CN1288459A - Organic nitrile derivatives and their use as pesticides - Google Patents

Organic nitrile derivatives and their use as pesticides Download PDF

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Publication number
CN1288459A
CN1288459A CN99802323A CN99802323A CN1288459A CN 1288459 A CN1288459 A CN 1288459A CN 99802323 A CN99802323 A CN 99802323A CN 99802323 A CN99802323 A CN 99802323A CN 1288459 A CN1288459 A CN 1288459A
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alkyl
halo
alkoxy
group
alkenyl
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R·G·豪尔
A·斯泰格
O·F·休特
A·帕斯休尔
M·克里兹
S·特拉斯
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Novartis AG
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Novartis AG
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
    • C07C255/66—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms having cyano groups and nitrogen atoms being part of hydrazine or hydrazone groups bound to the same carbon skeleton
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
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    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
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    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
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    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
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    • C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

In free form or in agrochemically acceptable form of salt compounds of formula (I), wherein: A1 and A2 each represent independently of one other an aryl or a heteroaryl radical; and A1 where appropriate is substituted with substituent (R3a)n1 and A2 where appropriate with substituent (R3b)n2; n1 and n2 are independently of one another 0, 1, 2, 3 or 4; and either R3a and R3b independently of one another are for example halogen, C1-C6alkyl, C2-C4alkinyl, halogen-C1-C6alkyl, halogen-C2-C4alkinyl, C1-C6alkoxy, halogen-C1-C6alkoxy, C2-C6alkenyloxy, C2-C6alkinyloxy or halogenC2-C6alkenyloxy; and R2 is R2a; R2a is for example -C1-C6alkyl-NR11R12, -COC9-C20alkyl, -C1-C6alkyl-O-C1-C6alkyl-O-C1-C6alkyl or -CH2O(C=O)C1-C6alkyl; or, at least one of the radicals R3a or R3b is -CR5=CR5R14, -NR11R12, C(=O)CN, -C(=O)C(=O)O-C1-C6alkyl, -CR7=NOR10, or a five or six-membered heteroaryl ring bonded by a carbon atom; R2 is R2a or R2b, wherein R2a is as defined hereinbefore; and R2b is for example hydrogen, -OH, C1-C6alkyl or C1C6alkoxy; R14 is for example hydrogen, halogen, C1-C6alkyl or halogen-C1-C6alkyl; X is O or S; p is 0, 1 or 2; R5 is independently H or C1-C8alkyl; R6 is for example independently H, C1-C8alkyl or C3-C6cycloalkyl; R7 is for example H, C1-C8alkyl, C2-C8alkenyl or halogen-C1-C8alkyl; R8 is for example C1-C8alkyl, C1-C8alkenyl or halogen-C1-C8alkyl; R9 is C1-C6alkyl, halogen-C1-C4alkyl or aryl; R10 is H, C1-C6alkyl, C3-C6cycloalkyl, phenyl or benzyl; R11 and R12 for example are independently of one another.

Description

Organic nitrile derivatives and its application as agricultural chemicals
The present invention relates to formula (I) compound, and, if appropriate, possible E/Z isomers, E/Z isomer mixtures and/or dynamic isomer, it is free or salt form in each case：(I), wherein：A1And A2It is mutually independent, and all represents monocyclic or aryl bicyclic or heteroaryl groups in all cases, and each heteroaryl groups are independently of one another containing the 1-4 hetero atoms for being selected from N, O and S；And A1Base (R can be substituted if appropriate3a)n1Substitution, and A2Base (R can be substituted if appropriate3b)n2Substitution；n1And n2It is 1,2,3 or 4 independently of one another, they depend on ring system A1And A2Substitution possibility；And or (A) R3aAnd R3bIt is hydrogen, halogen, C independently of one another1-C6Alkyl, halo-C1-C6Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, halo-C2-C4Alkenyl, halo-C2-C4Alkynyl, C1-C6Alkoxy, halo-C1-C6Alkoxy, C2-C6Alkenyloxy, C2-C6Alkynyloxy group, halo-C2-C6Alkenyloxy, halo-C2-C6Alkynyloxy group ,-OH ,-SF5,-CHO,-C(=O)-C1-C6Alkyl ,-C (=O)-halo-C1-C6Alkyl ,-C (=O)-OC1-C6Alkyl ,-C (=O)-O- halos-C1-C6Alkyl ,-O-C (=O) N (R6)2(two of which R6Substituent is mutually independent) ,-CN ,-NO2,-S(=O)2N(R6)2(two of which R6Substituent is mutually independent) ,-S (=O)p-C1-C6Alkyl ,-S (=O)p- halo-C1-C6Alkyl ,-O-S (=O)p-C1-C6Alkyl ,-O-S (=O)p- halo-C1-C6Alkyl, phenyl, benzyl, phenoxy group or benzyloxy, wherein phenyl, benzyl, phenoxy group or benzyloxy group are respectively unsubstituted or its aromatic ring and are selected from following group to be replaced 1-5 times independently of one another：Halogen, cyano group, NO2,C1-C6Alkyl, halo-C1-C6Alkyl, C1-C6Alkoxy and halo-C1-C6Alkoxy；And R2For R2a；Or, (B) R3aAnd R3bIndependently of one another as defined in (A), and group R3aOr R3bIn at least one be-CR5=CR5R14,-NR11R12,-C(=O)CN,-C(=O)C(=O)O-C1-C6Alkyl ,-CR15=NOR10Or five or six membered heteroaryl ring, wherein the heteroaryl ring, if appropriate, according to the substitution possibility of ring, can be selected from halogen, C by 1-31-C4Alkyl, C1-C4Haloalkyl, NO2Replace with CN substituent, and R2For R2aOr R2b；Or (C) R3aWith any implication defined in (A) above or (B)；   R3bFor hydrogen, halogen, C1-C6Alkyl, halo-C1-C6Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, halo-C2-C4Alkenyl, halo-C2-C4Alkynyl, C1-C6Alkoxy, halo-C1-C6Alkoxy, C2-C6Alkenyloxy, C2-C6Alkynyloxy group, halo-C2-C6Alkenyloxy, halo-C2-C6Alkynyloxy group ,-OH ,-SF5,-CHO,-C(=O)-C1-C6Alkyl ,-C (=O)-halo-C1-C6Alkyl ,-C (=O)-OC1-C6Alkyl ,-C (=O)-O- halos-C1-C6Alkyl ,-O-C (=O) N (R6)2(two of which R6Substituent is mutually independent) ,-CN ,-NO2, phenyl, benzyl, phenoxy group or benzyloxy, wherein phenyl, benzyl, phenoxy group or benzyloxy group are respectively unsubstituted or its aromatic ring and are selected from following substituent to be replaced 1-5 time independently of one another：Halogen, cyano group, NO2,C1-C6Alkyl, halo-C1-C6Alkyl, C1-C6Alkoxy and halo-C1-C6Alkoxy；- S (=O) on 4p-C1-C6Alkyl or the-S (=O) on 4p- halo-C1-C6Alkyl, condition is substituent R3bIn one be-S (=O)p-C1-C6Alkyl or-S (=O)p- halo-C1-C6Alkyl；And R2For R2aOr R2b；Wherein at (A), in (B) and (C) group, if appropriate, R2aFor-C1-C6Alkyl-NR11R12,-C(=X)-R7a,-COC9-C20Alkyl ,-CH2O(C=O)C1-C6Alkyl ,-C1-C6Alkyl-O-C1-C6Alkyl-O-C1-C6Alkyl ,-CH2O(C=O)C2-C6Alkenyl ,-CH2O(C=O)C2-C6Alkynyl ,-C (=S) OC2-C6Alkenyl ,-C (=S) OC2-C6Alkynyl ,-C (=S) SC1-C6Alkyl ,-C (=S) SC2-C6Alkenyl ,-C (=S) SC2-C6Alkynyl ,-C (=O) SC1-C6Alkyl ,-C (=O) SC2-C6Alkenyl ,-C (=O) SC2-C6Alkynyl ,-C (=S) NR11R12,-C(=O)NR10OR13,-CH2OC2-C6Alkenyl ,-CH2OC2-C6Alkynyl ,-CH2OC2-C6Halogenated alkenyl or-CH2OC2-C6Halo alkynyl；R2bFor hydrogen ,-OH, C1-C6Alkyl, C1-C6Alkoxy, C3-C6Cycloalkyl, C3-C6Alkenyl, C3-C6Alkynyl, halo-C1-C6Alkyl, halo-C3-C6Alkenyl, halo-C3-C6The aromatic ring of alkynyl, benzyl or benzoyl, wherein benzyl or benzoyl group is selected from halogen ,-CN, NO2、C1-C6Alkyl, C1-C6Alkoxy, halo-C1-C6Alkyl and halo-C1-C6The substituent of alkoxy replaces 1-3 times independently of one another；C1-C6Alkoxy -C1-C6Alkyl；Cyano group-C1-C6Alkyl ,-C (=X)-R7a,-C(=X)-R7b,-OC(=O)-R7a,   -C(=O)-C(=O)-R7a,-OC(=O)-R7b,-C(=O)-C(=O)-R7b,-S(=O)pN(R6)2(two of which R6Substituent is mutually independent)；Cyano group ,-C1-C6Alkyl-N (R5)-C(=O)-R8,-C1-C6Alkyl-S-C (=S)-R8,-C1-C6Alkyl-S (=O)p-R9,   -S(=O)p-R9, or-CH2-N(R10)-SO2-R9；X is O or S；P is 0,1 or 2；R5It independently is H or C1-C8Alkyl；R6It independently is H, C1-C8Alkyl, C3-C6The aromatic ring of cycloalkyl, phenyl or benzyl, wherein phenyl or benzyl can be selected from halogen ,-CN, NO if appropriate2、C1-C6Alkyl, C1-C4Alkoxy, halo-C1-C6Alkyl and halo-C1-C6The substituent of alkoxy replaces 1-3 times independently of one another；Or two alkyl group R6With their institute's keys with nitrogen-atoms together with form 5-7 yuan of rings, CH therein2Group, if appropriate, can be selected from O and S hetero atom substitution, or be replaced by NH, and 5-7 yuan of rings therein if appropriate can be by C1   -C4Alkyl replaces for 1 time or twice；R7aFor C1-C6Alkoxy -C1-C6Alkyl, CH2CH2CF2Cl,C1-C6Alkylthio group-C1-C6Alkyl, acyloxy-C1-C6Alkyl, halo-C3-C6Cycloalkyl, C3-C6Cycloalkyl-C1-C6Alkyl, halo-C3-C6Cycloalkyl-C1-C6Alkyl, aryloxy group-C1-C6Alkyl；Or phenyl, benzyl, phenoxy group or aryloxy group-C1-C6Alkyl, they are selected from halogen, nitro, cyano group, C by 1-31-C4Alkyl, halo-C1-C4Alkyl and halo-C1-C4The substituent substitution of alkoxy；R7bFor H, C1-C8Alkyl, C2-C8Alkenyl, halo-C1-C8Alkyl, halo-C2-C8Alkenyl, C1-C8Alkoxy, halo-C1-C8Alkoxy, C3-C6Cycloalkyl, phenyl, benzyl, phenoxy group, benzyloxy or-N (R6)2(two of which R6Group is mutually independent)；R8For C1-C8Alkyl, C1-C8Alkoxy, halo-C1-C8Alkyl, halo-C1-C8Alkoxy, C1-C8Alkylthio group, phenyl, benzyl or-N (R6)2(two of which R6Group is mutually independent)；R9For C1-C6Alkyl, halo-C1-C4Alkyl or aryl, the aryl is unsubstituted or be selected from following substituent and replace 1-3 times independently of one another：C1-C6Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C1-C4Alkoxy, halogen, cyano group, halo-C1-C4Alkyl, halo-C2-C4Alkenyl, halo-C2-C4Alkynyl, halo-C1-C4Alkoxy and nitro；R10For H, C1-C6Alkyl, C3-C6Cycloalkyl, phenyl or benzyl, wherein phenyl and benzyl group are that unsubstituted or its aromatic ring is selected from C1-C4Alkyl, C1-C4Alkoxy, halogen, cyano group, halo-C1-C4Alkyl, halo-C1-C4The substituent of alkoxy and nitro replaces 1-3 times independently of one another；R11And R12It is H, C independently of one another1-C6Alkyl, phenyl ,-COC1-C6Alkyl ,-COC1-C6Haloalkyl ,-CO phenyl, or form 5 or 6 yuan of saturations or unsaturation ring together is one or more wherein if appropriate, especially one, CH- or CH2- group is selected from O, N and S hetero atom substitution, and therein 5 or 6 yuan of rings can be selected from halogen, C by 1-3 if appropriate1-C4Alkyl, C1-C4Haloalkyl, C1-C4Halogenated alkoxy, NO2Replace independently of one another with CN substituent；Or two substituent Rs11And R12Ring is formed together：
Figure 9980232300111
Or Q is 2 or 3；And R13For H, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl；R14For hydrogen, C1-C6Alkyl, halo-C3-C6Alkyl, C1-C6Alkoxy, halo-C1-C6Alkoxy, C2-C6Alkenyloxy ,-CHO ,-C (=O)-C1-C6Alkyl ,-C (=O)-halo-C1-C6Alkyl ,-C (=O)-OC1-C6Alkyl ,-C (=O)-O- halos-C1-C6Alkyl ,-CN ,-NO2,  -S(=O)2N(R6)2(two of which R6Substituent is mutually independent) ,-S (=O)p-C1-C6Alkyl ,-S (=O)p- halo-C1-C6Alkyl ,-O-S (=O)p-C1-C6Alkyl ,-O-S (=O)p- halo-C1-C6Alkyl, phenyl, benzyl or benzyloxy, wherein phenyl, benzyl or benzyloxy substituents are respectively unsubstituted or its aromatic ring and are selected from halogen, cyano group, NO2、C1-C6Alkyl, halo-C1-C6Alkyl, C1-C6Alkoxy and halo-C1-C6The substituent of alkoxy replaces 1-5 times independently of one another；And R15For hydrogen, C1-C6Alkyl or halo-C1-C6Alkyl；The invention further relates to prepare and using the method for these compounds, E/Z isomers and dynamic isomer, its active component is selected from the agricultural chemicals of these compounds, E/Z isomers and dynamic isomer, and preparation and the method using these compositions；The invention further relates to prepare the intermediate product (free or salt form) of these compounds, if appropriate, their dynamic isomer (free or salt form), and preparation and the method using these intermediate products and its dynamic isomer.
Some phenyl hydazone derivatives are proposed as pesticide activity component in the literature.But in terms of pest control, the biological nature of these known compounds can not be completely satisfactory, this namely need production with insecticidal properties, be particularly useful for preventing and treating other compounds of insect and Acarina the reason for where；The present invention solves this problem by developing formula as described herein (I) compound.
Some formula (I) compounds include asymmetric carbon atom, therefore these compounds can exist with photoreactive forms.Due to there is C=N double bonds, the compounds of this invention can also exist with E and Z-type isomeric forms.The compounds of this invention can also have atropisomer.Therefore formula (I) should include all these possible isomers and its mixture, for example, racemic modification or E/Z isomer mixtures.
Unless otherwise indicated, general terms used herein has following meanings up and down：
Group and compound comprising carbon atom all include 1-8 carbon atom in each case, preferably 1-6 carbon atom, more particularly 1-4 carbon atom, especially 1 or 2 carbon atom, but unless otherwise stated.
Alkyl -- either in itself or being used as other groups and the structural constituent of compound (such as alkyl halide, alkoxy or alkylthio group) as group -- can be straight chain (i.e. methyl, ethyl, propyl group, butyl, amyl group or hexyl) or side chain (such as isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl or isohesyl), in each case will be with due regard to about the carbon number in group or compound.
Alkenyl -- either still it is used as structural constituent (such as alkenyloxy of other groups and compound in itself as group, alkenyl halogen or alkenyloxy halogen) -- can be (such as isopropenyl) of straight chain (such as vinyl, 1- methyl ethylenes, pi-allyl, 1- cyclobutenyls or 2- hexenyls) or side chain, in each case will be with due regard to about the carbon number in group or compound.
Alkynyl -- being either still used as other groups and the structural constituent of compound (such as alkynyl halogen) in itself as group -- can be (such as the 2- acetenyls propyl group or 2- propargyls isopropyl) of straight chain (such as propargyl, butynyl or 5- hexin bases) or side chain, in each case will be with due regard to about the carbon number in group or compound.
C3-C6Cycloalkyl is cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
Aryl refers to phenyl or naphthyl, especially phenyl.
Bicyclic heteroaryl refers to only in a ring (such as in quinolyl, quinoxalinyl, in indolinyl, benzothienyl or benzofuranyl) and can independently contain in two rings one or more heteroatomic groups (such as in pteridyl or purine radicals).
Halogen -- being either still used as other groups and the structural constituent of compound (such as halogenated alkane, alkenyl halide and halo alkynes) in itself as group -- refers to fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more preferably fluorine or chlorine, more particularly chlorine.
Carbon containing halo groups and compound (such as halogenated alkane, alkenyl halide or halo alkynes) can be partially halogenated or perhalogeno, and in the case of polyhalo, halogenic substituent can be with identical or different.Either as group in itself or as other groups and the structural constituent of compound (such as alkenyl halide), the example of haloalkyl can be replaced the methyl of 1-3 times by fluorine, chlorine and/or bromine, such as CHF2Or CF3；Replaced the ethyl of 1-5 times, such as CH by fluorine, chlorine and/or bromine2CF3,CF2CF3,CF2CCl3,CF2CHCl2,CF2CHF2,CF2CFCl2,CF2CHBr2,CF2CHClF,CF2CHBrF or CClFCHClF；Replaced the propyl group or isopropyl of 1-7 times, such as CH by fluorine, chlorine and/or bromine2CHBrCH2Br,CF2CHFCF3,CH2CF2CF3Or CH (CF3)2；And replaced the butyl or its any isomers of 1-9 times, such as CF (CF by fluorine, chlorine and/or bromine3)CHFCF3Or CH2(CF2)2CF3.Haloalkenyl group is, for example, CH2CH=CHCl,CH2CH=CCl2,CH2CF=CF2Or CH2CH=CHCH2Br.Halo alkynes is, for example, CH2C≡CF,CH2C≡CCH2Cl or CF2CF2C≡CCH2F。
As is well known to those skilled in the art, some formula (I) compounds can exist with tautomeric forms, particularly work as R2During for H.It will thus be appreciated that formula (I) compound that any part of the context of the invention is previously mentioned all also includes its corresponding dynamic isomer, do not refer to that the latter is also such specifically even if in each case.
Acid-addition salts can for example be formed by showing formula (I) compound of at least one basic center.For example, these salt are formed by following acid：Strong inorganic acid, such as inorganic acid, as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrogen halides；Strong organic carboxyl acid, such as C1-C4Alkanoic acid, if appropriate this carboxylic acid can be optionally substituted by halogen (such as acetic acid), such as dicarboxylic acids, if appropriate its can be undersaturated (such as oxalic acid, malonic acid, butanedioic acid, maleic acid, fumaric acid or phthalic acid), such as hydroxycarboxylic acid (such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid), or benzoic acid, or organic sulfonic acid, typically C1-C4Alkanesulfonic acid or aryl sulfonic acid, if appropriate its can be replaced by such as halogen, such as methanesulfonic acid or p- toluenesulfonic acid.In a broad sense, with least one acidic-group formula (I) compound can also be with alkali forming salt.Include such as metal salt with the acceptable acid addition salts that alkali is formed, typically alkali metal salt or alkali salt (such as sodium salt, sylvite or magnesium salts), or the salt formed with ammonia or organic amine, the organic amine is, for example, morpholine, piperidines, pyrrolidines, single-, two- or three low-grade alkylamines (such as ethamine, diethylamine, triethylamine or dimethyl propylamine) or single-, two- or trihydroxy-low-grade alkylamine (such as single-, two- or triethanolamine).If appropriate, corresponding inner salt can also be formed.Formula (I) compound of free form is within a context it can be appreciated that also inferred its corresponding salt, if instead properly, the salt is it can be appreciated that also inferred formula (I) free cpds.This is equally applicable to the dynamic isomer derivative and its salt of formula (I) compound.General all preferred free form in all cases.
In the scope of the invention, preferred following classes compound：(1) formula (I) compound, wherein A1And A2It is selected from following substituent independently of one another：
Figure 9980232300141
With
Particularly phenyl, naphthyl, pyridine radicals or thiadiazolyl group, more particularly phenyl or pyridine radicals, particularly phenyl；R3R in expression (I)3aAnd R3b；R3aAnd R3bIt is halogen ,-CN, NO independently of one another2, halo-C1-C2Alkyl, C1-C2Alkoxy or halo-C1-C2Alkoxy, halo-C2-C5Alkenyloxy or halo-C2-C5Alkynyloxy group；Especially chlorine ,-CN, CF3Or OCF3；If wherein m+n is more than 1, group R3aAnd R3bIt is mutually independent；R4For H, C1-C4Alkyl, phenyl or benzyl；Especially H and methyl；
N is 0-5, especially 1-3, and it depends on the substitution possibility of ring system, and A1In n values independently of A2In n values；
According to the substitution possibility of ring system, m is m values in 0-4, and A1 independently of A2In m values.
M+n sums are 0-5, especially 1,2 or 3；(2) formula (I) compound, wherein A2Represent selected from furyl, thienyl,With
Figure 9980232300162
Substituent, and R2For R2aOr R2b；(3) formula (I) compound, wherein A1And A2For phenyl；(4) formula (I) compound, wherein：R2aFor-C1-C6Alkyl-NR11R12,-C(=X)-R7a,-COC9-C20Alkyl ,-C1-C6Alkyl-O-C1-C6Alkyl-O-C1-C6Alkyl ,-CH2O(C=O)C1-C6Alkyl ,-CH2O(C=O)C2-C6Alkenyl ,-CH2O(C=O)C2-C6Alkynyl ,-C (=S) OC2-C6Alkenyl ,-C (=S) OC2-C6Alkynyl ,-C (=S) SC1-C6Alkyl ,-C (=S) SC2-C6Alkenyl ,-C (=S) SC2-C6Alkynyl ,-C (=O) SC1-C6Alkyl ,-C (=O) SC2-C6Alkenyl ,-C (=O) SC2-C6Alkynyl ,-C (=S) NR11R12,-C(=O)NR10OR13,-CH2OC2-C6Alkenyl ,-CH2OC2-C6Alkynyl ,-CH2OC2-C6Halogenated alkenyl or-CH2OC2-C6Halo alkynyl；Especially, R2aFor-CH2Alkyl-NR11R12,-COC9-C20Alkyl ,-C1-C2Alkyl-O-C1-C2Alkyl-O-C1-C2Alkyl ,-CH2O(C=O)C1-C2Alkyl ,-CH2O(C=O)C2-C4Alkenyl ,-CH2O(C=O)C2-C4Alkynyl ,-C (=S) OC2-C4Alkenyl ,-C (=S) OC2-C4Alkynyl ,-C (=S) SC1-C2Alkyl ,-C (=S) SC2-C4Alkenyl ,-C (=S) SC2-C4Alkynyl ,-C (=O) SC1-C2Alkyl ,-C (=O) SC2-C4Alkenyl ,-C (=O) SC2-C4Alkynyl, C1-C4Alkylthio group-C1-C2Alkyl ,-C (=S) NR11R12-C(=O)NR10OR13,-CH2OC2-C4Alkenyl ,-CH2OC2-C4Alkynyl ,-CH2OC2-C4Halogenated alkenyl or-CH2OC2-C4Halo alkynyl；Particularly R2aFor-CH2Alkyl-NR11R12,-COC9-C20Alkyl ,-C1-C2Alkyl-O-C1-C2Alkyl-O-C1-C2Alkyl ,-CH2O(C=O)C1-C2Alkyl ,-C (=O) SC1-C2Alkyl ,-CH2OC2-C4Alkenyl or-CH2OC2-C4Alkynyl；Particularly R2aFor-CON (OCH3)CH3,-C(O)NHCOCH3,-COSC2H5,-COSCH3,-CH2OC(O)(CH3)3,-CH2OC2H4OCH3,-CH2OCH2CH=CH2,-CH2OCH2C≡CH,-COC10H21；(5) formula (I) compound, wherein R2bFor hydrogen ,-C1-C4Alkyl ,-C1-C4Alkoxy -C1-C4Alkyl ,-C (=X)-R7a,-C(=O)-C1-C4Alkyl ,-C (=O)-halo-C3-C6Alkenyl ,-C (=O)-C3-C6Cycloalkyl ,-C (=O)-O-C1-C2Alkyl ,-C (=O)-C (=O)-O-C1-C2Alkyl ,-C (=O)-C (=O)-N (R6)2, cyano group, benzoyl or benzyl, the wherein aromatic ring of benzoyl or benzyl can be selected from halogen ,-CN ,-NO if necessary2, trifluoromethoxy and trifluoromethyl substituent replace 1-3 times independently of one another；Or be-C (=O)-N (R6)2；And two R6Substituent is H, C independently of one another1-C4Alkyl, C3-C6Cycloalkyl, phenyl or benzyl, wherein phenyl or benzyl can be selected from halogen ,-CN, C if necessary1-C4Alkyl, C1-C4Alkoxy, halo-C1-C2Alkyl and halo-C1-C2The substituent of alkoxy replaces 1 or 2 time independently of one another on aromatic ring；Or two alkyl group R6Five or hexatomic ring, CH therein are formed together with the nitrogen-atoms that they are connected2- group can replace by O atom or by NH if necessary, and therein five or hexatomic ring can be replaced if necessary by methyl；Especially R2bFor hydrogen, C1-C3Alkyl, C1-C2Alkoxy -C1-C2Alkyl ,-C (=O)-C1-C2Alkyl ,-C (=O)-fluoro-C4-C6Alkenyl ,-C (=O)-cyclopropyl ,-C (=O)-O-C1-C2Alkyl ,-C (=O)-C (=O)-O-C1-C2Alkyl ,-C (=O)-C (=O)-N (R6)2, cyano group, benzyl or o- nitrobenzyl；-C(=O)-N(R6)2；Or-C (=O)-C6H5, benzyl ring therein is equally selected from halogen, NO2, trifluoromethoxy and trifluoromethyl substituent replace 1-3 times；And
Two R6Group is H, C independently of one another1-C4The aromatic ring of alkyl, cyclopropyl, phenyl or benzyl, wherein phenyl or benzyl can be selected from chlorine ,-CN and OCF if necessary3Substituent replace independently of one another 1 or 2 time；Or two R6Alkyl forms hexatomic ring, and CH therein if appropriate together with the nitrogen-atoms that they are connected2- group is by O atom or by NCH3Substitution；(6) formula (I) compound, wherein A1For pyridine radicals；(7) formula (I) compound, wherein (R3a)n1For Cl, Cl2,Cl3,-(CF3)2,Cl-CF3,NO2,-CN,Cl2-NO2,-OCF3,-CF3,Cl-CF3,Cl2-CF3,Cl2-OCF3,-Cl2-F,Cl2-Br,Cl-CF3-F,Cl-Br-CH3,-(CH3)2-Br,Cl3-CF3,Cl2-F-CF3,F2-CF3-Cl,Cl2-CN,Cl2-CF3,Cl2-SCF3,Cl2-OCF3,Cl2-O2CF3,Cl2-SO2CH3,Cl2-OCF2Br,Cl2-OCF2H,Cl2-C2F5,(NO2)2-CF3,(NO2)2-Cl,Cl2-SO2CH3Or Cl2-OSO2CF3；Particularly 2-Cl, 2,3-Cl2,2,4-Cl2,2,6-Cl2,2,4,6-Cl3,3,5-(CF3)2,2-Cl-4-CF3,2-NO2,2-CN,3-CN,4-CN,2,6-Cl2-4-NO2,4-OCF3,4-CF3,3-CF3,2-Cl-4-CF3,2-Cl-4-NO2,2,6-Cl2-4-CF3,2,6-Cl2-4-OCF3,2,6-Cl2-4-F,2,6-Cl2-4-Br,2-Cl-4-CF3-6-F,2-Cl-4-Br-6-CH3,2,6-(CH3)2-4-Br,2,3,6-Cl3-4-CF3,2,6-Cl2-3-F-4-CF3,2,3-F2-4-CF3-6-Cl,2,6-Cl2-4-CN,2,4-Cl2-6-CF3,2,6-Cl2-4-SCF3,2,6-Cl2-4-SOCF3,2,6-Cl2-4-SO2CF3,2,6-Cl2-4-SO2CH3,2,6-Cl2-4-OCF2Br,2,6-Cl2-4-OCF2H,2,6-Cl2-4-C2F5,2,6-(NO2)2-4-CF3,2,6-(NO2)2-4-Cl,2,6-Cl2-4-OSO2CH3, or 2,6-Cl2-4-OSO2CF3；More particularly 2,3-Cl2,2,4-Cl2,2,6-Cl2,2,4,6-Cl3,3,5-(CF3)2,2-Cl-4-CF3,2-CN,3-CN,4-CN,2,6-Cl2-4-NO2,4-OCF3,4-CF3,3-CF3,2-Cl-4-CF3,2-Cl-4-NO2,2,6-Cl2-4-CF3,2,6-Cl2-4-OCF3,2,6-Cl2-4-F,2,6-Cl2-3-F-4-CF3,2,3-F2-4-CF3-6-Cl,2,6-Cl2-4-CN,2,4-Cl2-6-CF3,2,6-Cl2-4-SCF3,2,6-Cl2-4-SOCF3,2,6-Cl2-4-SO2CF3,2,6-Cl2-4-C2F5,2,6-(NO2)2-4-CF3,2,6-(NO2)2-4-Cl,2,6-Cl2-4-OSO2CH3, or 2,6-Cl2-4-OSO2CF3；(8) formula (I) compound, one of them (R3b)n2For-the S (=O) on 4- positionsp-C1-C6Alkyl or the-S (=O) on 4- positionsp- halo-C1-C6Alkyl；Particularly-S (=O)p-C1-C3Alkyl or-S (=O)p- halo-C1-C3Alkyl；More particularly-S (=O)p- halo-C1-C3Alkyl；Especially, wherein n2For 1 and R3bFor SOCF3,SOC2F5,SOCHF2,SOCF2Br,SOCF2Cl,SOCF2CF2Br,SOCF2CF2Cl,SCF3,SC2F5,SCHF2,SCF2Br,SCF2Cl,SCF2CF2Br,SCF2CF2Cl,SO2CF3,SO2C2F5,SO2CHF2,SO2CF2Br,SO2CF2Cl,SO2CF2CF2Br,SO2CF2CF2Cl, (9) formula (I) compound, wherein (R3b)n2For-CN, Cl, Cl2,F,F2,Br,-NO2,-(NO2)2,-NO2-CF3,CF3,-(CF3)2,-CN-CF3,Cl-CF3,F-CN,-Cl-CN,-OCF3,-Cl-NO2,-CH3-NO2,-OCH3-NO2,-C6H5,-C6H4-F,-C6H4-Cl,-C6H4-CF3,-C6H4-CF3,-C6H4-NO2,-C6H3-(CF3)2,-C6H3-Cl2,-C6H3-(Cl-F),-F-CN,F-NO2,Cl-NO2,Cl-NO2,-CHO,SCF3,SOCF3,SO2CF3Or-C (=O) CF3；Particularly
4-CN,3-CN,4-Cl,3,4-Cl2,2,3-Cl2,3,5-Cl2,2,5-Cl2,3,5-F2,2,6-F2,4-Br,2-F,4-NO2,2-NO2-4-CF3,3-CF3,4-CF3,3,5-(CF3)2,2-CN-4-CF3,2-Cl-4-CF3,2-F-4-CN,3-Cl-4-CN,4-OCF3,3-OCF3,4-Cl-3-NO2,2-Cl-4-NO2,3-CH3-4-NO2,3-OCH3-4-NO2,4-C6H5,4-C6H4-4-F,4-C6H4-4-Cl,4-C6H4-4-CF3,4-C6H4-3-CF3,4-C6H4-3-NO2,4-C6H3-(3,5-CF3)2,4-C6H3-2,4-Cl2,4-C6H3-3,4-Cl2,4-C6H3-3,5-Cl2,4-C6H3-(3-Cl-4-F),2-F-4-CN,2-F-4-NO2,2-Cl-4-NO2,4-Cl-3-NO2,4-CHO,4-SCF3,4-SOCF3,4-SO2CF3, or 4-C (=O) CF3；More particularly
4-CN,3-CN,4-Cl,3,4-Cl2,2,3-Cl2,3,5-Cl2,2,5-Cl2,3,5-F2,2,6-F2,2-F,2-NO2-4-CF3,4-NO2,3-CF3,4-CF3,3,5-(CF3)2,2-CN-4-CF3,2-Cl-4-CF3,2-F-4-CN,3-Cl-4-CN,4-OCF3,3-OCF3,4-Cl-3-NO2,2-Cl-4-NO2,3-CH3-4-NO2,3-OCH3-4-NO2,4-C6H5,2-F-4-CN,2-F-4-NO22-Cl-4-NO2,4-Cl-3-NO2,4-CHO,4-SCF3,4-SOCF3,4-SO2CF3Or 4-C (=O) CF3；(10) formula (I) compound, wherein R2bFor hydrogen；(11) formula (I) compound, wherein n1For 1,2,3 or 4, preferably 2 or 3；(12) formula (I) compound, wherein n2For 1 or 2, preferably 1；(13) formula (I) compound, wherein n1For 2,3, or 4, and n2For 1 or 2；(14) formula (I) compound, wherein R11And R12It is H, C independently of one another1-C2Alkyl, phenyl ,-COC1-C2Alkyl ,-CO phenyl, or five or hexa-atomic saturations or unsaturation ring are formed together, wherein a CH- or CH if appropriate2- group can be selected from O, N and S hetero atom substitution, and if appropriate therein five or hexatomic ring can by 1 or 2 be selected from C1-C2Alkyl, C1-C2Haloalkyl, NO2, CN substituent substitution；Or two substituent Rs11And R12Ring is formed together：
Figure 9980232300191
Or
Figure 9980232300192
And q is 2；Particularly R11And R12It is H, C independently of one another1-C2Alkyl, phenyl ,-COC1-C2Alkyl, more particularly-CO phenyl, H, methyl or ethyl.(15) formula (I) compound, wherein at least one R3aAnd/or R3bFor-CR5=CR5R14, and R14For hydrogen, C1-C6Alkyl, halo-C1-C6Alkyl ,-CHO ,-C (=O)-C1-C6Alkyl ,-C (=O)-halo-C1-C6Alkyl ,-C (=O)-OC1-C6Alkyl ,-C (=O)-O- halos-C1-C6Alkyl ,-CN ,-NO2,-S(=O)2N(R6)2(two of which R6Substituent is mutually independent) ,-S (=O)p-C1-C6Alkyl, phenyl, benzyl or benzyloxy；And R5For hydrogen or C1-C2Alkyl；Especially R3aOr R3bFor-CR5=CR5R14；R14For hydrogen, C1-C2Alkyl, halo-C1-C2Alkyl, phenyl or benzyl；And R15For methyl or CF3；(16) formula (I) compound, wherein R5It independently is H or C1-C2Alkyl；(17) formula (I) compound, wherein n2For 1, and (R3b)n2For SCH3,SCF3,SC2H5,SC2F5,SOCH3,SOC2H5,SOC2F5,SO2N(CH3)2,SO2N(C2H5)2,SO2CH3,SO2CF3,SO2C2H5,SO2C2F5,SOCF3,SOCHF2,SOCF2Br,SOCF2Cl,SOCF2CF2Br,SOCF2CF2Cl,SCHF2,SCF2Br,SCF2Cl,SCF2CF2Br,SCF2CF2Cl,SO2CHF2,SO2CF2Br,SO2CF2Cl,SO2CF2CF2Br or SO2CF2CF2Cl；Particularly SCF3,SC2F5,SOCF3 SOC2F5,SO2CF3Or SO2C2F5；And R2For R2aOr R2b, especially H ,-CH2OC2H5,-COCH3,-CH3,-CN,-CH2C≡CH,-C2H5,-COOCH3Or-CON (CH3)OCH3。
Within the scope of the present invention, listed by particularly preferred table 3-27 formula (I) compound and if appropriate their E/Z isomers and E/Z isomer mixtures.
It is a further object of the present invention to provide formula (I) compound for preparing free form or salt form and if appropriate their E/Z isomers, E/Z isomer mixtures, and/or its dynamic isomer method, this method includes：A) it is preparation wherein substituent A1And A2It is as defined above, and R2For formula (I) compound of hydrogen, aa) diazotising following formula: compound：
                 A1-NH2(III), wherein A1As defined in above formula (I), and ab) diazol is reacted with formula (IV) compound：
Figure 9980232300211
(IV), wherein A2As defined in above formula (I), and W is hydrogen or can remove group；Or b) be formula (I a) compound：
Figure 9980232300212
(I a), wherein A1,A2And R2Such as R in above-mentioned formula (I) compound2aAnd R2bDefined, make formula (II) compound：(II), wherein A1,A2And R2Such as R in above-mentioned formula (I) compound2aAnd R2bDefined, and Hal is halogen atom, preferably chlorine or bromine, especially chlorine, with metal cyanides, preferred as alkali cyanide especially reacts with Cymag；Or c) be formula (I) in R2It is not H compound, wherein R is preferably made in the presence of a base2Reacted for formula (I) compound and formula (V) compound of hydrogen：
                    R2- Q (V), wherein R2Such as R in above-mentioned formula (I)2aAnd R2bDefined, Q is leaving group, preferably chlorine, bromine or iodine, especially iodine；Or in each case, if desired, by formula (I) compound or its E/Z isomers or dynamic isomer of obtained free form or salt form are converted into formula (I) compound or its E/Z isomers or dynamic isomer of other free or salt forms according to the method described above or otherwise, separation according to the method described above or otherwise obtained E/Z isomer mixtures, and isomers needed for separating, and/or will as stated above or otherwise obtained formula (I) free cpds or its E/Z isomers or dynamic isomer change into salt, or formula (I) free cpds or its E/Z isomers or dynamic isomer will be converted into as stated above or with salt made from other methods, or it is converted into other salt.
Another object of the present invention is related to：D) formula (II a) compound and the method for its E/Z isomers and dynamic isomer if appropriate of free or salt form are prepared
Figure 9980232300221
(II a), wherein A1,A2And R2Such as R in above-mentioned formula (I) compound2aAnd R2bDefined, and Hal is halogen atom, this method includes making formula (VIII) compound：(VIII), wherein group A1And A2And R2With R in formula above (II a)2aAnd R2bDefinition it is identical, reacted with halogenating agent, or the e) method of formula (II b) compound
Figure 9980232300223
(II b), wherein R2With two group A1And A2With A in above-mentioned formula (I) compound1,A2,R2aAnd R2bDefinition it is identical, and Hal is halogen atom, and preferred chlorine, this method includes making formula (Ⅸ) compound：
Figure 9980232300231
(Ⅸ), wherein R2With two group A1And A2It is identical with the definition in above-mentioned formula (II b), reacted with N-bromosuccinimide or N-chlorosuccinimide in the presence of thioether, and in each case, if desired, by according to the method described above or formula (II) compound or its E/Z isomers or dynamic isomer of otherwise obtained free or salt form is converted into formula (II) compound or its E/Z isomers or dynamic isomer of other free or salt forms, separation according to the method described above or otherwise obtained E/Z isomer mixtures, and isomers needed for separating, and/or salt will be changed into as stated above or with formula (II) free cpds made from other methods or its E/Z isomers or dynamic isomer, or will as stated above or otherwise obtained salt is converted into formula (II) free cpds or its E/Z isomers or dynamic isomer, or it is converted into other salt.
React and carry out in a known manner described in the context of the invention, wherein as needed can be in cooling, room temperature, or carried out under heating condition, for example under the boiling temperature of about 0 DEG C-reaction medium, it is preferred that at about 20 DEG C-about+120 DEG C, carry out, and carried out if desired in sealing container in pressurization and inert atmosphere such as nitrogen or argon atmospher, and/or under anhydrous condition at a temperature of especially 60 DEG C -80 DEG C.Carried out it is preferred that reacting the normal pressure in blanket of nitrogen.Reactant can directly be reacted each other, that is, need not add solvent or diluent, for example, react in the molten state.However, in most cases, it is favourable to add atent solvent or diluent or their mixture.Particularly advantageous reaction condition is as described embodiments.
The separation of product can be carried out according to a conventional method, for example any proper combination of filtering, crystallization, distillation or chromatography or these methods.Scheme (variant) a)：Aa) diazotising is carried out under the conditions of well known to those skilled in the art, that is, carried out in the presence of strong inorganic acid such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrogen halides etc inorganic acid, using these it is sour when generally with the presence of water, but it is also possible to using bright sulfur acid.
According to the alkalescence of arylamine, the reaction can be carried out at a temperature of about -10 DEG C to about+20 DEG C, can even be carried out if necessary under higher temperature (such as 60 DEG C -80 DEG C).
Reaction time preferably about 1- about 2 hours.
Product is not separated generally, but is directly further used in the next step.
Particularly preferred reaction condition is as described in embodiment H6/a.Ab) reaction is generally carried out in the presence of water, while it is preferred that there is organic carboxyl acid, such as formic acid, monoxone, trifluoroacetic acid, cyanoacetic acid, oxalic acid, malonic acid, butanedioic acid, maleic acid, fumaric acid or phthalic acid；Particularly preferably add acetic acid.
The electrophilic group that group W refers to be easy to remove under universal reaction condition can be removed.Particularly suitable has-C (=O) R or-OC (=O) R, wherein R to be H, C1-C4Alkyl, halo-C1-C4Alkyl, C1-C4Alkoxy, halo-C1-C4Alkoxy ,-CN, or organic sulfonic acid ester, such as C1-C4Alkane or aromatic yl sulphonate, if necessary they can be replaced by such as halogen, such as methane, fluoroform or p- tosylate.
The reaction is suitable at about -10 DEG C to about+30 DEG C, is carried out at a temperature of preferably approximately 0 DEG C to about+25 DEG C.
Reaction time preferably approximately 0.5- about 8 hours, about especially 2- about 4 hours.Scheme b)
It is transition metal cyanide compound suitable for reaction, such as CuCN or Ni (CN)2, and alkaline-earth metal and alkali metal cyanide；Especially KCN and NaCN.
The example of solvent or diluent is：Aromatics, aliphatic series and clicyclic hydrocarbon and halogenated hydrocarbons, such as benzene, toluene, dimethylbenzene, 1,3,5- trimethylbenzene, 1,2,3,4- tetrahydronaphthalenes, chlorobenzene, dichloro-benzenes, bromobenzene, petroleum ether, hexane, hexamethylene, dichloromethane, chloroform, tetrachloromethane, dichloroethanes, trichloro ethylene or tetrachloro-ethylene；Esters, such as ethyl acetate；Ethers, such as ether, dipropyl ether, Di Iso Propyl Ether, butyl oxide, t-butyl methyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, dimethoxy Anaesthetie Ether, tetrahydrofuran or dioxane；Ketone, such as acetone, MEK or methyl iso-butyl ketone (MIBK)；Alcohols, such as methanol, ethanol, propyl alcohol, isopropanol, butanol, ethylene glycol or glycerine；Amide-type, such as DMF, N, N- diethylformamides, DMA, 1-METHYLPYRROLIDONE or HMPA；Nitrile, such as acetonitrile or propionitrile；And sulfoxide type, such as dimethyl sulfoxide, or water.It is preferred that alcohol and water or alcohol/aqueous mixtures.
The reaction is preferably carried out at a temperature of about 0 DEG C-about 80 DEG C, preferably approximately 20 DEG C-about 30 DEG C, is carried out under the reflux temperature of room temperature-reactant mixture in many cases.
Reaction time preferably approximately 0.1- about 24 hours, about especially 3- about 5 hours.
In scheme b) preferred embodiment in, formula (II) compound is reacted at room temperature in ethanol/water mixed liquor with Cymag.Scheme c)
In formula (V) compound, suitable leaving group Q is, for example, hydroxyl, C1-C8Alkoxy, halo-C1-C8Alkoxy, C1-C8Alkanoyloxy, sulfydryl, C1-C8Alkylthio group, halo-C1-C8Alkylthio group, C1-C8Alkylsulfonyloxy, halo-C1-C8Alkylsulfonyloxy, phenylsulfonyloxy, tosyloxy and halogen, preferably tosyloxy, trifluoro-methanesulfonyl oxy or halogen, especially halogen, particularly bromine or chlorine.
Suitable alkali for promoting reaction is hydroxide, hydride, amide, alkoxide, acetate, carbonate, dialkylamides or the alkylsilyl-amides of such as alkali metal or alkaline-earth metal, alkylamine, Alkylenediamine, Cycloalkyl amine (can be N- alkylations if appropriate, and be if appropriate undersaturated), basic heterocycles, ammonium hydroxide and carbocyclic amines.The example has：Sodium hydroxide, sodium hydride, Sodamide, sodium methoxide, sodium acetate, and sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, hydrofining, lithium diisopropylamine, double (trimethyl silyl) ammonification potassium, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclo-hexylamine, N- cyclohexyl-N, N- dimethyl amines, N, N- diethylanilines, pyridine, 4- (N, N- dimethylamino) pyridine, quinuclidine, N-methylmorpholine, hydroxide benzyltrimethylammon.um and the carbon -5- alkene (DBU) of 1,5- diazabicyclo [5.4.0] 11.The alkoxide of the carbonate of preferred as alkali and alkaline-earth metal, alkylamine and alkali metal or alkaline-earth metal.
The example of solvent or diluent has：Aromatics, aliphatic series and clicyclic hydrocarbon, typically benzene, toluene, dimethylbenzene, 1,3,5- trimethylbenzene, 1,2,3,4-tetrahydro-naphthalene, chlorobenzene, dichloro-benzenes, bromobenzene, petroleum ether, hexane, hexamethylene；Ethers, such as ether, dipropyl ether, diisopropyl ether, butyl oxide, t-butyl methyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, dimethoxy Anaesthetie Ether, tetrahydrofuran or dioxane；Esters, such as ethyl acetate and methyl acetate；And sulfoxide type, such as dimethyl sulfoxide.It is preferred that ethers (such as t-butyl methyl ether, tetrahydrofuran or dioxane) and esters (such as ethyl acetate).
Reaction is preferably carried out at a temperature of about 0 DEG C-about+120 DEG C, preferably approximately 0 DEG C-about+80 DEG C.
Reaction time preferably about 0.1- about 24 hours, about especially 0.5- about 2 hours.Scheme d)
The reaction is preferably carried out in presence of an acid catalyst, such as carboxylic acid, such as formic acid, acetic acid, malonic acid or oxalic acid, or also sulfonic acid, such as C1-C4Alkyl or aryl sulfonic acid, if necessary the sulfonic acid can be replaced by such as halogen, such as methane, fluoroform or p- toluenesulfonic acid.
Particularly suitable solvent should be suitable for azeotropic water removing.The example of this kind of solvent or diluent has：Aromatics, aliphatic series and clicyclic hydrocarbon and halogenated hydrocarbons, such as benzene, toluene, dimethylbenzene, 1,3,5- trimethylbenzene, 1,2,3,4- tetrahydronaphthalenes, chlorobenzene, dichloro-benzenes, bromobenzene, petroleum ether, hexane, hexamethylene, dichloromethane, chloroform, tetrachloromethane, dichloroethanes, trichloro ethylene or tetrachloro-ethylene；Esters, such as ethyl acetate；Ethers, such as dipropyl ether, Di Iso Propyl Ether, butyl oxide, t-butyl methyl ether, dimethoxy Anaesthetie Ether；Ketone, such as methyl iso-butyl ketone (MIBK)；Alcohols, such as ethanol, propyl alcohol, isopropanol, butanol, ethylene glycol or glycerine.
The reaction is preferably carried out at a temperature of about 60 DEG C-about 180 DEG C, preferably 80 DEG C-about 130 DEG C.Reaction is to carry out at the reflux temperature of the reaction medium under most of situations.
It is preferred that reaction time be about 6- about 72 hours, especially about 12- about 48 hours.
In scheme d) preferred form in, reaction is in C1-C4Carried out in the presence of carboxylic acid in 80 DEG C -140 DEG C in alcohol or aromatic hydrocarbons.Scheme e)
It is preferred that halogenating agent be Cl2,Br2,SOCl2,SO2Cl2,POCl3,PCl3,PCl5And COCl2。
The example of solvent or diluent has：Aromatics, aliphatic series and clicyclic hydrocarbon and halogenated hydrocarbons, such as benzene, toluene, dimethylbenzene, 1,3,5- trimethylbenzene, 1,2,3,4- tetrahydronaphthalenes, chlorobenzene, dichloro-benzenes, bromobenzene, petroleum ether, hexane, hexamethylene, dichloromethane, chloroform, tetrachloromethane, dichloroethanes, trichloro ethylene or tetrachloro-ethylene；Esters, such as ethyl acetate；Ethers, such as ether, dipropyl ether, Di Iso Propyl Ether, butyl oxide, t-butyl methyl ether, glycol dimethyl ether, dimethoxydiethylether, tetrahydrofuran or dioxane；Ketone, such as acetone, MEK or methyl iso-butyl ketone (MIBK)；Amide-type, such as DMF, N, N- diethylformamides, DMA, 1-METHYLPYRROLIDONE or HMPA；Nitrile, such as acetonitrile or propionitrile.
The reaction is preferably carried out at a temperature of about 0 DEG C-about 180 DEG C, preferably approximately 50 DEG C-about 100 DEG C.Reaction is what is carried out at a temperature of between the reflux temperature of room temperature and reactant mixture under many circumstances.
Reaction time is not key；It is preferred that reaction time be about 0.1- about 24 hours, especially from about 3- about 6 hours.
According to the number of such as asymmetric carbon atom and its absolute and relative configuration, formula (I), (II a), the compound of (II b) and (VIII) can exist with any possible isomers or its form of mixtures, such as pure isomers, such as enantiomer and/or diastereoisomer or isomer mixture, such as mixture of enantiomers, such as racemic modification；The present invention is not only related to pure isomers, and further relates to all possible isomer mixture, and all should so understand within a context, even if not referring to that detailed spatial chemistry also should so understand specifically in each case.
According to the inventive method (method therefor depend on initial substance and selected reactions steps) or the otherwise non-enantiomer mixture and racemic mixture of obtained formula (I), (II a), (II b) and (VIII) compound, pure diastereoisomer or racemic modification can be separated into a known manner, and the physicochemical property that this is attributed to wherein each component is different.For example, above-mentioned separation can be completed by fractional crystallization, distillation and/or chromatography.
The fractionation for the mixture of enantiomers (such as racemic modification) that can accordingly obtain can be completed using known method; for example; with optically active solvent recrystallization, use chiral adsorbent chromatography; crack, split by forming inclusion compound such as using the high pressure lipuid chromatography (HPLC) (HPLC) of acetylcellulose, using suitable microorganism, with specific immobilised enzymes; chiral crown ether is such as used, wherein only coordinating a kind of enantiomer.
According to the present invention, in addition to separating corresponding isomer mixture, pure diastereomer or enantiomer can also be made using generally known cis-selectivity or enantioselective synthesis method, for example, implementing the inventive method using the educt with corresponding suitable stereo chemistry.
If each one-component shows different biological efficacies, all preferable separate or synthesis have the isomers (such as enantiomer) or isomer mixture (such as mixture of enantiomers) of more high bioactivity in all cases.
Resulting formula (I), (II a), (II b) and (VIII) compound for its hydrate forms and/or can also include other solvents, for example, the if necessary solvent used in crystalline solid forms compound.
The present invention relates to all these modes of methods described, according to these modes, people can the inventive method any stage by the compound that can be used as raw material or intermediate, and carry out all or some the step of wherein omit, either use or produce derivative or the starting material of salt form and/or its racemic modification or enantiomer-especially at reaction conditions-.
In the methods of the invention, starting material used and intermediate can preferably produce those for starting the formula (I) compound herein, because they are particularly useful.
The present invention is more particularly directed to the preparation method described in embodiment H1, H2, H4 and H5.
According to the present invention, initiation material and intermediate product for formula (I) compound, particularly formula (II), (III), (IV) and (VIII) compound, these compounds are new, their purposes and prepare their method and equally constitute the object of the invention.
Formula (II a), (II b) and (VIII) compound and their purposes in terms of formula (I) compound constitute another object of the present invention.
Formula (III)-(VI) and (Ⅸ) compound are known, or can be prepared by known method.
Another object of the present invention is related to applying equation (I) compound (wherein A1,A2And A3Be defined as above formula (I)) preventing and treating pest and disease damage method.
For pest control application, formula (I) compound is valuable prevention and/or therapeutical active substance, and very favorable biocidal activity spectrum can be provided, while have favourable tolerance to warm-blooded animal, fish and plant, in addition in the case of low concentration it is also such.The present composition is all active to all or single stages of development of display normal sensitivity and resistant insect (such as insect or Acarina).Desinsection, ovicidal and/or the miticidal effect of the present composition can be showed directly, also insect (such as when casting off a skin) or its ovum can be killed at once or over time, or show indirectly, spawning quantity and/or incubation rate are such as reduced, and also shows the Superior efficacy corresponding at least 50-60% destruction rate (death rate).
The insect includes, for example：
Lepidoptera, coleoptera, Orthoptera, Isoptera nibbles (worm) mesh, Anoplura, Mallophaga, Thysanoptera, Semiptera, Homoptera, Hymenoptera, Diptera, Siphonaptera, Thysanoptera and Acarina；The category class and kind class pest being especially preferred for use in described in preventing and treating EP-A-736252, its content is incorporated to herein to be incorporated by reference.
Utilize inventive compound; it can prevent and treat and appear in plant; on crop and ornamental plant especially in agricultural, gardening and forest; or appear in harmful organism on the plant parts (such as fruit, flower, leaf, stem, stem tuber or root) of these plants; suppress or eliminate them, and this protective effect is also kept to the part grown after some plants from without occurring insect pest.
In application of the present invention, target body crop especially includes：Cereal, such as wheat, barley, rye, oat, paddy rice, corn or sorghum；Beet, such as sugar beet and fodder beet；Fruit, such as the operatic circle, drupe and berry (such as apple, pears, Lee, peach, apricot, cherry or berry, such as strawberry, raspberry and blackberry, blueberry)；Legume, such as Kidney bean class, French beans class, pea class or big beans；Oilseed plant, such as rape, leaf mustard, opium poppy, olive, sunflower, coconut, castor-oil plant, cocoa bean or peanut；Mellon plant, such as pumpkin, cucumber or muskmelon；Fibre plant, such as cotton, flax, hemp or jute；Tangerine fruit, such as orange, lemon, grape or citrus；Vegetables, such as spinach, lettuce, Lu Zheng, cabbage, carrot, onion, tomato, potato or pimiento；Lauraceae, such as avocado, Chinese cassia tree or camphor；And tobacco, nut, coffee, eggplant, sugarcane, tea, pepper, grape, hops, banana plant, natural rubber plant and ornamental plant.
Inventive compound is particularly suitable for preventing and treating raise crop such as the insect in cotton, fruit, corn and soybean, rape and greengrocery and acarina pest, particularly take food the insect with damage crops, such as Mexico's Anthonomusgrandis, band spot cucumber is chrysomelid, tobacco budworm larva, diamondback moth and Spodoptera littoralis, and Tetranychidae, such as Tetranychus.
Other adaptation fields of inventive compound are protection storing products and material, and in terms of health, especially protect domestic animal and livestock to resist the species pestinfestation.
Therefore, the present invention relates to agricultural chemicals, it includes formula (I) compound, wherein A1,A2And R2It is defined as above except formula (I), but 1- Phenylhydrazono -2- nitrilo- ethylo benzenes.Missible oil, suspension concentrate for example including at least one inventive compound, can Direct spraying or dilutable solution, can be coated paste, dilute emulsion, agent of dusting, soluble powder, dispersible powder, wettable powder, pulvis, granule or the encapsulation agent being encapsulated in polymer (specifically used formulation is selected according to the main environment of predetermined purpose and surrounding).
In these compositions, use pure active component, solid active agent is used with specified particle size, or the auxiliary agents such as filler (such as solvent or solid carrier) that formulation art is usually used preferably is processed with least one, or surface active cpd (surfactant) is used together.
According to the present invention, suitable adjuvant used in composition, such as solvent, solid carrier, surface active cpd, nonionic surfactant, cationic surfactant and anion surfactant are identical with described in EP-A-736252 (files 20400), and it is for reference to include these contents herein for purposes of the present invention.
0.1-99%, especially 0.1-95% active components and 1-99.9% are generally comprised in composition, especially 5-99.9%, at least one solid or liquid adjuvants, wherein the 0-25% of composition weight, especially 0.1-20% are generally surfactant (% refers both to percetage by weight in all cases).As commercially available prod be often although concentrate composition it is furthermore preferred that end user usually using diluted composition, the concentration of wherein active component is significant lower.For example, it is preferable to composition particularly including as described in EP-A-736252.
By adding other desinsections, tick mite killing and/or Fungicidal substance, the activity profile of the present composition can be significantly widened, and adapt to common situation.For example, additional active component can be following various materials：Organic phosphorus compound, nitrophenols and its derivative, formamidine, urea, carbamates, pyrethroid, chlorinated hydrocarbon and thuricade-1.The composition of the present invention can also include other solids or liquid auxiliary agent, such as such as stabilizer, vegetable oil, it can be at least partially epoxidized (such as epoxidised coconut oil, rape seed oil or soya-bean oil), such as defoamer, silicone oil if appropriate, preservative, viscosity modifier, adhesive and/or thickener, and fertilizer or other can obtain the active component of certain effects, such as tick mite killing agent, bactericide, nematicide, invertebrate poison or selective herbicide.
The present composition is prepared in known manner.For example, in the presence of without adjuvant it is made by grinding and/or sieving solid active agent or mixture of active principles to such as specified particle size, and in the presence of having at least one auxiliary agent, then prepared for example, by close mixing and/or grinding active component or mixture of active principles and auxiliary agent.The method and formula (I) compound for preparing the present composition equally also constitute the purpose of the present invention in the application for preparing these Composition Aspects.
Using the method for composition, that is, the method for described kind of class pest of control, as spraying, atomizing, dust, apply, dress seed, disseminate or pour and (these application processes are selected according to predetermined purpose and main environment situation), and the present composition control described kind of class pest in terms of application also constitute the object of the invention.The typical concentration of active component is 0.1-1000ppm, preferably 0.1-500ppm.Amount of application is usually per hectare (ha=about 2.471 acre) 1-2000g active component (a.i.), especially 10g-1000g a.i./ha, and preferably 20g-600g a.i./ha.
For crop protection, application process preferably is to be sprayed onto active component on the blade face of plant (foliage spray), and application times and amount of application infect degree depending on the insect.But, active component can also be by using fluid composition with squirting plant growth, (interior to inhale) is penetrated into plant by root through soil, or penetrated into by the way that the compound of solid form (such as granule) is applied into soil by root in plant (soil application).For rice crop, granule can be measured in the rice field for being applied to and pouring water.
The present composition is also adapted to protect plant propagation material, such as seed (such as fruit, stem tuber or grain) and plant cutting, to resist fungal infection and animal pests.Propagating materials can first use compositions-treated before cultivation is started, for example, first seed is dressed seed before planting.The active component of the present invention can also be used for seed (coating) by being soaked seed in fluid composition or being coated them with solid composite coating.The present composition can also apply when propagating materials is cultivated, for example, apply when seed is seeded into ditch dug with a plow.The processing method of plant propagation material and so processed propagating materials are the further object of the present invention.
The present invention is illustrated with the following example, but they do not produce any limitation to the present invention.Prepare EXAMPLE Example H1：Prepare following formula 4- nitrobenzoic acids-N '-(2,6- dichlor-4-trifluoromethyls phenyl) hydrazides：
Stirring and 0-5 DEG C at, the 150ml dichloromethane solutions of 35.85g 4- nitrobenzoyl chlorides are added drop-wise in 45.1g 2, the 1000ml dichloromethane solutions of 6- dichlor-4-trifluoromethyl phenylhydrazines in about 60 minutes, then room temperature continue stir 60 minutes.While mixture is stirred vigorously, in addition 20.4g triethylamines in 20 minutes.Thereafter continue to stir 3 hours at room temperature.Organic phase is washed with water three times (each 500ml), and sodium sulphate is dried and removes solvent with rotary evaporator.Residue obtains the product that fusing point is 188-190 DEG C after re crystallization from toluene.Embodiment H2：Prepare following formula 4- { 1- [(2,6- dichlor-4-trifluoromethyls phenyl) hydrazono-]-chloromethyl }-nitrobenzene：
Under room temperature and stirring, 33.9g thionyl chlorides are added dropwise into the 600ml toluene solutions of 69.3g 4- nitrobenzoic acids-N '-(2,6- dichlor-4-trifluoromethyl phenyl)-hydrazides.Then heating mixture is to 105 DEG C and stirs 6 hours.After cooling, mixture is concentrated to dry, residue toluene crystallization using rotary evaporator.Obtain the title compound (compound 1.20) that fusing point is 117-118 DEG C.Embodiment H3：Listed other compounds can be made according to the similar approach described in embodiment H2 in table 1.Table 1：Following formula: compound：No.    (R3a)n1               (R3b)n2           mp℃1.1    2,6-Cl2-4-CF3         4-Br              124-1251.2    2,6-Cl2-4-CF3         4-COCF3           107-1081.3    2,6-Cl2-4-CF3         3-NO2-4-Cl        141-1431.4    2,6-Cl2-4-CF3         2-F-4-NO2         88-901.5    2,6-Cl2-4-CF3         4-SCF3            137-1381.6    2,6-Cl2-4-CF3         4-SCH3            89-901.7    2,4-Cl2-6-CF3         4-NO2             128-1291.8    2-Cl-4-CF3-6-F          4-NO2             135-1371.9    2,6-Cl2-3-F-4-CF3     4-NO2             143-1441.10   2,3,6-Cl3-4-CF3       4-NO2             121-1231.11   2,4,6-Cl3               4-SO2CH3The 2,4,6-Cl of amorphous substance 1.123               4-SCH3            78-791.13   2,4,6-Cl3              4-F                  97-981.15   2,6-Cl2-4-CF3         4-SO2N(CH3)2    163-1641.16   2,4,6-Cl3               4-CHO              152-1541.17   2,6-(NO2)2-4-CF3     4-NO2             189-1911.18   2-Cl-4-OCF3-6-NO2     4-NO2             147-1481.19   2-Cl-4-CF3              3-NO2-4-Cl        188-1901.20   2,6-Cl2-4-CF3         4-NO2117-118 embodiments H4：Prepare following formula 4- { 1- [(2,6- dichlor-4-trifluoromethyls phenyl) hydrazono-] -2- nitrilo-s ethyl } nitrobenzene：
In about 1 hour, 51.5g solids 4- { 1- [(2,6- dichlor-4-trifluoromethyl phenyl) hydrazono-] chloromethyl } nitrobenzene is added portionwise in the solution of 240ml and 160ml ethanol to 10.7g Cymags.Reactant mixture is stirred at room temperature 18 hours, is subsequently poured into 6 liters of frozen water.Filtering precipitate, is washed three times, and then is dissolved in ethyl acetate, then is washed with 15%NaCl solution.Organic phase is dried with sodium sulphate, filters and is concentrated by evaporation with rotary evaporator to dry.Residue toluene crystallization.Thus the title compound that fusing point is 160-161 DEG C is obtained.Embodiment H5：Prepare following formula 4- { 1- [(2,6- dichlor-4-trifluoromethyls phenyl)-N- methyl-N-methoxy carbamoyls hydrazono-] -2- nitrilo-s ethyl } nitrobenzene：
At room temperature, 0.44g fine-powdered potassium tert-butoxides are added into the 50ml tetrahydrofuran solutions of 1.2g 4- { 1- [(2,6- dichlor-4-trifluoromethyl phenyl) hydrazono-] -2- nitrilo-s ethyl } nitrobenzene.Stir mixture 10 minutes, obtain dark red solution.Then add 0.48g methylmethoxyaminos formyl chloride and stir mixture 3 hours.Solvent is removed using rotary evaporator, and then dissolves the residue in ethyl acetate.Ethyl acetate phase is washed with water and sodium chloride solution, and sodium sulphate is dried, and is concentrated by evaporation under vacuo to dry.Residue uses hexane by silica gel column chromatography: tetrahydrofuran (5: 1) elution.6-14 grades of cuts are concentrated by evaporation, title compound (compound 2.1), fusing point is obtained：96-97℃.Embodiment 6：Listed other compounds can also be made according to the similar approach described in embodiment H5 in table 2 and 3.Table 2：Following formula: compound：C3H3F2Cyc represents fluoro- ring propyl- 1- bases 4-C (NOMe) CF of 2,2- bis-3Represent substituent 4-C (=NOCH3)CF3No.       (R3a)n1          (R3b)n2      R2                  mp(℃)2.1       2,6-Cl2-4-CF3    4-NO2        -CON(OCH3)CH3      96-972.2       2,6-Cl2-4-CF3    4-NO2        -COSC2H5          198-1992.3       2,6-Cl2-4-CF3    4-NO2        -COSCH3             198-2002.4       2,6-Cl2-4-CF3    4-NO2        -CH2OC(O)C(CH3)3  87-90 No.    (R3a)n1            (R3b)n2         R2                  mp(℃) 2.5    2,6-Cl2-4-CF3       4-NO2          -CH2OC2H4OCH3  63-65 2.6    2,6-Cl2-4-CF3       4-NO2          -CH2OCH2CH=CH2   73-74 2.7    2,6-Cl2-4-CF3       4-NO2          -CH2OCH2C≡CH     99-100 2.8    2,6-Cl2-4-CF3       4-SOCF3        -H                  157-158 2.9    2,6-Cl2-4-CF3       4-SO2CF3       -H                 108-109 2.10   2,6-Cl2-4-CF3       4-SCF3         -H                  156 2.11   2,6-Cl2-4-CF3       4-SOCF3        -CH2OC2H52.12 2,6-Cl of oil2-4-CF3       4-SO2CF3       -CH2OC2H52.13 2,6-Cl of oil2-4-CF3       4-SCH3         -H                  147-149 2.14   2,6-Cl2-4-CF3       4-SO2N(CH3)2  -H                201-202 2.15   2,6-Cl2-4-CF3       4-SO2N(CH3)2 -CH2OC2H5       136 2.16   2,6-Cl2-4-CF3       4-SCH3         -CH2OC2H5        80-81 2.17   2,6-Cl2-4-CF3       4-F             -H                  126-128 2.18   2,6-Cl2-4-CF3       4-F             -CH2OC2H52.19 2,4,6-Cl of oil3            4-SCF3         -H                  126-127 2.20   2,4,6-Cl3            4-SOCF3        -H                  133-135 2.21   2,4,6-Cl3            4-SO2CF3       -H                 146-148 2.22   2,4,6-Cl3            4-SCH3         -H                  113 2.23   2,4,6-Cl3            4-SO2CH3       -H                 205-206 2.24   2,4,6-Cl3            4-SOCH3        -H                  216-217 2.25   2,4,6-Cl3            4-SOCF3        -CH2OC2H52.26 2,4,6-Cl of oil3            4-SO2CF3       -CH2OC2H5      86-88 2.27   2,4,6-Cl3            4-SO2CH3       -CH2OC2H5      104-105 2.28   2,4,6-Cl3            4-SOCH3        -CH2OC2H52.29 2-Cl-4-OCF of oil3-6-NO2   4-NO2          -H                   175-176 2.30   2-Cl-4-OCF3-6-NO2   4-NO2          -CH3               125-126 2.31   2-Cl-4-OCF3-6-NO2   4-NO2          -CH2OC2H5        94-95 2.32   2-Cl-4-OCF3-6-NO2   4-NO2          -CO2C2H5The 2,6-Cl of resin 2.332-4-CF3       4-NH2          -CH2OC2H5        142-143 2.34   2,6-Cl2-4-CF3       4-NO2          -COC4H9n           149-150 2.35   2,6-Cl2-4-CF3       4-NO2          -COCH(CH3)2        138-139 2.36   2,6-Cl2-4-CF3       4-NO2          -COCH2C(CH3)3    135-136 No.     (R3a)n1                 (R3b)n2        R2                  mp(℃) 2.37    2,6-Cl2-4-CF3           4-NO2          -COCH2C6H5       129-131 2.38    2,6-Cl2-4-CF3           4-NO2          -COC3H7n           142-143 2.39    2,6-Cl2-4-CF3           4-NO2          -COCH2CH2Cl        140-142 2.40    2,6-Cl2-4-CF3           4-NO2          -COC5H11n          144-145 2.41    2,6-Cl2-4-CF3           4-NO2          -COC10H212.42 2,6-Cl of oil2-4-CF3           4-NO2          -COC7H15n          85-86 2.43    2-Cl-4-OCF3-6-NO2       4-CN             -H                   191-193 2.44    2-Cl-4-OCF3-6-NO2       4-CN             -CH2OC2H5        60-61 2.45    2-Cl-4-OCF3-6-NH2       4-CN             -CH2OC2H5The 2,6-Cl of resin 2.462-4-CF3           4-NO2          -COCH2OCH3         152-153 2.47    2,6-Cl2-4-CF3           4-NO2          -COCH2C3H3F2cyc 154-155 2.48    2,6-Cl2-4-CF3           4-NHCOCH3      -CH2OC2H5        129-130 2.49    2,6-Cl2-4-CF3           4-NHCOCF3      -CH2OC2H5        155-156 2.50    2,6-Cl2-4-CF3           4-N-Pyrrol       -CH2OC2H5        104-105 2.51    2-Cl-4-OCF3-6-            4-CN             -CH2OC2H5        136-137
     NHCOCH3 2.52    2-Cl-4-OCF3-6-            4-CN             -CH2OC2H5       86-87
     NHCOCH3 2.53    2,6-Cl2-4-CF3           4-SC2F5        -H                  134-135 2.54    2,6-Cl2-4-CF3           4-SOC2F5       -H                  142-143 2.55    2,6-Cl2-4-CF3           4-SO2C2F5      -H                 153-158 2.56    2,6-Cl2-4-CF3           4-SOC2F5       -CH2OC2H5The 2,6-Cl of resin 2.572-4-CF3           4-SOC2F5       -COCH3The 2,6-Cl of resin 2.582-4-CF3           4-SOC2F5       -CO2CH3The 2,6-Cl of resin 2.592-4-CF3           4-SOC2F5       -CH3The 2,6-Cl of resin 2.602-4-CF3           4-SO2C2F5      -CH2OC2H5The 2,6-Cl of amorphous substance 2.612-4-CF3           4-SO2C2F5      -COCH3The 2,6-Cl of amorphous substance 2.622-4-CF3           4-SO2C2F5      -CH3The 2,6-Cl of solid 2.632-4-CF3           4-SOCF3The 2,6-Cl of-CN resins 2.642-4-CF3           4-SOCF3          -CH2The 2,6-Cl of C ≡ CH resins 2.652-4-CF3           4-SOCF3          -C2H5The 2,6-Cl of resin 2.662-4-CF3           4-SOCF3          -COOCH3Resin No. (R3a)n1                   (R3b)n2            R2                       mp(℃)2.67      2,6-Cl2-4-CF3            4-SOCF3           -COCH3The 2,6-Cl of amorphous substance 2.682-4-CF3            4-SOCF3           -CON(CH3)OCH3The 2,6-Cl of resin 2.692-4-CF3            4-SOCF3           -CH3The 2,6-Cl of amorphous substance 2.702-4-CF3            4-SO2CF3          -CON(CH3)OCH3          106-1072.71      2,6-Cl2-4-CF3            4-SO2CF3          -COOCH3The 2,6-Cl of amorphous substance 2.722-4-CF3            4-SO2CF3          -CH2The 2,6-Cl of C ≡ CH resins 2.732-4-CF3            4-SO2CF3          -COCH3The 2,6-Cl of amorphous substance 2.742-4-CF3            4-SO2CF3          -C2H5The 2,6-Cl of resin 2.752-4-CF3            4-SO2CF3          -CH3The 2,6-Cl of resin 2.762-4-CF3            4-SOCF3           -CH2CH2N(C2H5)2The 2,6-Cl of amorphous substance 2.772-4-CF3            4-SO2CF3          -CH2CH2N(C2H5)22.78 2,4,6-Cl of oil3                  4-SO2CF3          -CH2CH2N(C2H5)22.79 2,6-Cl of oil2-4-CF3            4-NO2             -COCH2OC(O)CH3           175-1772.80      2,6-Cl2-4-CF3            4-NO2             -COCH2SCH3The 2,6-Cl of resin 2.812-4-CF3            4-NO2             -CO(CH3)2OC(O)CH3      149-1502.82      2,4,6-Cl3                  4-SCF3            -COCH2C3H3F2cyc      97-982.83      2,4,6-Cl3                  4-SOCF3           -COCH2C3H3F2cyc      91-932.84      2,4,6-Cl3                  4-SO2CF3          -COCH2C3H3F2cyc    153-1542.85      2,6-Cl2-4-CF3            4-SCF3            -COCH2C3H3F2cyc      75-772.86      2,6-Cl2-4-CF3            4-SOCF3           -COCH2C3H3F2cyc      114-1152.87      2,6-Cl2-4-CF3            4-SO2CF3          -COCH2C3H3F2cyc     154-1552.88      2-Cl-4-CF3-6-F             4-NO2             -COCH2C3H3F2cyc      113-1142.89      2,6-Cl2-3-F-4-CF3        4-NO2             -COCH2C3H3F2cyc       103-1042.90      2,4-Cl2-6-CF3            4-NO2             -COCH2C3H3F2cyc       174-1752.91      2,4,6-Cl3                  4-NO2             -COCH2C3H3F2cyc       153-1542.92      2,4,6-Cl3                  4-CN              -COCH2C3H3F2cyc        134-1352.93      2,6-Cl2-4-CF3            3-CH3-4-NO2       -COCH2C3H3F2cyc      138-1392.94      2,6-Cl2-4-CF3            4-C(NOMe)CF3      -CH2OC2H5The 2,6-Cl of resin 2.952-4-CF3            4-C(NOMe)CF3      -H                          145-1462.96      2,4,6-Cl3                  4-C(NOMe)CF3      -CH2OC2H5              92-932.97      2,4,6-Cl3                  4-C(NOMe)CF3      -H                         134-1352.98      2,4,6-Cl3                  4-CH=NOH          -CH2OC2H5Oily No. (R3a)n1           (R3b)n2         R2                           mp(℃)2.99       2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H5The 2,6-Cl of amorphous substance 2.1002-4-CF3     4-NO2           -COCH2OC6H4-4-NO2         189-1922.101      2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H4The 2,6-Cl of -4-F amorphous substances 2.1022-4-CF3     4-NO2           -COCH2OC6H4-4-Br           146-1482.103      2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H4-4-CF3         155-1582.104      2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H4-3-CF3         111-1142.105      2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H4The 2,6-Cl of -2-F resins 2.1062-4-CF3     4-NO2           -COCH2OC6H4-3-NO2         140-1432.107      2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H4-3-Br           125-1282.108      2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H4-3-F            112-1142.109      2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H4-4-Cl           143-1472.110      2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H4-3-CH3-4-Cl     163-1672.111      2,6-Cl2-4-CF3     4-NO2           -COCH2OC6H4-3-Cl,4-F       150-1532.112      2,6-Cl2-4-CF3     4-SON(CH3)2The 2,6-Cl of-H resins 2.1132-4-CF3     4-SOCF3         -CH2OCH3The 2,6-Cl of resin 2.1142-4-CF3     4-SO2CF3        -CH2OCH3The 2,6-Cl of resin 2.1152-4-CF3     4-SOCF3         -CH(CH3)2                    91-922.116      2,6-Cl2-4-CF3     4-SO2CF3        -CH(CH3)2The 2,6-Cl of resin 2.1172-4-CF3     4-SOCF3         -CH2OCH(CH3)2The 2,6-Cl of amorphous substance 2.1182-4-CF3     4-SO2CF3        -CH2OCH(CH3)2The 2,6-Cl of amorphous substance 2.1192-4-CF3     4-SCF2H         H                             152-1532.120      2,6-Cl2-4-CF3     4-SCF2H         -COCH3                       110-1122.121      2,6-Cl2-4-CF3     4-SOCF2H        -COCH3The 2,6-Cl of amorphous substance 2.1222-4-CF3     4-SO2CF2H       -COCH3                      174-1762.123      2,6-Cl2-4-CF3     4-SCF2H         -CH2OC2H5                  91-922.124      2,6-Cl2-4-CF3     4-SOCF2H        -CH2OC2H5                  94-962.125      2,6-Cl2-4-CF3     4-SO2CF2H       -CH2OC2H5                182-1842.126      2,4,6-Cl3          4-SOCF3         -COCH3The 2,4,6-Cl of amorphous substance 2.1273          4-SO2CF3        -COCH3                       152-1542.128      2,4,6-Cl3          4-SOCF3         -COOCH3                       181-1832.129      2,4,6-Cl3          4-SO2CF3        -COOCH3                      170-1722.130      2,4,6-Cl3          4-SOCF3         -C2H5                        83-87No.      (R3a)n1            (R3b)n2        R2                mp(℃)2.131    2,4,6-Cl3          4-SO2CF3       -C2H5             72-742.132    2,4,6-Cl3          4-SOCF3        -CH3                80-842.133    2,4,6-Cl3          4-SO2CF3       -CH3               120-1242.134    2,4,6-Cl3          4-SOCF3        -CH2OCH(CH3)2The 2,4,6-Cl of resin 2.1353          4-SOCF3        -CH(CH3)2          103-1082.136    2,4,6-Cl3          4-SCF3         -CH2OC2H5         84-862.137    2,4,6-Cl3          4-SCHF2        H                     113-1142.138    2,4,6-Cl3          4-SOCHF2       H                     160-1612.139    2,4,6-Cl3          4-SO2CHF2      H                    194-1952.140    2,4,6-Cl3          4-SCHF2        -CH2OC2H5The 2,4,6-Cl of resin 2.1413          4-SOCHF2       -CH2OC2H5         111-1132.142    2,4,6-Cl3          4-SO2CHF2      -CH2OC2H5         168-1692.143    2,4,6-Cl3          4-SOCHF2       -COCH3                146-1482.144    2,4,6-Cl3          4-SO2CHF2      -COCH3               187-1892.145    2,4,6-Cl3          4-SCHF2        -COCH3                97-992.146    2,6-Cl2-4-CF3     4-SC2F5        -CH32.147 2,6-Cl of oil2-4-CF3     4-NO2          -COCH2CH2CF2Cl     189-1902.148    2,4,6-Cl3          4-CN           -COCH2CH2CF2Cl       167-1682.149    2,6-Cl2-4-CF3      3-CH3-4-NO2    -COCH2CH2CF2Cl   108-1092.150    2,4,6-Cl3          4-NO2          -COCH2CH2CF2Cl      157-1582.151    2,4-Cl2-6-CF3      4-NO2          -COCH2CH2CF2Cl    143-1442.152    2-Cl-4-CF3-6-F     4-NO2          -COCH2CH2CF2Cl      152-1532.153    2,6-Cl2-3-F-4-CF3  4-NO2          -COCH2CH2CF2Cl    126-1272.154    2,6-Cl2-4-CF3      4-SCF3         -COCH2CH2CF2Cl    121-1222.155    2,6-Cl2-4-CF3      4-SOCF3        -COCH2CH2CF2Cl    129-1302.156    2,6-Cl2-4-CF3      4-SO2CF3       -COCH2CH2CF2Cl   165-1662.157    2,3,6-Cl3-4-CF3    4-NO2          -COCH2CH2CF2Cl    128-1292.158    2,4,6-Cl3          4-SCF3         -COCH2CH2CF2Cl      88-892.159    2,4,6-Cl3          4-SOCF3        -COCH2CH2CF2Cl      63-652.160    2,4,6-Cl3          4-SO2CF3       -COCH2CH2CF2Cl    143-1442.161    2,4,6-Cl3          4-SC2F5        -H                    103-1042.162    2-Cl-4-CF3-6-F     4-SC2F5        -H                    100-101No.        (R3a)n1               (R3b)n2       R2           mp(℃)2.163      2,3,6-Cl3-4-CF3       4-SC2F5       -H           119-1202.164      2,6-Cl2-3-F-4-CF3     4-SC2F5       -H           101-1022.165      2,6-Cl2-4-NO2         4-SC2F5       -H           139-1402.166      2,4-Cl2-6-CF3         4-SC2F5       -H           93-942.167      2,4,6-Cl3             4-SC2F5       -CH2OC2H5The 2,4,6-Cl of resin 2.1683             4-SC2F5       -COOCH3      104-1052.169      2,4,6-Cl3             4-SC2F5       -COCH3       102-1032.170      2,4,6-Cl3             4-SC2F5       -CH3The 2-Cl-4-CF of resin 2.1713-6-F        4-SC2F5       -CH2OC2H5The 2-Cl-4-CF of resin 2.1723-6-F        4-SC2F5       -COOCH3      80-812.173      2-Cl-4-CF3-6-F        4-SC2F5       -COCH3       86-872.174      2-Cl-4-CF3-6-F        4-SC2F5       -CH3The 2,3,6-Cl of resin 2.1753-4-CF3       4-SC2F5       -CH2OC2H5The 2,3,6-Cl of resin 2.1763-4-CF3       4-SC2F5       -COOCH3The 2,3,6-Cl of resin 2.1773-4-CF3       4-SC2F5       -COCH3The 2,3,6-Cl of resin 2.1783-4-CF3       4-SC2F5       -CH3The 2,6-Cl of resin 2.1792-3-F-4-CF3     4-SC2F5       -CH2OC2H5The 2,6-Cl of resin 2.1802-3-F-4-CF3     4-SC2F5       -COOCH3The 2,6-Cl of resin 2.1812-3-F-4-CF3     4-SC2F5       -COCH3The 2,6-Cl of resin 2.1822-3-F-4-CF3     4-SC2F5       -CH3The 2,6-Cl of resin 2.1832-4-NO2         4-SC2F5       -CH2OC2H5The 2,6-Cl of resin 2.1842-4-NO2         4-SC2F5       -COOCH3The 2,6-Cl of resin 2.1852-4-NO2         4-SC2F5       -COCH3       92-942.186      2,6-Cl2-4-NO2         4-SC2F5       -CH3The 2,4,6-Cl of resin 2.1873             4-SOC2F5      -CH2OC2H5The 2,4,6-Cl of resin 2.1883             4-SO2C2F5     -CH2OC2H5  103-1042.189      2,4-Cl2-6-CF3         4-SC2F5       -CH2OC2H5The 2,4-Cl of resin 2.1902-6-CF3         4-SC2F5       -COOCH3The 2,4-Cl of resin 2.1912-6-CF3         4-SC2F5       -COCH3The 2,4-Cl of resin 2.1922-6-CF3         4-SC2F5       -CH3The 2-Cl-4-CF of resin 2.1933-6-F        4-SOC2F5      -CH2OC2H5The 2-Cl-4-CF of resin 2.1943-6-F        4-SO2C2F5     -CH2OC2H5Resin No. (R3a)n1               (R3b)n2              R2           mp(℃)2.195     2,3,6-Cl3-4-CF3       4-SOC2F5         -CH2OC2H5The 2,3,6-Cl of resin 2.1963-4-CF3       4-SO2C2F5        -CH2OC2H5The 2,6-Cl of resin 2.1972-3-F-4-CF3     4-SOC2F5         -CH2OC2H5The 2,6-Cl of resin 2.1982-3-F-4-CF3     4-SO2C2F5        -CH2OC2H5The 2,6-Cl of resin 2.1992-4-NO2         4-SOC2F5         -CH2OC2H52.200     2,6-Cl2-4-NO2         4-SO2C2F5        -CH2OC2H52.201     2,4-Cl2-6-CF3         4-SOC2F5         -CH2OC2H5The 2,4-Cl of resin 2.2022-6-CF3         4-SO2C2F5        -CH2OC2H5   108-1102.203     2,4,6-Cl3              4-SOC2F5         -COOCH3The 2,4,6-Cl of resin 2.2043              4-SO2C2F5        -COOCH3        131-1332.205     2-Cl-4-CF3-6-F         4-SOC2F5         -COOCH3The 2-Cl-4-CF of resin 2.2063-6-F         4-SO2C2F5        -COOCH3The 2,3,6-Cl of resin 2.2073-4-CF3       4-SOC2F5         -COOCH3The 2,3,6-Cl of resin 2.2083-4-CF3       4-SO2C2F5        -COOCH3The 2,6-Cl of resin 2.2092-3-F-4-CF3     4-SOC2F5         -COOCH32.210     2,6-Cl2-3-F-4-CF3     4-SO2C2F5        -COOCH32.211     2,6-Cl2-4-NO2         4-SOC2F5         -COOCH32.212     2,6-Cl2-4-NO2         4-SO2C2F5        -COOCH32.213     2,3,6-Cl3-4-CF3       4-SOC2F5         -COOCH32.214     2,3,6-Cl3-4-CF3       4-SO2C2F5        -COOCH32.215     2,4,6-Cl3              4-SOC2F5         -COCH32.216     2,4,6-Cl3              4-SO2C2F5        -COCH32.217     2,4,6-Cl3              4-SCF2CHFCF3     -H2.218     2,4,6-Cl3              4-                   -H
                              SOCF2CHFCF32.219     2,4,6-Cl3               4-                  -H
                              SO2CF2CHFCF32.220     2,6-Cl2-4-CF3         4-SCF2CHFCF3       -H2.221     2,6-Cl2-4-CF3         4-                    -H
                              SOCF2CHFCF32.222     2,6-Cl2-4-CF3         4-                    -H
                              SO2CF2CHFCF3 No.     (R3a)n1            (R3b)n2         R2               mp(℃)   2.223   2,6-(NO2)2-4-CF3    H              -H               180-181 2.224   2,6-(NO2)2-         H               -H
     4-CF3-5-Cl 2.225   2,6-(NO2)2          H                 -H 2.226   2,6-(NO2)2-4-CF3    4-NO2         -CH3 2.227   2,6-(NO2)2-         4-NO2          -COOCH3
     4-CF3-5-Cl 2.228   2,6-(NO2)2          4-NO2          -CH2OC2H5 2.229   2,6-(NO2)2-4-CF3    4-SCF3         -CH3 2.230   2,6-(NO2)2-         4-SOCF3        -COOCH3
     4-CF3-5-Cl 2.231   2,6-(NO2)2          4-SON(CH3)2    -CH2OC2H5 2.232   2,6-(NO2)2-4-CF3    4-SO2N(CH3)2 -CH2OCH(CH3)2 2.233   2,6-(NO2)2-         4-SCH3         -COCH2C3H3F2cyc
     4-CF3-5-Cl 2.234   2,6-(NO2)2          4-F             -COCH2OC6H4-4-F 2.235   2,6-(NO2)2-4-CF3    4-Br           -CH3 2.236   2,6-(NO2)2-         4-SOCF3        -COOCH3
     4-CF3-5-F 2.237   2,6-(NO2)2          4-F             -CH2OC2H5 2.238   2,6-(NO2)2-4-CF3    4-Br           -CH3 2.239   2,6-(NO2)2-4-       4-SOCF3        -COOCH3
     CF3-5-F 2.240   2,6-(NO2)2          4-F             -CH2OC2H5 2.241   2,6-(NO2)2-4-CF3    4-Br           -CH2OCH(CH3)2 2.242   2,6-(NO2)2-         4-SOCF3        -COCH2C3H3F2cyc
     4-CF3-5-Cl 2.243   2,6-(NO2)2          4-SOCF3        -COCH2OC6H4- 4-F tables 3：Following formula: compound：
Figure 9980232300442
Table A
        R2                  (R3b)n2A.1)        -CON(OCH3)CH3      4-CNA.2)        -CON(OCH3)CH3      4-NO2A.3)        -CON(OCH3)CH3      4-CF3A.4)        -CON(OCH3)CH3      2-Cl-4-NO2A.5)        -CON(OCH3)CH3      3-CH3-4-NO2A.6)        -CON(OCH3)CH3      4-ClA.7)        -CON(OCH3)CH3      4-C6H4-4-NO2A.8)        -CON(OCH3)CH3      4-C6H4-2-NO2A.9)        -CON(OCH3)CH3      4-SCF3A.10)       -CON(OCH3)CH3      4-SOCF3A.11)       -CON(OCH3)CH3      4-SO2CF3A.12)       -CON(OCH3)CH3      2-F-4-CNA.13)       -CON(OCH3)CH3      2-F-4-NO2A.14)       -CON(OCH3)CH3      4-COCF3A.15)       -CON(OCH3)CH3      4-CHOA.16)       -CON(OCH3)CH3      4-Cl-3-NO2A.17)       -CON(OCH3)CH3      4-NH2A.18)       -CON(OCH3)CH3      3-Cl-4-CNA.19)       -CON(OCH3)CH3      3-OCH3-4-NO2A.20)       -CON(OCH3)CH3      3-Cl-4-NO2A.21)       -CON(OCH3)CH3      3-F-4-NO2A.22)       -CON(OCH3)CH3      4-C6H4-4-CNA.23)       -CON(OCH3)CH3      4-C6H4-2-CNA.24)       -C(O)NHOCH3         4-CNA.25)       -C(O)NHOCH3         4-NO2A.26)       -C(O)NHOCH3         4-CF3A.27)       -C(O)NHOCH3         2-Cl-4-NO2A.28)       -C(O)NHOCH3         3-CH3-4-NO2A.29)       -C(O)NHOCH3         4-ClA.30)       -C(O)NHOCH3         4-C6H4-4-NO2
      R2               (R3b)n2A.31)    -C(O)NHOCH3    4-C6H4-2-NO2A.32)    -C(O)NHOCH3    4-SCF3A.33)    -C(O)NHOCH3    4-SOCF3A.34)    -C(O)NHOCH3    4-SO2CF3A.35)    -C(O)NHOCH3    2-F-4-CNA.36)    -C(O)NHOCH3    2-F-4-NO2A.37)    -C(O)NHOCH3    4-COCF3A.38)    -C(O)NHOCH3    4-CHOA.39)    -C(O)NHOCH3    4-Cl-3-NO2A.40)    -C(O)NHOCH3    4-NH2A.41)    -C(O)NHOCH3    3-Cl-4-CNA.42)    -C(O)NHOCH3    3-OCH3-4-NO2A.43)    -C(O)NHOCH3    3-Cl-4-NO2A.44)    -C(O)NHOCH3    3-F-4-NO2A.45)    -C(O)NHOCH3    4-C6H4-4-CNA.46)    -C(O)NHOCH3    4-C6H4-2-CNA.47)    -COSC2H5      4-CNA.48)    -COSC2H5      4-NO2A.49)    -COSC2H5      4-CF3A.50)    -COSC2H5      2-Cl-4-NO2A.51)    -COSC2H5      3-CH3-4-NO2A.52)    -COSC2H5      4-ClA.53)    -COSC2H5      4-C6H4-4-NO2A.54)    -COSC2H5      4-C6H4-2-NO2A.55)    -COSC2H5      4-SCF3A.56)    -COSC2H5      4-SOCF3A.57)    -COSC2H5      4-SO2CF3A.58)    -COSC2H5      2-F-4-CNA.59)    -COSC2H5      2-F-4-NO2A.60)    -COSC2H5      4-COCF3A.61)    -COSC2H5      4-CHOA.62)    -COSC2H5      4-Cl-3-NO2
      R2                    (R3b)n2 A.63)    -COSC2H5           4-NH2 A.64)    -COSC2H5           3-Cl-4-CN A.65)    -COSC2H5           3-OCH3-4-NO2 A.66)    -COSC2H5           3-Cl-4-NO2 A.67)    -COSC2H5           3-F-4-NO2 A.68)    -COSC2H5           4-C6H4-4-CN A.69)    -COSC2H5           4-C6H4-2-CN A.70)    -COSCH3             4-CN A.71)    -COSCH3             4-NO2 A.72)    -COSCH3             4-CF3 A.73)    -COSCH3             2-Cl-4-NO2 A.74)    -COSCH3             3-CH3-4-NO2 A.75)    -COSCH3             4-Cl A.76)    -COSCH3             4-C6H4-4-NO2 A.77)    -COSCH3             4-C6H4-2-NO2 A.78)    -COSCH3             4-SCF3 A.79)    -COSCH3             4-SOCF3 A.80)    -COSCH3             4-SO2CF3 A.81)    -COSCH3             2-F-4-CN A.82)    -COSCH3             2-F-4-NO2 A.83)    -COSCH3             4-COCF3 A.84)    -COSCH3             4-CHO A.85)    -COSCH3             4-Cl-3-NO2 A.86)    -COSCH3             4-NH2 A.87)    -COSCH3             3-Cl-4-CN A.88)    -COSCH3             3-OCH3-4-NO2 A.89)    -COSCH3             3-Cl-4-NO2 A.90)    -COSCH3             3-F-4-NO2 A.91)    -COSCH3             4-C6H4-4-CN A.92)    -COSCH3             4-C6H4-2-CN A.93)    -CH2OC(O)C(CH3)3  4-CN A.94)    -CH2OC(O)C(CH3)3  4-NO2
       R2                      (R3b)n2A.95)      -CH2OC(O)C(CH3)3    4-CF3A.96)      -CH2OC(O)C(CH3)3    2-Cl-4-NO2A.97)      -CH2OC(O)C(CH3)3    3-CH3-4-NO2A.98)      -CH2OC(O)C(CH3)3    4-ClA.99)      -CH2OC(O)C(CH3)3    4-C6H4-4-NO2A.100)     -CH2OC(O)C(CH3)3    4-C6H4-2-NO2A.101)     -CH2OC(O)C(CH3)3    4-SCF3A.102)     -CH2OC(O)C(CH3)3    4-SOCF3A.103)     -CH2OC(O)C(CH3)3    4-SO2CF3A.104)     -CH2OC(O)C(CH3)3    2-F-4-CNA.105)     -CH2OC(O)C(CH3)3    2-F-4-NO2A.106)     -CH2OC(O)C(CH3)3    4-COCF3A.107)     -CH2OC(O)C(CH3)3    4-CHOA.108)     -CH2OC(O)C(CH3)3    4-Cl-3-NO2A.109)     -CH2OC(O)C(CH3)3    4-NH2A.110)     -CH2OC(O)C(CH3)3    3-Cl-4-CNA.111)     -CH2OC(O)C(CH3)3    3-OCH3-4-NO2A.112)     -CH2OC(O)C(CH3)3    3-Cl-4-NO2A.113)     -CH2OC(O)C(CH3)3    3-F-4-NO2A.114)     -CH2OC(O)C(CH3)3    4-C6H4-4-CNA.115)     -CH2OC(O)C(CH3)3    4-C6H4-2-CNA.116)     -CH2OC2H4OCH3      4-CNA.117)     -CH2OC2H4OCH3      4-NO2A.118)     -CH2OC2H4OCH3      4-CF3A.119)     -CH2OC2H4OCH3      2-Cl-4-NO2A.120)     -CH2OC2H4OCH3      3-CH3-4-NO2A.121)     -CH2OC2H4OCH3      4-ClA.122)     -CH2OC2H4OCH3      4-C6H4-4-NO2A.123)     -CH2OC2H4OCH3      4-C6H4-2-NO2A.124)     -CH2OC2H4OCH3      4-SCF3A.125)     -CH2OC2H4OCH3      4-SOCF3A.126)     -CH2OC2H4OCH3      4-SO2CF3
        R2                   (R3b)n2 A.127)     -CH2OC2H4OCH3    2-F-4-CN A.128)     -CH2OC2H4OCH3    2-F-4-NO2 A.129)     -CH2OC2H4OCH3    4-COCF3 A.130)     -CH2OC2H4OCH3    4-CHO A.131)     -CH2OC2H4OCH3    4-Cl-3-NO2 A.132)     -CH2OC2H4OCH3    4-NH2 A.133)     -CH2OC2H4OCH3    3-Cl-4-CN A.134)     -CH2OC2H4OCH3    3-OCH3-4-NO2 A.135)     -CH2OC2H4OCH3    3-Cl-4-NO2 A.136)     -CH2OC2H4OCH3    3-F-4-NO2 A.137)     -CH2OC2H4OCH3    4-C6H4-4-CN A.138)     -CH2OC2H4OCH3    4-C6H4-2-CN A.139)     -CH2OCH2CH=CH2    4-CN A.140)     -CH2OCH2CH=CH2    4-NO2 A.141)     -CH2OCH2CH=CH2    4-CF3 A.142)     -CH2OCH2CH=CH2    2-Cl-4-NO2 A.143)     -CH2OCH2CH=CH2    3-CH3-4-NO2 A.144)     -CH2OCH2CH=CH2    4-Cl A.145)     -CH2OCH2CH=CH2    4-C6H4-4-NO2 A.146)     -CH2OCH2CH=CH2    4-C6H4-2-NO2 A.147)     -CH2OCH2CH=CH2    4-SCF3 A.148)     -CH2OCH2CH=CH2    4-SOCF3 A.149)     -CH2OCH2CH=CH2    4-SO2CF3 A.150)     -CH2OCH2CH=CH2    2-F-4-CN A.151)     -CH2OCH2CH=CH2    2-F-4-NO2 A.152)     -CH2OCH2CH=CH2    4-COCF3 A.153)     -CH2OCH2CH=CH2    4-CHO A.154)     -CH2OCH2CH=CH2    4-Cl-3-NO2 A.155)     -CH2OCH2CH=CH2    4-NH2 A.156)     -CH2OCH2CH=CH2    3-Cl-4-CN A.157)     -CH2OCH2CH=CH2    3-OCH3-4-NO2 A.158)     -CH2OCH2CH=CH2    3-Cl-4-NO2
       R2                   (R3b)n2A.159)    -CH2OCH2CH=CH2   3-F-4-NO2A.160)    -CH2OCH2CH=CH2   4-C6H4-4-CNA.161)    -CH2OCH2CH=CH2   4-C6H4-2-CNA.162)    -CH2OCH2C≡CH     4-CNA.163)    -CH2OCH2C≡CH     4-NO2A.164)    -CH2OCH2C≡CH     4-CF3A.165)    -CH2OCH2C≡CH     2-Cl-4-NO2A.166)    -CH2OCH2C≡CH     3-CH3-4-NO2A.167)    -CH2OCH2C≡CH     4-ClA.168)    -CH2OCH2C≡CH     4-C6H4-4-NO2A.169)    -CH2OCH2C≡CH     4-C6H4-2-NO2A.170)    -CH2OCH2C≡CH     4-SCF3A.171)    -CH2OCH2C≡CH     4-SOCF3A.172)    -CH2OCH2C≡CH     4-SO2CF3A.173)    -CH2OCH2C≡CH     2-F-4-CNA.174)    -CH2OCH2C≡CH     2-F-4-NO2A.175)    -CH2OCH2C≡CH     4-COCF3A.176)    -CH2OCH2C≡CH     4-CHOA.177)    -CH2OCH2C≡CH     4-Cl-3-NO2A.178)    -CH2OCH2C≡CH     4-NH2A.179)    -CH2OCH2C≡CH     3-Cl-4-CNA.180)    -CH2OCH2C≡CH     3-OCH3-4-NO2A.181)    -CH2OCH2C≡CH     3-Cl-4-NO2A.182)    -CH2OCH2C≡CH     3-F-4-NO2A.183)    -CH2OCH2C≡CH     4-C6H4-4-CNA.184)    -CH2OCH2C≡CH     4-C6H4-2-CNA.185)    -COC10H21         4-CNA.186)    -COC10H21         4-NO2A.187)    -COC10H21         4-CF3A.188)    -COC10H21         2-Cl-4-NO2
       R2           (R3b)n2A.189)    -COC10H21    3-CH3-4-NO2A.190)    -COC10H21    4-ClA.191)    -COC10H21    4-C6H4-4-NO2A.192)    -COC10H21    4-C6H4-2-NO2A.193)    -COC10H21    4-SCF3A.194)    -COC10H21    4-SOCF3A.195)    -COC10H21    4-SO2CF3A.196)    -COC10H21    2-F-4-CNA.197)    -COC10H21    2-F-4-NO2A.198)    -COC10H21    4-COCF3A.199)    -COC10H21    4-CHOA.200)    -COC10H21    4-Cl-3-NO2A.201)    -COC10H21    4-NH2A.202)    -COC10H21    3-Cl-4-CNA.203)    -COC10H21    3-OCH3-4-NO2A.204)    -COC10H21    3-Cl-4-NO2A.205)    -COC10H21    3-F-4-NO2A.206)    -COC10H21    4-C6H4-4-CNA.207)    -COC10H21    4-C6H4-2-CNA.208)    -H             4-SCF3A.209)    -H             4-SOCF3A.210)    -H             4-SO2CF3A.211)    -H             4-SC2F5A.212)    -H             4-SOC2F5A.213)    -H             4-SO2C2F5A.214)    -H             4-SCF2HA.215)    -H             4-SOCF2HA.216)    -H             4-SO2CF2HA.217)    -H             4-SCF2ClA.218)    -H             4-SOCF2ClA.219)    -H             4-SO2CF2ClA.220)    -H             4-SF5
      R2          (R3b)n2A.221)    -H         SCF2BrA.222)    -H         SOCF2BrA.223)    -H         SO2CF2BrA.224)    -H         SCF2CF2BrA.225)    -H         SOCF2CF2BrA.226)    -H         SO2CF2CF2BrA.227)    -CH3      4-SCF3A.228)    -CH3      4-SOCF3A.229)    -CH3      4-SO2CF3A.230)    -CH3      4-SC2F5A.231)    -CH3      4-SOC2F5A.232)    -CH3      4-SO2C2F5A.233)    -CH3      4-SCF2HA.234)    -CH3      4-SOCF2HA.235)    -CH3      4-SO2CF2HA.236)    -CH3      4-SCF2ClA.237)    -CH3      4-SOCF2ClA.238)    -CH3      4-SO2CF2ClA.239)    -CH3      4-SF5A.240)    -CH3      SCF2BrA.241)    -CH3      SOCF2BrA.242)    -CH3      SO2CF2BrA.243)    -CH3      SCF2CF2BrA.244)    -CH3      SOCF2CF2BrA.245)    -CH3      SO2CF2CF2BrA.246)    -C2H5    4-SCF3A.247)    -C2H5    4-SOCF3A.248)    -C2H5    4-SO2CF3A.249)    -C2H5    4-SC2F5A.250)    -C2H5    4-SOC2F5A.251)    -C2H5    4-SO2C2F5A.252)    -C2H5    4-SCF2H
          R2              (R3b)n2A.253)        -C2H5        4-SOCF2HA.254)        -C2H5        4-SO2CF2HA.255)        -C2H5        4-SCF2ClA.256)        -C2H5        4-SOCF2ClA.257)        -C2H5        4-SO2CF2ClA.258)        -C2H5        4-SF5A.259)        -C2H5        SCF2BrA.260)        -C2H5        SOCF2BrA.261)        -C2H5        SO2CF2BrA.262)        -C2H5        SCF2CF2BrA.263)        -C2H5        SOCF2CF2BrA.264)        -C2H5        SO2CF2CF2BrA.265)        -CH(CH3)2    4-SCF3A.266)        -CH(CH3)2    4-SOCF3A.267)        -CH(CH3)2    4-SO2CF3A.268)        -CH(CH3)2    4-SC2F5A.269)        -CH(CH3)2    4-SOC2F5A.270)        -CH(CH3)2    4-SO2C2F5A.271)        -CH(CH3)2    4-SCF2HA.272)        -CH(CH3)2    4-SOCF2HA.273)        -CH(CH3)2    4-SO2CF2HA.274)        -CH(CH3)2    4-SCF2ClA.275)        -CH(CH3)2    4-SOCF2ClA.276)        -CH(CH3)2    4-SO2CF2ClA.277)        -CH(CH3)2    4-SF5A.278)        -CH(CH3)2    SCF2BrA.279)        -CH(CH3)2    SOCF2BrA.280)        -CH(CH3)2    SO2CF2BrA.281)        -CH(CH3)2    SCF2CF2BrA.282)        -CH(CH3)2    SOCF2CF2BrA.283)        -CH(CH3)2    SO2CF2CF2BrA.284)        -COCH3         4-SCF3
       R2            (R3b)n2A.285)     -COCH3      4-SOCF3A.286)     -COCH3      4-SO2CF3A.287)     -COCH3      4-SC2F5A.288)     -COCH3      4-SOC2F5A.289)     -COCH3      4-SO2C2F5A.290)     -COCH3      4-SCF2HA.291)     -COCH3      4-SOCF2HA.292)     -COCH3      4-SO2CF2HA.293)     -COCH3      4-SCF2ClA.294)     -COCH3      4-SOCF2ClA.295)     -COCH3      4-SO2CF2ClA.296)     -COCH3      4-SF5A.297)     -COCH3      SCF2BrA.298)     -COCH3      SOCF2BrA.299)     -COCH3      SO2CF2BrA.300)     -COCH3      SCF2CF2BrA.301)     -COCH3      SOCF2CF2BrA.302)     -COCH3      SO2CF2CF2BrA.303)     -COC2H5    4-SCF3A.304)     -COC2H5    4-SOCF3A.305)     -COC2H5    4-SO2CF3A.306)     -COC2H5    4-SC2F5A.307)     -COC2H5    4-SOC2F5A.308)     -COC2H5    4-SO2C2F5A.309)     -COC2H5    4-SCF2HA.310)     -COC2H5    4-SOCF2HA.311)     -COC2H5    4-SO2CF2HA.312)     -COC2H5    4-SCF2ClA.313)     -COC2H5    4-SOCF2ClA.314)     -COC2H5    4-SO2CF2ClA.315)     -COC2H5    4-SF5A.316)     -CO2CH3    4-SCF3
      R2            (R3b)n2A.317)    -COC2H5     SCF2BrA.318)    -COC2H5     SOCF2BrA.319)    -COC2H5     SO2CF2BrA.320)    -COC2H5     SCF2CF2BrA.321)    -COC2H5     SOCF2CF2BrA.322)    -CO2CH3     SO2CF2CF2BrA.323)    -CO2CH3     4-SOCF3A.324)    -CO2CH3     4-SO2CF3A.325)    -CO2CH3     4-SC2F5A.326)    -CO2CH3     4-SOC2F5A.327)    -CO2CH3     4-SO2C2F5A.328)    -CO2CH3     4-SCF2HA.329)    -CO2CH3     4-SOCF2HA.330)    -CO2CH3     4-SO2CF2HA.331)    -CO2CH3     4-SCF2ClA.332)    -CO2CH3     4-SOCF2ClA.333)    -CO2CH3     4-SO2CF2ClA.334)    -CO2CH3     4-SF5A.335)    -CO2CH3     SCF2BrA.336)    -CO2CH3     SOCF2BrA.337)    -CO2CH3     SO2CF2BrA.338)    -CO2CH3     SCF2CF2BrA.339)    -CO2CH3     SOCF2CF2BrA.340)    -CO2CH3     SO2CF2CF2BrA.341)    -CO2C2H5   4-SCF3A.342)    -CO2C2H5   4-SOCF3A.343)    -CO2C2H5   4-SO2CF3A.344)    -CO2C2H5   4-SC2F5A.345)    -CO2C2H5   4-SOC2F5A.346)    -CO2C2H5   4-SO2C2F5A.347)    -CO2C2H5   4-SCF2HA.348)    -CO2C2H5   4-SOCF2H
        R2               (R3b)n2A.349)     -CO2C2H5      4-SO2CF2HA.350)     -CO2C2H5      4-SCF2ClA.351)     -CO2C2H5      4-SOCF2ClA.352)     -CO2C2H5      4-SO2CF2ClA.353)     -CO2C2H5      4-SF5A.354)     -CO2C2H5      SCF2BrA.355)     -CO2C2H5      SOCF2BrA.356)     -CO2C2H5      SO2CF2BrA.357)     -CO2C2H5      SCF2CF2BrA.358)     -CO2C2H5      SOCF2CF2BrA.359)     -CO2C2H5      SO2CF2CF2BrA.360)     -CH2OC2H5     4-SCF3A.361)     -CH2OC2H5     4-SOCF3A.362)     -CH2OC2H5     4-SO2CF3A.363)     -CH2OC2H5     4-SC2F5A.364)     -CH2OC2H5     4-SOC2F5A.365)     -CH2OC2H5     4-SO2C2F5A.366)     -CH2OC2H5     4-SCF2HA.367)     -CH2OC2H5     4-SOCF2HA.368)     -CH2OC2H5     4-SO2CF2HA.369)     -CH2OC2H5     4-SCF2ClA.370)     -CH2OC2H5     4-SOCF2ClA.371)     -CH2OC2H5     4-SO2CF2ClA.372)     -CH2OC2H5     4-SF5A.373)     -CH2OC2H5     SCF2BrA.374)     -CH2OC2H5     SOCF2BrA.375)     -CH2OC2H5     SO2CF2BrA.376)     -CH2OC2H5     SCF2CF2BrA.377)     -CH2OC2H5     SOCF2CF2BrA.378)     -CH2OC2H5     SO2CF2CF2BrA.379)     -CH2OCH3        4-SCF3A.380)     -CH2OCH3        4-SOCF3
         R2                 (R3b)n2A.381)       -CH2OCH3           4-SO2CF3A.382)       -CH2OCH3           4-SC2F5A.383)       -CH2OCH3           4-SOC2F5A.384)       -CH2OCH3           4-SO2C2F5A.385)       -CH2OCH3           4-SCF2HA.386)       -CH2OCH3           4-SOCF2HA.387)       -CH2OCH3           4-SO2CF2HA.388)       -CH2OCH3           4-SCF2ClA.389)       -CH2OCH3           4-SOCF2ClA.390)       -CH2OCH3           4-SO2CF2ClA.391)       -CH2OCH3           4-SF5A.392)       -CH2OCH3           SCF2BrA.393)       -CH2OCH3           SOCF2BrA.394)       -CH2OCH3           SO2CF2BrA.395)       -CH2OCH3           SCF2CF2BrA.396)       -CH2OCH3           SOCF2CF2BrA.397)       -CH2OCH3           SO2CF2CF2BrA.398)       -CH2O-n-C3H7      4-SCF3A.399)       -CH2O-n-C3H7      4-SOCF3A.400)       -CH2O-n-C3H7      4-SO2CF3A.401)       -CH2O-n-C3H7      4-SC2F5A.402)       -CH2O-n-C3H7      4-SOC2F5A.403)       -CH2O-n-C3H7      4-SO2C2F5A.404)       -CH2O-n-C3H7      4-SCF2HA.405)       -CH2O-n-C3H7      4-SOCF2HA.406)       -CH2O-n-C3H7      4-SO2CF2HA.407)       -CH2O-n-C3H7      4-SCF2ClA.408)       -CH2O-n-C3H7      4-SOCF2ClA.409)       -CH2O-n-C3H7      4-SO2CF2ClA.410)       -CH2O-n-C3H7      4-SF5A.411)       -CH2O-n-C3H7      SCF2BrA.412)       -CH2O-n-C3H7      SOCF2Br
         R2                          (R3b)n2A.413)       -CH2O-n-C3H7            SO2CF2BrA.414)       -CH2O-n-C3H7            SCF2CF2BrA.415)       -CH2O-n-C3H7            SOCF2CF2BrA.416)       -CH2O-n-C3H7            SO2CF2CF2BrA.417)       -CH2N(CH3)CO2CH3       4-SCF3A.418)       -CH2N(CH3)CO2CH3       4-SOCF3A.419)       -CH2N(CH3)CO2CH3       4-SO2CF3A.420)       -CH2N(CH3)CO2CH3       4-SC2F5A.421)       -CH2N(CH3)CO2CH3       4-SOC2F5A.422)       -CH2N(CH3)CO2CH3       4-SO2C2F5A.423)       -CH2N(CH3)CO2CH3       4-SCF2HA.424)       -CH2N(CH3)CO2CH3       4-SOCF2HA.425)       -CH2N(CH3)CO2CH3       4-SO2CF2HA.426)       -CH2N(CH3)CO2CH3       4-SCF2ClA.427)       -CH2N(CH3)CO2CH3       4-SOCF2ClA.428)       -CH2N(CH3)CO2CH3       4-SO2CF2ClA.429)       -CH2N(CH3)CO2CH3       4-SF5A.430)       -CH2N(CH3)CO2CH3       SCF2BrA.431)       -CH2N(CH3)CO2CH3       SOCF2BrA.432)       -CH2N(CH3)CO2CH3       SO2CF2BrA.433)       -CH2N(CH3)CO2CH3       SCF2CF2BrA.434)       -CH2N(CH3)CO2CH3       SOCF2CF2BrA.435)       -CH2N(CH3)CO2CH3       SO2CF2CF2BrA.436)       -CH2N(CH3)SO2CH3       4-SCF3A.437)       -CH2N(CH3)SO2CH3       4-SOCF3A.438)       -CH2N(CH3)SO2CH3       4-SO2CF3A.439)       -CH2N(CH3)SO2CH3       4-SC2F5A.440)       -CH2N(CH3)SO2CH3       4-SOC2F5A.441)       -CH2N(CH3)SO2CH3       4-SO2C2F5A.442)       -CH2N(CH3)SO2CH3       4-SCF2HA.443)       -CH2N(CH3)SO2CH3       4-SOCF2HA.444)       -CH2N(CH3)SO2CH3       4-SO2CF2H
        R2                          (R3b)n2A.445)      -CH2N(CH3)SO2CH3       4-SCF2ClA.446)      -CH2N(CH3)SO2CH3       4-SOCF2ClA.447)      -CH2N(CH3)SO2CH3       4-SO2CF2ClA.448)      -CH2N(CH3)SO2CH3       4-SF5A.449)      -CH2N(CH3)SO2CH3       SCF2BrA.450)      -CH2N(CH3)SO2CH3       SOCF2BrA.451)      -CH2N(CH3)SO2CH3       SO2CF2BrA.452)      -CH2N(CH3)SO2CH3       SCF2CF2BrA.453)      -CH2N(CH3)SO2CH3       SOCF2CF2BrA.454)      -CH2N(CH3)SO2CH3       SO2CF2CF2Br tables 4：
Below formula compound：
Figure 9980232300601
(1b), wherein (R3a)n1For 2,6-Cl2-4-CF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 5：
Formula (I b) compound, wherein (R3a)n1For 2,4,6-Cl3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 6：
Formula (I b) compound, wherein (R3a)n1For 2-C1-4-CF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 7：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-NO2, and R2(R3b)n2Respectively correspond to any row in Table A.Table 8：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-OCF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 9：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2- 4-F, and R2(R3b)n2Respectively correspond to any row in Table A.Table 10：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2- 4-Br, and R2(R3b)n2Respectively correspond to any row in Table A.Table 11：
Formula (I b) compound, wherein (R3a)n1For 2-C1-4-CF3- 6-F, and R2(R3b)n2Respectively correspond to any row in Table A.Table 12：
Formula (I b) compound, wherein (R3a)n1For 2,3,6-Cl3-4-CF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 13：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-3-F-4-CF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 14：
Formula (I b) compound, wherein (R3a)n1For 2,3-F2-4-CF3- 6-Cl, and R2(R3b)n2Respectively correspond to any row in Table A.Table 15：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2- 4-CN, and R2(R3b)n2Respectively correspond to any row in Table A.Table 16：
Formula (I b) compound, wherein (R3a)n1For 2,4-Cl2-6-CF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 17：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-SCF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 18：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-SOCF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 19：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-SO2CF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 20：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-SO2CH3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 21：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-OCF2Br, and R2(R3b)n2Respectively correspond to any row in Table A.Table 22：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-OCF2H, and R2(R3b)n2Respectively correspond to any row in Table A.Table 23：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-C2F5, and R2(R3b)n2Respectively correspond to any row in Table A.Table 24：
Formula (I b) compound, wherein (R3a)n1For 2,6- (NO2)2-4-CF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 25：
Formula (I b) compound, wherein (R3a)n1For 2,6- (NO2)2- 4-Cl, and R2(R3b)n2Respectively correspond to any row in Table A.Table 26：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-OSO2CH3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 27：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-OSO2CF3, and R2(R3b)n2Respectively correspond to any row in Table A.Table 28：
Formula (I b) compound, wherein (R3a)n1For 2,6-Cl2-4-SF5, and R2(R3b)n2Respectively correspond to any row in Table A.
The formulation examples of the compounds of this invention, that is, solution, granule, pulvis, wettable powder, missible oil, coated granule and suspension-concentrates, are shown in all kinds listed by embodiment F1-F10 in such as EP-A-580553 (file number 19164).Biological Examples：Embodiment B1：To tobacco budworm (Heliothis virescens) ovicidal action
It will be attached to the of short duration immersion in the acetone/water solution comprising the tested mixture of active principles of 400ppm of the tobacco budworm ovum on filter paper.After solution to be tested is air-dried, above-mentioned ovum is being accompanied into culture in Ti Shi wares.After 6 days, the hatching percentage (the reduction percentage of incubation rate) of ovum is compared with control group.
Listed compound shows good confrontation tobacco budworm activity in table 3-5.Particularly compound 2.1-2.5,2.8-2.13 and 3.7 shows the action effect more than 80%.Embodiment B2：Effect to Spodoptera littoralis (Spodoptera littoralis) caterpillar
To the aqueous emulsion of soybean plant strain seedling spraying active component containing 400ppm.After spray film deposit to be painted is air-dried, 10 Spodoptera littoralis (Spodoptera littoralis) third-instar larvae is put on soybean plant strain and plant is placed in plastic containers.After three days, them are evaluated.By comparing the dead larvae number on processing plant and untreated plant and taking food (feeding) extent of injury, determine insect population reduction percentage and take food injury and reduce percentage (% activity ratios).
In this experiment, the compound in table 1 shows good confrontation Spodoptera littoralis (Spodoptera littoralis) effect.Particularly compound 2.1-2.5,2.7-2.18 and 3.7-3.9 show the action effect more than 80%.Embodiment 3：To the effect with chrysomelid (Diabrotica balteata) larva of spot cucumber
To the aqueous emulsion of corn seedling spraying active component containing 400ppm.After spray film deposit to be painted is air-dried, chrysomelid (Diabrotica balteata) second instar larvae of 10 band spot cucumber is inoculated with corn seedling, then moves into corn seedling in plastic containers.Them are evaluated after six days.By comparing the dead larvae number on processing plant and untreated plant, the reduction percentage (% activity ratios) of insect population is determined.
In this experiment, the compound in table 3-5 shows good confrontation band chrysomelid (Diabrotica balteata) effect of spot cucumber.Particularly compound 2.1-2.4,2.6,2.7,2.11,2.25-2.28 and 3.9 shows the action effect more than 80%.Embodiment B4：Effect to diamondback moth (Plutella xylostella) caterpillar
To the aqueous emulsion of cabbage plant shoots spraying active component containing 400ppm.After spray film deposit to be painted is air-dried, 10 diamondback moth (Plutella xylostella) third-instar larvaes are moved on cabbage plant and move into plant in plastic containers.Them are evaluated after three days.By comparing the dead larvae number on processing plant and untreated plant and taking food (feeding) extent of injury, determine insect population reduction percentage and take food injury and reduce percentage (% activity ratios).
In this experiment, the compound in table 3-5 shows good confrontation diamondback moth (Plutella xylostella) effect.Embodiment B5：Effect to cotton spider mites (Tetranychus urticae)
Soybean plant strain seedling is inoculated with the mixed population of cotton spider mites (Tetranychus urticae), after 1 day, the aqueous emulsion for the active component containing 400ppm of spraying.25 DEG C are cultivated plant 6 days, are then evaluated.By comparing ovum, larva and adult number dead on processing plant and untreated plant, determine insect population and reduce percentage (% activity ratios).
In this experiment, the compound in table 3-5 shows good confrontation cotton spider mites (Tetranychus urticae) effect.Embodiment B6：Effect to bean aphid (Aphis craccivora)
Pea seedling, the aqueous emulsion for the active component containing 400ppm of then spraying are contaminated with bean aphid (Aphis craccivora), and then is cultivated at 20 DEG C.They are evaluated behind 3 days and 6 days respectively.By comparing aphid number dead on processing plant and untreated plant, determine insect population and reduce percentage (% activity ratios).
In this experiment, the compound in table 3-5 shows good confrontation bean aphid (Aphiscraccivora) effect.Particularly compound 2.7,2.22 and 3.8 shows the action effect more than 80%.Embodiment B7：Effect to black peach aphid (Myzus persicae)
Pea seedling, the aqueous emulsion for the active component containing 400ppm of then spraying are contaminated with black peach aphid (Myzus persicae), and then is cultivated at 20 DEG C.They are evaluated behind 3 days and 6 days respectively.By comparing aphid number dead on processing plant and untreated plant, determine insect population and reduce percentage (% activity ratios).
In this experiment, the compound in table 3-5 shows good confrontation black peach aphid (Myzuspersicae) effect.Particularly compound 3.7 and 3.13 shows the action effect more than 80%.

Claims (14)

  1. Formula 1. (I) compound：
    Figure 9980232300021
    Wherein：A1And A2It is mutually independent, and represents monocyclic or aryl bicyclic or heteroaryl groups in each case, and each heteroaryl groups are independently of one another containing the 1-4 hetero atoms for being selected from N, O and S；And A if appropriate1Base (R can be substituted3a)n1Substitution, and A if appropriate2Base (R can be substituted3b)n2Substitution；n1And n2It is 1,2,3 or 4 independently of one another, they depend on ring system A1And A2Substitution possibility；And or (A) R3aAnd R3bIt is hydrogen, halogen, C independently of one another1-C6Alkyl, halo-C1-C6Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, halo-C2-C4Alkenyl, halo-C2-C4Alkynyl, C1-C6Alkoxy, halo-C1-C6Alkoxy, C2-C6Alkenyloxy, C2-C6Alkynyloxy group, halo-C2-C6Alkenyloxy, halo-C2-C6Alkynyloxy group ,-OH ,-SF5,-CHO,-C(=O)-C1-C6Alkyl ,-C (=O)-halo-C1-C6Alkyl ,-C (=O)-OC1-C6Alkyl ,-C (=O)-O- halos-C1-C6Alkyl ,-O-C (=O) N (R6)2(two of which R6Substituent is mutually independent) ,-CN ,-NO2,-S(=O)2N(R6)2(two of which R6Substituent is mutually independent) ,-S (=O)p-C1-C6Alkyl ,-S (=O)p- halo-C1-C6Alkyl ,-O-S (=O)p-C1-C6Alkyl ,-O-S (=O)p- halo-C1-C6Alkyl, phenyl, benzyl, phenoxy group or benzyloxy, wherein phenyl, benzyl, phenoxy group or benzyloxy group are respectively unsubstituted or its aromatic ring and are selected from following substituent to be replaced 1-5 times independently of one another：Halogen, cyano group, NO2,C1-C6Alkyl, halo-C1-C6Alkyl, C1-C6Alkoxy and halo-C1-C6Alkoxy；And R2For R2a；Or, (B) R3aAnd R3bIndependently of one another as defined in (A), and group R3aOr R3bIn at least one be-CR5=CR5R14,-NR11R12,-C(=O)CN,-C(=O)C(=O)O-C1-C6Alkyl ,-CR15=NOR10Or five or six membered heteroaryl ring, wherein the heteroaryl ring, if appropriate, according to the substitution possibility of ring, can be selected from halogen, C by 1-31-C4Alkyl, C1-C4Haloalkyl, NO2Replace with CN substituent, and R2For R2aOr R2b；Or (C) R3aWith any implication defined in (A) above or (B)；   R3bFor hydrogen, halogen, C1-C6Alkyl, halo-C1-C6Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, halo-C2-C4Alkenyl, halo-C2-C4Alkynyl, C1-C6Alkoxy, halo-C1-C6Alkoxy, C2-C6Alkenyloxy, C2-C6Alkynyloxy group, halo-C2-C6Alkenyloxy, halo-C2-C6Alkynyloxy group ,-OH ,-SF5,-CHO,-C(=O)-C1-C6Alkyl ,-C (=O)-halo-C1-C6Alkyl ,-C (=O)-OC1-C6Alkyl ,-C (=O)-O- halos-C1-C6Alkyl ,-O-C (=O) N (R6)2(two of which R6Substituent is mutually independent) ,-CN ,-NO2, phenyl, benzyl, phenoxy group or benzyloxy, wherein phenyl, benzyl, phenoxy group or benzyloxy group are respectively unsubstituted or its aromatic ring and are selected from following substituent to be replaced 1-5 time independently of one another：Halogen, cyano group, NO2,C1-C6Alkyl, halo-C1-C6Alkyl, C1-C6Alkoxy and halo-C1-C6Alkoxy；- S (=O) on 4p-C1-C6Alkyl or the-S (=O) on 4p- halo-C1-C6Alkyl, condition is substituent R3bIn one be-S (=O)p-C1-C6Alkyl or-S (=O)p- halo-C1-C6Alkyl；And R2For R2aOr R2b；Wherein at (A), in (B) and (C) group, if appropriate, R2aFor-C1-C6Alkyl-NR11R12,-C(=X)-R7a,-COC9-C20Alkyl ,-CH2O(C=O)C1-C6Alkyl ,-C1-C6Alkyl-O-C1-C6Alkyl-O-C1-C6Alkyl ,-CH2O(C=O)C2-C6Alkenyl ,-CH2O(C=O)C2-C6Alkynyl ,-C (=S) OC2-C6Alkenyl ,-C (=S) OC2-C6Alkynyl ,-C (=S) SC1-C6Alkyl ,-C (=S) SC2-C6Alkenyl ,-C (=S) SC2-C6Alkynyl ,-C (=O) SC1-C6Alkyl ,-C (=O) SC2-C6Alkenyl ,-C (=O) SC2-C6Alkynyl ,-C (=S) NR11R12,-C(=O)NR10OR13,-CH2OC2-C6Alkenyl ,-CH2OC2-C6Alkynyl ,-CH2OC2-C6Halogenated alkenyl or-CH2OC2-C6Halo alkynyl；R2bFor hydrogen ,-OH, C1-C6Alkyl, C1-C6Alkoxy, C3-C6Cycloalkyl, C3-C6Alkenyl, C3-C6Alkynyl, halo-C1-C6Alkyl, halo-C3-C6Alkenyl, halo-C3-C6Alkynyl, benzyl or benzoyl, wherein benzyl or benzoyl group are selected from halogen ,-CN, NO on aromatic ring2、C1-C6Alkyl, C1-C6Alkoxy, halo-C1-C6Alkyl and halo-C1-C6The substituent of alkoxy replaces 1-3 times independently of one another；C1-C6Alkoxy -C1-C6Alkyl；Cyano group-C1-C6Alkyl ,-C (=X)-R7a,-C(=X)-R7b,-OC(=O)-R7a,-C(=O)-C(=O)-R7a,-OC(=O)-R7b,-C(=O)-C(=O)-R7b,-S(=O)pN(R6)2(two of which R6Substituent is mutually independent)；Cyano group ,-C1-C6Alkyl-N (R5)-C(=O)-R8,-C1-C6Alkyl-S-C (=S)-R8,-C1-C6Alkyl-S (=O)p-R9,-S(=O)p-R9Or-CH2-N(R10)-SO2-R9；X is O or S；P is 0,1 or 2；R5It independently is H or C1-C8Alkyl；R6It independently is H, C1-C8Alkyl, C3-C6The aromatic ring of cycloalkyl, phenyl or benzyl, wherein phenyl or benzyl can be selected from halogen ,-CN, NO if appropriate2、C1-C6Alkyl, C1-C4Alkoxy, halo-C1-C6Alkyl and halo-C1-C6The substituent of alkoxy replaces 1-3 times independently of one another；Or two alkyl group R6With their institute's keys with nitrogen-atoms together with form 5-7 yuan of rings, CH therein2Group, if appropriate, can be selected from O and S hetero atom substitution, or be replaced by NH, and wherein 5-7 yuan of rings if appropriate can be by C1-C4Alkyl replaces for 1 time or twice；R7aFor C1-C6Alkoxy -C1-C6Alkyl, CH2CH2CF2Cl,C1-C6Alkylthio group-C1-C6Alkyl, acyloxy-C1-C6Alkyl, halo-C3-C6Cycloalkyl, C3-C6Cycloalkyl-C1-C6Alkyl, halo-C3-C6Cycloalkyl-C1-C6Alkyl, aryloxy group-C1-C6Alkyl；Or phenyl, benzyl, phenoxy group or aryloxy group-C1-C6Alkyl, they are selected from halogen, nitro, cyano group, C by 1-31-C4Alkyl, halo-C1-C4Alkyl and halo-C1-C4The substituent substitution of alkoxy；R7bFor H, C1-C8Alkyl, C2-C8Alkenyl, halo-C1-C8Alkyl, halo-C2-C8Alkenyl, C1-C8Alkoxy, halo-C1-C8Alkoxy, C3-C6Cycloalkyl, phenyl, benzyl, phenoxy group, benzyloxy or-N (R6)2(two of which R6Group is mutually independent)；R8For C1-C8Alkyl, C1-C8Alkoxy, halo-C1-C8Alkyl, halo-C1-C8Alkoxy, C1-C8Alkylthio group, phenyl, benzyl or-N (R6)2(two of which R6Group is mutually independent)；R9For C1-C6Alkyl, halo-C1-C4Alkyl or aryl, the aryl is unsubstituted or be selected from following substituent and replace 1-3 times independently of one another：C1-C6Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C1-C4Alkoxy, halogen, cyano group, halo-C1-C4Alkyl, halo-C2-C4Alkenyl, halo-C2-C4Alkynyl, halo-C1-C4Alkoxy and nitro；R10For H, C1-C6Alkyl, C3-C6Cycloalkyl, phenyl or benzyl, wherein phenyl and benzyl group are that unsubstituted or its aromatic ring is selected from C1-C4Alkyl, C1-C4Alkoxy, halogen, cyano group, halo-C1-C4Alkyl, halo-C1-C4The substituent of alkoxy and nitro replaces 1-3 times independently of one another；R11And R12It is H, C independently of one another1-C6Alkyl, phenyl ,-COC1-C6Alkyl ,-COC1-C6Haloalkyl ,-CO phenyl, or form 5 or 6 yuan of saturations or unsaturation ring together is one or more wherein if appropriate, especially one, CH- or CH2- group can be selected from O, N and S hetero atom substitution, and therein 5 or 6 yuan of rings can be selected from halogen, C by 1-3 if appropriate1-C4Alkyl, C1-C4Haloalkyl, C1-C4Halogenated alkoxy, NO2Replace independently of one another with CN substituent；Or two substituent Rs11And R12Ring is formed together：Or
    Figure 9980232300052
    Q is 2 or 3；And R13For H, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl；R14For hydrogen, C1-C6Alkyl, halo-C3-C6Alkyl, C1-C6Alkoxy, halo-C1-C6Alkoxy, C2-C6Alkenyloxy ,-CHO ,-C (=O)-C1-C6Alkyl ,-C (=O)-halo-C1-C6Alkyl ,-C (=O)-OC1-C6Alkyl ,-C (=O)-O- halos-C1-C6Alkyl ,-CN ,-NO2,  -S(=O)2N(R6)2(two of which R6Substituent is mutually independent) ,-S (=O)p-C1-C6Alkyl ,-S (=O)p- halo-C1-C6Alkyl ,-O-S (=O)p-C1-C6Alkyl ,-O-S (=O)p- halo-C1-C6Alkyl, phenyl, benzyl, or benzyloxy, wherein phenyl, benzyl or benzyloxy substituents are respectively unsubstituted or its aromatic ring and are selected from halogen, cyano group, NO2、C1-C6Alkyl, halo-C1-C6Alkyl, C1-C6Alkoxy and halo-C1-C6The substituent of alkoxy replaces 1-5 times independently of one another；And R16For hydrogen, C1-C6Alkyl or halo-C1-C6Alkyl；And, if appropriate, possible E/Z isomers, E/Z isomer mixtures and/or dynamic isomer, include its free form or salt form in each case, prepare and apply these compounds, the method of E/Z isomers and dynamic isomer, its active component is selected from these compounds, the agricultural chemicals of E/Z isomers and dynamic isomer, and preparation and the method using these compositions, prepare the intermediate product of the free or salt form of these compounds, if appropriate, the dynamic isomer of their free or salt form, and the method for preparation and these intermediate products of application and its dynamic isomer.
  2. 2. formula (I) compound according to claim 1, it is free form.
  3. 3. formula (I) compound according to claim 1, wherein A1And A2For phenyl.
  4. 4. according to claim 1-3 formula (I) compound, wherein R2aFor-C1-C6Alkyl-NR11R12,-COC9-C20Alkyl ,-C1-C6Alkyl-O-C1-C6Alkyl-O-C1-C6Alkyl ,-CH2O(C=O)C1-C6Alkyl ,-CH2O(C=O)C2-C6Alkenyl ,-CH2O(C=O)C2-C6Alkynyl ,-C (=S) OC2-C6Alkenyl ,-C (=S) OC2-C6Alkynyl ,-C (=S) SC1-C6Alkyl ,-C (=S) SC2-C6Alkenyl ,-C (=S) SC2-C6Alkynyl ,-C (=O) SC1-C6Alkyl ,-C (=O) SC2-C6Alkenyl ,-C (=O) SC2-C6Alkynyl ,-C (=S) NR11R12,-C(=O)NR10OR13,-CH2OC2-C6Alkenyl ,-CH2OC2-C6Alkynyl ,-CH2OC2-C6Halogenated alkenyl or-CH2OC2-C6Halo alkynyl.
  5. 5. according to claim 1-4 formula (I) compound, wherein n1For 2,3 or 4, and n2For 1 or 2.
  6. 6. a kind of composition pesticide, it includes formula (I) compound of at least one claim 1 as active component, and at least one adjuvant, and formula (I) compound therein is acceptable salt form on free form or agricultural chemicals.
  7. 7. a kind of method for preventing and treating insect pest processed, it includes the composition that claim 6 is applied to insect or its habitat.
  8. 8. method according to claim 7, this method is used for the insect for preventing and treating insect and Acarina.
  9. 9. preparing the method for the composition comprising at least one adjuvant of claim 6, this method includes close mixing and/or grinding active component and adjuvant.
  10. 10. application of formula (I) compound of acceptable salt form in the composition for preparing claim 6 on the free form or agricultural chemicals of claim 1.
  11. 11. application of claim 6 composition in terms of pest control.
  12. 12. the purposes of claim 11, the purposes is to be used to protect plant propagation material.
  13. 13. the method for claim 7, this method is used to protect plant propagation material, it includes the cultivation place for handling the plant propagation material or the processing plant propagation material.
  14. 14. the plant propagation material handled according to claim 13 methods described.
CN99802323A 1998-01-22 1999-01-20 Organic nitrile derivatives and their use as pesticides Pending CN1288459A (en)

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