US20040039220A1

US20040039220A1 - Process for the preparation of pesticides

Info

Publication number: US20040039220A1
Application number: US10/644,298
Authority: US
Inventors: Saleem Farooq; Stephan Trah; Hugo Ziegler; Rene Zurfluh
Original assignee: Individual
Current assignee: Individual
Priority date: 1995-12-07
Filing date: 2003-08-19
Publication date: 2004-02-26
Also published as: BR9611813A; DE69620246T2; CN1111155C; HUP9903814A3; ZA9610281B; PL327197A1; AU717468B2; AU2838697A; ATE215067T1; DE69620246D1; EP0876333B1; KR19990071886A; HUP9903814A2; US6156923A; CA2238868A1; DK0876333T3; IL124451A0; CZ173198A3; AR004869A1; JP2000501089A

Abstract

The invention relates to a process for the preparation of compounds of the formula

or, if appropriate, a tautomer thereof, in each case in the free form or in salt form, in which A, X, Y, Z, R₂, R₃, R₄, R₅, R₇, R₉and n are as defined in claim 1 and the C═N double bond marked with E has the E configuration, which comprises

a1) reacting either a compound of the formula (II) mentioned above with a compound of the formula (III) mentioned above, in which X₁is a leaving group, or

a2) a compound of the formula (IV) mentioned above, if appropriate in the presence of a base, with a compound of the formula (V) mentioned above, or

b1) reacting a compound of the formula (VI) mentioned above with a compound of the formula R₇-A-X₂(VII), in which X₂is a leaving group, and either further reacting the compound thus obtainable, of the formula (IV), for example according to method a2), or

b2) reacting it with hydroxylamine or a salt thereof, if appropriate in the presence of a basic or acid catalyst, and further reacting the compound thus obtainable, of the formula (II), for example according to method a1), or

c) reacting a compound of the formula (VIII), mentioned above with a C₁-C₆alkyl nitrite and further reacting the compound thus obtainable, of the formula (VI), for example according to method b), the E isomers of the compounds of the formulae (II), (IV) and (VI), a process for their preparation and their use for the preparation of compounds of the formula (I).

Description

and, where appropriate, their tautomers, in each case in the free form or salt form, in which either

X is CH or N, Y is OR ₁and Z is 0,

or

X is N, Y is NHR ₈and Z is O, S or S(═O);

R ₁is C₁-C₄alkyl;

R ₂is H, C₁-C₄alkyl, halogeno-C₁-C₄alkyl, C₃-C₆cycloalkyl or C₁-C₄alkoxymethyl;

R ₃and R₄independently of one another are H, C₁-C₄alkyl, C₁-C₄alkoxy, OH, CN, NO₂, a (C₁-C₄alkyl)₃—Si group, where the alkyl groups can be identical or different, halogen, (C₁-C₄alkyl)S(═O)_m, (halogeno-C₁-C₄alkyl)S(═O)_m, halogeno-C₁-C₄alkyl or halogeno-C₁-C₄alkoxy;

R ₅is C₁-C₆alkyl, halogeno-C₁-C₆alkyl, C₁-C₆alkoxy, halogeno-C₁-C₆alkoxy, C₁-C₆-alkylthio, halogen-C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, halogeno-C₁-C₆-alkylsulfinyl, C₁-C₆alkylsulfonyl, halogeno-C₁-C₆alkylsulfonyl, C₁-C₆alkoxy-C₁-C₆alkyl, halogeno-C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl, halogeno-C₁-C₆alkylthio-C₁-C₆alkyl, C₁-C₆alkylsulfinyl-C₁-C₆alkyl, halogeno-C₁-C₆-alkylsulfinyl-C₁-C₆alkyl, C₁-C₆-alkylsulfonyl-C₁-C₆alkyl, halogeno-C₁-C₆-alkylsulfonyl-C₁-C₆alkyl, C₁-C₆-alkylcarbonyl, halogeno-C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxycarbonyl, halogeno-C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylaminocarbonyl, C₁-C₄-alkoxyiminomethyl; di(C₁-C₆alkyl)-aminocarbonyl, where the alkyl groups can be identical or different; C₁-C₆-alkylaminothiocarbonyl; di(C₁-C₆alkyl)-aminothiocarbonyl, where the alkyl groups can be identical or different; C₁-C₆-alkylamino, di(C₁-C₆alkyl)-amino, where the alkyl groups can be identical or different; halogen, NO₂, CN, SF₅, thioamido, thiocyanatomethyl; an unsubstituted or mono- to tetrasubstituted C₁-C₄alkylenedioxy group, where the substituents are selected from the group consisting of C₁-C₄alkyl and halogen; or QR₆, where, if n is greater than 1, the radicals R₅can be identical or different;

R ₆is C₂-C₆alkenyl or C₂-C₆alkynyl which are unsubstituted or substituted by 1 to 3 halogen atoms; (C₁-C₄alkyl)₃Si, where the alkyl groups can be identical or different; CN; or an unsubstituted or mono- to pentasubstituted C₃-C₆cycloalkyl, aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen, C₁-C₆alkyl, halogeno-C₁-C₆alkyl, C₁-C₆alkoxy, halogeno-C₁-C₆alkoxy, phenoxy, naphthoxy and CN;

A either is a direct bond, C ₁—C₁₀alkylene, —C(═O)—, —C(═S)— or halogeno-C₁-C₁₀alkylene and R₇is a radical R₁₀,

or is C ₁-C₁₀alkylene, —C(═O)—, —C(═S)— or halogeno-C₁-C₁₀alkylene and

R ₇is OR₁₀, N(R₁₀)₂, where the radicals R₁₀can be identical or different, or —S(═O)_qR₁₀;

R ₈is H or C₁-C₄alkyl;

R ₉is methyl, fluoromethyl or difluoromethyl;

R ₁₀is H; an x unsubstituted or substituted C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl group, where the substituents are selected from the group consisting of halogen; (C₁-C₄alkyl)₃Si, where the alkyl groups can be identical or different; C₃-C₆cyclo-alkyl, which is unsubstituted or substituted by halogen; C₁-C₆alkoxycarbonyl, which is unsubstituted or substituted by halogen; unsubstituted or substituted aryl, where the substituents are selected from the group consisting of halogen, halogeno-C₁-C₄alkyl and CN; a (C₁-C₄alkyl)₃Si group, where the alkyl groups can be identical or different; C₃-C₆cycloalkyl, which is unsubstituted or substituted by halogen; C₁-C₆alkoxycarbonyl which is unsubstituted or substituted by halogen; or an unsubstituted or substituted aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen and halogeno-C₁-C₄alkyl; Q is a direct bond, C₁-C₈alkylene, C₂-C₆alkenylene, C₂-C₆alkynylene, O, O(C₁-C₆alkylene), (C₁-C₆alkylene)O, S(═O)_p, S(═O)_p(C₁-C₆alkylene) or (C₁-C₆alkylene)S(═O)_p;

m is 0, 1 or 2;

n is 0, 1, 2, 3, 4 or 5;

p is 0, 1 or 2; and

q is 0, 1 or 2,

and the C═N double bond marked with E has the E configuration,

which comprises

a1) reacting either a compound of the formula

in which A, R ₂, R₅, R₇and n are as defined for formula I and the C═N double bond marked with E has the E configuration, or a tautomer thereof, in each case in the free form or in salt form, if appropriate in the presence of a base, with a compound of the formula

which is known or can be prepared by methods known per se and in which X, Y, Z, R ₃, R₄and R₉are as defined for formula I and X₁is a leaving group, or a tautomer thereof, in each case in the free from or in salt form, or

a2) reacting a compound of the formula

in which A, R ₂, R₅, R₁and n are as defined for formula I and the C═N double bond marked with E has the E configuration, or a tautomer thereof, in each case in the free form or in the salt form, if appropriate in the presence of a base, with a compound of the formula

which is known or can be prepared by methods known per se and

in which X, Y, Z, R ₃, R₄and R₉are as defined for formula I, or a tautomer thereof, in each case in the free form or in salt form, or

b1) reacting a compound of the formula

in which R ₂, R₅and n are as defined for formula I and the C═N double bond marked with E has the E configuration, or a tautomer thereof, in each case in the free form or in salt form, if appropriate in the presence of a base, with a compound of the formula

R₇-A-X₂ (VII),

which is known or can be prepared by methods known per se and

in which A and R ₇are as defined for formula I and X₂is a leaving group, and either further reacting the compound thus obtainable, of the formula IV, for example according to method a2), or

b2) reacting it with hydroxylamine or a salt thereof, if appropriate in the presence of a base or acid catalyst, and further reacting the compound thus obtainable, of the formula II, for example according to method a1), or

c) reacting a compound of the formula

which is known or can be prepared by methods known per se and

in which R ₂, R₃and n are as defined for formula I, or a tautomer thereof, in each case in the free form or in salt form, if appropriate in the presence of a base, with a C₁-C₆alkyl nitrite, and further reacting the compound thus obtainable, of the formula VI, for example according to method b),

the E isomers of the compounds of the formulae II, IV and VI, or a tautomer thereof, in each case in the free form or in salt form, a process for their preparation and their use for the preparation of compounds of the formula I.

The compounds of the formula I are known pesticides. The processes known to date for their preparation give mixtures of E and Z isomers in respect of the C═N double bond marked with E in formula I of different composition, depending on the process. Since the biological properties of the E isomers are in each case found to be superior to those of the mixtures and of the Z isomers, there is a need to develop preparation processes for compounds of the formula I haying the isomerically pure E configuration. This object is achieved by the preparation process according to the invention.

Unless defined differently, the general terms used above and below are defined as follows.

Carbon-containing groups and compounds in each case contain 1 up to and including 8, preferably 1 up to and including 6, in particular 1 up to and including 4, especially 1 or 2, carbon atoms.

Alkyl—as a group per se and as a structural element of other groups and compounds, such as of halogenoalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, halogenoalkoxycarbonyl, alkylaminocarbonyl,alkoxyiminomethyl, alkylaminothiocarbonyl and alkylamino—is, in each case taking into due consideration the number, included from case to case, of carbon atoms contained in the corresponding group or compound, either straight-chain, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

Alkenyl—as a group per se and as a structural element of other groups and compounds, such as of halogenoalkenyl—is, in each case under due consideration of the number, included from case to case, of carbon atoms contained in the corresponding group or compound, either straight-chain, for example vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, for example iso-propenyl.

Alkynyl—as a group per se and as a structural element of other groups and compounds, such as of halogenoalkynyl—is, in each case under due consideration of the number, included from case to case, of carbon atoms contained in the corresponding group or compound, either straight-chain, for example propargyl, 2-butynyl or 5-hexynyl, or branched, for example 2-ethynylpropyl or 2-propargylisopropyl.

C ₃-C₆cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkylene—as a group per se and as a structural element of other groups and compounds, such as of O(alkylene), (alkylene)O, S(═O) _p(alkylene), (alkylene)S(═O)_por alkylenedioxy—is, in each case under-due consideration of the number, included from case to case, of carbon atoms contained in the corresponding group or compound, either straight-chain, for example —CH₂CH₂—, —CH₂CH₂CH₂— or —CH₂CH₂CH₂CH₂—, or branched, for example —CH(CH₃)—, —CH(C₂H₅)—, —C(CH₃)₂—, —CH(CH₃)CH₂— or —CH(CH₃)CH(CH₃)—.

Alkenylene is, in each case under due consideration of the number, from case to case, of carbon atoms contained in the corresponding compound, either straight-chain, for example vin-1,2-ylene, all-1,3-ylene, but-1-en-1,4-ylene or hex-2-en-1,6-ylene, or branched, for example 1-methylvin-1,2-ylene.

Alkynylene is, in each case under due consideration of the number, from case to case, of carbon atoms contained in the corresponding compound, either straight-chain, for example propargylene, 2-butynylene or 5-hexynylene, or branched, for example 2-ethynylpropylene or 2-propargylisopropylene.

Aryl is phenyl or naphthyl, in particular phenyl.

Heterocyclyl is a 5- to 7-membered aromatic or non-aromatic ring having one to three heteroatoms, which are selected from the group consisting of N, O and S. 5- and 6-membered rings which contain a nitrogen atom as a heteroatom and, if appropriate, a further heteroatom, preferably nitrogen or sulfur, in particular nitrogen, are preferred.

Halogen—as a group per se and as a structural element of other groups and-compounds, such as of halogenoalkyl, halogenoalkenyl and halogenoalkynyl—is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, in particular fluorine or chlorine, very especially fluorine.

Halogen-substituted carbon-containing groups and compounds, such as halogenoalkyl, halogenoalkenyl or halogenoalkynyl, can be partly halogenated or perhalogenated, and in the case of polyhalogenation, the halogen substituents can be identical or different. Examples of halogenoalkyl—as a group per se and as a structural element of other groups and compounds, such as of halogenoalkenyl are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF ₂or CF₃; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH₂CF₃, CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; propyl or isopropyl which is mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃or CH(CF₃) 2; and butyl or one of its isomers which is mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF₃)—CHFCF₃or CH₂(CF₂)₂CF₃. Halogenoalkenyl is, for example, CH₂CH═CHCl, CH₂CH═CCl₂, CH₂CF═CF₂or CH₂CH═CHCH₂Br. Halogenoalkynyl is, for example, CH₂C≡CF, CH₂C≡CCH₂Cl or CF₂CF₂C≡CCH₂F.

Some compounds I to VI and VII can be present as tautomers, as is familiar to the expert, in particular if AR ₇is H. Compounds I above and below are therefore also to be understood as meaning corresponding tautomers, even if the latter are not mentioned specifically in each case.

Compounds I to VI and VIII which contain at least one basic centre, can form, for example, acid addition salts. These are formed, for example, with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid, or a hydrogen halide acid, with strong inorganic carboxylic acids, such as C ₁-C₄alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as dicarboxylic acids which are saturated or unsaturated, for example oxalic, malonic, succinic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C₁-C₄alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds I with at least one acid group can furthermore form salts with bases. Suitable salts with bases are, for example, metal salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or trihydroxy-lower alkylamine, for example mono-, di- or triethanolamine. Furthermore, where appropriate, corresponding inner salts can be formed. Agrochemically advantageous salts are preferred in the context of the invention; however, salts which have disadvantages for agrochemical uses, for example salts which are toxic to bees or fish, which are employed, for example, for isolation or purification of free compounds I or agrochemically usable salts thereof, are also included. Compounds of the formulae I to VI and VIII in the free form and in the form of their salts are also to be understood above and below as meaning the corresponding salts or the free compounds I to VI and VIII. The same applies to tautomers of compounds of the formulae I to VI and VIII and salts thereof. In general, the free form is in each case preferred.

The reactions described above and below are carried out in a manner known per se, for example in the absence or usually in the presence of a suitable solvent or diluent or a mixture thereof, the reaction being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range from about −80° C. up to the boiling point of the reaction medium, preferably from about 0° C. up to about 150° C., and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Particularly advantageous reaction conditions can be seen from the examples.

The starting materials mentioned above and below, which are used for the preparation of the compounds I, in each case in the free form or in salt form, are known or can be prepared by methods known per se, for example in accordance with the following statements.

Variants a1/a2)

Suitable leaving groups X ₁in compounds III are, for example, hydroxyl, C₁-C₈alkoxy, halogeno-C₁-C₈alkoxy, C₁-C₈alkanoyloxy, mercapto, C₁-C₈alkylthio, halogeno-C₁-C₈alkylthio, C₁-C₈alkanesulfonyloxy, halogeno-C₁-C₈alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy and halogen, in particular halogen.

Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, N-alkylated or non-alkylated, saturated or unsaturated cycloalkylamines, basic heterocyclic compounds, ammonium hydroxides and carbocyclic amines. Examples are sodium hydroxide, hydride, amide, methanolate, acetate and carbonate, potassium tert-butanolate, hydroxide, carbonate, and hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropyl-ethyl-amine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethyl-amine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyl-trimethyl-ammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. However, the addition of an inert solvent or diluent or of a mixture thereof is usually advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenohydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also serve as the solvent or diluent.

The reaction is advantageously carried out in a temperature range from about 0° C. up to about 180° C., preferably from about 10° C. up to about 80° C., in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

The reaction is preferably carried out under normal pressure.

The reaction can be carried out without an inert gas atmosphere; preferably, however, it is carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.

The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is preferred.

The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.

In a preferred embodiment of variants a1/a2), a compound II is reacted with a compound III at 0° C. to 80° C., preferably 10° C. to 30° C., in an inert solvent, preferably an amide, in particular N,N-dimethylformamide in the presence of a metal hydride, preferably sodium hydride.

Particularly preferred conditions for the reaction are described in Examples H1 d) and H 3f).

The compounds of the formula III are known or can be prepared analogously to known compounds.

The compounds I are known. However, their preparation according to the prior art has a large number of serious industrial, ecological, economic and other disadvantages.

Thus, in the preparation processes according to the prior art, as a rule E/Z isomer mixtures with respect to the C═N double bond marked with E in formula I are obtained. Since the biological properties of the E isomers are in each case found to be superior to those of the mixtures and of the Z isomers in each case, the processes according to the prior art have the significant disadvantage that products are produced which are either significantly less active as E/Z mixtures or from which the Z isomers must be removed in order to increase their biological activity, which means that many unnecessary handling operations must be carried out for separation of isomers, which has the effect of being very time-consuming, blocks valuable production lines for a long time and is associated with high additional energy costs. The removal of the less active Z isomer also leads to additional enormous losses in yield, which in turn not only is problematic and ecologically disadvantageous, but also renders the process according to the prior art much more expensive and consequently economically of no interest. The industrial, ecological, economic and other disadvantages of the processes according to the prior art are not limited to those described above, these latter being intended to serve only as a few examples of the large number of disadvantages of the processes according to the prior art. The disadvantages of the processes according to the prior art cause serious problems even when the processes are carried out on a laboratory scale. When the processes are carried out on a larger scale, these disadvantages intensify considerably. In the end, however, the aim is to carry out a specific process on an industrial scale if this process is to be suitable for preparing products for agrochemical purposes.

According to the process of the present invention, the compounds I are prepared by reaction of the compound II with a compound III or by reaction of the compound IV with a compound V. These processes according to the invention have extremely surprising industrial, ecological, economic and other advantages compared with the processes from the prior art. Since the compounds II or, respectively, IV are present in the preparation process according to the invention as pure E isomers in respect of the C═N double bond marked with E, only the E isomer of the compounds I is produced in the present process, which has the effect of an enormous saving in time and at the same time a high saving in cost and energy, since no valuable production lines are blocked for a long time for separation of the isomers, and at the same time the amount of biologically more active E isomer produced by per unit time is much higher than in the processes according to the prior art. The resources such as starting products and energy are consequently utilized to the optimum in the present process, which not only very greatly simplifies the process and renders it ecologically advantageous, but consequently renders it cheaper and therefore of greater economic interest. This means that all the disadvantages of the processes according to the prior art which can be attributed to the formation of E/Z isomers are avoided. The industrial, ecological, economic and other advantages of the process according to the invention are not limited only to those described above, these latter being intended to serve only as a few examples of the large number of advantages inherent in this process. Due to all the abovementioned advantages of the present process, the serious problems which occur in the processes according to the prior art are avoided even at the stage of a laboratory process. If the present process is used on a larger scale, these advantages prove to be even much more significant, which has the effect that these advantages first allow the process to be used on an industrial scale.

For this reason, all the industrial, ecological, economic and other disadvantages of the processes according to the prior art are surprisingly advantageously overcome in the preparation of compounds I by the present process.

Variant b)

The process according to variant b) is carried out by first reacting compound VI with compound VII, if appropriate further reacting the resulting product IV, if appropriate after isolation, with hydroxylamine or a salt thereof, and further reacting the resulting products 11 or, respectively, IV, if appropriate after isolation, in accordance with variants a1/a2), for example in the manner described above, to give the compounds I.

Suitable leaving groups X ₂in the compounds VII are, for example, those which are mentioned as examples for X₁in variants a1/a2).

Suitable bases for facilitating the reaction are, for example, those which are mentioned in variants a1/a2).

The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. However, the addition of an inert solvent or diluent or of a mixture thereof is usually advantageous. Examples of such solvents or diluents are those mentioned in variants a1/a2).

The reaction is advantageously carried out in a temperature range from about 0° C. to about 180° C., preferably from about 10° C. to about 80° C., in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

The reaction is preferably carried out under normal pressure.

The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 5 hours, is preferred.

The product is isolated by customary methods, for example filtration, crystallization, distillation or chromatography or any suitable combination of these processes.

In a preferred embodiment of variant b), a compound VI is reacted with a compound VII at 0° C. to 80° C., preferably 10° C. to 60° C., in an inert solvent, preferably a nitrile, in particular acetonitrile, in the presence of a metal carbonate, preferably potassium carbonate, and the compound IV thus obtainable is then further reacted, preferably in accordance with method a2).

Particularly preferred conditions for the reaction are described in Examples H 1b) to 1d) and H 3d) to 3f).

The compounds of the formula VII are known or can be prepared analogously to known compounds.

The present process according to the invention of variant b), which in principle is an advantageous combination of an O-alkylation reaction with process variants a1/a2) according to the invention, has all the great advantages compared with the prior art which have already been discussed above for the process according to the invention of variants a1/a2). In particular, the process of variant b) ensures that the E configuration of the C═N double bond marked with E in compound VI is retained. Furthermore, however, the process according to the invention of variant b) also has further industrial, ecological, economic and other advantages which are connected with the specific property that the intermediate product IV initially formed is not purified but is directly further processed as the moist crude product, in the case of intermediate isolation, or in situ in the reaction mixture, if it is not isolated. This missing purification step on the intermediate product mentioned is of advantage, for example, in as much as it is not necessary to dry it, which not only saves energy and further resources, but also enormously increases the safety of the preparation process, since the possible danger of a dust explosion of the dry intermediate product is averted completely. The savings in resources are even greater if the intermediate product is further reacted without purification, since, for example, no additional solvents are consumed for the recrystallization. The process of variant b) is of particular advantage compared with the individual process steps of the alkylation reaction of variants a1/a2) carried out in that the total reaction time in the process of variant b) is much shorter, which consequently leads to a much higher production of reaction product I per unit time and therefore to a much more efficient utilization of the valuable production lines. Furthermore, the total yield of reaction product I is surprisingly good when the process of variant b) is employed, and, compared with the combined yields of the individual process steps of the alkylation reaction and variants a1/a2) carried out, is in the same percentage range or even better. The industrial, ecological, economic and other advantages of the process according to the invention of variant b) are not limited to those described above, these latter being intended to serve only as a few examples of the large number of advantages inherent in the process according to the invention of variant b).

By using process variant b) according to the invention for preparation of the compounds I, a large number of industrial, ecological, economic and other advantages can therefore surprisingly be utilized efficiently.

Variant c)

The process according to variant c) is carried out by first reacting compound VIII with an alkylnitrite and further reacting the resulting product VI, if appropriate after isolation, in accordance with variant b), for example in the manner described above, to give the compounds I.

The reaction is advantageously carried out in a temperature range from about 0° C. to about 180° C., preferably from about 0° C. to about 60° C., in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

The reaction is preferably carried out under normal pressure.

The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 3 hours, is preferred.

In a preferred embodiment of variant c), a compound VIII is reacted with an alkyl nitrite at 0° C. to 80° C., preferably 0° C. to 40° C., in an inert solvent, preferably an alcohol, in particular methanol, in the presence of a metal alcoholate, preferably sodium methanolate, and the compound VI thus obtainable is then further reacted, preferably in accordance with method b).

Particularly preferred conditions for the reactions are described in Examples H 3d) to 3f).

The compounds of the formula VIII are known or can be prepared analogously to known compounds.

The present process according to the invention of variant c), which in principle is an advantageous combination of an oximation reaction with process variants a1/a2) and b) according to the invention, has all the great advantages compared with the prior art which have already been discussed above for the processes according to the invention of variants a1/a2) and b). Furthermore, the present oximation process for the preparation of the compounds VI surprisingly result exclusively in the E configuration of the C═N double bond marked with E in formula VI. It is thus ensured that the particular starting products II, IV or, respectively, VI in the subsequent processes according to the invention for the preparation of the compounds I, for example in process variants a1/a2) and b), are pure E isomers.

A large number of industrial, ecological, economic and other advantages can therefore surprisingly be utilized efficiently by using process variants c) according to the invention for the preparation of the compounds of the formula I.

The E isomers of the compounds of the formulae II, IV and VI and tautomers thereof, in each case in the free form or in salt form, are novel and the present invention likewise relates to them.

The present invention furthermore relates to a process for the preparation of the E isomers of a compound of the formula VI or of a tautomer thereof, in each case in the free form or in salt form, according to the abovementioned process c),

a process for the preparation of the E isomers of a compound of the formula IV, or of a tautomer thereof, in each case in the free form or in salt form, according to the abovementioned process b1), and

a process for the preparation of the E isomers of a compound of the formula II, or of a tautomer thereof, in each case in the free form or in salt form, according to the abovementioned process b2).

The process conditions for the preparation of these intermediate products can be seen from the abovementioned processes a), b) and c).

PREPARATION EXAMPLES

Example H1

Methyl 2-[[[(1-methyl-2-phenyl-2-E-[(2-propynyl)oxyimino]-ethylidene)amino]oxy]methyl]α-(methoxymethylene)-phenylacetate (Compound 1.16)

H1a) 1-Phenyl-1,2-propanedione 1-E-oxime [0107]
69.7 g of a 30% solution of sodium methylate in methanol are added dropwise to a solution of 40.2 g of 1-phenyl-2-propanone and 36.1 g of isopentyl nitrite in 460 ml of methanol at 20-25°, while cooling. The reaction mixture is then further stirred at room temperature for 1 hour. After the solution has been concentrated in vacuo, the residue is dissolved in 600 ml of water, the solution is acidified with 10% hydrochloric acid, the product which precipitates out is filtered off and dissolved in ethyl acetate and the organic phase is washed twice with water, dried with sodium sulfate and evaporated in vacuo. The residue is stirred up in hexane and filtered. The title product is thus obtained with a melting of 168-70° C. [0108]
H1b) 1-Phenyl-1,2-propanedione 1-E-[(2-propynyl)oxime][0109]
A mixture of 14 g of 1-phenyl-1,2-propanedione 1-E-oxime, 11.9 g of 1-bromo-2-propyne, 13.8 g of potassium carbonate and 0.5 g of potassium iodide in 170 ml of acetonitrile is stirred at 50° for 2 hours, the solvent is then distilled off in vacuo and the residue is dissolved again in ethyl acetate. The organic phase is washed in each case twice with water and saturated sodium chloride solution, dried with sodium sulfate and evaporated in vacuo. After recrystallization of the residue from hexane, 1-phenyl-1,2-propanedione 1-E-[(2-propynyl)oxime] is obtained with a melting point of 54-56° C. [0110]
H1d) 1-Phenyl-1,2-propanedione 1-E-[(2-propynyl)oxime]-2-oxime [0111]
A mixture of 14.3 g of 1-phenyl-12-propanedione 1-E-[(2-propynyl)oxime], 10.3 g of hydroxylamine hydrochloride and 11.7 g of pyridine in 230 ml of ethanol is boiled under reflux for 1 hour and then concentrated in vacuo, and 800 ml of water are added to the residue. The product which has precipitated out is filtered off and dissolved in ethyl acetate and the solution is washed three times with water, dried with sodium sulfate and evaporated in vacuo. The residue is suspended in hexane and filtered. The title product is thus obtained with a melting point of 163-165° C. [0112]
H1e) Methyl 2-[[[(1-methyl-2-phenyl-2-E-[(2-propynyl)oxyimino]ethy-lidene)amino]oxy]-methyl]-α-(methoxymethylene)-phenylacetate [0113]
A solution of 5 g of 1-phenyl-1,2-propanedione 1-E-[(2-propynyl)oxime]-2-oxime in 24 ml of N,N-dimethylformamide is added dropwise to a suspension of 1.16 g of sodium hydride (about 55% in oil) in 45 ml of N,N-dimethylformamide at room temperature and the mixture is further stirred for 10 minutes. 6.5 g of methyl 2-(bromomethyl)-α-(methoxymethylene)-phenylacetate in 24 ml of N,N-dimethylformamide are then added dropwise and the reaction mixture is further stirred at room temperature for 1 hour. Thereafter, the mixure is acidified with acetic acid and evaporated in vacuo. The residue is dissolved in ethyl acetate and the solution is washed three times with water and twice with saturated sodium chloride solution, dried with sodium sulfate and evaporated in vacuo. After recrystallization of the residue from hexane/ethyl acetate, the title compound is obtained with a melting point of 82-84°. [0114]

Example H2

Methyl 2-[[[(1-methyl-2-(4-fluorophenyl)-2-E-[(2-propynyl)oxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetate (compound 1.44)

The title compound with a melting point of 91-93″-can be prepared in a manner analogous to that described in Example H1, starting from 1-(4-fluorophenyl)-2-propanone. [0115]

Example H3

Methyl 2-[[[(1-methyl-2-(4-(3-trifluoromethylphenylmethoxy)-phenyl) 2-E-[(2-propynyl)oxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetate (compound 1.240)

H3a) 1-(4-Hydroxyphenyl)-2′-propanone [0116]
A mixture of 82 g of 1-(4-methoxyphenyl)-2-propanone, 500 ml of acetic acid and 500 ml of aqueous hydrobromic acid is boiled under reflux for 2 hours and then evaporated in vacuo. The oily residue is extracted four times with 700 ml of hexane/ether (5:2) each time, the extract is evaporated and the residue is chromatographed over silica gel using hexane/ethyl acetate (3:1). 1-(4-Hydroxyphenyl)-2-propanone is thus obtained with a melting point of 40-41°. [0117]
H3b) 1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-2-propanone [0118]
A mixture of 5.8 g of 1-(4-hydroxyphenyl)-2-propanone, 61.6 g of potassium carbonate, 72.3 g of 1-(chloromethyl)-3-(trifluoromethyl)-benzene, and 1 g of potassium iodide in 800 ml of acetone is boiled under reflux for 5 hours. Thereafter, the reaction mixture is filtered and the filtrate is evaporated in vacuo. The residue is then dissolved in diethyl ether and the ethereal phase is washed three times with water, dried with sodium sulfate and evaporated. The 1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-2-propanone thus obtainable is employed in the next reaction stage without further purification. [0119]
H3c) 1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-oxime [0120]
45 g of a 30% solution of sodium methanolate in methanol are slowly added dropwise to a solution of 59.6 g of 1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-2-propanone and 23.4 g of isopentyl nitrite in 300 ml of methanol such that the temperature does not exceed 20-25°. The reaction mixture is then further stirred at room temperature for 1 hour and thereafter evaporated in vacuo. The residue is dissolved in 600 ml of water and the solution is acidified with 10% hydrochloric acid. The precipitate which separates out is filtered off and dissolved in ethyl acetate and the organic phase is washed twice with water, dried with sodium sulfate and evaporated. After the crude product has been suspended in hexane and filtered, 1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-oxime is obtained with a melting point of 134-136°. [0121]
H3d) 1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)oxime][0122]
A mixture of 6 g of 1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-oxime, 2.4 g of 1-bromo-2-propyne, 2.6 g of potassium carbonate and 0.5 g of potassium iodide in 40 ml of acetonitrile is boiled under reflux for 1 hour and then evaporated in vacuo and the residue is dissolved in ethyl acetate. The organic phase is washed twice with water and once with saturated sodium chloride solution, dried with sodium sulfate and evaporated. The crude 1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)oxime] thus obtainable is further processed without further purification. [0123]
H3e) 1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)oxime]-2-oxime [0124]
A mixture of 5.9 g of 1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)oxime], 2.3 g of hydroxylamine hydrochloride and 2.6 g of pyridine in 60 ml of ethanol is boiled under reflux for 1 hour and then concentrated in vacuo, and 200 ml of water are added to the residue. The product which has precipitated out is filtered off and dissolved in ethyl acetate, and the solution is washed twice with water and once with saturated sodium chloride solution, dried with sodium sulfate and evaporated in vacuo. The residue is suspended in hexane and filtered. 1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)oxime]-2-oxime is thus obtained with a melting point of 114-115°. [0125]
H3f) Methyl 2-[[[(1-methyl-2-(4-(3-trifluoromethylphenylmethoxy)-phenyl)-2-E-[(2-propynyl)oxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetate [0126]
A solution of 5.5 g of 1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)oxime]-2-oxime in 25 ml of N,N-dimethylformamide is added dropwise to a suspension of 0.7 g of sodium hydride (about 55% in oil) in 25 ml of N,N-dimethylformamide and the mixture is further stirred at room temperature for 10 minutes. 4 g of methyl 2-(bromomethyl)-α-(methoxymethylene)-phenylacetate in 15 ml of N,N-dimethylformamide are then added dropwise and the reaction mixture is further stirred at room temperature for 1 hour. Thereafter, the mixture is acidified with acetic acid and evaporated in vacuo at 50°. The residue is dissolved in ethyl acetate and the solution is washed twice with water and once with saturated sodium chloride solution, dried with sodium sulfate and evaporated in vacuo. After purification by chromatography (silica gel, ethyl acetate/hexane 1:3), the title compound is obtained as a resin. [0127]

Example H4

Methyl 2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetate (compound 1.366)

H4a) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione 1-E-oxime [0128]
16.7 g of a 30% solution of sodium methylate in methanol are added dropwise to a solution of 22.5 g of 1-[4-(4-chlorophenoxy)-phenyl]-2-propanone and 10.3 g of isopentyl nitrite in 120 ml of methanol at 20-25°, while cooling. The reaction mixture is then further stirred at room temperature for 1 hour. After the solution has been concentrated in vacuo, the residue is dissolved in 300 ml of water and the solution is acidified with 10% hydrochloric acid, the product which precipitates out is filtered off and dissolved in ethyl acetate and the organic phase is washed twice with water, dried with sodium sulfate and evaporated in vacuo. The residue is stirred up in hexane and filtered. The title product is thus obtained with a melting point of 154-155° C. [0129]
H4b) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione 1-E-[(2-ethyl)oxime][0130]
A mixture of 6 g of) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione 1-E-oxime, 3.3 g of ethyl bromide, 3.5 g of potassium carbonate and 0.5 g of potassium iodide in 30 ml of acetonitrile is stirred at 50° for 2 hours, the solvent is then distilled off in vacuo and the residue is dissolved again in ethyl acetate. The organic phase is washed in each case twice with water and saturated sodium chloride solution, dried with sodium sulfate and evaporated in vacuo. After recrystallization of the residue from hexane, the title product is obtained with a melting point of 77-78° C. [0131]
H4c) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione 1-E-[(2-ethyl)oxime]-2-oxime [0132]
A mixture of 5.5 g of 1-[4-(4-chlorophenoxy)-phenyl]-1,2-propanedione 1-E-[(2-ethyl)oxime], 2.4 g of hydroxylamine hydrochloride and 2.7 g of pyridine in 50 ml of ethanol is boiled under reflux for 1 hour and then concentrated in vacuo, and 800 ml of water are added to the residue. The product which has precipitated out is filtered off and dissolved in ethyl acetate and the solution is washed three times with water, dried with sodium sulfate and evaporated in vacuo. The residue is suspended in hexane and filtered. The title product is thus obtained in a pure form with a melting point of 176-177° C. [0133]
H4d) Methyl 2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetate. [0134]
A solution of 4.7 g of 1-[4-(4-chlorophenoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)-oxime]-2-oxime in 25 ml of N,N-dimethylformamide is added dropwise to a suspension of 0.65 g of sodium hydride (about 55% in oil) in 20 ml of N,N-dimethylformamide and the mixture is further stirred at room temperature for 10 minutes. 4 g of methyl 2-(bromomethyl)-α-(methoxymethylene)-phenylacetate in 15 ml of N,N-dimethylformamide are then added dropwise and the reaction mixture is further stirred at room temperature for 1 hour. Thereafter, the mixture is acidified with acetic acid and evaporated in vacuo at 50°. The residue is dissolved in ethyl acetate and the solution is washed twice with water and once with saturated sodium chloride solution, dried with sodium sulfate and evaporated in vacuo. After purification by flash chromatography (silica gel, ethyl acetate/hexane 1:3), the title compound is obtained with a melting point of 87-89° C. [0135]

Example H5

Methyl 2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxy-imino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetate (compound 2.366)

The title compound with a melting point of 90 to 93° C. is obtained in a manner analogous to that described in Example H4 from 1-[4-(4-chlorophenoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)oxime]-2-oxime and methyl 2-(bromomethyl)-α-(methoxyimino)-phenylacetate. [0136]

Example H6

2-[[[(1-Methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxy-imino]ethylidene)amino]oxy]_m!ethyl]-α-(methoxyimino)-phenytacetic acid methylamide (compound 3.366)

13,3 g of methyl 2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxyimino]ethyliene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetate are left to stand together with 80 ml of dimethylformamide and 9.2 ml of an 8 molar solution of methylamine in ethanol at room temperature for two days. The mixture is concentrated at 50° C., n-hexane is added and the mixture is cooled to room temperature and filtered. The residue is dried under a high vacuum. The title compound is obtained with a melting point of 126-129° C. [0137]

Example H7

The other compounds listed in Tables 1 to 3 can also be prepared in a manner analogous to that described in Examples H1 to H6. In the “physical data” column of the tables, the temperatures stated in each case designate the melting point of the compound in question c.propyl is cyclopropyl. [0138]

TABLE 1

Compounds of the general formula

I.1,

in which X is CH and Y is oxygen and the combination of substituents R ₂, (R₅)_xand A-R₇for a compound in each case corresponds to a line in Table A. The compound numbers of the following table correspond to the particular numbers in Table A.

	TABLE 2


	Compound No.	Phys. Data(Melting point ° C.)

	1.14	75-77°
	1.16	82-84°
	1.22	111-113°
	1.42	Resin
	1.44	91-93°
	1.50	Resin
	1.70	Resin
	1.72	Resin
	1.78	Resin
	1.225	102-103°
	1.226	81-83°
	1.227	Resin
	1.233	Resin
	1.234	73-75°
	1.238	Resin
	1.240	Resin
	1.241	Resin
	1.242	Resin
	1.244	Resin
	1.245	Resin
	1.294	Resin
	1.296	112-114°
	1.366	87-89°

Compounds of the general formula I.1, in which [0140]
X is nitrogen and [0141]
Y is oxygen [0142]
and the combination of substituents R[0143] ₂, (R₅)_nand A-R₇for a compound in each case corresponds to a line in Table A.

TABLE 3

Compound No. Melting point (° C.)

2.198 75-77

2.254 80-82

2.309 106-108

2.310 102-104

2.366 90-93
Compounds of the general formula I.1, in which [0144]
X is nitrogen and [0145]
Y is NH and [0146]
the combination of substituents R[0147] ₂, (R₅)_nand A-R₇for a compound in each case corresponds to a line in Table A.

Compound No. Melting point (° C.)

3.198 75-77

3.254 112-114

3.309 89-91

3.310 88-90

3.366 126-129

TABLE A


Com-
pound
No.	R₂	(R₅)_n	A-R₇

1	CH₃	H	CH₃
2	CH₃	H	C₂H₅
3	CH₃	H	n-C₃H₇
4	CH₃	H	i-C₃H₇
5	CH₃	H	n-C₄H₉
6	CH₃	H	n-C₆H₁₃
7	CH₃	H	CH₂F
8	CH₃	H	CHF₂
9	CH₃	H	CH₂CF₃
10	CH₃	H	CH₂CH═CH₂
11	CH₃	H	CH₂CH═CHCH₃
12	CH₃	H	CH₂CH═C(CH₃)₂
13	CH₃	H	CH₂CH═CHCl
14	CH₃	H	CH₂CH═CCl₂
15	CH₃	H	CH₂C(CH₃)═CH₂
16	CH₃	H	CH₂C≡CH
17	CH₃	H	CH₂Si(CH₃)₃
18	CH₃	H	CH₂-c.propyl-2,2-Cl₂
19	CH₃	H	CH₂CN
20	CH₃	H	CH₂COOC₂H₅
21	CH₃	H	CH(CH₃)COOC₂H₅
22	CH₃	H	CH₂C₆H₄-3-CF₃
23	CH₃	H	CH₂C₆H₄-4-F
24	CH₃	H	CH₂C₆H₄-3-F
25	CH₃	H	CH₂C₆H₄-2-F
26	CH₃	H	C(═O)OC₂H₅
27	CH₃	H	C(═O)NHCH₃
28	CH₃	H	C(═O)C(═O)OC₂H₅
29	CH₃	4-F	CH₃
30	CH₃	4-F	C₂H₅
31	CH₃	4-F	n-C₃H₇
32	CH₃	4-F	i-C₃H₇
33	CH₃	4-F	n-C₄H₉
34	CH₃	4-F	n-C₆H₁₃
35	CH₃	4-F	CH₂F
36	CH₃	4-F	CHF₂
37	CH₃	4-F	CH₂CF₃
38	CH₃	4-F	CH₂CH═CH₂
39	CH₃	4-F	CH₂CH═CHCH₃
40	CH₃	4-F	CH₂CH═C(CH₃)₂
41	CH₃	4-F	CH₂CH═CHCl
42	CH₃	4-F	CH₂CH═CCl₂
43	CH₃	4-F	CH₂C(CH₃)═CH₂
44	CH₃	4-F	CH₂C≡CH
45	CH₃	4-F	CH₂Si(CH₃)₃
46	CH₃	4-F	CH₂-c.propyl-2,2-Cl₂
47	CH₃	4-F	CH₂CN
48	CH₃	4-F	CH₂COOC₂H₅
49	CH₃	4-F	CH(CH₃)COOC₂H₅
50	CH₃	4-F	CH₂C₆H₄-3-CF₃
51	CH₃	4-F	CH₂C₆H₄-4-F
52	CH₃	4-F	CH₂C₆H₄-3-F
53	CH₃	4-F	CH₂C₆H₄-2-F
54	CH₃	4-F	C(═O)OC₂H₅
55	CH₃	4-F	C(═O)NHCH₃
56	CH₃	4-F	C(═O)C(═O)OC₂H₅
57	CH₃	4-OCH₃	CH₃
58	CH₃	4-OCH₃	C₂H₅
59	CH₃	4-OCH₃	n-C₃H₇
60	CH₃	4-OCH₃	i-C₃H₇
61	CH₃	4-OCH₃	n-C₄H₉
62	CH₃	4-OCH₃	n-C₆H₁₃
63	CH₃	4-OCH₃	CH₂F
64	CH₃	4-OCH₃	CHF₂
65	CH₃	4-OCH₃	CH₂CF₃
66	CH₃	4-OCH₃	CH₂CH═CH₂
67	CH₃	4-OCH₃	CH₂CH═CHCH₃
68	CH₃	4-OCH₃	CH₂CH═C(CH₃)₂
69	CH₃	4-OCH₃	CH₂CH═CHCl
70	CH₃	4-OCH₃	CH₂CH═CCl₂
71	CH₃	4-OCH₃	CH₂C(CH₃)═CH₂
72	CH₃	4-OCH₃	CH₂C≡CH
73	CH₃	4-OCH₃	CH₂Si(CH₃)₃
74	CH₃	4-OCH₃	CH₂-c.propyl-2,2-Cl₂
75	CH₃	4-OCH₃	CH₂CN
76	CH₃	4-OCH₃	CH₂COOC₂H₅
77	CH₃	4-OCH₃	CH(CH₃)COOC₂H₅
78	CH₃	4-OCH₃	CH₂C₆H₄-3-CF₃
79	CH₃	4-OCH₃	CH₂C₆H₄-4-F
80	CH₃	4-OCH₃	CH₂C₆H₄-3-F
81	CH₃	4-OCH₃	CH₂C₆H₄-2-F
82	CH₃	4-OCH₃	C(═O)OC₂H₅
83	CH₃	4-OCH₃	C(═O)NHCH₃
84	CH₃	4-OCH₃	C(═O)C(═O)OC₂H₅
85	CH₃	4-OC₂H₅	CH₃
86	CH₃	4-OC₂H₅	C₂H₅
87	CH₃	4-OC₂H₅	n-C₃H₇
88	CH₃	4-OC₂H₅	i-C₃H₇
89	CH₃	4-OC₂H₅	n-C₄H₉
90	CH₃	4-OC₂H₅	n-C₆H₁₃
91	CH₃	4-OC₂H₅	CH₂F
92	CH₃	4-OC₂H₅	CHF₂
93	CH₃	4-OC₂H₅	CH₂CF₃
94	CH₃	4-OC₂H₅	CH₂CH═CH₂
95	CH₃	4-OC₂H₅	CH₂CH═CHCH₃
96	CH₃	4-OC₂H₅	CH₂CH═C(CH₃)₂
97	CH₃	4-OC₂H₅	CH₂CH═CHCl
98	CH₃	4-OC₂H₅	CH₂CH═CCl₂
99	CH₃	4-OC₂H₅	CH₂C(CH₃)═CH₂
100	CH₃	4-OC₂H₅	CH₂C≡CH
101	CH₃	4-OC₂H₅	CH₂Si(CH₃)₃
102	CH₃	4-OC₂H₅	CH₂-c.propyl-2,2-Cl₂
103	CH₃	4-OC₂H₅	CH₂CN
104	CH₃	4-OC₂H₅	CH₂COOC₂H₅
105	CH₃	4-OC₂H₅	CH(CH₃)COOC₂H₅
106	CH₃	4-OC₂H₅	CH₂C₆H₄-3-CF₃
107	CH₃	4-OC₂H₅	CH₂C₆H₄-4-F
108	CH₃	4-OC₂H₅	CH₂C₆H₄-3-F
109	CH₃	4-OC₂H₅	CH₂C₆H₄-2-F
110	CH₃	4-OC₂H₅	C(═O)OC₂H₅
111	CH₃	4-OC₂H₅	C(═O)NHCH₃
112	CH₃	4-OC₂H₅	C(═O)C(═O)OC₂H₅
113	CH₃	4-O-n-C₃H₇	CH₃
114	CH₃	4-O-n-C₃H₇	C₂H₅
115	CH₃	4-O-n-C₃H₇	n-C₃H₇
116	CH₃	4-O-n-C₃H₇	i-C₃H₇
117	CH₃	4-O-n-C₃H₇	n-C₄H₉
118	CH₃	4-O-n-C₃H₇	n-C₆H₁₃
119	CH₃	4-O-n-C₃H₇	CH₂F
120	CH₃	4-O-n-C₃H₇	CHF₂
121	CH₃	4-O-n-C₃H₇	CH₂CF₃
122	CH₃	4-O-n-C₃H₇	CH₂CH═CH₂
123	CH₃	4-O-n-C₃H₇	CH₂CH═CHCH₃
124	CH₃	4-O-n-C₃H₇	CH₂CH═C(CH₃)₂
125	CH₃	4-O-n-C₃H₇	CH₂CH═CHCl
126	CH₃	4-O-n-C₃H₇	CH₂CH═CCl₂
127	CH₃	4-O-n-C₃H₇	CH₂C(CH₃)═CH₂
128	CH₃	4-O-n-C₃H₇	CH₂C≡CH
129	CH₃	4-O-n-C₃H₇	CH₂Si(CH₃)₃
130	CH₃	4-O-n-C₃H₇	CH₂-c.propyl-2,2-Cl₂
131	CH₃	4-O-n-C₃H₇	CH₂CN
132	CH₃	4-O-n-C₃H₇	CH₂COOC₂H₅
133	CH₃	4-O-n-C₃H₇	CH(CH₃)COOC₂H₅
134	CH₃	4-O-n-C₃H₇	CH₂C₆H₄-3-CF₃
135	CH₃	4-O-n-C₃H₇	CH₂C₆H₄-4-F
136	CH₃	4-O-n-C₃H₇	CH₂C₆H₄-3-F
137	CH₃	4-O-n-C₃H₇	CH₂C₆H₄-2-F
138	CH₃	4-O-n-C₃H₇	C(═O)OC₂H₅
139	CH₃	4-O-n-C₃H₇	C(═O)NHCH₃
140	CH₃	4-O-n-C₃H₇	C(═O)C(═O)OC₂H₅
141	CH₃	2-CH₃	CH₃
142	CH₃	2-CH₃	C₂H₅
143	CH₃	2-CH₃	n-C₃H₇
144	CH₃	2-CH₃	i-C₃H₇
145	CH₃	2-CH₃	n-C₄H₉
146	CH₃	2-CH₃	n-C₆H₁₃
147	CH₃	2-CH₃	CH₂F
148	CH₃	2-CH₃	CHF₂
149	CH₃	2-CH₃	CH₂CF₃
150	CH₃	2-CH₃	CH₂CH═CH₂
151	CH₃	2-CH₃	CH₂CH═CHCH₃
152	CH₃	2-CH₃	CH₂CH═C(CH₃)₂
153	CH₃	2-CH₃	CH₂CH═CHCl
154	CH₃	2-CH₃	CH₂CH═CCl₂
155	CH₃	2-CH₃	CH₂C(CH₃)═CH₂
156	CH₃	2-CH₃	CH₂C≡CH
157	CH₃	2-CH₃	CH₂Si(CH₃)₃
158	CH₃	2-CH₃	CH₂-c.propyl-2,2-Cl₂
159	CH₃	2-CH₃	CH₂CN
160	CH₃	2-CH₃	CH₂COOC₂H₅
161	CH₃	2-CH₃	CH(CH₃)COOC₂H₅
162	CH₃	2-CH₃	CH₂C₆H₄-3-CF₃
163	CH₃	2-CH₃	CH₂C₆H₄-4-F
164	CH₃	2-CH₃	CH₂C₆H₄-3-F
165	CH₃	2-CH₃	CH₂C₆H₄-2-F
166	CH₃	2-CH₃	C(═O)OC₂H₅
167	CH₃	2-CH₃	C(═O)NHCH₃
168	CH₃	2-CH₃	C(═O)C(═O)OC₂H₅
169	CH₃	4-OCH₂Si(CH₃)₃	CH₃
170	CH₃	4-OCH₂Si(CH₃)₃	C₂H₅
171	CH₃	4-OCH₂Si(CH₃)₃	n-C₃H₇
172	CH₃	4-OCH₂Si(CH₃)₃	i-C₃H₇
173	CH₃	4-OCH₂Si(CH₃)₃	n-C₄H₉
174	CH₃	4-OCH₂Si(CH₃)₃	n-C₆H₁₃
175	CH₃	4-OCH₂Si(CH₃)₃	CH₂F
176	CH₃	4-OCH₂Si(CH₃)₃	CHF₂
177	CH₃	4-OCH₂Si(CH₃)₃	CH₂CF₃
178	CH₃	4-OCH₂Si(CH₃)₃	CH₂CH═CH₂
179	CH₃	4-OCH₂Si(CH₃)₃	CH₂CH═CHCH₃
180	CH₃	4-OCH₂Si(CH₃)₃	CH₂CH═C(CH₃)₂
181	CH₃	4-OCH₂Si(CH₃)₃	CH₂CH═CHCl
182	CH₃	4-OCH₂Si(CH₃)₃	CH₂CH═CCl₂
183	CH₃	4-OCH₂Si(CH₃)₃	CH₂C(CH₃)═CH₂
184	CH₃	4-OCH₂Si(CH₃)₃	CH₂C≡CH
185	CH₃	4-OCH₂Si(CH₃)₃	CH₂Si(CH₃)₃
186	CH₃	4-OCH₂Si(CH₃)₃	CH₂-c.propyl-2,2-Cl₂
187	CH₃	4-OCH₂Si(CH₃)₃	CH₂CN
188	CH₃	4-OCH₂Si(CH₃)₃	CH₂COOC₂H₅
189	CH₃	4-OCH₂Si(CH₃)₃	CH(CH₃)COOC₂H₅
190	CH₃	4-OCH₂Si(CH₃)₃	CH₂C₆H₄-3-CF₃
191	CH₃	4-OCH₂Si(CH₃)₃	CH₂C₆H₄-4-F
192	CH₃	4-OCH₂Si(CH₃)₃	CH₂C₆H₄-3-F
193	CH₃	4-OCH₂Si(CH₃)₃	CH₂C₆H₄-2-F
194	CH₃	4-OCH₂Si(CH₃)₃	C(═O)OC₂H₅
195	CH₃	4-OCH₂Si(CH₃)₃	C(═O)NHCH₃
196	CH₃	4-OCH₂Si(CH₃)₃	C(═O)C(═O)OC₂H₅
197	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₃
198	CH₃	4-OCH₂C₆H₄-4-CF₃	C₂H₅
199	CH₃	4-OCH₂C₆H₄-4-CF₃	n-C₃H₇
200	CH₃	4-OCH₂C₆H₄-4-CF₃	i-C₃H₇
201	CH₃	4-OCH₂C₆H₄-4-CF₃	n-C₄H₉
202	CH₃	4-OCH₂C₆H₄-4-CF₃	n-C₆H₁₃
203	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂F
204	CH₃	4-OCH₂C₆H₄-4-CF₃	CHF₂
205	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂CF₃
206	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂CH═CH₂
207	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂CH═CHCH₃
208	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂CH═C(CH₃)₂
209	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂CH═CHCl
210	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂CH═CCl₂
211	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂C(CH₃)═CH₂
212	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂C≡CH
213	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂Si(CH₃)₃
214	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂-c.propyl-2,2-Cl₂
215	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂CN
216	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂COOC₂H₅
217	CH₃	4-OCH₂C₆H₄-4-CF₃	CH(CH₃)COOC₂H₅
218	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂C₆H₄-3-CF₃
219	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂C₆H₄-4-F
220	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂C₆H₄-3-F
221	CH₃	4-OCH₂C₆H₄-4-CF₃	CH₂C₆H₄-2-F
222	CH₃	4-OCH₂C₆H₄-4-CF₃	C(═O)OC₂H₅
223	CH₃	4-OCH₂C₆H₄-4-CF₃	C(═O)NHCH₃
224	CH₃	4-OCH₂C₆H₄-4-CF₃	C(═O)C(═O)OC₂H₅
225	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₃
226	CH₃	4-OCH₂C₆H₄-3-CF₃	C₂H₅
227	CH₃	4-OCH₂C₆H₄-3-CF₃	n-C₃H₇
228	CH₃	4-OCH₂C₆H₄-3-CF₃	i-C₃H₇
229	CH₃	4-OCH₂C₆H₄-3-CF₃	n-C₄H₉
230	CH₃	4-OCH₂C₆H₄-3-CF₃	n-C₆H₁₃
231	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂F
232	CH₃	4-OCH₂C₆H₄-3-CF₃	CHF₂
233	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂CF₃
234	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂CH═CH₂
235	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂CH═CHCH₃
236	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂CH═C(CH₃)₂
237	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂CH═CHCl
238	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂CH═CCl₂
239	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂C(CH₃)═CH₂
240	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂C≡CH
241	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂Si(CH₃)₃
242	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂-c.propyl-2,2-Cl₂
243	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂CN
244	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂COOC₂H₅
245	CH₃	4-OCH₂C₆H₄-3-CF₃	CH(CH₃)COOC₂H₅
246	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂C₆H₄-3-CF₃
247	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂C₆H₄-4-F
248	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂C₆H₄-3-F
249	CH₃	4-OCH₂C₆H₄-3-CF₃	CH₂C₆H₄-2-F
250	CH₃	4-OCH₂C₆H₄-3-CF₃	C(═O)OC₂H₅
251	CH₃	4-OCH₂C₆H₄-3-CF₃	C(═O)NHCH₃
252	CH₃	4-OCH₂C₆H₄-3-CF₃	C(═O)C(═O)OC₂H₅
253	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₃
254	CH₃	4-OCH₂C₆H₄-2-CF₃	C₂H₅
255	CH₃	4-OCH₂C₆H₄-2-CF₃	n-C₃H₇
256	CH₃	4-OCH₂C₆H₄-2-CF₃	i-C₃H₇
257	CH₃	4-OCH₂C₆H₄-2-CF₃	n-C₄H₉
258	CH₃	4-OCH₂C₆H₄-2-CF₃	n-C₆H₁₃
259	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂F
260	CH₃	4-OCH₂C₆H₄-2-CF₃	CHF₂
261	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂CF₃
262	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂CH═CH₂
263	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂CH═CHCH₃
264	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂CH═C(CH₃)₂
265	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂CH═CHCl
266	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂CH═CCl₂
267	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂C(CH₃)═CH₂
268	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂C≡CH
269	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂Si(CH₃)₃
270	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂-c.propyl-2,2-Cl₂
271	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂CN
272	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂COOC₂H₅
273	CH₃	4-OCH₂C₆H₄-2-CF₃	CH(CH₃)COOC₂H₅
274	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂C₆H₄-3-CF₃
275	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂C₆H₄-4-F
276	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂C₆H₄-3-F
277	CH₃	4-OCH₂C₆H₄-2-CF₃	CH₂C₆H₄-2-F
278	CH₃	4-OCH₂C₆H₄-2-CF₃	C(═O)OC₂H₅
279	CH₃	4-OCH₂C₆H₄-2-CF₃	C(═O)NHCH₃
280	CH₃	4-OCH₂C₆H₄-2-CF₃	C(═O)C(═O)OC₂H₅
281	CH₃	4-OCH₂C₆H₄-4-F	CH₃
282	CH₃	4-OCH₂C₆H₄-4-F	C₂H₅
283	CH₃	4-OCH₂C₆H₄-4-F	n-C₃H₇
284	CH₃	4-OCH₂C₆H₄-4-F	i-C₃H₇
285	CH₃	4-OCH₂C₆H₄-4-F	n-C₄H₉
286	CH₃	4-OCH₂C₆H₄-4-F	n-C₆H₁₃
287	CH₃	4-OCH₂C₆H₄-4-F	CH₂F
288	CH₃	4-OCH₂C₆H₄-4-F	CHF₂
289	CH₃	4-OCH₂C₆H₄-4-F	CH₂CF₃
290	CH₃	4-OCH₂C₆H₄-4-F	CH₂CH═CH₂
291	CH₃	4-OCH₂C₆H₄-4-F	CH₂CH═CHCH₃
292	CH₃	4-OCH₂C₆H₄-4-F	CH₂CH═C(CH₃)₂
293	CH₃	4-OCH₂C₆H₄-4-F	CH₂CH═CHCl
294	CH₃	4-OCH₂C₆H₄-4-F	CH₂CH═CCl₂
295	CH₃	4-OCH₂C₆H₄-4-F	CH₂C(CH₃)═CH₂
296	CH₃	4-OCH₂C₆H₄-4-F	CH₂C≡CH
297	CH₃	4-OCH₂C₆H₄-4-F	CH₂Si(CH₃)₃
298	CH₃	4-OCH₂C₆H₄-4-F	CH₂-c.propyl-2,2-Cl₂
299	CH₃	4-OCH₂C₆H₄-4-F	CH₂CN
300	CH₃	4-OCH₂C₆H₄-4-F	CH₂COOC₂H₅
301	CH₃	4-OCH₂C₆H₄-4-F	CH(CH₃)COOC₂H₅
302	CH₃	4-OCH₂C₆H₄-4-F	CH₂C₆H₄-3-CF₃
303	CH₃	4-OCH₂C₆H₄-4-F	CH₂C₆H₄-4-F
304	CH₃	4-OCH₂C₆H₄-4-F	CH₂C₆H₄-3-F
305	CH₃	4-OCH₂C₆H₄-4-F	CH₂C₆H₄-2-F
306	CH₃	4-OCH₂C₆H₄-4-F	C(═O)OC₂H₅
307	CH₃	4-OCH₂C₆H₄-4-F	C(═O)NHCH₃
308	CH₃	4-OCH₂C₆H₄-4-F	C(═O)C(═O)OC₂H₅
309	CH₃	4-OC₆H₄-3-CF₃	CH₃
310	CH₃	4-OC₆H₄-3-CF₃	C₂H₅
311	CH₃	4-OC₆H₄-3-CF₃	n-C₃H₇
312	CH₃	4-OC₆H₄-3-CF₃	i-C₃H₇
313	CH₃	4-OC₆H₄-3-CF₃	n-C₄H₉
314	CH₃	4-OC₆H₄-3-CF₃	n-C₆H₁₃
315	CH₃	4-OC₆H₄-3-CF₃	CH₂F
316	CH₃	4-OC₆H₄-3-CF₃	CHF₂
317	CH₃	4-OC₆H₄-3-CF₃	CH₂CF₃
318	CH₃	4-OC₆H₄-3-CF₃	CH₂CH═CH₂
319	CH₃	4-OC₆H₄-3-CF₃	CH₂CH═CHCH₃
320	CH₃	4-OC₆H₄-3-CF₃	CH₂CH═C(CH₃)₂
321	CH₃	4-OC₆H₄-3-CF₃	CH₂CH═CHCl
322	CH₃	4-OC₆H₄-3-CF₃	CH₂CH═CCl₂
323	CH₃	4-OC₆H₄-3-CF₃	CH₂C(CH₃)═CH₂
324	CH₃	4-OC₆H₄-3-CF₃	CH₂C≡CH
325	CH₃	4-OC₆H₄-3-CF₃	CH₂Si(CH₃)₃
326	CH₃	4-OC₆H₄-3-CF₃	CH₂-c.propyl-2,2-Cl₂
327	CH₃	4-OC₆H₄-3-CF₃	CH₂CN
328	CH₃	4-OC₆H₄-3-CF₃	CH₂COOC₂H₅
329	CH₃	4-OC₆H₄-3-CF₃	CH(CH₃)COOC₂H₅
330	CH₃	4-OC₆H₄-3-CF₃	CH₂C₆H₄-3-CF₃
331	CH₃	4-OC₆H₄-3-CF₃	CH₂C₆H₄-4-F
332	CH₃	4-OC₆H₄-3-CF₃	CH₂C₆H₄-3-F
333	CH₃	4-OC₆H₄-3-CF₃	CH₂C₆H₄-2-F
334	CH₃	4-OC₆H₄-3-CF₃	C(═O)OC₂H₅
335	CH₃	4-OC₆H₄-3-CF₃	C(═O)NHCH₃
336	CH₃	4-OC₆H₄-3-CF₃	C(═O)C(═O)OC₂H₅
337	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₃
338	C₂H₅	4-OCH₂C₆H₄-3-CF₃	C₂H₅
339	C₂H₅	4-OCH₂C₆H₄-3-CF₃	n-C₃H₇
340	C₂H₅	4-OCH₂C₆H₄-3-CF₃	i-C₃H₇
341	C₂H₅	4-OCH₂C₆H₄-3-CF₃	n-C₄H₉
342	C₂H₅	4-OCH₂C₆H₄-3-CF₃	n-C₆H₁₃
343	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂F
344	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CHF₂
345	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂CF₃
346	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂CH═CH₂
347	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂CH═CHCH₃
348	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂CH═C(CH₃)₂
349	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂CH═CHCl
350	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂CH═CCl₂
351	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂C(CH₃)═CH₂
352	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂C≡CH
353	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂Si(CH₃)₃
354	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂-c.propyl-2,2-Cl₂
355	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂CN
356	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂COOC₂H₅
357	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH(CH₃)COOC₂H₅
358	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂C₆H₄-3-CF₃
359	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂C₆H₄-4-F
360	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂C₆H₄-3-F
361	C₂H₅	4-OCH₂C₆H₄-3-CF₃	CH₂C₆H₄-2-F
362	C₂H₅	4-OC₆H₄-3-CF₃	C(═O)OC₂H₅
363	C₂H₅	4-OCH₂C₆H₄-3-CF₃	C(═O)NHCH₃
364	C₂H₅	4-OCH₂C₆H₄-3-CF₃	C(═O)C(═O)OC₂H₅
365	CH₃	4-OC₆H₄-4-Cl	CH₃
366	CH₃	4-OC₆H₄-4-Cl	C₂H₅
367	CH₃	4-OC₆H₄-4-Cl	n-C₃H₇
368	CH₃	4-OC₆H₄-4-Cl	i-C₃H₇
369	CH₃	4-OC₆H₄-4-Cl	n-C₄H₉
370	CH₃	4-OC₆H₄-4-Cl	n-C₆H₁₃
371	CH₃	4-OC₆H₄-4-Cl	CH₂F
372	CH₃	4-OC₆H₄-4-Cl	CHF₂
373	CH₃	4-OC₆H₄-4-Cl	CH₂CF₃
374	CH₃	4-OC₆H₄-4-Cl	CH₂CH═CH₂
375	CH₃	4-OC₆H₄-4-Cl	CH₂CH═CHCH₃
376	CH₃	4-OC₆H₄-4-Cl	CH₂CH═C(CH₃)₂
377	CH₃	4-OC₆H₄-4-Cl	CH₂CH═CHCl
378	CH₃	4-OC₆H₄-4-Cl	CH₂CH═CCl₂
379	CH₃	4-OC₆H₄-4-Cl	CH₂C(CH₃)═CH₂
380	CH₃	4-OC₆H₄-4-Cl	CH₂C≡CH
381	CH₃	4-OC₆H₄-4-Cl	CH₂Si(CH₃)₃
382	CH₃	4-OC₆H₄-4-Cl	CH₂-c.propyl-2,2-Cl₂
383	CH₃	4-OC₆H₄-4-Cl	CH₂CN
384	CH₃	4-OC₆H₄-4-Cl	CH₂COOC₂H₅
385	CH₃	4-OC₆H₄-4-Cl	CH(CH₃)COOC₂H₅
386	CH₃	4-OC₆H₄-4-Cl	CH₂C₆H₄-3-CF₃
387	CH₃	4-OC₆H₄-4-Cl	CH₂C₆H₄-4-F
388	CH₃	4-OC₆H₄-4-Cl	CH₂C₆H₄-3-F
389	CH₃	4-OC₆H₄-4-Cl	CH₂C₆H₄-2-F
390	CH₃	4-OC₆H₄-4-Cl	C(═O)OC₂H₅
391	CH₃	4-OC₆H₄-4-Cl	C(═O)NHCH₃
392	CH₃	4-OC₆H₄-4-Cl	C(═O)C(═O)OC₂H₅
393	CH₃	4-OC₆H₄-3-Cl	CH₃
394	CH₃	4-OC₆H₄-3-Cl	C₂H₅
395	CH₃	4-OC₆H₄-3-Cl	n-C₃H₇
396	CH₃	4-OC₆H₄-3-Cl	i-C₃H₇
397	CH₃	4-OC₆H₄-3-Cl	n-C₄H₉
398	CH₃	4-OC₆H₄-3-Cl	n-C₆H₁₃
399	CH₃	4-OC₆H₄-3-Cl	CH₂F
400	CH₃	4-OC₆H₄-3-Cl	CHF₂
401	CH₃	4-OC₆H₄-3-Cl	CH₂CF₃
402	CH₃	4-OC₆H₄-3-Cl	CH₂CH═CH₂
403	CH₃	4-OC₆H₄-3-Cl	CH₂CH═CHCH₃
404	CH₃	4-OC₆H₄-3-Cl	CH₂CH═C(CH₃)₂
405	CH₃	4-OC₆H₄-3-Cl	CH₂CH═CHCl
406	CH₃	4-OC₆H₄-3-Cl	CH₂CH═CCl₂
407	CH₃	4-OC₆H₄-3-Cl	CH₂C(CH₃)═CH₂
408	CH₃	4-OC₆H₄-3-Cl	CH₂C≡CH
409	CH₃	4-OC₆H₄-3-Cl	CH₂Si(CH₃)₃
410	CH₃	4-OC₆H₄-3-Cl	CH₂-c.propyl-2,2-Cl₂
411	CH₃	4-OC₆H₄-3-Cl	CH₂CN
412	CH₃	4-OC₆H₄-3-Cl	CH₂COOC₂H₅
413	CH₃	4-OC₆H₄-3-Cl	CH(CH₃)COOC₂H₅
414	CH₃	4-OC₆H₄-3-Cl	CH₂C₆H₄-3-CF₃
415	CH₃	4-OC₆H₄-3-Cl	CH₂C₆H₄-4-F
416	CH₃	4-OC₆H₄-3-Cl	CH₂C₆H₄-3-F
417	CH₃	4-OC₆H₄-3-Cl	CH₂C₆H₄-2-F
418	CH₃	4-OC₆H₄-3-Cl	C(═O)OC₂H₅
419	CH₃	4-OC₆H₄-3-Cl	C(═O)NHCH₃
420	CH₃	4-OC₆H₄-3-Cl	C(═O)C(═O)OC₂H₅
421	CH₃	4-OC₆H₄-2-Cl	CH₃
242	CH₃	4-OC₆H₄-2-Cl	C₂H₅
423	CH₃	4-OC₆H₄-2-Cl	n-C₃H₇
424	CH₃	4-OC₆H₄-2-Cl	i-C₃H₇
425	CH₃	4-OC₆H₄-2-Cl	n-C₄H₉
426	CH₃	4-OC₆H₄-2-Cl	n-C₆H₁₃
427	CH₃	4-OC₆H₄-2-Cl	CH₂F
428	CH₃	4-OC₆H₄-2-Cl	CHF₂
429	CH₃	4-OC₆H₄-2-Cl	CH₂CF₃
430	CH₃	4-OC₆H₄-2-Cl	CH₂CH═CH₂
431	CH₃	4-OC₆H₄-2-Cl	CH₂CH═CHCH₃
432	CH₃	4-OC₆H₄-2-Cl	CH₂CH═C(CH₃)₂
433	CH₃	4-OC₆H₄-2-Cl	CH₂CH═CHCl
434	CH₃	4-OC₆H₄-2-Cl	CH₂CH═CCl₂
435	CH₃	4-OC₆H₄-2-Cl	CH₂C(CH₃)═CH₂
436	CH₃	4-OC₆H₄-2-Cl	CH₂C≡CH
437	CH₃	4-OC₆H₄-2-Cl	CH₂Si(CH₃)₃
438	CH₃	4-OC₆H₄-2-Cl	CH₂-c.propyl-2,2-Cl₂
439	CH₃	4-OC₆H₄-2-Cl	CH₂CN
440	CH₃	4-OC₆H₄-2-Cl	CH₂COOC₂H₅
441	CH₃	4-OC₆H₄-2-Cl	CH(CH₃)COOC₂H₅
442	CH₃	4-OC₆H₄-2-Cl	CH₂C₆H₄-3-CF₃
443	CH₃	4-OC₆H₄-2-Cl	CH₂C₆H₄-4-F
444	CH₃	4-OC₆H₄-2-Cl	CH₂C₆H₄-3-F
445	CH₃	4-OC₆H₄-2-Cl	CH₂C₆H₄-2-F
446	CH₃	4-OC₆H₄-2-Cl	C(═O)OC₂H₅
447	CH₃	4-OC₆H₄-2-Cl	C(═O)NHCH₃
448	CH₃	4-OC₆H₄-2-Cl	C(═O)C(═O)OC₂H₅
449	CH₃	4-OC₆H₄-4-F	CH₃
450	CH₃	4-OC₆H₄-4-F	C₂H₅
451	CH₃	4-OC₆H₄-4-F	n-C₃H₇
452	CH₃	4-OC₆H₄-4-F	i-C₃H₇
453	CH₃	4-OC₆H₄-4-F	n-C₄H₉
454	CH₃	4-OC₆H₄-4-F	n-C₆H₁₃
455	CH₃	4-OC₆H₄-4-F	CH₂F
456	CH₃	4-OC₆H₄-4-F	CHF₂
457	CH₃	4-OC₆H₄-4-F	CH₂CF₃
458	CH₃	4-OC₆H₄-4-F	CH₂CH═CH₂
459	CH₃	4-OC₆H₄-4-F	CH₂CH═CHCH₃
460	CH₃	4-OC₆H₄-4-F	CH₂CH═C(CH₃)₂
461	CH₃	4-OC₆H₄-4-F	CH₂CH═CHCl
462	CH₃	4-OC₆H₄-4-F	CH₂CH═CCl₂
463	CH₃	4-OC₆H₄-4-F	CH₂C(CH₃)═CH₂
464	CH₃	4-OC₆H₄-4-F	CH₂C≡CH
465	CH₃	4-OC₆H₄-4-F	CH₂Si(CH₃)₃
466	CH₃	4-OC₆H₄-4-F	CH₂-c.propyl-2,2-Cl₂
467	CH₃	4-OC₆H₄-4-F	CH₂CN
468	CH₃	4-OC₆H₄-4-F	CH₂COOC₂H₅
469	CH₃	4-OC₆H₄-4-F	CH(CH₃)COOC₂H₅
470	CH₃	4-OC₆H₄-4-F	CH₂C₆H₄-3-CF₃
471	CH₃	4-OC₆H₄-4-F	CH₂C₆H₄-4-F
472	CH₃	4-OC₆H₄-4-F	CH₂C₆H₄-3-F
473	CH₃	4-OC₆H₄-4-F	CH₂C₆H₄-2-F
474	CH₃	4-OC₆H₄-4-F	C(═O)OC₂H₅
475	CH₃	4-OC₆H₄-4-F	C(═O)NHCH₃
476	CH₃	4-OC₆H₄-4-F	C(═O)C(═O)OC₂H₅
477	CH₃	4-OC₆H₄-3-F	CH₃
478	CH₃	4-OC₆H₄-3-F	C₂H₅
479	CH₃	4-OC₆H₄-3-F	n-C₃H₇
480	CH₃	4-OC₆H₄-3-F	i-C₃H₇
481	CH₃	4-OC₆H₄-3-F	n-C₄H₉
482	CH₃	4-OC₆H₄-3-F	n-C₆H₁₃
483	CH₃	4-OC₆H₄-3-F	CH₂F
484	CH₃	4-OC₆H₄-3-F	CHF₂
485	CH₃	4-OC₆H₄-3-F	CH₂CF₃
486	CH₃	4-OC₆H₄-3-F	CH₂CH═CH₂
487	CH₃	4-OC₆H₄-3-F	CH₂CH═CHCH₃
488	CH₃	4-OC₆H₄-3-F	CH₂CH═C(CH₃)₂
489	CH₃	4-OC₆H₄-3-F	CH₂CH═CHCl
490	CH₃	4-OC₆H₄-3-F	CH₂CH═CCl₂
491	CH₃	4-OC₆H₄-3-F	CH₂C(CH₃)═CH₂
492	CH₃	4-OC₆H₄-3-F	CH₂C≡CH
493	CH₃	4-OC₆H₄-3-F	CH₂Si(CH₃)₃
494	CH₃	4-OC₆H₄-3-F	CH₂-c.propyl-2,2-Cl₂
495	CH₃	4-OC₆H₄-3-F	CH₂CN
496	CH₃	4-OC₆H₄-3-F	CH₂COOC₂H₅
497	CH₃	4-OC₆H₄-3-F	CH(CH₃)COOC₂H₅
498	CH₃	4-OC₆H₄-3-F	CH₂C₆H₄-3-CF₃
499	CH₃	4-OC₆H₄-3-F	CH₂C₆H₄-4-F
500	CH₃	4-OC₆H₄-3-F	CH₂C₆H₄-3-F
501	CH₃	4-OC₆H₄-3-F	CH₂C₆H₄-2-F
502	CH₃	4-OC₆H₄-3-F	C(═O)OC₂H₅
503	CH₃	4-OC₆H₄-3-F	C(═O)NHCH₃
504	CH₃	4-OC₆H₄-3-F	C(═O)C(═O)OC₂H₅
505	CH₃	4-OC₆H₄-2-F	CH₃
506	CH₃	4-OC₆H₄-2-F	C₂H₅
507	CH₃	4-OC₆H₄-2-F	n-C₃H₇
508	CH₃	4-OC₆H₄-2-F	i-C₃H₇
509	CH₃	4-OC₆H₄-2-F	n-C₄H₉
510	CH₃	4-OC₆H₄-2-F	n-C₆H₁₃
511	CH₃	4-OC₆H₄-2-F	CH₂F
512	CH₃	4-OC₆H₄-2-F	CHF₂
513	CH₃	4-OC₆H₄-2-F	CH₂CF₃
514	CH₃	4-OC₆H₄-2-F	CH₂CH═CH₂
515	CH₃	4-OC₆H₄-2-F	CH₂CH═CHCH₃
516	CH₃	4-OC₆H₄-2-F	CH₂CH═C(CH₃)₂
517	CH₃	4-OC₆H₄-2-F	CH₂CH═CHCl
518	CH₃	4-OC₆H₄-2-F	CH₂CH═CCl₂
519	CH₃	4-OC₆H₄-2-F	CH₂C(CH₃)═CH₂
520	CH₃	4-OC₆H₄-2-F	CH₂C≡CH
521	CH₃	4-OC₆H₄-2-F	CH₂Si(CH₃)₃
522	CH₃	4-OC₆H₄-2-F	CH₂-c.propyl-2,2-Cl₂
523	CH₃	4-OC₆H₄-2-F	CH₂CN
524	CH₃	4-OC₆H₄-2-F	CH₂COOC₂H₅
525	CH₃	4-OC₆H₄-2-F	CH(CH₃)COOC₂H₅
526	CH₃	4-OC₆H₄-2-F	CH₂C₆H₄-3-CF₃
527	CH₃	4-OC₆H₄-2-F	CH₂C₆H₄-4-F
528	CH₃	4-OC₆H₄-2-F	CH₂C₆H₄-3-F
529	CH₃	4-OC₆H₄-2-F	CH₂C₆H₄-2-F
530	CH₃	4-OC₆H₄-2-F	C(═O)OC₂H₅
531	CH₃	4-OC₆H₄-2-F	C(═O)NHCH₃
532	CH₃	4-OC₆H₄-2-F	C(═O)C(═O)OC₂H₅
533	CH₃	4-OC₆H₄-4-Br	CH₃
534	CH₃	4-OC₆H₄-4-Br	C₂H₅
535	CH₃	4-OC₆H₄-4-Br	n-C₃H₇
536	CH₃	4-OC₆H₄-4-Br	i-C₃H₇
537	CH₃	4-OC₆H₄-4-Br	n-C₄H₉
538	CH₃	4-OC₆H₄-4-Br	n-C₆H₁₃
539	CH₃	4-OC₆H₄-4-Br	CH₂F
540	CH₃	4-OC₆H₄-4-Br	CHF₂
541	CH₃	4-OC₆H₄-4-Br	CH₂CF₃
542	CH₃	4-OC₆H₄-4-Br	CH₂CH═CH₂
543	CH₃	4-OC₆H₄-4-Br	CH₂CH═CHCH₃
544	CH₃	4-OC₆H₄-4-Br	CH₂CH═C(CH₃)₂
545	CH₃	4-OC₆H₄-4-Br	CH₂CH═CHCl
546	CH₃	4-OC₆H₄-4-Br	CH₂CH═CCl₂
547	CH₃	4-OC₆H₄-4-Br	CH₂C(CH₃)═CH₂
548	CH₃	4-OC₆H₄-4-Br	CH₂C≡CH
549	CH₃	4-OC₆H₄-4-Br	CH₂Si(CH₃)₃
550	CH₃	4-OC₆H₄-4-Br	CH₂-c.propyl-2,2-Cl₂
551	CH₃	4-OC₆H₄-4-Br	CH₂CN
552	CH₃	4-OC₆H₄-4-Br	CH₂COOC₂H₅
553	CH₃	4-OC₆H₄-4-Br	CH(CH₃)COOC₂H₅
554	CH₃	4-OC₆H₄-4-Br	CH₂C₆H₄-3-CF₃
555	CH₃	4-OC₆H₄-4-Br	CH₂C₆H₄-4-F
556	CH₃	4-OC₆H₄-4-Br	CH₂C₆H₄-3-F
557	CH₃	4-OC₆H₄-4-Br	CH₂C₆H₄-2-F
558	CH₃	4-OC₆H₄-4-Br	C(═O)OC₂H₅
559	CH₃	4-OC₆H₄-4-Br	C(═O)NHCH₃
560	CH₃	4-OC₆H₄-4-Br	C(═O)C(═O)OC₂H₅
561	CH₃	4-OC₆H₄-3-Br	CH₃
562	CH₃	4-OC₆H₄-3-Br	C₂H₅
563	CH₃	4-OC₆H₄-3-Br	n-C₃H₇
564	CH₃	4-OC₆H₄-3-Br	i-C₃H₇
565	CH₃	4-OC₆H₄-3-Br	n-C₄H₉
566	CH₃	4-OC₆H₄-3-Br	n-C₆H₁₃
567	CH₃	4-OC₆H₄-3-Br	CH₂F
568	CH₃	4-OC₆H₄-3-Br	CHF₂
569	CH₃	4-OC₆H₄-3-Br	CH₂CF₃
570	CH₃	4-OC₆H₄-3-Br	CH₂CH═CH₂
571	CH₃	4-OC₆H₄-3-Br	CH₂CH═CHCH₃
572	CH₃	4-OC₆H₄-3-Br	CH₂CH═C(CH₃)₂
573	CH₃	4-OC₆H₄-3-Br	CH₂CH═CHCl
574	CH₃	4-OC₆H₄-3-Br	CH₂CH═CCl₂
575	CH₃	4-OC₆H₄-3-Br	CH₂C(CH₃)═CH₂
576	CH₃	4-OC₆H₄-3-Br	CH₂C≡CH
577	CH₃	4-OC₆H₄-3-Br	CH₂Si(CH₃)₃
578	CH₃	4-OC₆H₄-3-Br	CH₂-c.propyl-2,2-Cl₂
579	CH₃	4-OC₆H₄-3-Br	CH₂CN
580	CH₃	4-OC₆H₄-3-Br	CH₂COOC₂H₅
581	CH₃	4-OC₆H₄-3-Br	CH(CH₃)COOC₂H₅
582	CH₃	4-OC₆H₄-3-Br	CH₂C₆H₄-3-CF₃
583	CH₃	4-OC₆H₄-3-Br	CH₂C₆H₄-4-F
584	CH₃	4-OC₆H₄-3-Br	CH₂C₆H₄-3-F
585	CH₃	4-OC₆H₄-3-Br	CH₂C₆H₄-2-F
586	CH₃	4-OC₆H₄-3-Br	C(═O)OC₂H₅
587	CH₃	4-OC₆H₄-3-Br	C(═O)NHCH₃
588	CH₃	4-OC₆H₄-3-Br	C(═O)C(═O)OC₂H₅
589	CH₃	4-OC₆H₄-2-Br	CH₃
590	CH₃	4-OC₆H₄-2-Br	C₂H₅
591	CH₃	4-OC₆H₄-2-Br	n-C₃H₇
592	CH₃	4-OC₆H₄-2-Br	i-C₃H₇
593	CH₃	4-OC₆H₄-2-Br	n-C₄H₉
594	CH₃	4-OC₆H₄-2-Br	n-C₆H₁₃
595	CH₃	4-OC₆H₄-2-Br	CH₂F
596	CH₃	4-OC₆H₄-2-Br	CHF₂
597	CH₃	4-OC₆H₄-2-Br	CH₂CF₃
598	CH₃	4-OC₆H₄-2-Br	CH₂CH═CH₂
599	CH₃	4-OC₆H₄-2-Br	CH₂CH═CHCH₃
600	CH₃	4-OC₆H₄-2-Br	CH₂CH═C(CH₃)₂
601	CH₃	4-OC₆H₄-2-Br	CH₂CH═CHCl
602	CH₃	4-OC₆H₄-2-Br	CH₂CH═CCl₂
603	CH₃	4-OC₆H₄-2-Br	CH₂C(CH₃)═CH₂
604	CH₃	4-OC₆H₄-2-Br	CH₂C≡CH
605	CH₃	4-OC₆H₄-2-Br	CH₂Si(CH₃)₃
606	CH₃	4-OC₆H₄-2-Br	CH₂-c.propyl-2,2-Cl₂
607	CH₃	4-OC₆H₄-2-Br	CH₂CN
608	CH₃	4-OC₆H₄-2-Br	CH₂COOC₂H₅
609	CH₃	4-OC₆H₄-2-Br	CH(CH₃)COOC₂H₅
610	CH₃	4-OC₆H₄-2-Br	CH₂C₆H₄-3-CF₃
611	CH₃	4-OC₆H₄-2-Br	CH₂C₆H₄-4-F
612	CH₃	4-OC₆H₄-2-Br	CH₂C₆H₄-3-F
613	CH₃	4-OC₆H₄-2-Br	CH₂C₆H₄-2-F
614	CH₃	4-OC₆H₄-2-Br	C(═O)OC₂H₅
615	CH₃	4-OC₆H₄-2-Br	C(═O)NHCH₃
616	CH₃	4-OC₆H₄-2-Br	C(═O)C(═O)OC₂H₅
617	CH₃	4-OC₆H₃-2,4-Cl₂	CH₃
618	CH₃	4-OC₆H₃-2,4-Cl₂	C₂H₅
619	CH₃	4-OC₆H₃-2,4-Cl₂	n-C₃H₇
620	CH₃	4-OC₆H₃-2,4-Cl₂	i-C₃H₇
621	CH₃	4-OC₆H₃-2,4-Cl₂	n-C₄H₉
622	CH₃	4-OC₆H₃-2,4-Cl₂	n-C₆H₁₃
623	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂F
624	CH₃	4-OC₆H₃-2,4-Cl₂	CHF₂
625	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂CF₃
626	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂CH═CH₂
627	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂CH═CHCH₃
628	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂CH═C(CH₃)₂
629	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂CH═CHCl
630	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂CH═CCl₂
631	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂C(CH₃)═CH₂
632	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂C≡CH
633	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂Si(CH₃)₃
634	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂-c.propyl-2,2-Cl₂
635	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂CN
636	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂COOC₂H₅
637	CH₃	4-OC₆H₃-2,4-Cl₂	CH(CH₃)COOC₂H₅
638	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂C₆H₄-3-CF₃
639	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂C₆H₄-4-F
640	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂C₆H₄-3-F
641	CH₃	4-OC₆H₃-2,4-Cl₂	CH₂C₆H₄-2-F
642	CH₃	4-OC₆H₃-2,4-Cl₂	C(═O)OC₂H₅
643	CH₃	4-OC₆H₃-2,4-Cl₂	C(═O)NHCH₃
644	CH₃	4-OC₆H₃-2,4-Cl₂	C(═O)C(═O)OC₂H₅
645	CH₃	4-OC₆H₃-3,4-Cl₂	CH₃
646	CH₃	4-OC₆H₃-3,4-Cl₂	C₂H₅
647	CH₃	4-OC₆H₃-3,4-Cl₂	n-C₃H₇
648	CH₃	4-OC₆H₃-3,4-Cl₂	i-C₃H₇
649	CH₃	4-OC₆H₃-3,4-Cl₂	n-C₄H₉
650	CH₃	4-OC₆H₃-3,4-Cl₂	n-C₆H₁₃
651	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂F
652	CH₃	4-OC₆H₃-3,4-Cl₂	CHF₂
653	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂CF₃
654	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂CH═CH₂
655	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂CH═CHCH₃
656	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂CH═C(CH₃)₂
657	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂CH═CHCl
658	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂CH═CCl₂
659	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂C(CH₃)═CH₂
660	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂C≡CH
661	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂Si(CH₃)₃
662	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂-c.propyl-2,2-Cl₂
663	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂CN
664	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂COOC₂H₅
665	CH₃	4-OC₆H₃-3,4-Cl₂	CH(CH₃)COOC₂H₅
666	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂C₆H₄-3-CF₃
667	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂C₆H₄-4-F
668	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂C₆H₄-3-F
669	CH₃	4-OC₆H₃-3,4-Cl₂	CH₂C₆H₄-2-F
670	CH₃	4-OC₆H₃-3,4-Cl₂	C(═O)OC₂H₅
671	CH₃	4-OC₆H₃-3,4-Cl₂	C(═O)NHCH₃
672	CH₃	4-OC₆H₃-3,4-Cl₂	C(═O)C(═O)OC₂H₅
673	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₃
674	CH₃	4-OC₆H₃-2-Cl,4-Br	C₂H₅
675	CH₃	4-OC₆H₃-2-Cl,4-Br	n-C₃H₇
676	CH₃	4-OC₆H₃-2-Cl,4-Br	i-C₃H₇
677	CH₃	4-OC₆H₃-2-Cl,4-Br	n-C₄H₉
678	CH₃	4-OC₆H₃-2-Cl,4-Br	n-C₆H₁₃
679	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂F
680	CH₃	4-OC₆H₃-2-Cl,4-Br	CHF₂
681	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂CF₃
682	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂CH═CH₂
683	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂CH═CHCH₃
684	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂CH═C(CH₃)₂
685	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂CH═CHCl
686	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂CH═CCl₂
687	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂C(CH₃)═CH₂
688	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂C≡CH
689	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂Si(CH₃)₃
690	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂-c.propyl-2,2-Cl₂
691	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂CN
692	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂COOC₂H₅
693	CH₃	4-OC₆H₃-2-Cl,4-Br	CH(CH₃)COOC₂H₅
694	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂C₆H₄-3-CF₃
695	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂C₆H₄-4-F
696	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂C₆H₄-3-F
697	CH₃	4-OC₆H₃-2-Cl,4-Br	CH₂C₆H₄-2-F
698	CH₃	4-OC₆H₃-2-Cl,4-Br	C(═O)OC₂H₅
699	CH₃	4-OC₆H₃-2-Cl,4-Br	C(═O)NHCH₃
700	CH₃	4-OC₆H₃-2-Cl,4-Br	C(═O)C(═O)OC₂H₅
701	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₃
702	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	C₂H₅
703	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	n-C₃H₇
704	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	i-C₃H₇
705	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	n-C₄H₉
706	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	n-C₆H₁₃
707	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂F
708	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CHF₂
709	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂CF₃
710	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂CH═CH₂
711	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂CH═CHCH₃
712	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂CH═C(CH₃)₂
713	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂CH═CHCl
714	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂CH═CCl₂
715	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂C(CH₃)═CH₂
716	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂C≡CH
717	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂Si(CH₃)₃
718	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂-c.propyl-2,2-Cl₂
719	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂CN
720	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂COOC₂H₅
721	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH(CH₃)COOC₂H₅
722	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂C₆H₄-3-CF₃
723	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂C₆H₄-4-F
724	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂C₆H₄-3-F
725	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	CH₂C₆H₄-2-F
726	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	C(═O)OC₂H₅
727	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	C(═O)NHCH₃
728	CH₃	4-OC₆H₃-3,4-(—OCH₂O—)	C(═O)C(═O)OC₂H₅
729	CH₃	4-OC₆H₄-4-SCH₃	CH₃
730	CH₃	4-OC₆H₄-4-SCH₃	C₂H₅
731	CH₃	4-OC₆H₄-4-SCH₃	n-C₃H₇
732	CH₃	4-OC₆H₄-4-SCH₃	i-C₃H₇
733	CH₃	4-OC₆H₄-4-SCH₃	n-C₄H₉
734	CH₃	4-OC₆H₄-4-SCH₃	n-C₆H₁₃
735	CH₃	4-OC₆H₄-4-SCH₃	CH₂F
736	CH₃	4-OC₆H₄-4-SCH₃	CHF₂
737	CH₃	4-OC₆H₄-4-SCH₃	CH₂CF₃
738	CH₃	4-OC₆H₄-4-SCH₃	CH₂CH═CH₂
739	CH₃	4-OC₆H₄-4-SCH₃	CH₂CH═CHCH₃
740	CH₃	4-OC₆H₄-4-SCH₃	CH₂CH═C(CH₃)₂
741	CH₃	4-OC₆H₄-4-SCH₃	CH₂CH═CHCl
742	CH₃	4-OC₆H₄-4-SCH₃	CH₂CH═CCl₂
743	CH₃	4-OC₆H₄-4-SCH₃	CH₂C(CH₃)═CH₂
744	CH₃	4-OC₆H₄-4-SCH₃	CH₂C≡CH
745	CH₃	4-OC₆H₄-4-SCH₃	CH₂Si(CH₃)₃
746	CH₃	4-OC₆H₄-4-SCH₃	CH₂-c.propyl-2,2-Cl₂
747	CH₃	4-OC₆H₄-4-SCH₃	CH₂CN
748	CH₃	4-OC₆H₄-4-SCH₃	CH₂COOC₂H₅
749	CH₃	4-OC₆H₄-4-SCH₃	CH(CH₃)COOC₂H₅
750	CH₃	4-OC₆H₄-4-SCH₃	CH₂C₆H₄-3-CF₃
751	CH₃	4-OC₆H₄-4-SCH₃	CH₂C₆H₄-4-F
752	CH₃	4-OC₆H₄-4-SCH₃	CH₂C₆H₄-3-F
753	CH₃	4-OC₆H₄-4-SCH₃	CH₂C₆H₄-2-F
754	CH₃	4-OC₆H₄-4-SCH₃	C(═O)OC₂H₅
755	CH₃	4-OC₆H₄-4-SCH₃	C(═O)NHCH₃
756	CH₃	4-OC₆H₄-4-SCH₃	C(═O)C(═O)OC₂H₅
757	CH₃	4-OC₆H₄-4-OCH₃	CH₃
758	CH₃	4-OC₆H₄-4-OCH₃	C₂H₅
759	CH₃	4-OC₆H₄-4-OCH₃	n-C₃H₇
760	CH₃	4-OC₆H₄-4-OCH₃	i-C₃H₇
761	CH₃	4-OC₆H₄-4-OCH₃	n-C₄H₉
762	CH₃	4-OC₆H₄-4-OCH₃	n-C₆H₁₃
763	CH₃	4-OC₆H₄-4-OCH₃	CH₂F
764	CH₃	4-OC₆H₄-4-OCH₃	CHF₂
765	CH₃	4-OC₆H₄-4-OCH₃	CH₂CF₃
766	CH₃	4-OC₆H₄-4-OCH₃	CH₂CH═CH₂
767	CH₃	4-OC₆H₄-4-OCH₃	CH₂CH═CHCH₃
768	CH₃	4-OC₆H₄-4-OCH₃	CH₂CH═C(CH₃)₂
769	CH₃	4-OC₆H₄-4-OCH₃	CH₂CH═CHCl
770	CH₃	4-OC₆H₄-4-OCH₃	CH₂CH═CCl₂
771	CH₃	4-OC₆H₄-4-OCH₃	CH₂C(CH₃)═CH₂
772	CH₃	4-OC₆H₄-4-OCH₃	CH₂C≡CH
773	CH₃	4-OC₆H₄-4-OCH₃	CH₂Si(CH₃)₃
774	CH₃	4-OC₆H₄-4-OCH₃	CH₂-c.propyl-2,2-Cl₂
775	CH₃	4-OC₆H₄-4-OCH₃	CH₂CN
776	CH₃	4-OC₆H₄-4-OCH₃	CH₂COOC₂H₅
777	CH₃	4-OC₆H₄-4-OCH₃	CH(CH₃)COOC₂H₅
778	CH₃	4-OC₆H₄-4-OCH₃	CH₂C₆H₄-3-CF₃
779	CH₃	4-OC₆H₄-4-OCH₃	CH₂C₆H₄-4-F
780	CH₃	4-OC₆H₄-4-OCH₃	CH₂C₆H₄-3-F
781	CH₃	4-OC₆H₄-4-OCH₃	CH₂C₆H₄-2-F
782	CH₃	4-OC₆H₄-4-OCH₃	C(═O)OC₂H₅
783	CH₃	4-OC₆H₄-4-OCH₃	C(═O)NHCH₃
784	CH₃	4-OC₆H₄-4-OCH₃	C(═O)C(═O)OC₂H₅
785	CH₃	4-OC₆H₄-4-t-butyl	CH₃
786	CH₃	4-OC₆H₄-4-t-butyl	C₂H₅
787	CH₃	4-OC₆H₄-4-t-butyl	n-C₃H₇
788	CH₃	4-OC₆H₄-4-t-butyl	i-C₃H₇
789	CH₃	4-OC₆H₄-4-t-butyl	n-C₄H₉
790	CH₃	4-OC₆H₄-4-t-butyl	n-C₆H₁₃
791	CH₃	4-OC₆H₄-4-t-butyl	CH₂F
792	CH₃	4-OC₆H₄-4-t-butyl	CHF₂
793	CH₃	4-OC₆H₄-4-t-butyl	CH₂CF₃
794	CH₃	4-OC₆H₄-4-t-butyl	CH₂CH═CH₂
795	CH₃	4-OC₆H₄-4-t-butyl	CH₂CH═CHCH₃
796	CH₃	4-OC₆H₄-4-t-butyl	CH₂CH═C(CH₃)₂
797	CH₃	4-OC₆H₄-4-t-butyl	CH₂CH═CHCl
798	CH₃	4-OC₆H₄-4-t-butyl	CH₂CH═CCl₂
799	CH₃	4-OC₆H₄-4-t-butyl	CH₂C(CH₃)═CH₂
800	CH₃	4-OC₆H₄-4-t-butyl	CH₂C≡CH
801	CH₃	4-OC₆H₄-4-t-butyl	CH₂Si(CH₃)₃
802	CH₃	4-OC₆H₄-4-t-butyl	CH₂-c.propyl-2,2-Cl₂
803	CH₃	4-OC₆H₄-4-t-butyl	CH₂CN
804	CH₃	4-OC₆H₄-4-t-butyl	CH₂COOC₂H₅
805	CH₃	4-OC₆H₄-4-t-butyl	CH(CH₃)COOC₂H₅
806	CH₃	4-OC₆H₄-4-t-butyl	CH₂C₆H₄-3-CF₃
807	CH₃	4-OC₆H₄-4-t-butyl	CH₂C₆H₄-4-F
808	CH₃	4-OC₆H₄-4-t-butyl	CH₂C₆H₄-3-F
809	CH₃	4-OC₆H₄-4-t-butyl	CH₂C₆H₄-2-F
810	CH₃	4-OC₆H₄-4-t-butyl	C(═O)OC₂H₅
811	CH₃	4-OC₆H₄-4-t-butyl	O(═O)NHCH₃
812	CH₃	4-OC₆H₄-4-t-butyl	C(═O)C(═O)OC₂H₅
813	CH₃	4-OC₆H₄-4-CF₃	CH₃
814	CH₃	4-OC₆H₄-4-CF₃	C₂H₅
815	CH₃	4-OC₆H₄-4-CF₃	n-C₃H₇
816	CH₃	4-OC₆H₄-4-CF₃	i-C₃H₇
817	CH₃	4-OC₆H₄-4-CF₃	n-C₄H₉
818	CH₃	4-OC₆H₄-4-CF₃	n-C₆H₁₃
819	CH₃	4-OC₆H₄-4-CF₃	CH₂F
820	CH₃	4-OC₆H₄-4-CF₃	CHF₂
821	CH₃	4-OC₆H₄-4-CF₃	CH₂CF₃
822	CH₃	4-OC₆H₄-4-CF₃	CH₂CH═CH₂
823	CH₃	4-OC₆H₄-4-CF₃	CH₂CH═CHCH₃
824	CH₃	4-OC₆H₄-4-CF₃	CH₂CH═C(CH₃)₂
825	CH₃	4-OC₆H₄-4-CF₃	CH₂CH═CHCl
826	CH₃	4-OC₆H₄-4-CF₃	CH₂CH═CCl₂
827	CH₃	4-OC₆H₄-4-CF₃	CH₂C(CH₃)═CH₂
828	CH₃	4-OC₆H₄-4-CF₃	CH₂C≡CH
829	CH₃	4-OC₆H₄-4-CF₃	CH₂Si(CH₃)₃
830	CH₃	4-OC₆H₄-4-CF₃	CH₂-c.propyl-2,2-Cl₂
831	CH₃	4-OC₆H₄-4-CF₃	CH₂CN
832	CH₃	4-OC₆H₄-4-CF₃	CH₂COOC₂H₅
833	CH₃	4-OC₆H₄-4-CF₃	CH(CH₃)COOC₂H₅
834	CH₃	4-OC₆H₄-4-CF₃	CH₂C₆H₄-3-CF₃
835	CH₃	4-OC₆H₄-4-CF₃	CH₂C₆H₄-4-F
836	CH₃	4-OC₆H₄-4-CF₃	CH₂C₆H₄-3-F
837	CH₃	4-OC₆H₄-4-CF₃	CH₂C₆H₄-2-F
838	CH₃	4-OC₆H₄-4-CF₃	C(═O)OC₂H₅
839	CH₃	4-OC₆H₄-4-CF₃	C(═O)NHCH₃
840	CH₃	4-OC₆H₄-4-CF₃	C(═O)C(═O)OC₂H₅
841	CH₃	4-OC₆H₄-2-CF₃	CH₃
842	CH₃	4-OC₆H₄-2-CF₃	C₂H₅
843	CH₃	4-OC₆H₄-2-CF₃	n-C₃H₇
844	CH₃	4-OC₆H₄-2-CF₃	i-C₃H₇
845	CH₃	4-OC₆H₄-2-CF₃	n-C₄H₉
846	CH₃	4-OC₆H₄-2-CF₃	n-C₆H₁₃
847	CH₃	4-OC₆H₄-2-CF₃	CH₂F
848	CH₃	4-OC₆H₄-2-CF₃	CHF₂
849	CH₃	4-OC₆H₄-2-CF₃	CH₂CF₃
850	CH₃	4-OC₆H₄-2-CF₃	CH₂CH═CH₂
851	CH₃	4-OC₆H₄-2-CF₃	CH₂CH═CHCH₃
852	CH₃	4-OC₆H₄-2-CF₃	CH₂CH═C(CH₃)₂
853	CH₃	4-OC₆H₄-2-CF₃	CH₂CH═CHCl
854	CH₃	4-OC₆H₄-2-CF₃	CH₂CH═CCl₂
855	CH₃	4-OC₆H₄-2-CF₃	CH₂C(CH₃)═CH₂
856	CH₃	4-OC₆H₄-2-CF₃	CH₂C≡CH
857	CH₃	4-OC₆H₄-2-CF₃	CH₂Si(CH₃)₃
858	CH₃	4-OC₆H₄-2-CF₃	CH₂-c.propyl-2,2-Cl₂
859	CH₃	4-OC₆H₄-2-CF₃	CH₂CN
860	CH₃	4-OC₆H₄-2-CF₃	CH₂COOC₂H₅
861	CH₃	4-OC₆H₄-2-CF₃	CH(CH₃)COOC₂H₅
862	CH₃	4-OC₆H₄-2-CF₃	CH₂C₆H₄-3-CF₃
863	CH₃	4-OC₆H₄-2-CF₃	CH₂C₆H₄-4-F
864	CH₃	4-OC₆H₄-2-CF₃	CH₂C₆H₄-3-F
865	CH₃	4-OC₆H₄-2-CF₃	CH₂C₆H₄-2-F
866	CH₃	4-OC₆H₄-2-CF₃	C(═O)OC₂H₅
867	CH₃	4-OC₆H₄-2-CF₃	C(═O)NHCH₃
868	CH₃	4-OC₆H₄-2-CF₃	C(═O)C(═O)OC₂H₅
869	CH₃	4-OCH₂C₆H₄-4-Cl	CH₃
870	CH₃	4-OCH₂C₆H₄-4-Cl	C₂H₅
871	CH₃	4-OCH₂C₆H₄-4-Cl	n-C₃H₇
872	CH₃	4-OCH₂C₆H₄-4-Cl	i-C₃H₇
873	CH₃	4-OCH₂C₆H₄-4-Cl	n-C₄H₉
874	CH₃	4-OCH₂C₆H₄-4-Cl	n-C₆H₁₃
875	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂F
876	CH₃	4-OCH₂C₆H₄-4-Cl	CHF₂
877	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂CF₃
878	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂CH═CH₂
879	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂CH═CHCH₃
880	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂CH═C(CH₃)₂
881	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂CH═CHCl
882	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂CH═CCl₂
883	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂C(CH₃)═CH₂
884	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂C≡CH
885	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂Si(CH₃)₃
886	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂-c.propyl-2,2-Cl₂
887	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂CN
888	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂COOC₂H₅
889	CH₃	4-OCH₂C₆H₄-4-Cl	CH(CH₃)COOC₂H₅
890	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂C₆H₄-3-CF₃
891	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂C₆H₄-4-F
892	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂C₆H₄-3-F
893	CH₃	4-OCH₂C₆H₄-4-Cl	CH₂C₆H₄-2-F
894	CH₃	4-OCH₂C₆H₄-4-Cl	C(═O)OC₂H₅
895	CH₃	4-OCH₂C₆H₄-4-Cl	C(═O)NHCH₃
896	CH₃	4-OCH₂C₆H₄-4-Cl	C(═O)C(═O)OC₂H₅
797	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₃
898	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	C₂H₅
899	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	n-C₃H₇
900	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	i-C₃H₇
901	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	n-C₄H₉
902	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	n-C₆H₁₃
903	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂F
904	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CHF₂
905	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂CF₃
906	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂CH═CH₂
907	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂CH═CHCH₃
908	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂CH═C(CH₃)₂
909	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂CH═CHCl
910	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂CH═CCl₂
911	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂C(CH₃)═CH₂
912	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂C≡CH
913	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂Si(CH₃)₃
914	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂-c.propyl-2,2-Cl₂
915	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂CN
916	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂COOC₂H₅
917	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH(CH₃)COOC₂H₅
918	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂C₆H₄-3-CF₃
919	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂C₆H₄-4-F
920	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂C₆H₄-3-F
921	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	CH₂C₆H₄-2-F
922	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	C(═O)OC₂H₅
923	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	C(═O)NHCH₃
924	CH₃	4-OCH₂C₆H₃-3,4-Cl₂	C(═O)C(═O)OC₂H₅

In Tables 2.1 and 2.2, the [0149] ¹³C-NMR data of the compounds 1-[4-(3-trifluoromethyl-phenylmethoxy)-phenyl]-1,2-propanedione 1-E-[methyloxime]-2-oxime and 1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-Z-[methyloxime]-2-oxime (which was prepared by one of the known processes and from which the E/Z isomer mixture formed in the preparation was isolated) or, respectively, methyl 2-[[[(1-methyl-2-(4-(3-trifluormethylphenylmethoxy)-phenyl)-2-E-[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetate (compound A225 in Table 1) are shown. The similar chemical shifts of atoms 1 and 4 of compound A in Table 2.1 and those in Table 2.2 confirm the E configuration of the compounds of the formula I.
Table 2.1: [0150] ¹³C-NMR shifts and ¹J_CCcoupling constants of 1-[4-(3trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-[methyloxime]-2-oxime (A) and 1-[43(3-trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-Z-[methyloxime]-2-oxime (B)

A

B

Compound Atom No. Shift δ (ppm) Coupling ¹Jcc (Hz)

A 1 125.6 J₁₂= 56.0

3 155.0 J₂₃= 72.0

4 10.1 J₃₄= 43.0

B 1 127.8 J₁₂= 69.0

3 152.1 J₂₃= 56.5

4 14.4 J₃₄= 41.5
Table 2.2: [0151] ¹³C-NMR shifts of methyl 2-[[[(1-methyl-2-(4-(3-trifluoromethylphenylmethoxy)-phenyl)-2-E-[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetate (compound 0.225)

Atom No. Shift δ (ppm)

1 124.9

2 155.1

3 155.0

4 11.1

Claims

What is claimed is:

1. A process for the preparation of a compound of the formula

X is CH or N, Y is OR₁and Z is O, or

X is N, Y is NHR₈and Z is O, S or S(═O);

R₁is C₁-C₄alkyl;

R₂is H, C₁-C₄alkyl, halogeno-C₁-C₄alkyl, C₃-C₆cycloalkyl or C₁-C₄alkoxymethyl;

R₃and R₄independently of one another are H, C₁-C₄alkyl, C₁-C₄alkoxy, OH, CN, NO₂, a (C₁-C₄alkyl)₃-Si group, where the alkyl groups can be identical or different, halogen, (C₁-C₄alkyl)S(═O)_m, (halogeno-C₁-C₄alkyl)S(═O)_m, halogeno-C₁-C₄alkyl or halogeno-C₁-C₄alkoxy;

R₅is C₁-C₆alkyl, halogeno-C₁-C₆alkyl, C₁-C₆alkoxy, halogeno-C₁-C₆alkoxy, C₁-C₆-alkylthio, halogen-C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, halogeno-C₁-C₆-alkylsulfinyl, C₁-C₆alkylsulfonyl, halogeno-C₁-C₆alkylsulfonyl, C₁-C₆alkoxy-C₁-C₆alkyl, halogeno-C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl, halogeno-C₁-C₆alkylthio-C₁-C₆alkyl, C₁-C₆alkylsulfinyl-C₁-C₆alkyl, halogeno-C₁-C₆-alkylsulfinyl-C₁-C₆alkyl, C₁-C₆-alkylsulfonyl-C₁-C₆alkyl, halogeno-C₁-C₆-alkylsulfonyl-C₁-C₆alkyl, C₁-C₆-alkylcarbonyl, halogeno-C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxycarbonyl, halogeno-C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylaminocarbonyl, C₁-C₄-alkoxyiminomethyl; di(C₁-C₆alkyl)-aminocarbonyl, where the alkyl groups can be identical or different; C₁-C₆-alkylaminothiocarbonyl; di(C₁-C₆alkyl)-aminothiocarbonyl, where the alkyl groups can be identical or different; C₁-C₆-alkylamino, di(C₁-C₆alkyl)-amino, where the alkyl groups can be identical or different; halogen, NO₂, CN, SF₅, thioamido, thiocyanatomethyl; an unsubstituted or mono- to tetrasubstituted C₁-C₄alkylenedioxy group, where the substituents are selected from the group consisting of C₁-C₄alkyl and halogen; or QR₆, where, if n is greater than 1, the radicals R₅can be identical or different;

R₆is C₂-C₆alkenyl or C₂-C₆alkynyl, which are unsubstituted or substituted by 1 to 3 halogen atoms; (C₁-C₄alkyl)₃Si, where the alkyl groups can be identical or different; CN; or an unsubstituted or mono- to pentasubstituted C₃-C₆cycloalkyl, aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen, C₁-C₆alkyl, halogeno-C₁-C₆alkyl, C₁-C₆alkoxy, halogeno-C₁-C₆alkoxy, phenoxy, naphthoxy and CN;

A either is a direct bond, C₁-C₆akylene, —C(═O)—, —C(═S)— or halogeno-C₁-C₁₀alkylene and R₇is a radical R₁₀,

or is C₁-C₁₀alkylene, —C(═O)—, —C(═S)— or halogeno-C₁-C₁₀alkylene and

R₇is OR₁₀, N(R₁₀)₂, where the radicals R₁₀can be identical or different, or —S(═O)_qR₁₀;

R₈is H or C₁-C₄alkyl;

R₉is methyl, fluoromethyl or difluoromethyl;

R₁₀is H; an unsubstituted or substituted C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl group, where the substituents are selected from the group consisting of halogen; (C₁-C₄alkyl)₃Si, where the alkyl groups can be identical or different; Cs-C₆cyclo-alkyl, which is unsubstituted or substituted by halogen; C₁-C₆alkoxycarbonyl, which is unsubstituted or substituted by halogen; unsubstituted or substituted aryl, where the substituents are selected from the group consisting of halogen, halogeno-C₁-C₄alkyl and CN; a (C₁-C₄alkyl)₃Si group, where the alkyl groups can be identical or different; C₃-C₆cycloalkyl, which is unsubstituted or substituted by halogen; C₁-C₆alkoxycarbonyl which is unsubstituted or substituted by halogen; or an unsubstituted or substituted aryl or heterocyclyl group, where the substituents are selected from the group consisting of halogen and halogeno-C₁-C₄alkyl;

Q is a direct bond, C₁-C₈alkylene, C₂-C₆alkenylene, C₂-C₆alkynylene, O, O(C₁-C₆alkylene), (C₁-C₆alkylene)O, S(═O)_p, S(═O)_p(C₁-C₆alkylene) or (C₁-C₆alkylene)S(═O)_p;

m is 0, 1 or 2;

n is 0, 1, 2, 3, 4 or 5;

p is 0, 1 or 2; and

q is 0, 1 or 2,

and the C═N double bond marked with E has the E configuration,

which comprises

a1) reacting either a compound of the formula

in which A, R₂, R₅, R₇and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, or a possible tautomer thereof, in each case in the free form or in salt form, with a compound of the formula

in which X, Y, Z, R₃, R₄and R₉are as defined for formula (I) and X₁is a leaving group, or a tautomer thereof, in each case in the free from or in salt form, or

a2) reacting a compound of the formula

in which A, R₂, R₅, R₇and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, or a possible tautomer thereof, in each case in the free form or in the salt form with a compound of the formula

in which X, Y, Z, R₃, R₄and R₉are as defined for formula (I), or, if appropriate, a tautomer thereof, in each case in the free form or in salt form, or

b1) reacting a compound of the formula

in which R₂, R₅and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, or a possible tautomer thereof, in each case in the free form or in salt form with a compound of the formula

R₇-A-X₂ (VII),

in which A and R₇are as defined for formula (I) and X₂is a leaving group, and either further reacting the compound thus obtainable, of the formula (IV), for example according to method a2), or

b2) reacting it with hydroxylamine or a salt thereof and further reacting the compound thus obtainable, of the formula (II), for example according to method a1), or

c) reacting a compound of the formula

in which R₂, R₃and n are as defined for formula (I),

or a possible tautomer thereof, in each case in the free form or in salt form with a C₁-C₆alkyl nitrite and further reacting the compound thus obtainable, of the formula (VI), for example according to method b).

2. A process according to claim 1 for the preparation of a compound of the formula (I), which comprises reacting a compound of the formula (II) with a compound of the formula (III).

3. A process according to claim 2, wherein a compound of the formula (III) in which X₁is halogen is used.

4. A process according to claim 2, wherein a compound of the formula (III) in which X₁is chlorine is used.

5. A process according to claim 2, wherein the reaction is carried out in the presence of a base.

6. A process according to claim 5, wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.

7. A process according to claim 6, wherein the base is sodium hydride.

8. A process according to claim 2, wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.

9. A process according to claim 8, wherein the solvent is selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and hexamethylphosphoric acid triamide.

10. A process according to claim 9, wherein the solvent is N,N-dimethylformamide.

11. A process according to claim 2, wherein the reaction is carried out in a temperature range from about 10° to about 30°.

12. A process according to claim 2, wherein the reaction time is between about 0.5 and about 2 hours.

13. A process according to claim 1 for the preparation of a compound of the formula (I), which comprises reacting the compound of the formula (IV), with a compound of the formula (V).

14. A process according to claim 13, wherein the reaction is carried out in the presence of a base.

15. A process according to claim 14, wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.

16. A process according to claim 15, wherein the base is sodium hydroxide.

17. A process according to claim 13, wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.

18. A process according to claim 17, wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol.

19. A process according to claim 18, wherein the reaction is carried out in methanol.

20. A process according to claim 13, wherein the reaction is carried out in a temperature range from about 10° to about 30°.

21. A process according to claim 13, wherein the reaction time is between about 0.5 and about 2 hours.

22. A process according to claim 1 for the preparation of a compound of the formula (I), which comprises reacting the compound of the formula (VI), with a compound of the formula (VII), and either reacting the compound thus obtainable, of the formula (IV), according to the process according to claim 13, or reacting it with hydroxylamine or a salt thereof, if appropriate in the presence of a basic or acid catalyst, and further reacting the compound thus obtainable, of the formula (II), according to the process according to claim 2.

23. A process according to claim 22, wherein a compound of the formula (VII) in which X₂is halogen is used.

24. A process according to claim 22, wherein a compound of the formula (VII) in which X₂is chlorine is used.

25. A process according to claim 22, wherein the reaction of the compound of the formula (VI) with the compound of the formula (VII) is carried out in the presence of a base.

26. A process according to claim 25, wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.

27. A process according to claim 26, wherein the base is potassium carbonate.

28. A process according to claim 22, wherein the reaction of the compound of the formula (VI) with the compound of the formula (VII) is carried out in the presence of a solvent or diluent or of a mixture thereof.

29. A process according to claim 28, wherein the solvent is selected from the group consisting of acetonitrile and propionitrile.

30. A process according to claim 29, wherein the reaction is carried out in acetonitrile.

31. A process according to claim 22, wherein the reaction of the compound of the formula (VI) with the compound of the formula (VII) is carried out in a temperature range of about 10° to about 80°.

32. A process according to claim 22, wherein the duration of the reaction of the compound of the formula (VI) with the compound of the formula (VII) is between about 0.5 and about 2 hours.

33. A process according to claim 1 for the preparation of a compound of the formula (I), which comprises reacting the compound of the formula (VIII), with a C₁-C₆alkyl nitrite and further reacting the compound thus obtainable, of the formula (VI), according to the process according to claim 22.

34. A process according to claim 33, wherein the reaction is carried out in the presence of a base.

35. A process according to claim 34, wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.

36. A process according to claim 35, wherein the base is sodium methanolate.

37. A process according to claim 33, wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.

38. A process according to claim 37, wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol.

39. A process according to claim 38, wherein the reaction is carried out in methanol.

40. A process according to claim 33, wherein the reaction is carried out in a temperature range from about 0° C. to about 60° C.

41. A process according to claim 33, wherein the reaction time is between about 0.5 and about 3 hours.

42. A process for the preparation of a compound of the formula

in which A, R₂, R₅, R₇and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, which comprises reacting the compound of the formula

in which R₂, R₅and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, with a compound of the formula

R₇-A-X₂ (VII),

in which A and R₇are as defined for formula (I) and X₂is a leaving group.

43. A process according to claim 42, wherein a compound of the formula (VII) in which X₂is halogen is used.

44. A process according to claim 43, wherein a compound of the formula (VII) in which X₂is chlorine is used.

45. A process according to claim 42, wherein the reaction is carried out in the presence of a base.

46. A process according to claim 45, wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides and alkylsilylamides.

47. A process according to claim 46, wherein the base is potassium carbonate.

48. A process according to claim 47, wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.

49. A process according to claim 48, wherein the solvent is selected from the group consisting of acetonitrile and propionitrile.

50. A process according to claim 49, wherein the reaction is carried out in acetonitrile.

51. A process according to claim 42, wherein the reaction is carried out in a temperature range from about 10° to about 80°.

52. A process according to claim 42, wherein the reaction time is between about 0.5 and about 2 hours.

53. A process for the preparation of a compound of the formula

in which A, R₂, R₅, R₇and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, with hydroxylamine or a salt thereof.

54. A process according to claim 53, wherein the reaction is carried out with hydroxylamine hydrochloride.

55. A process according to claim 53, wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.

56. A process according to claim 55, wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol.

57. A process according to claim 56, wherein the reaction is carried out in ethanol.

58. A process according to claim 53, wherein the reaction is carried out in a temperature range from about 20° to about 100°.

59. A process according to claim 53, wherein the reaction time is between about 0.5 and about 2 hours.

60. A process for the preparation of a compound of the formula

in which R₂, R₅and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, which comprises reacting the compound of the formula

in which R₂, R₅and n are as defined for formula (I), with a C₁-C₆alkylnitrite.

61. A process according to claim 60, wherein the reaction is carried out in the presence of a base.

62. A process according to claim 61, wherein the reaction is carried out in the presence of a base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamide and alkylsilylamides.

63. A process according to claim 62, wherein the base is sodium methanolate.

64. A process according to claim 60, wherein the reaction is carried out in the presence of a solvent or diluent or of a mixture thereof.

65. A process according to claim 64, wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol.

66. A process according to claim 65, wherein the reaction is carried out in methanol.

67. A process according to claim 60, wherein the reaction is carried out in a temperature range from about 0° to about 40°.

68. A process according to claim 60, wherein the reaction time is between about 0.5 and about 2 hours.

69. A compound of the formula

in which A, R₂, R₅, R₇and n are as defined in claim 1 for formula (I) and the C═N double bond marked with E has the E configuration, or if appropriate a tautomer thereof, in each case in the free form or in salt form.

70. A compound of the formula

in which A, R₂, R₅, R₇and n are as defined in claim 1, for formula (I) and the C═N double bond marked with E has the E configuration, or if appropriate a tautomer thereof, in each case in the free form or in salt form.

71. A compound of the formula

in which R₂, R₅and n are as defined for formula (I) and the C═N double bond marked with E has the E configuration, or if appropriate a tautomer thereof, in each case in the free form or in salt form.