile added. After 3 hours of refluxing, the mixture is concentrated and the residue is chromatographed. (SiO ₂ / hexane / ethyl acetate 1: 1).
Yield: 0.75 g = 89.4% of theory
Mp: 153-154 ° C

Example 1.2 N- [1- (3-chloro-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridin-2-yl) -4-nitro - 5-pyrazolyl] propionic acid amide

8.72 g (29.7 mmol) of N- [1- (3-chloro-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridin-2-yl) -5-pyrazolyl] propionic acid amide are suspended in 33 ml of glacial acetic acid. With ice cooling, 3.31 g (32.5 mmol) of acetic anhydride are added at 0-5 ° C. Then 1.93 g (31 mmol) of fuming nitric acid are added dropwise. After stirring for 6 hours at room temperature, the mixture is concentrated. The residue is taken up in dichloromethane, neutralized with sodium hydrogen carbonate solution and washed with sodium chloride solution. The organic phase is dried over magnesium sulfate and concentrated. The residue is purified by column chromatography (SiO ₂ / hexane / ethyl acetate 1: 1).
Yield: 6.03 g = 60% of theory
Mp .: 46-49 ° C

Example 2.0 N- [1- (4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl) -4-nitro-5-pyrazolyl] -2,2,2- trifluoroacetic acid amide

0.79 g (2.1 mmol) of N- [1- (5-difluoromethoxy-1-methyl-3-pyrazolyl) -4-nitro-5-pyrazolyl] -2- 2,2-trifluoroacetic acid amide are suspended in 35 ml of dichloromethane and treated with 0.17 ml of sulfuryl chloride. The mixture is stirred for 1 hour at room temperature. The reaction solution is concentrated.
Yield: 0.77 g = 89.5% of theory
Mp: 136-139 ° C

Example 2.1 N- [1- (4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl) -4-nitro-5-pyrazolyl] - acetic acid amide

1.3 g (5.0 mmol) of 5-amino-1- (4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl) pyrazole are dissolved in 20 ml of glacial acetic acid and mixed with 0.55 g (5.4 mmol ) Acetic anhydride added. After 2 hours of stirring at room temperature, the reaction solution is cooled to 0 ° C. and 0.4 g (6.4 mmol) of concentrated nitric acid are added dropwise. After stirring for 8 hours at room temperature, the reaction mixture is poured into ice water and extracted with ethyl acetate. The organic phase is dried over magnesium sulfate and concentrated. The residue is purified by column chromatography (SiO ₂ / hexane / ethyl acetate 1: 1).
Yield: 1.4 g = 81.5% of theory
Mp: 132 ° C

The following compounds are produced in an analogous procedure:

The following examples explain the possible uses of the invention Links:

Example of use A

The plant species listed were in the greenhouse before emergence with the Compounds listed treated in an application rate of 0.1 kg of active ingredient / ha. For this purpose the compound was used as an emulsion with 500 liters of water / ha evenly sprayed over the plants. Here showed three weeks after treatment the compounds of the invention have an excellent weed action. The comparative agent did not show the same effectiveness.

In the following table mean:

Example of use B

In the greenhouse, the plant species listed after emergence with the Compounds listed treated in an application rate of 0.3 active ingredient / ha. The For this purpose, compounds became the same as an emulsion with 500 liters of water / ha sprayed moderately over the plants. The compounds of the invention show 2 weeks after treatment an excellent weed action. The Comparative agents did not show the same effectiveness.

In the following table mean:

Example of use C

In the greenhouse, the compounds listed in the table with the mentioned Application rate applied. For this purpose, the active ingredients were on the water surface pipetted.

Echinochloa crus-galli, Cyperus difformis, Scirpus juncoides and Monochoria vaginalis in the pre-emergence and in the 1st-3rd Leaf stage used.

In the table mean:

As the table shows, the compounds according to the invention are very effective against Echinochloa crus-galli, Cyperus difformis, Scirpus juncoides and Monochoria vaginalis.

Claims (6)

1. Substituted pyrazole derivatives of the general formula I in the
R ¹ C ₁ -C ₄ alkyl,
R ^{2 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkoxy, mono- or poly-halogen-substituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio or C ₁ -C ₄ alkoxy,
R ¹ and R ² together form the group - (CH ₂ ) _m -,
R ^{3 is} hydrogen or halogen,
R ^{4 is} hydrogen or C ₁ -C ₄ alkyl,
R ^{5 is} hydrogen, nitro, cyano or the group -COOR ⁷ , R ^{6 is} hydrogen, halogen, C ₁ -C ₄ alkyl or the group -NR ¹¹ R ¹² , R ⁷ , R ⁸ and R ⁹ independently of one another are hydrogen or C ₁ -C ₄ -alkyl,
R ⁸ and R ⁹ together with the adjacent nitrogen atom form a 5- or 6-membered saturated carbocyclic ring,
R ¹⁰ is hydrogen, C ₁ -C ₄ alkyl, mono- or polysubstituted by halogen-substituted C ₁ -C ₄ alkyl,
R ¹¹ and R ¹² independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₂ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, phenyl, C ₁ -C ₄ -alkyl mono- or polysubstituted by halogen, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or phenyl, where if R ⁵ = hydrogen, nitro, cyano or the group -COOR ⁷ or -C (O) NR ⁸ R ⁹ , R ¹¹ and R ¹² does not represent hydrogen,
R ¹¹ and R ¹² together with the nitrogen atom form a five- or six-membered saturated carbocyclic or aromatic ring,
R ^{13 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,
R ¹³ and R ¹⁴ together form the group - (CH ₂ ) p-,
R ¹⁴ and R ^{15 are} independently hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, phenyl, mono- or polysubstituted by halogen C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, phenyl or the group -XR ¹⁸ or -NR ¹⁹ R ²⁰ ,
R ^{16 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₁ -C ₄ alkyl carbonyl, cyano-C ₁ -C ₃ alkyl or C ₁ - C ₄ alkoxycarbonyl-C ₁ -C ₃ alkyl,
R ^{17 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, cyano-C ₁ -C ₃ alkyl or C ₁ -C ₄ alkoxycarbonyl-C ₁ -C ₃ -alkyl,
R ^{18 is} C ₁ -C ₄ alkyl or mono- or polysubstituted by halogen-substituted C ₁ -C ₄ alkyl,
R ¹⁹ and R ²⁰ independently of one another are hydrogen or C _1-4 -alkyl,
m = 3 or 4,
n = 0, 1 or 2,
p = 2 or 3 and
X is oxygen or sulfur. 2. Substituted pyrazole derivatives according to claim 1 of the general formula I in which
R ^{1 is} methyl,
R ² butyl, methoxy or difluoromethoxy,
R ¹ and R ² together form the group - (CH ₂ ) ₄ -,
R ^{3 is} hydrogen or chlorine,
R ^{4 is} hydrogen,
R ^{5 is} hydrogen, nitro, cyano or the group -C (X) R ¹⁰ ,
R ^{6 is} hydrogen, chlorine, bromine, C ₁ -C ₄ -alkyl or the group -NR ¹¹ R ¹² , -NR ¹³ C (X) R ¹⁴ , -OR ¹⁶ or -S (O) _n R ¹⁷ ,
R ^{10 is} methyl or trifluoromethyl,
R ¹¹ and R ^{12 are} independently hydrogen, methyl or ethyl, where if R ⁵ = hydrogen, nitro or cyano, R ¹¹ and R ^{12 are} not hydrogen,
R ¹¹ and R ¹² together with the nitrogen atom form a pyrrole ring,
R ^{13 is} hydrogen or methyl,
R ¹⁴ is hydrogen, C ₁ -C ₄ alkyl, cyclopropyl, mono- or polysubstituted by chlorine-substituted C ₁ -C ₄ alkyl, phenyl or the group -OR ¹⁸ or -NR ¹⁹ R ^20,
R ¹⁶ and R ¹⁷ independently of one another are methyl, ethyl, methoxycarbonyl-C ₁ -C ₃ -alkyl or ethoxycarbonyl-C ₁ -C ₃ -alkyl,
R ^{18 is} methyl, ethyl or chlorophenyl,
R ¹⁹ and R ²⁰ independently of one another are hydrogen, methyl or ethyl,
n = 0, 1 or 2 and
X is oxygen or sulfur. 3. A process for the preparation of compounds of general formula I, characterized in that

• A) a compound of general formula II in which R ¹ , R ² and R ^{3 have} the meanings given under the general formula I, with compounds of the general formula III in which R ⁴ and R ^{5 have} the meanings given in the general formula I and Y represents C ₁ -C ₆ -alkoxy, hydroxy or halogen, or if R ^{5 represents} hydrogen
• B) a compound of the general formula II in which R ¹ , R ² and R ^{3 have} the meanings given in the general formula I, with 2-haloacrylonitriles of the formula IIIa or with 2,3-dihalopropionitriles of the formula IIIb in which Hal represents halogen, or if R ^{3 represents} halogen,
• C) a compound of the general formula Ia in which R ¹ , R ² , R ⁵ , R ¹¹ and R ^{12 have} the meanings given in the general formula I, first with a halogenating agent to give a compound of the general formula Ib in which R ¹ , R ² , R ⁵ , R ¹¹ and R ^{12 have} the meanings given in the general formula I and Hal is halogen, can react and then react further to give the desired compounds, or if R ^{5 is} for the group - C (S) R ¹⁰ and R ^{6 represent} amino
• D) a compound of the general formula Ic in which R ¹ , R ² , R ³ , R ⁴ and R ^{10 have} the meanings given in the general formula I, reacted with Lawesson's reagent, or if R ^{6 represents} the group -OR ¹⁶
• E) a compound of the general formula Id in which R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings given in the general formula I, first by diazotization to give a compound of the general formula Ie in which R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings given in the general formula I, then by boiling to give compounds of the general formula If in which R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings given in the general formula I, can react further and then with a compound of the general formula IVXR ¹⁶ (IV) in the R ¹⁶ which in general Formula I has the meaning given and X represents an escape group, or if R ^{5 is} nitro and R ^{6 is} the group -SR ¹⁷
• F) Compounds of the general formula Ig in which R ¹ , R ² , R ³ and R ^{4 have} the meanings given in general formula I and Hal represents halogen, with a nucleophilic compound of the general formula V⊖SR ¹⁷ (V) in R ¹⁷ which in general Formula I has the meaning given, or if R ^{6 is} the group S (O) _n R ¹⁷ , in which n = 1 or 2, is
• G) Compounds of the general formula Ih in which R ¹ , R ² , R ³ , R ⁴ and R ^{17 have} the meanings given in general formula I, by stepwise oxidation with metachloroperbenzoic acid.

4. Agents with herbicidal activity, characterized by a content of at least a compound according to claims 1 and 2. 5. Agent with herbicidal action according to claim 4, in a mixture with carrier and / or auxiliary substances.   6. Use of compounds according to claims 1 and 2 for combating monocotyledonous and dicotyledonous weed species in main agricultural crops.