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]α-(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]-α-(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)-α-(methoxymethylene)-phenylacetate in 24 ml of N,N-dimethylformamide are then added dropwise and the reaction mixture is further stirred at room temperature for 1 hour. Thereafter, the mixure is acidified with acetic acid and evaporated in vacuo. The residue is dissolved in ethyl acetate and the solution is washed three times with water and twice with saturated sodium chloride solution, dried with sodium sulfate and evaporated in vacuo. After recrystallization of the residue from hexane/ethyl acetate, the title compound is obtained with a melting point of 82-84°.

Example H2

Methyl 2-[[[(1-methyl-2-(4-fluorophenyl)-2-E-[(2-propynyl)oxyimino]ethylidene)amino]oxy]methyl]-α-(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]-α-(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]-α-(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)-α-(methoxymethylene)-phenylacetate in 15 ml of N,N-dimethylformamide are then added dropwise and the reaction mixture is further stirred at room temperature for 1 hour. Thereafter, the mixture is acidified with acetic acid and evaporated in vacuo at 50°. The residue is dissolved in ethyl acetate and the solution is washed twice with water and once with saturated sodium chloride solution, dried with sodium sulfate and evaporated in vacuo. After purification by chromatography (silica gel, ethyl acetate/hexane 1:3), the title compound is obtained as a resin.

Example H4

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

[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]-α-(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)-α-(methoxymethylene)-phenylacetate in 15 ml of N,N-dimethylformamide are then added dropwise and the reaction mixture is further stirred at room temperature for 1 hour. Thereafter, the mixture is acidified with acetic acid and evaporated in vacuo at 50°. The residue is dissolved in ethyl acetate and the solution is washed twice with water and once with saturated sodium chloride solution, dried with sodium sulfate and evaporated in vacuo. After purification by flash chromatography (silica gel, ethyl acetate/hexane 1:3), the title compound is obtained with a melting point of 87-89° C.

Example H5

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

[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)-α-(methoxyimino)-phenylacetate.

Example H6

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

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

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.

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.

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.

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.

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]

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]-α-(methoxymethylene)-phenylacetate (compound A225 in Table 1) are shown. The similar chemical shifts of atoms 1 and 4 of compound A in Table 2.1 and those in Table 2.2 confirm the E configuration of the compounds of the formula I.

[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)

10
A
11
B
Compound	Atom No.	Shift δ (ppm)	Coupling 1Jcc (Hz)
A	1	125.6	J12 = 56.0
	3	155.0	J23 = 72.0
	4	10.1	J34 = 43.0
B	1	127.8	J12 = 69.0
	3	152.1	J23 = 56.5
	4	14.4	J34 = 41.5

[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]-α-(methoxymethylene)-phenylacetate (compound 0.225)

12
Atom No. Shift δ (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

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

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

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

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

70. A compound of the formula

71. A compound of the formula