Process for the preparation of pesticides

Abstract

The invention relates to a process for the preparation of compounds of the formula 1

Description

[0001] The invention relates to a process for the preparation of compounds of the formula 2

[0002] and, where appropriate, their tautomers, in each case in the free form or salt form, in which either

[0003] X is CH or N, Y is OR1 and Z is 0,

[0004] or

[0005] X is N, Y is NHR8 and Z is O, S or S(═O);

[0006] R1 is C1-C4alkyl;

[0007] R2 is H, C1-C4alkyl, halogeno-C1-C4alkyl, C3-C6cycloalkyl or C1-C4alkoxymethyl;

[0008] R3 and R4 independently 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;

[0009] R5 is 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 R5 can be identical or different;

[0010] R6 is C2-C6alkenyl or C2-C6 alkynyl 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;

[0011] A either is a direct bond, C1—C10alkylene, —C(═O)—, —C(═S)— or halogeno-C1-C10alkylene and R7 is a radical R10,

[0012] or is C1-C10alkylene, —C(═O)—, —C(═S)— or halogeno-C1-C10alkylene and

[0013] R7 is OR10, N(R10)2, where the radicals R10 can be identical or different, or —S(═O)qR10;

[0014] R8 is H or C1-C4alkyl;

[0015] R9 is methyl, fluoromethyl or difluoromethyl;

[0016] R10 is 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;

[0017] m is 0, 1 or 2;

[0018] n is 0, 1, 2, 3, 4 or 5;

[0019] p is 0, 1 or 2; and

[0020] q is 0, 1 or 2,

[0021] and the C═N double bond marked with E has the E configuration,

[0022] which comprises

[0023] a1) reacting either a compound of the formula 3

[0024] in which A, R2, R5, R7 and 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 4

[0025] which is known or can be prepared by methods known per se and in which X, Y, Z, R3, R4 and R9 are as defined for formula I and X1 is a leaving group, or a tautomer thereof, in each case in the free from or in salt form, or

[0026] a2) reacting a compound of the formula 5

[0027] in which A, R2, R5, R1 and 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 6

[0028] which is known or can be prepared by methods known per se and

[0029] in which X, Y, Z, R3, R4 and R9 are as defined for formula I, or a tautomer thereof, in each case in the free form or in salt form, or

[0030] b1) reacting a compound of the formula 7

[0031] in which R2, R5 and 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),

[0032] which is known or can be prepared by methods known per se and

[0033] in which A and R7 are as defined for formula I and X2 is a leaving group, and either further reacting the compound thus obtainable, of the formula IV, for example according to method a2), or

[0034] 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

[0035] c) reacting a compound of the formula 8

[0036] which is known or can be prepared by methods known per se and

[0037] in which R2, R3 and 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),

[0038] 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.

[0039] 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.

[0040] Unless defined differently, the general terms used above and below are defined as follows.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] C3-C6cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

[0046] 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)p or 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)—.

[0047] 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.

[0048] 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.

[0049] Aryl is phenyl or naphthyl, in particular phenyl.

[0050] 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.

[0051] 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.

[0052] 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 CHF2 or 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, CH2CF2CF3 or 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)—CHFCF3 or CH2(CF2)2CF3. Halogenoalkenyl is, for example, CH2CH═CHCl, CH2CH═CCl2, CH2CF═CF2 or CH2CH═CHCH2Br. Halogenoalkynyl is, for example, CH2C≡CF, CH2C≡CCH2Cl or CF2CF2C≡CCH2F.

[0053] Some compounds I to VI and VII can be present as tautomers, as is familiar to the expert, in particular if AR7 is 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.

[0054] 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 C1-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.

[0055] 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.

[0056] 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.

[0057] Variants a1/a2)

[0058] Suitable leaving groups X1 in 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.

[0059] 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).

[0060] 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.

[0061] 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.

[0062] The reaction is preferably carried out under normal pressure.

[0063] 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.

[0064] 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.

[0065] The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.

[0066] 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.

[0067] Particularly preferred conditions for the reaction are described in Examples H1 d) and H 3f).

[0068] The compounds of the formula III are known or can be prepared analogously to known compounds.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] Variant b)

[0074] 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.

[0075] Suitable leaving groups X2 in the compounds VII are, for example, those which are mentioned as examples for X1 in variants a1/a2).

[0076] Suitable bases for facilitating the reaction are, for example, those which are mentioned in variants a1/a2).

[0077] 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).

[0078] 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.

[0079] The reaction is preferably carried out under normal pressure.

[0080] 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.

[0081] 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.

[0082] The product is isolated by customary methods, for example filtration, crystallization, distillation or chromatography or any suitable combination of these processes.

[0083] 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).

[0084] Particularly preferred conditions for the reaction are described in Examples H 1b) to 1d) and H 3d) to 3f).

[0085] The compounds of the formula VII are known or can be prepared analogously to known compounds.

[0086] 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).

[0087] 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.

[0088] Variant c)

[0089] 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.

[0090] Suitable bases for facilitating the reaction are, for example, those which are mentioned in variants a1/a2).

[0091] 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).

[0092] 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.

[0093] The reaction is preferably carried out under normal pressure.

[0094] 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.

[0095] 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.

[0096] The product is isolated by customary methods, for example filtration, crystallization, distillation or chromatography or any suitable combination of these processes.

[0097] 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).

[0098] Particularly preferred conditions for the reactions are described in Examples H 3d) to 3f).

[0099] The compounds of the formula VIII are known or can be prepared analogously to known compounds.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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),

[0104] 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

[0105] 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).

[0106] 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]&agr;-(methoxymethylene)-phenylacetate (Compound 1.16)

[0107] H1a) 1-Phenyl-1,2-propanedione 1-E-oxime

[0108] 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.

[0109] H1b) 1-Phenyl-1,2-propanedione 1-E-[(2-propynyl)oxime]

[0110] 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.

[0111] H1d) 1-Phenyl-1,2-propanedione 1-E-[(2-propynyl)oxime]-2-oxime

[0112] 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.

[0113] H1e) Methyl 2-[[[(1-methyl-2-phenyl-2-E-[(2-propynyl)oxyimino]ethy-lidene)amino]oxy]-methyl]-&agr;-(methoxymethylene)-phenylacetate

[0114] 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)-&agr;-(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°.

Example H2

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

[0115] 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.

Example H3

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

[0116] H3a) 1-(4-Hydroxyphenyl)-2′-propanone

[0117] 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°.

[0118] H3b) 1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-2-propanone

[0119] 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.

[0120] H3c) 1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-oxime

[0121] 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°.

[0122] H3d) 1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)oxime]

[0123] 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.

[0124] H3e) 1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione 1-E-[(2-propynyl)oxime]-2-oxime

[0125] 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°.

[0126] H3f) Methyl 2-[[[(1-methyl-2-(4-(3-trifluoromethylphenylmethoxy)-phenyl)-2-E-[(2-propynyl)oxyimino]ethylidene)amino]oxy]methyl]-&agr;-(methoxymethylene)-phenylacetate

[0127] 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)-&agr;-(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.

Example H4

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

[0128] H4a) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione 1-E-oxime

[0129] 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.

[0130] H4b) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione 1-E-[(2-ethyl)oxime]

[0131] 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.

[0132] H4c) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione 1-E-[(2-ethyl)oxime]-2-oxime

[0133] 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.

[0134] H4d) Methyl 2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxyimino]ethylidene)amino]oxy]methyl]-&agr;-(methoxymethylene)-phenylacetate.

[0135] 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)-&agr;-(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.

Example H5

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

[0136] 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)-&agr;-(methoxyimino)-phenylacetate.

Example H6

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

[0137] 13,3 g of methyl 2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxyimino]ethyliene)amino]oxy]methyl]-&agr;-(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.

Example H7

[0138] 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. 1 TABLE 1 Compounds of the general formula 9 I.1,

[0139] in which X is CH and Y is oxygen and the combination of substituents R2, (R5)x and A-R7 for 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. 2 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°

[0140] Compounds of the general formula I.1, in which

[0141] X is nitrogen and

[0142] Y is oxygen

[0143] and the combination of substituents R2, (R5)n and A-R7 for a compound in each case corresponds to a line in Table A. 3 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

[0144] Compounds of the general formula I.1, in which

[0145] X is nitrogen and

[0146] Y is NH and

[0147] the combination of substituents R2, (R5)n and A-R7 for a compound in each case corresponds to a line in Table A. 4 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

[0148] 5 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

[0149] In Tables 2.1 and 2.2, the 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]-&agr;-(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.

[0150] Table 2.1: 13C-NMR shifts and 1JCC coupling 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) 6 10 A 11 B Compound Atom No. Shift &dgr; (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

[0151] Table 2.2: 13 C-NMR shifts of methyl 2-[[[(1-methyl-2-(4-(3-trifluoromethylphenylmethoxy)-phenyl)-2-E-[methoxyimino]ethylidene)amino]oxy]methyl]-&agr;-(methoxymethylene)-phenylacetate (compound 0.225) 7 12 Atom No. Shift &dgr; (ppm) 1 124.9 2 155.1 3 155.0 4 11.1

Claims

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

13

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 OR1 and Z is O, or

X is N, Y is NHR8 and Z is O, S or S(═O);

R1 is C1-C4alkyl;

R2 is H, C1-C4alkyl, halogeno-C1-C4alkyl, C3-C6cycloalkyl or C1-C4alkoxymethyl;

R3 and R4 independently 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;

R5 is 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 R5 can be identical or different;

R6 is C2-C6alkenyl or C2-C6 alkynyl, 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 R7 is a radical R10,

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

R7 is OR10, N(R10)2, where the radicals R10 can be identical or different, or —S(═O)qR10;

R8 is H or C1-C4alkyl;

R9 is methyl, fluoromethyl or difluoromethyl;

R10 is 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

14

in which A, R2, R5, R7 and 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

15

in which X, Y, Z, R3, R4 and R9 are as defined for formula (I) and X1 is 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

16

in which A, R2, R5, R7 and 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

17

in which X, Y, Z, R3, R4 and R9 are 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

18

in which R2, R5 and 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 R7 are as defined for formula (I) and X2 is 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

19

in which R2, R3 and 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 X1 is halogen is used.

4. A process according to claim 2, wherein a compound of the formula (III) in which X1 is 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 X2 is halogen is used.

24. A process according to claim 22, wherein a compound of the formula (VII) in which X2 is 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-C6 alkyl 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

20

in which A, R2, R5, R7 and 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

21

in which R2, R5 and 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 R7 are as defined for formula (I) and X2 is a leaving group.

43. A process according to claim 42, wherein a compound of the formula (VII) in which X2 is halogen is used.

44. A process according to claim 43, wherein a compound of the formula (VII) in which X2 is 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

22

in which A, R2, R5, R7 and 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

23

in which A, R2, R5, R7 and 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

24

in which R2, R5 and 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

25

in which R2, R5 and 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

26

in which A, R2, R5, R7 and 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

27

in which A, R2, R5, R7 and 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

28

in which R2, R5 and 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.