CA2316835A1 - 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
CA2316835A1
CA2316835A1 CA002316835A CA2316835A CA2316835A1 CA 2316835 A1 CA2316835 A1 CA 2316835A1 CA 002316835 A CA002316835 A CA 002316835A CA 2316835 A CA2316835 A CA 2316835A CA 2316835 A1 CA2316835 A1 CA 2316835A1
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Canada
Prior art keywords
c6alkyl
halogen
independently
another
phenyl
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Abandoned
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CA002316835A
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French (fr)
Inventor
Roger Graham Hall
Arthur Steiger
Ottmar Franz Huter
Alfons Pascual
Miroslav Kriz
Stephan Trah
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Syngenta Participations AG
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Individual
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Publication of CA2316835A1 publication Critical patent/CA2316835A1/en
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    • C—CHEMISTRY; METALLURGY
    • 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
    • A01N37/34—Nitriles
    • A—HUMAN NECESSITIES
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    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
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    • A01N41/04—Sulfonic acids; Derivatives thereof
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
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    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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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<
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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
    • A01N47/08—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 the carbon atom having one or more single bonds to nitrogen atoms
    • 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
    • C—CHEMISTRY; METALLURGY
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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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    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
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    • C07C323/23—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
    • 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
    • C07C323/35—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
    • 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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    • C07C323/50—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 carboxyl groups bound to the same carbon skeleton
    • C07C323/62—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 carboxyl 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
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (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

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 <u>either</u> 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 halogen-C2-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;
<u>or</u>, 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 C1-C6alkoxy; 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 H, C1-C6alkyl or phenyl;
and where applicable the possible E/Z isomers, E/Z isomer mixtures and/or tautomers thereof, in free form or in agrochemically acceptable form, can be used as agrochemical active ingredients and may be prepared in a known manner.

Description

i~YO 99/37603 PCT/EP99/00363 -1_ The invention relates to a compound of formula A, N . N ~ A (I), wherein A, and A2 are independent of one another and in each case represent a monocyclic or bicyclic aryl or heteroaryi radical, and each heteroaryl radical independently of the other having 1 up to and including 4 hetero atoms selected from the group consisting of N, O and S; and A, is substituted where appropriate with substituent (R~)~, and A? where appropriate with substituent (R~),~;
n, and n2 are independently of one another 1, 2, 3 or 4, depending on the possibilities for substitution on ring system A, and A2; and gither (A) R~, and Ra, -independently of one another are hydrogen, halogen; C,-CBalkyl, halogen-C,-Csaikyl, C~-C,alkenyl, C2-C,alkinyl, halogen-C2-C,alkenyl, halogen-C2-C,alkinyl, C,-CBalkoxy, halogen-C,-Cs-alkoxy, CZ-Csalkenyloxy, C2-Csalkinyloxy, halogen-C2-Cealkenyloxy, halogen-CZ-Cealkinyloxy, -OH, -SF5, -CHO, -C(=O)-C,-Cs-alkyl, -C(=O)-halogen-C,-Csalkyl, -C(=O)-OC,-Cgalkyl, -C(=O)-O-halogen-C,-Cealkyl, -O-C(=O)N(Rs)2 (wherein both Re substituents are independent of one another), -CN, ~N02, -S(=O)2N(Re)2 (wherein both RB substituents are independent of one another), -S(-O)p.C,_Csalkyl, -S(=O)p-halogen-C,-Csalkyl, -O-S(=O)p-C,-Csalkyl, -O-S(=O)P-halogen-C,-Csalkyl, phenyl, benzyl, phenoxy or benzyloxy, wherein each of the phenyl, benzyl, phenoxy, or benzyloxy radicals is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, N02, C,-Cealkyl, halogen-C,-Cealkyl, C,-Csalkoxy and halogen-C,-Csalkoxy; and R2 is R2,~ Qi, (B) R~, and R~ independently of one another as defined under (A) and at least one of the radicals R~, or R~ is -CRS=CRSR", -NR"R,2, -C(=O)CN, -C(=O)C(=O)O-C,-Csalkyl, -CR,~NOR,a or a five or six-membered heteroaryl ring, wherein the said heteroaryl ring is substituted, where appropriate, depending on the substitution possibilities on _2_ -the ring, with 1 to 3 substituents selected from the group consisting of halogen, C,-C4alkyl, C,-C,haioalkyl, N02 and CN; and R2 is R2, or Rn,; or (C) Rte, has one of the meanings defined hereinbefore under (A) or {B);
R~ is hydrogen, halogen, C,-Csalkyl, halogen-C,-Cealkyl, CZ-Caalkenyl, C2-C4alkinyl, halogen-C2-C4alkenyl, halogen-C2-C4alkinyl, C,-Csalkoxy, halogen-C,-CBalkoxy, C2-Cealkenyloxy, C2-Cgalkinyloxy, halogen-C2-Cealkenyloxy, halogen-C2-CBalkinyloxy, -OH, -SFS, -CHO, -C(=O)-C,-CBalkyl, -C(=O)-halogen-C,-Csalkyl, -C(=O)-OC,-Cgalkyl, -C(=O)-O-halogen-C,-Csaikyl, -O-C(=O)N(Rg)2 (wherein the two Re substituents are independent of one another), -CN, -N02, phenyl, benzyl, phenoxy or benzyioxy, wherein each of the phenyl, benzyl, phenoxy, or benzyloxy radicals is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, N02, C,-Cealkyl, halogen-C,-Cgalkyl, C,-Cealkoxy and halogen-C,-Cealkoxy; -S(=O)p C,-Csalkyl in the 4-position or -S(=O)P-halogen-C,-Cealkyl in the 4-position, with the proviso, that one of the substituents R~ is -S(=O)p C,-Cealkyl or -S(=O)p-halogen-C,-CBalkyl; and R2 is R28 or R~,;
and in the groups (A), (B) and (C), where appropriate, R~ is -C,-Cgalkyl-NR"R,2, -C(=X)-R~a, -COC9-Czoalkyl, -CH20{C=O)C,-Cgalkyl, -C,-CBalkyl-O-C,-Cgalkyl-O-C,-Cealkyl, -CH20(C=O)C2-Cs alkenyl, -CH20(C=O)C2-Cealkinyl, -C(=S)OC2-Csalkenyl, -C(=S)OC2-Csaikinyf, -C(=S)SC,-Cgalkyl, -C(=S)SC2-Csalkenyl, -C(=S)SC2-CBalkinyl, -C(=O)SC,-Csalkyl, -C(=O)SC2-Csalkenyl, -C(=O)SC2-Csalkinyi, -C(=S)NR"R,2, -C(=O)NR,oOR,3, -CH20C2-Csalkenyl, -CHZOC2-Cealkinyl, -CH20C2-Cshaloalkenyl or -CH20C2-Cghaloalkinyt;
R~ is hydrogen, -OH, C,-Csalkyl, C,-Csalkoxy, C3-Cecycloalkyl, C3-Csalkenyl, C3-Cealkinyl, halogen-C,-Csalkyl, halogen-C3-Csalkenyl, halogen-Cs-Csalkinyl, benzyl or benzoyl, wherein the benzyl or benzoyl radical is substituted in the aromatic ring independently of one another once to three times by substituents selected from the group consisting of halogen, -CN, N02, C,-Csalkyl, C,-Cealkoxy, halogen-C,-Cealkyl and halogen-C,-Csalkoxy; C,-C~alkoxy-C,-Cealkyl, cyano-C,-Cgalkyl, -C(=X)-R,a, -C(=X)-Rte, -~(=O)-R~a~ -C(=O)-C(=O)-R~a, -OC(=O)-Rya, -C(=O)-C(=O)-R~a~ -S(=O)cN(Rs)2 (wherein the two Re substituents are independent of one another); cyano, -C,-Cgalkyl--3- _ N(R5)-C(=O)-Re, -C,-Cgalkyl-S-C(=S)-Re, -C,-Csalkyl-S(=O)p Ra, -S(=O)p-Ra, or -CH2-N(R~o)-S02-Ra;
X is O or S;
p is 0, 1 or 2;
R5 is independently H or C,-Cealkyl;
Rg is independently H, C,-CBalkyl, C3-Cgcycloalkyl, phenyl or benzyl, wherein the phenyl or benzyl group is substituted in the aromatic ring where appropriate independently of one another once to three times with substituents selected from the group consisting of halogen, -CN, N02, C,-Csalkyl, C,-C4aikoxy, halogen-C,-Cgalkyl and halogen-C,-Csalkoxy; or two alkyl radicals Re, together with the nitrogen atom to which they are bonded, form a five to seven-membered ring, wherein a CHa group, where appropriate, is substituted by a heteroatom selected from the group consisting of O
and S, or is substituted by NH, and wherein the five to seven-membered ring, where appropriate, is substituted once or twice with C,-C,,alkyl;
R~, is C,-Cgalkoxy-C,-Cgalkyl, CH2CH2CF2CI, C,-Cealkylthio-C,-Cealkyi; acyloxy-C,-Cealkyl, halogen-C3-Cecycloalkyl, C3-CgcyClOalkyl-C,-Cgalkyl, haiOgen-C3-Cg-cycl08lkyl-C,-Csalkyl, aryloxy-C,-Csalkyl; or phenyl, benzyl, phenoxy or aryloxy-C,-Csalkyl, which are substituted with 1 to 3 substituents selected form the group consisting of halogen, vitro, cyano, C,-C4-alkyl, halogen-C,-C4-alkyl and halogen-C,-C4-alkoxy;
R~ is H, C,-Csalkyl, C2-Caalkenyl, halo-C~-Cealkyi, halo-C2-Cealkenyl, C,-Cealkoxy, halo-C,-Cealkoxy, C3-Cecycloalkyl, phenyl, benzyl, phenoxy, benzyloxy or -N(Rs)2 (in which the two Re are independent of one another);
Re is C,-Cealkyl, C,-Cealkoxy, halogen-C,-Csalkyl, halogen-C,-Cealkoxy, C,-CBaikylthio, phenyl, benzyl or -N(Re)2 (wherein the two RB radicals are independent of one another);
Rs is C~-Ceaikyl, halogen-C,-C4alkyl or aryl, which is unsubstituted or substituted once to three times, independently of one another, with subsituents selected from the group consisting of C,-Cealkyl, C2-C,,alkenyl, C2-C,aikinyl, C,-C4alkoxy, halogen, cyano, halogen-C~-C,alkyl, halogen-C2-C,alkenyl, halogen-CZ-C4aikinyl, halogen-C,-C4alkoxy and vitro;
R,o is H, C,-Csalkyl, C3-Cecycloalkyl, phenyl oder benzyl, wherein the phenyl and benzyi radicals are unsubstituted or substituted in the aromatic ring once to three times independently of one another with substituents selected from the group consisting of -4- _ C,-C,,alkyl, C,-C4alkoxy, halogen, cyano, halogen-C,-C,,alkyl, halogen-C,-C,alkoxy and nitro;
R" and R,2 are independently of one another H, C,-Ce alkyl, phenyl, -COC,-Cealkyl, -COC,-Cghaloalkyl, -COphenyl, or together form a five or six-member saturated or unsaturated ring, wherein if appropriate one or more, especially one, of the CH- or CH2-groups is or are substituted by a heteroatom selected from the group consisting of O, N and S, and wherein the five or six-membered ring if appropriate is indepen-dently of each other substituted with 1. to 3 substituents selected from the group consisting of halogen, C,-C4alkyl, C,-C4hatoalkyl, C,-C4haloalkoxy, N02 and CN; or the two substituents R" and R,2 together form a ring X X
( H2)q or i X X
q is 2 or 3; and R,3 is H, C,-C$alkyl, Cz-Csalkenyl, C2-Caalkinyl;
R,,, is hydrogen, C,-Csalkyl, halogen-C3-Csalkyl, C,-Csalkoxy, halogen-C,-Cgalkoxy, C2-Cealkenyloxy, -CHO, -C(=O)-C,-Cealkyl, -C(=O)-halogen-C,-Csalkyl, -C(=O)-OC,-Csalkyl, -C(=O)-O-halogen-C,-Cealkyl, -CN, -NOZ, -S(=O)2N(R6)2 (wherein the two Re substituents are independent of one another), -S(=O)p C,-Csalkyl, -S(=O)P-halogen-C,-Csalkyl, -O-S(=O)P C,-Caalkyl, -O-S(=O)P halogen-C,-Csalkyl, phenyl, benzyl, or benzyloxy wherein each of the phenyl, benzyl, or benzyloxy substituents is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, N02, C,-Cealkyl, halogen-C,-Csalkyl, C,-Csalkoxy and halogen-C,-Csalkoxy; and R,5 is hydrogen, C,-Csalkyl or halogen-C,-Cealkyl;
and, if appropriate, to the possible E/Z isomers, FJZ isomer mixtures andlor tautomers, in each case in free form or in the form of a salt, to a method for the preparation and use of these compounds, E2 isomers and tautomers, pesticides, whose active ingredient is selected from these compounds, E2 isomers and tautomers, and to a method for the preparation and use of these compositions, intermediate products, in free form or in the form of a salt, for the preparation of these compounds, and where appropriate their 1~V0 99137603 PC"f/EP99/00363 .5_ tautomers, in free form or in the form of a salt, and to a method for the preparation and use of these intermediate products and their tautomers.
In the literature, certain phenylhydrazone derivatives are proposed as active ingredients in pesticides. The biological properties of these known compounds, however, are not fully satisfactory in the field of pest control, which is why there is a need to produce further compounds with pesticidal properties, especially for the control of insects and members of the order acarina; this problem is solved according to the invention with the development of the present compounds of formula (I).
Some compounds of formula (I) comprise asymmetrical carbon atoms, as a result of which the compounds may occur in an optically active form. Owing to the presence of the C=N
double bond, the compounds may occur in E and Z isomeric forms. Atropisomers of the compounds may also occur. Formula (I) should encompass all these possible isomeric forms and mixtures thereof, for example racemates or mixtures of E2 isomers.
The general terms used hereinbefore and hereinafter have the following meanings, unless defined othervvise.
Groups and compounds containing carbon comprise, unless defined otherwise, in each case 1 to 8 inclusive, preferably 1 to 6 inclusive, more particularly 1 to 4 inclusive, especially 1 or 2, carbon atoms.
Alkyl - as a group per se and as a structural component of other groups and compounds, such as alkyl halide, alkoxy or alkylthio - is, in each case with due consideration to the number of carbon atoms in the group or compound concerned, either straight-chained, i.e.
methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tart-butyl, isopentyl, neopentyl or isohexyl.
Alkenyl - as a group per se and as a structural component of other groups and compounds, such as alkenoxy, alkenyl halide or alkenoxy halide - is, in each case with due consideration to the number of carbon atoms in the group or compound concerned, either stra~lght-chained, e.g. vinyl, 1-methylvinyl, allyl, 1-butenyl oder 2-hexenyl, or branched, such as isopropenyl.
Alkinyl - as a group per se and as a structural component of other groups and compounds, such as alkinyl halide - is, in each case with due consideration to the number of carbon -s- _ atoms in the group or compound concerned, either straight-chained, e.g.
propargyl, 2-butinyl or 5-hexinyl, or branched, such as 2-ethinylpropyl or 2-propargylisopropyl.
C3-Cecycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Aryl is phenyl or naphthyl, especially phenyl.
Bicyclic heteroaryl is taken to mean a radical which may independently contain one or more heteroatoms only in one ring - such as for example in quinolinyl, quinoxalinyl, indolinyl, benzothiophenyl or benzofuranyl - as well as in both rings - such as for example in pteridinyl or purinyl.
Halogen - as a group per se and as a structural component of other groups and compounds, such as alkyl halide, alkenyl halide and alkinyl halide - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, and quite particularly chlorine.
Halogen-substituted groups and compounds containing carbon, such as alkyl halide, alkenyl halide or alkinyl halide, may be partly halogenated or perhalogenated, where in the case of repeated halogenation the halogen substituents may be the same or different.
Examples of alkyl halide - as a group per se and as a structural component of other groups and compounds, such as alkenyl halide - are methyl substituted once to three times by fluorine, chlorine and/or bromine, such as CHF2 or CF3; ethyl substituted once to five times by fluorine, chlorine and/or bromine, such as CHZCF3, CF2CF3, CFZCCI3, CF2CHCI2, CF2CHF2, CF2CFCI2, CF2CHBr2, CF2CHCIF, CF2CHBrF or CCIFCHCIF; propyl or isopropyl substituted once to seven times by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH{CF3) 2; and butyl or one of the isomers thereof substituted once to nine times by fluorine, chlorine and/or bromine, such as CF(CF3)CHFCF3 or CH2{CF2) 2CF3. Alkenyl halide is for example CH2CH=CHCI, CH2CH=CCI2, CH2CF=CF2 or CHZCH=CHCH2Br. Alkinyl halide is for example CH2C~CF, CH2C--__CCH2CI or CF2CF2C--CCH2F.
Some compounds of formula (I) may, as is familiar to persons skilled in the art, occur as tautomers, especially if R2 is H. Accordingly, any reference to compounds of formula (I) hereinbefore and hereinafter is understood to include also their corresponding tautomers, even if the latter are not specifically mentioned in each case.

WO 99/37b03 PCT/EP99/00363 _7_ _ Compounds of formula (I) which show at least one basic centre may form, for example, acid addition salts. These are formed, for example, with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide, with strong organic carboxylic acids, such as C,-C4alkanecarboxylic acids substituted if appropriate by halogen, e.g. acetic acid, such as dicarboxylic acids unsaturated if appropriate, e.g. oxalic, malonic, succinic, malefic, fumaric or phthalic acid, such as hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, typically C,-C,alkanesulfonic or arylsulfonic acids substituted where appropriate for example by halogen, e.g. methanesulfonic or p-toluenesulfonic acid. In a broader sense, compounds of formula (I) with at least one acid group can form salts with bases. Suitable salts with bases are for example metal salts, typically alkali or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl, diethyl, methyl or dimethyipropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine.
Corresponding internal salts where appropriate may also be formed. Compounds of formula (I) in free fomn are hereinbefore and hereinafter taken to imply also their corresponding salts, and the salts where applicable are taken to mean also the free compounds of formula (I). The same applies for tautomeric derivatives of compounds of formula (I) and salts thereof. In each case, the free form is generally preferred.
The following forms are preferred within the scope of this invention:
(1 ) A compound of formula (I), wherein A, and A2 are independently of one another a substituent selected from the group consisting of / / S N ~'~~~(Rs)n\~(Rs)n \ /\ -~- ~
~N~(~,~ ~N~(R3)n N O
(R3)~ (R3)" (R~m Re ~~ (R3)n ~~ (R3)~ . N (R3,~\ ~~ (R3~~
S O S N O S

_g_ N_N R3 (N~Ra N_N Rs N~Rs N_~Rs ~N Rs ~N~N ~ ~ ~ .N ~ N N
N O ~ N
R, R4 R4 N (~)n N (R3)n N (R3)~ (R3)n (R3)n~N ~
N N N NON ~ J
Ro R . (~)m N
(R3)m R
(R3)m 3)m N R3 ) (R3)n ~ ~N J N~ ~ n .Si (R3)n (R3)n v r and ~+ r N-p ~-O
O O
especially phenyl, naphthyl, pyridyl or thiadiazolyl, very especially phenyl or pyridyl, in particular phenyl;
R3 corresponds to Rte, and R~, of formula (I);
R~, artd R~ are independently of one another halogen, -CN, N02, halogen-C,-Czalkyl, C~-C2alkoxy or halogen-C,-C2alkoxy, halogen-C2-Csalkenoxy or halogen-C2-CSalkinyioxy;
espeaally chlorine, -CN, CF3 or OCF3; wherein, if m + n is greater than 1, the radicals R~
and R,~ are independent of one another;
R, is H, C,-C~alkyl, phenyl or benzyl; especially H and methyl;
n is 0 to 5, especially 1 to 3, depending on the possibility for substitution on the ring system, and the values of n in A, are independent of the values of n in A2;
m is 0 to 4, depending on the possibility for substitution on the ring system, and the values of m in A, are independent of the values of m in A2;

the sum of m + n is 0 to 5; especially 1, 2 or 3;
(2) A compound of formula (I), wherein A2 corresponds to substituents selected from the w group consisting of furanyl, thienyl, ~ S ~" , I ~. ~~, and ~ , ~~ , and N-'O N-O
O
R2 is R28 or Rn,;
(3) A compound of formula (I), wherein A, and A2 are phenyl;
(4) A compound of formula (I), wherein Rte, is -C,-Cealkyl-NR~,R,2, -C(=X)-R,e, -COCs-C~alkyl, -C~-C$alkyl-O-C,-CBalkyl-O-C,-Cealkyl, -CH20(C=O)C,-Cgalkyl, -CH20(C=O)C2-CBalkenyl, -CH20(C=O)C2-Csalkinyl, -C(=S)OC2-Cealkenyl, -C(=S)OC2-Cealkinyl, -C(=S)SC,-Cealkyl, -C(=S)SC2-Csalkenyl, -C(=S)SCz-Csalkinyl, -C(=O)SC,-Cealkyl, -C(=O)SC2-Cealkenyl, -C(=O)SCz-Csalkinyl, -C(=S)NR"R,Z, -C(=O)NRaoOR,3, -CH20C2-Cgalkenyl, -CH20C2-Csalkinyl, -CH20C2-Cshaloalkenyl or -CH20C2-Cghaloalkinyl; especially, R~, is -CHzalkyl-NR"R~2, -COC9-Czoalkyl, -C,-C2alkyl-O-C,-Czalkyl-O-C,-C2alkyl, -CH20(C=O)C,-C2alkyl, -CH20(C=O)C2-C4alkenyl, -CH20(C=O)C2-C4alkinyl, -C(=S)OC2-C4alkenyl, -C(=S)OC2-C4alkinyl, -C(=S)SC,-C2alkyl, -C(=S)SC2-C4aikenyl, -C(=S)SCZ-C4alkinyl, -C{=O)SC,-C2alkyl, -C(=O)SC2-C4alkenyl, -C(=O)SC2-C4alkinyl, C,-C4alkylthio-C,-Czalkyl, -C(=S)NR"R,2, -C(=O)NR,oOR,3, -CHZOC2-Cealkenyl, -CH20C2-C4alkinyl, -CH20C2-C4haioalkenyl or -CH20C2-C,haloalkinyl; in particular R~ is -CH2alkyl-NR"R~2, -COC9-C~alkyl, -C,-Czalkyl-O-Cf-C2alkyl-O-C~-C2alkyl, -CH20(C=O)C,-Czalkyl, -C{=O)SC,-C2alkyl, -CH20C2-C4alkenyl, or -CH20C2-C4alkinyl; in particular Rte, is -CON(OCH3)CH3, -C(O)NHCOCH3, -COSCZHS, -COSCH3, -CH20C(O)C(CH3)s, CH20C2H40CH3, -CHZOCH2CH=CH2, -CH20CH2C-CH, -COC,oH2,;
(5) A compound of formula (I), wherein R~ is hydrogen, C,-C4alkyl, C,-C4alkoxy-C,-C4alkyl, -C(=X)-R~e, -C(=O)-C,-C4alkyl , -C(=O)-halogen-C3-Csalkenyl , -C(=O)-C3-Cgcycloalkyl , -C(=O)-O-C,-C2alkyl, -C(=O)-C(=O)-O-C,-Czalkyl, -C(=O)-C(=O)-N(Rg)2, cyano, benzoyl or benzyl, wherein the benzoyl or benzyl radical is substituted in the aromatic ring if necessary, independently of one another, once ~WO 99/37603 PCT/EP99/00363 to three times with a substituent selected from the group consisting of halogen, -CN, -NOz, trifiuoromethoxy and trifluoromethyl; or-C(=O)-N(R6)2; and the twa Rs substituents are, independently of one another, H, C,-C4alkyl, C3-Cscycloalkyl, phenyl or benzyl, wherein the phenyl or benzyl group if necessary, independently of each other, is substituted in the aromatic ring once or twice with substituents selected from the group consisting of halogen, -CN, C,-C4alkyl, C,-Cealkoxy, halogen-C,-C2alkyl and halogen-C,-Czalkoxy; or two alkyl radicals R6 together with the nitrogen atom to which they are attached form a five or six-membered ring, wherein a CH2-group if necessary is substituted by an O atom or by NH, and wherein the five or six-membered ring is substituted if necessary with methyl; especially R~, is hydrogen, C,-C3alkyl, C,-C2alkoxy-C,-C2alkyl, -C(=O)-C,-Czallkyl , -C(=O)-fluoro-C,-Cealkenyl , -C(=O)-cyclopropyl , -C(=O)-O-C,-C2alkyl, -C(=O)-C(=O)-O-C,-C2alkyl, -C(=O)-C(=O)-N(Re)2, cyano, benzyl or o-nitrobenzyl; -C(=O)-N(Re)2; or -C(=O)-CsHs, wherein the phenyl ring is likewise substituted once to three times with a substituent selected from the group consisting of halogen, N02, trifluoromethoxy and trifluoromethyl;
and the two Re radicals are, independently of one another, H, C,-C,alkyl, cyclopropyl, phenyl or benzyl, wherein the phenyl or benzyl group, if necessary, independently of one another, is substituted in the aromatic ring once or twice by substituents selected from the group consisting of chlorine, -CN and OCF3; or two Re alkyl radicals together with the nitrogen atom to which they are attached form a six-membered ring and wherein a CH2-group where applicable is substituted by an O atom or by NCH3;
(6) A compound of formula (I), wherein A, is a pyridyl radical;
(7) A compound of formula (I), wherein (R~,)nt IS CI, C12, CI3, -(CF3)2, CI-CF3, NO2, -CN, CI2-NO2, -OCF3, -CF3, CI-CF3, CI2-CF3, CIZ-OCF3, -C12-F, CI2-Br, CI-CF3-F, CI-Br-CH3, -(CHa)Z-Br, CI3-CF3, CI2-F-CF3, F2-CF3-CI, CI2-CN, CI2-CF3, CI2-SCF3, CI2-OCF3, CIz-O2CF3, CI2-SO2CH3, CI2-OCF2Br, CI2-OCF2H, CI2-C2F5, (NO2)2-CF3, (N02)2-Cl, CI2-S02GH30r CI2-OSO2CF3; espeClally 2-CI, 2,3-CI2, 2,4-CI2, 2,6-CI2, 2,4,6-CI3, 3,5-(CF3)Z, 2-CI-4-CF3, 2-NO2, 2-CN, 3-CN, 4-CN, 2,6-CI2-4-N02, 4-OCF3, 4-CF3, 3-CF3, 2-CI-4-CF3, 2-CI-4-N02, 2,6-CI2-4-CF3, 2,6-CI2-4-OCF3, 2,6-CI2-4-F, 2,6-CI2-4-Br, 2-CI-4-CF3-6-F, 2-CI-4-Br-6-CH3; 2,6-(CH3)2-4-Br, 2,3,6-CI3-4-CF3, 2,6-CIx3-F-4-CF3, 2,3-F2-4-CF3-6-CI, 2,6-CI2-4-CN, 2,4-CI2-6-CF3, 2,6-CI2-4-SCF3, 2,6-CI2-4-WO 99/37603 _ SOCF3, 2,6-Clz-4-S02CF3, 2,6-Clz-4-S02CH3, 2,6-Clz-4-OCF2Br, 2,6-Clz-4-OCFZH, 2,6-Clz-4-C2Fs, 2,6-(NOz)z-4-CF3, 2,6-(NOz)z-4-CI, 2,6-Clz-4-OS02CH3, or 2,6-Clz-4-OS02CF3; very especially 2,3-Clz, 2,4-Clz, 2,6-Clz, 2,4,6-CI3, 3,5-(CF3)z, 2-CI-4-CF3, 2-CN, 3-CN, 4-CN, 2,6-Clz-4-NOz, 4-OCF3, 4-CF3, 3-CF3, 2-CI-4-CF3, 2-CI-4-NOz, 2,6-Clz-4-CF3, 2,6-Clz-4-OCF3, 2,6-Clz-4-F, 2,6-Clz-3-F-4-CF3, 2,3-Fz-4-CF3-6-CI, 2,6-Clz-4-CN, 2,4-Clz-6-CF3, 2,6-CI2-4-SCF3, 2,6-CI2-4-SOCF3, 2,6-Clz-4-S02CF3, 2,6-Clz-4-C2F5, 2,6-(NOz)2-4-CF3, 2,6-(NOz)z-4-CI, 2,6-CI2-4-OS02CHs, or 2,6-Clz-4-OS02CF3;
(8) A compound of formula (I), wherein one (R~,)"z is -S(=O)p-C,-Cgalkyl in the 4-position or -S(=O)p-halogen-C,-Csalkyl in the 4-position; especially -S(=O)p C,-C3alkyl or -S(=O)p-halogen-C,-C3alkyl; more specifically is -S(=O)p halogen-C,-C3alkyl;
very especially, wherein nz is 1 and R~ is SOCF3, SOC2F5, SOCHFz, SOCF2Br, SOCF2C1, SOCF2CFZBr, SOCF2CF2CI, SCF3, SC2F5~ SCHFz, SCFZBr, SCF2CI, SCF2CF2Br, SCF2CF2CI, S02CF3, S02CzF5, S02CHFz, S02CF2Br, S02CF2CI, S02CF2CFzBr, S02CFzCF2Cl;
(9) A compound of formula (I), wherein (R~)"z is -CN, CI, Clz, F, F2, Br, -NOz, -(NOz)z, -NOz-CF3, CF3, -(CF~)z, -CN-CF3, CI-CF3, F-CN, -CI-CN, -OCF3, -CI-NOz, -CH3-NOz, -OCH3-NOz, -CsH5, -CeH4-F, -CeH4-CI, -CgH4-CF3, -CsH4-CFs, -CsHe-NOz, -CsH3-(CF3)z, -CgH3-Clz, -CsH3-(CI-F), -F-CN, F-NOz, CI-NOz, CI-NOz, -CHO, SCF3, SOCF3, S02CF3 or -C(=O)CF3; especially 4-CN, 3-CN, 4-CI, 3,4-Clz, 2,3-Clz, 3,5-Clz, 2,5-Clz, 3,5-Fz, 2,6-Fz, 4-Br, 2-F, 4-NOz, 2-N02-4-CF3, 3-CF3, 4-CF3, 3,5-(CF3)z, 2-CN-4-CF3, 2-CI-4-CF3, 2-F-4-CN, 3-CI-4-CN, 4-OCF3, 3-OCF3, 4-CI-3-NOz, 2-CI-4-NOz, 3-CH3-4-NOz, 3-OCH3-4-NOz, 4-CsHS, 4-CsH4-4-F, 4-CgH4-4-CI, 4-CeH4-4-CF3, 4-CsH4-3-CF3, 4-CBHe-3-N02, 4-CsH3-(3,5-CF3)z, 4-CgH3-2,4-Clz; 4-CBH3-3,4-CI2, 4-CBH3-3,5-Clz, 4-CeH3-(3-CI-4-F), 2-F-4-CN, 2-F-4-N02, 2-CI-4-NOz, 4-CI-3-NOz, 4-CHO, 4-SCF3, 4-SOCF3, 4-S02CFs or 4-C(=O)CF3; very especially 4-CN, 3-CN, 4-CI, 3,4-Clz, 2,3-Clz, 3,5-Clz, 2,5-CI2, 3,5-Fz, 2,6-Fz, 2-F, 2-NOz-4-CF3, 4-NOz, 3-CF3, 4-CF3, 3,5-(CF3)2, 2-CN-4.-CF3, 2-CI-4-CF3, 2-F-4-CN, 3-CI-4-CN, 4-OCF3, 3-OCF3, 4-CI-3-NOz, 2-CI-4-NOz, 3-CH3-4-NOz, 3-OCH3-4-NOz, 4-CsHS, 2-F-4-CN, 2-F-4-NOz, 2-C!-4-NOz, 4-CI-3-NOz, 4-CHO, 4-SCF3, 4-SOCF3, 4-S02CF3 or 4-C(=O)CF3;
(10) A compound of formula (I), wherein Rzd is hydrogen;
(11 ) A compound of formula (I), wherein n, is 1, 2, 3 or 4, preferably 2 or 3;

~WO 99/37603 PCT/EP99/00363 _~2_ _ (12) A compound of formula (I), wherein n2 is 1 or 2, preferably 1;
(13) A compound of formula (1), wherein n, is 2, 3, or 4 and n2 is 1 or 2;
(14) A compound of formula (I), wherein R" and R,2 are independently of one another H, C,-C2alkyl, phenyl, -COC,-C2alkyl, -COphenyl, or together form a five or six-membered saturated or unsaturated ring, wherein one of the CH- or CH2-groups if applicable is substituted by a heteroatom selected from the group consisting of O, N and S, and wherein the five or six-membered ring if applicable is substituted with 1 or 2 substituents selected from the group consisting of C,-C2alkyl, C,-C2haloalkyl, N02, CN; or the two substituents R" and R,2 together form a ring X X
or X X
and q is 2; especially R" and R,2 are independently of one another H, C,-Czalkyi, phenyl, -COC,-C2alkyl, -COphenyl, very especially H, methyl or ethyl.
(15) A compound of formula (I), wherein at least one R~ and/or R~ is/are -CR5=CRSR,a and R,e is hydrogen, C,-Csalkyl, halogen-C,-Cealkyi, -CHO, -C(=O)-C,-Csalkyl, -C(=O)-halogen-C,-Cgalkyl, -C(=O)-OC,-Csalkyl, -C(=O)-O-halogen-C,-Csalkyl, -CN, -NOZ, -S(=O)2N(Fis)2 (wherein the two Re substituents are independent of one another), -S(=O)P
C,-Csalkyl, phenyl, benzyl or benzyloxy; and R5 is hydrogen or C,-Czalkyl;
e~ecially an R~, or R~ is -CR5=CRSR,4;
R,,, is hydrogen, C,-Czalkyl, halogen-C,-Czalkyl, phenyl or benzyl; and R,5 is methyl or CF3;
(16) A compound of formula (I), wherein R5 is independently H or C,Czalkyl;
(17) A compound of formula (I), wherein 1~V0 X9/37603 PCT/EP99/00363 n2 is 1 and (R~)"2 is SCH3, SCF3, SCZHs, SC2F5, SOCH3, SOC2H5, SOC2F5, S02N(CH3)2, S02N(C2H5)2, SOzCH3, SO2CF3, SO2C2H5, SO2C2F5, SOCF3, SOCHF2, SOCF2Br, SOCF2Cl, SOCF2CF2Br, SOCFZCF2CI, SCHF2, SCFZBr, SCF2CI, SCFZCFZBr, SCF2CF2CI, SOZCHF2, S02CF2Br, S02CF2CI, S02CF2CF2Br or SOZCF2CF2CI; in particular SCF3, SC2Fs, SOCF3, SOC2F5, S02CF3 Or SO2C2F5; and R2 is R2a or Rte, especially H, -CH20C2H5, -COCH3, -CH3, -CN, -CH2C~H, -C2H5, -or -CON(CH3)OCH3.
Especially preferred within the scope of this invention are the compounds of formula (I) listed in Tables 3 to 27 and, where applicable, the E/Z isomers and E/Z
isomeric mixtures thereof.
A further object of the invention is the method for preparing the compounds of formula (I) and where appropriate their E2 isomers, FJZ isomeric mixtures, and/or tautomers thereof in each case in free form or in the form of a salt, comprising either a) for the preparation of a compound of formula (I), wherein the substituents A, and A2 are as defined hereinbefore, and R2 is hydrogen, aa) the diazotization of a compound of formula A,-NH2 (III), wherein A, is as defined hereinbefore under formula (I), and ab) reaction of the diazonium salt with a compound of formula CN
Az wherein A2 is as defined hereinbefore under formula (I) and W is hydrogen or a removable group; or b) for the preparation of a compound of formula CN
N . ~ (la), ~WO 99/37603 PCT/EP99/00363 wherein A,, A2 and R2 are as defined hereinbefore for R28 and R~ in the compounds of formula (I), the reaction of a compound of formula R2 Hal (II), A~ N A2 wherein A,, A2 and R2 are as defined hereinbefore for R2s and R~ in the compounds of formula (I) and Hal is a halogen atom, preferably chlorine or bromine, especially chlorine, with a metal cyanide, preferably an alkaline metal cyanide, especially with sodium cyanide;
or c) for the preparation of a compound of formula (I), wherein R2 is different from H, the reaction of a compound of formula (I), wherein R2 is hydrogen, with a compound of formula RrQ N), wherein R2 is as defined hereinbefore for Rte, and R~, in formula (I) and Q is a leaving group, preferably chlorine, bromine or iodine, especially iodine, preferably in the presence of a base; or and in each case, if so desired, the conversion of a compound of formula (I) or an FJZ
isomer or tautomer thereof in free form or in the form of a salt and obtainable by means of the method or by other means to another compound of formula (I) or an E2 isomer or tautomer thereof in free form or in the form of a salt, the separation of a mixture of FJZ
isomers obtainable by means of the method or by other means, and the isolation of the desired isomer, and/or the conversion of a free compound of formula (I) or an E2 isomer or tautomer thereof, obtainable by means of the method or by other means, to a salt, or the conversion of a salt, obtainable by means of the method or by other means, of a compound of formula (I) or of an E/Z isomer or tautomer thereof to the free compound of formula (I) or an FJZ isomer or tautomer thereof, or to another salt.
A further object of the invention is a method for the preparation of a compound d) of formula i~VO 99/37603 PCT/)rP99100363 R2 Hal (Ila), /N.N~A
A~ z wherein A,, A2 and RZ are as defined hereinbefore for R28 and R2b in the compounds of formula (I) and Hal is a halogen atom, and where applicable the FJZ isomers and tautomers thereof, in free form or in the form of a salt, comprising the reaction of a compound of formula N
N ~ VIII
i Az H
wherein the radicals A, and Az and R2 have the same meaning as defined hereinbefore under formula (Ila) for R28 and R2b, with a halogenation agent, or e) of formula R2 Hal i 'l /N~N~A (Ilb), A1 z wherein R2 and the two radicals A, and A2 have the same meaning as defined hereinbefore for A,, A2, R~, and Rte, under formula (I) and Hal is a halogen atom, preferably chlorine, comprising the reaction of a compound of formula N. ~ (IX)~
A, N
wherein R2 and the two radicals A, and Aa have the same meaning as defined hereinbefore under formula (Ilb), with N-bromosuccinimide or N-chlorosuccinimide in the presence of a thio ether, and in each case, if so desired, the conversion of a compound of formula (II) or an E2 isomer or tautomer thereof in free form or in the form of a salt and obtainable by means of the method or by other means to another compound of formula (II) or an E/Z
isomer or tautomer thereof in free form or in the form of a salt, the separation of a mixture of E2 -16- _ isomers obtainable by means of the method or by other means, and the isolation of the desired isomer, and/or the conversion of a free compound of formula (II) or an FJZ isomer or tautomer thereof, obtainable by means of the method or by other means, to a salt, or the conversion of a salt, obtainable by means of the method or by other means, of a compound of formula (II) or of an E/Z isomer or tautomer thereof to the free compound of formula (II) or an E/Z isomer or tautomer thereof, or to another salt.
The reactions described hereinbeore and hereinafter are carried out in known manner, wherein the work may be performed, depending on requirements, with cooling, at room temperature, or with heating, e.g. in a temperature range from about 0°C to the boiling temperature of the reaction medium, preferably from about 20°C to about +120°C, especially at 60°C to 80°C and, if necessary, in a closed container, under pressure and in an inert gas atmosphere, e.g. under nitrogen or argon, and/or under anhydrous conditions.
Preferred are reactions carried out at normal pressure under nitrogen. The reaction partners can be reacted with one another as they are, i.e. without the addition of a solvent or diluent, e.g. in the melt. In most cases, however, the addition of an inert solvent or diluent, or a mixture thereof, is of advantage. Especially advantageous reaction conditions are described in the Examples.
The isolation of the products takes place according to usual methods, e.g. by filtration, crystallization, distillation or chromatography or any suitable combination of these methods.
Vari; n~ t al:
aa) Diazotization takes place under conditions familiar to persons skilled in the art, i.e. in the presence of strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide, usually in the presence of water, but also in pure sulfuric acid.
Depending on the basicity of the aromatic amine, the reaction takes place in a temperature range from about -10°C to about +20°C, or if necessary even at a higher temperature, for example at 60°C to 80°C.
The reaction time is preferably about 1 to about 2 hours.
The product is usually not isolated, but processed further in the next reaction step.
Especially preferred conditions for the reaction are desc~bed in Example H6/a.

_~7-ab) The reaction usually takes place in the presence of water and preferably in the presence of an organic carboxylic acid, such as formic acid, chloroacetic acid, trifluoroacetic acid, cyanoacetic acid, oxalic, malonic, succinic, malefic, fumaric or phthalic acid; especially preferred is the addition of acetic acid.
A removable group W is taken to mean an electrophilic group which is readily removable under the prevailing reaction conditions. Especially suitable for this are -C(=O)R or -OC(=O)R, wherein R is H, C,-C,,alkyl, halogen-C,-C4alkyt, C,-Caalkoxy, halogen-C,-C,,alkoxy, -CN, or organic sulfonates, such as C,-C4alkane or arylsulfonates substituted if necessary for example by halogen, e.g. methane, trifluoromethane or p-toluenesulfonate.
The reaction is advantageously carried out within a temperature range of about -10°C to about +30°C, preferably from about 0°C to about +25°C.
The reaction time of about 0.5 to about 8 hours is preferred, especially about 2 to about 4 hours.
Variant bl:
Suitable for the reaction are transition metal cyanides, such as CuCN or Ni(CN) 2, as well as alkaline earth and alkaline metal cyanides; especially KCN and NaCN.
Examples of solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesityiene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxan; ketones, such as acetone, methyl ethyl ketone or methyl isobuty! ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N
diethylformamide, N,N dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide;
nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide, or water. Preferred are alcohols and water or alcohol / water mixtures.
The reaction is advantageously carried out within a temperature range from about 0°C to about 80°C, preferably from about 20°C to about 30°C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

The reaction time of about 0.1 to about 24 hours is preferred, especially about 3 to about 5 hours.
In a preferred form of variant b), a compound of formula (II) is reacted in an ethanol / water mixture with sodium cyanide at room temperature.
~lairiant cl:
Suitable leaving groups Q in compounds of formula (V) are for example hydroxy, C,-Cealkoxy, halogen-C,-Csalkoxy, C,-Cealkanoyloxy, mercapto, C,-Cealkylthio, halogen-C~-Csalkylthio, C,-Cealkanesulfonyloxy, halogen-C,-Csalkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy or halogen, especially halogen, in particular bromine or chlorine.
Suitable bases for facilitating the reaction are e.g. alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, cycloalkylamines (N-alkylated where appropriate and unsaturated where appropriate), basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples are: sodium hydroxide, hydride, amide, methanolate, acetate, and carbonate, potassium tart-butanolate, hydroxide, carbonate, hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU). Preferred are alkaline metal and earth alkaline metal carbonates, alkylamines and alkaline metal or earth alkaline metal alkanolates.
Examples of solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons, typically benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethylether, dimethoxydiethylether, tetrahydrofuran or dioxan; esters, such as ethyl acetate and methyl acetate; and sulfoxides, such as dimethyl sulfoxide. Preferred are ethers, such as tert-butyl methyl ether, tetrahydrofuran or dioxan, and esters, such as ethyl acetate.

The reaction is advantageously carried out within a temperature range from about 0°C to about +120°C, preferably from about 0°C to about +80°C.
The reaction time of about 0.1 to about 24 hours is preferred, especially about 0.5 to about 2 hours.
Variant d~.
The reaction preferably takes place in the presence of an acid catalyst, for example in the presence of a carboxylic acid, such as formic acid, acetic acid, malonic acid or oxalic acid, or also a sulfonic acid, such as C,-C4alkane or arylsuifonic acid substituted if necessary for example by halogen, e.g. methane, trifluoromethane or p-toluenesulfonic acid.
Especially suitable are solvents which are suited to azeotropic removal of water. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachioromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as dipropyl ether, diisopropyi ether, dibutyi ether, tart-butyl methyl ether, dimethoxydiethyl ether;
ketones, such as methyl isobutyl ketone; alcohols, such as ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol.
The reaction is advantageously carried out within a temperature range of about 60°C to about 180°C, preferably 80°C to about 130°C, in many cases at the reflux temperature of the reaction medium.
The preferred reaction time is about 6 to about 72 hours, espeaaily about 12 to about 48 hours.
in a preferred form of variant d), the reaction is carried out at 80° C
to 140°C in an alcohol or an aromatic hydrocarbon in the presence of C,-C,carboxylic acid.
Preferred halogenation agents are CI2, Br2, SOCIz, SOzCl2, POCI3, PCI3, PCIS
and COCIZ.
Examples of solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and hakigenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chkirobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichioroethane, trichforoethene or -wo ~r~~6o3 Pc~r~w~roo~
-20- _ tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxan; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; amides, such as N,N-dimethylformamide, N,N
diethyiformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitrites, such as acetonitrile or propionitrile.
The reaction is advantageously carried out within a temperature range from about 0°C to about 180°C, preferably from about 50°C to about 100°C, in many cases in the range between room temperature and the reflex temperature of the reaction mixture.
'The reaction time is not critical; a reaction time of about 0.1 to about 24 hours is preferred, especially about 3 to about 6 hours.
The compounds of formulae (I), (Ila), (Ilb) and (Vlll) may be present in the form of one of the possible isomers or as a mixture thereof, depending for example on the number and the absolute and relative configuration of the asymmetric carbon atoms as pure isomers, such as enantiomers and/or diastereomers or isomer mixtures, such as mixtures of enantiomers, for example racemates; the invention relates both to the pure isomers and to ail possible isomeric mixtures, and is hereinbefore and hereinafter understood as doing so, even if stereochemical details are not specifically mentioned in every case.
Diastereomer mixtures and racemate mixtures of compounds of formulae (I), (Ila), (Ilb) and (VIII), obtainable as described in the method - depending on the starting materials and working pnxedures selected- or by other means, can, owing to the physicochemical differences of the constituents, be separated in known manner into the pure diastereorners ar raoemates, for example by fractionated crystallization, distillation and/or chromatography.
the resolution of correspondingly obtainable mixtures of enantiomers, such as racemates, c;an be achieved by known methods, for example by recrystallization from an optically active sohrent, by chromatography on chiral adsorbents, e.g. high-pressure liquid chromatography (HPLC) on acetyl cellulose, by the use of suitable microorganisms, by cleavage with specific immobilized enzymes, through the formation of inclusion compounds, e.g. using chiral crown ether, wherein only one enantiomer is complexed.
Rcoording to the invention, apart from isolation of corresponding isomer mixtures, generally known methods of diastereoselective or enantioselective synthesis can also be applied to obtain pure diastereomers or enantiomers, e.g. by carrying out the method of the invention using educts with correspondingly suitable stereochemistry.
It is of advantage to isolate or synthesize the biologically more active isomer in each case, e.g. enantiomer or mixture of isomers, e.g. enantiomer mixture, if the individual components show differences in biological efficacy.
Compounds of formula (I), (Ila), (Ilb) and (VIII) can also be obtained in the form of their hydrates and/or also can include other solvents used for example where necessary for the crystallization of compounds present in solid form.
The invention relates to all those forms of the method, according to which one starts from a compound obtainable as a primary material or an intermediate at any stage of the method and carries out all or some of the missing steps, or uses, or - especially under the reaction conditions - produces a starting material in the form of a derivative or a salt and/or its racemate or enantiomer.
In the method of the present invention, the starting materials and intermediates used are preferably those that lead to the compounds of formula (I) described at the beginning as being especially useful.
The invention relates in particular to the manufacturing processes described in Examples H1, H2, H4 and H5.
Starting materials and intermediate products used according to the invention for the preparation of compounds of formula (I), and in particular the compounds of formulae (II), (III), (IV) and (VIII), which are new, and their use and methods for their preparation likewise form an object of the invention.
Compounds of formulae (Ila), (Ilb) and (VIII) as well as the use thereof for the preparation of compounds of formula (I) represent a further object of the invention.
The compounds of formulae (III) to (VI) and (IX) are known or can be prepared according to known methods.
A further object of the invention is a method for controlling pests using a compound of formula (I), wherein A,, A2 and R2 have the same meaning as defined hereinbefore for formula (I).
The compounds of formula (I) according to the invention are active substances of preventive and/or curative merit for use in pest control and offer a very favourable spectrum of biocidal activity with favourable tolerability in warm-blooded animals, fish, and plants even at low concentrations. The compositions according to the invention are active against all or individual development stages of anima! pests showing normal sensitivity, and also of those showing resistance, for example insects or members of the order acarina.
The insecticidal, ovicidal, and/or acaricidal effect of the compositions of the invention can manifest itself directly, i.e. killing the pests either immediately or after some time has elapsed, for example when moulting occurs, or the eggs thereof, or indirectly, e.g. reducing the number of eggs laid and/or the hatching rate, good efficacy corresponding to a destruction rate (mortality) of at least 50 to 60%.
The animal pests include for example:
Members of the orders lepidoptera, coteoptera, orthoptera, isoptera, psocoptera, anoplura, mallophaga, thysanoptera, heteroptera, homoptera, hymenoptera, diptera, siphonaptera, thysanura and acarina; especially preferred is the control of .pests of the genera and species which are described in EP-A-736'252 , and which are included here by reference.
Pests of said type which occur on plants, especially on crops and ornamentals in agriculture, horticulture and forestry, or on parts of such plants, such as fruits, blooms, leaves, stems, tubers or roots, can be controlled, i.e. kept in check or eradicated, using the active ingredients of the invention, this protection remaining for parts of some plants whose growth does not occur until later.
Target crops within the scope of this application include especially cereals, such as wheat, barley, rye, oats, rice, com or sorghum; beet, such as sugar beet or fodder beet; fruit, e.g.
ponies, drupes and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, e.g. strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybean; oleaginous fruits, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as pumpkins, cucumbers or melons; fibrous plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or paprika;
lauraceae, such as avocado, cinnamon or camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamentals.
The active ingredients of the invention are especially suitable for the control of insects and members of the order acarina, in particular crop-eating and damaging insects, such as -23- _ Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cultivated plants of cotton, fruit, maize, soya, rape and vegetables.
Other indication areas for the active ingredients of the invention are the protection of stored products and stores and of material and, in the hygiene sector, in particular the protection of domestic animals and livestock against pests of said type.
The invention therefore relates also to pesticides which comprise a compound of formula (I), wherein A,, A2 and Rz have the same meaning as defined hereinbetore for formula (I), with the exception of 1-phenylhydrazono-2-nitriloethylbenzene, such as emulsifiable concentrates, suspension concentrates, ready-to-spray or ready-to-dilute solutions, coatatile pastes, dilute emulsions, spray powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymeric substances (chosen in accordance with the intended objectives and prevailing circumstances), comprising at least one active ingredient of the invention.
In these compositions, the active ingredient is employed in pure form, the solid active ingredients in a specific particle size, or preferably together with - at least - one of the adjuvants conventionally used in the art of formulation, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).
Suitable adjuvants, such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, and anionic surfactants in the compositions used according to the invention, are the same as those which are described in EP-A-736'252 (CASE 20400) and which are included in the present object of the invention by reference.
As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of - at least - one solid or liquid adjuvant, wherein 0 to 25°~, especially 0.1 to 20%, of the composition may as a rule be surfactant (% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient. Preferred compositions are thus composed in particular as described in EP-A-736'252 .
The activity of the compositions of the invention can be substantially broadened and adapted to prevailing circumstances by adding other insecticidal, acaricidal, and/or fungicidal substances. Additional active ingredients are, for example, substances from the following classes: organophosphorus compounds, nitrophenols and derivatives, formamidine, urea, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations. The compositions of the invention can also comprise other solid or liquid adjuvants, such as stabilizers, e.g. vegetable oils, epoxidized where appropriate (e.g. epoxidized coconut oil, rapeseed oil or soya oil), antifoams, e.g.
silicone oil, preservatives, viscosity modulators, binders and/or tackifiers, and also fertilizers or other active ingredients to achieve specific effects,.e.g. acaricides, bactericides, nematocides, molluscicides or selective herbicides.
The compositions of the invention are prepared in a known manner, in the absence of adjuvants, for example, by grinding and/or sieving a solid active ingredient or active ingredient mixture, e.g. to a specific particle size, and in the presence of at least one adjuvant, for example, by intimately mixing and/or grinding the active ingredient or the mixture of active ingredients with the adjuvant(s). These methods for preparing compositions of the invention and the use of compounds of formula (I) for preparing these compositions likewise form an object of the invention.
The methods of application for the compos'ttions, i.e. the methods of controlling pests of said type, such as spraying, atomizing, dusting, coating, dressing, scattering or pouring (chosen in accordance with the intended objectives and prevailing circumstances), and the use of the compositions for controlling pests of said type are further objects of the invention.
Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The rates of application are generally 1 to 2000 g of active ingredient {a.i.) per hectare (ha = approximately 2.471 acres), especially 10 to 1000 g a.iJha, and preferably 20 to 600 g a.i./ha.
A preferred method of application for crop protection is to apply the active ingredient to the foliage of the plants (leaf application), the number of applications and the rate of application depending on the intensity of infestation by the pest in question. However, the active ingredients can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). With paddy rice cultures, granules may be metered into the flooded paddy field.

The compositions of the invention are also suitable for protecting plant propagation material, e.g. seeds, such as fruits, tubers or grains, or plant seedlings, from fungal infections and animal pests. The propagation material can be treated with the composition before the start of cultivation, seeds for example being dressed before they are sown. The active ingredients of the invention can also be applied to seeds (coating) by either soaking the seeds in a liquid composition or coating them with a solid composition.
The composition can also be given when the propagation material is introduced to the place of cultivation, e.g. when the seeds are sown in the seed furrow. The treatment procedures for plant propagation material and the propagation material thus treated are further objects of the invention.
The invention is illustrated by the following examples. They do not impose any limitation on the invention. Temperatures are given in degrees Celsius.
Preparative exams, I
Example H1: Preparation of 4-nitrobenzoic acid-N'-(2,6-dichloro-4-trifluoromethylphenyl)-hydrazide of formula CI H O
I
/ ~ N.N /
I
CI H ~ N~..O
I
O_ A solution of 35.85 g 4-nitrobenzoyl chloride in 150 ml dichloromethane is added dropwise over a period of about 60 minutes to 45.1 g 2,6-dichloro-4-trifluoromethylphenylhydrazine in 1000 ml dichloromethane while stirring at 0 to 5°C, and the stirring is then continued for a further 60 minutes at room temperature. For 20 minutes the mixture is vigorously stirred while 20.4 g triethylamine is fed in. Stirring is then continued for 3 hours at room temperature. The organic phase is washed three times with 500 ml of water each time, dried on sodium sulfate and the solvents removed in the rotary evaporator.
After recrystallization of the residue from toluene, the title product is obtained at a melting point of 188-190°C.
example H2: Preparation of 4-{ 1-[(2,6-dichloro-4-trifluoromethylphenyl)hydrazono]-chioromethyl}-nihobenzene of formula CI H CI
I
/ N~Ni /
F ~ ~ CI \ ~ N~~-O

F Or To a solution of 69.3 g 4-nitrobenzoic acid-N'-(2,6-dichloro-4-trifluoromethylphenyl)-hydrazide in 600 ml toluene, 33.9 g thionyl chloride is added dropwise while stirring at room temperature. The mixture is then heated to 105°C and stirred for 6 hours. After cooling, the mixture is concentrated to dryness by evaporation on the rotary evaporator and the residue crystallized out from toluene. The title compound is obtained at a melting point of 117-118°C {compound 1.20).
Exam Ip a H3: The other compounds listed in Table 1 can be prepared in a manner analogous to that described under Example H2.
T le 1: Compounds of formula H CI
I
/ N.Ni /
(R3b)n2 NO. (R~)"~ {R~)r~2 mp C

1.1 2,6-CI2-4-CF3 4-Br 124-125 1.2 2,6-CI2-4-CF3 4-COCF3 107-108 1.3 2,6-CI2-4-CF9 3-N02-4-CI 141-143 1.4 2,6-CI2-4-CF3 2-F-4-NOZ 88-90 1.5 2,6-Ci2-4-CF3 4-SCF3 137-138 1.6 2,6-CI2-4-CF3 4-SCH3 89-90 1.7 2,4-CI2-6-CF3 4-N02 128-129 1.8 2-CI-4-CF3-6-F 4-N02 135-137 1.9 2,6-CI2-3-F-4-CF3 4-N02 143-144 1.10 2,3,6-CI3-4-CF3 4-N02 121-123 1.11 2,4,6-CI3 4-S02CH3 Amorphous 1.12 2,4,6-CI3 4-SCH3 78-79 1.13 2,4,6-CI3 4-SCF3 92-94 1.14 2,6-CI2-4-CF3 4-F 97-98 ~VU 99/37603 PCT/EP99/00363 No. (R~)", (R~)~ mp C

1.15 2,6-CI2-4-CF3 4-S02N(CH3}2 163-164 1.16 2,4,6-CI3 4-CHO 152-154 1.17 2,6-(N02)2-4-CF3 4-N02 189-i 1.18 2-CI-4-OCF3-6-NO2 4-N02 147-148 1.19 2-CI-4-CF3 3-N02-4-CI 188-190 1.20 2,6-CI2-4-CF3 4-N02 117-118 Exam Ip a H4: Preparation of 4-{1-[(2,6-dichloro-4-trifluoromethylphenyl)hydrazono)-2-nitriloethyl}nitrobenzene of formula CI H
I
N~
F \ C~ :O
F
F
To 10.7 g sodium cyanide in 240 ml water and 160 ml ethanol, 51.5 g solid 4-~1-[(2,6-dichloro-4-trifluoromethylphenyl}hydrazono)chloromethyi}nitrobenzene is added in portions over a period of about one hour. The reaction mixture is stirred for 18 hours at room temperature and then poured onto 6 I of ice water. The precipitate is filtered, washed three times with water, dissolved in ethyl acetate and washed with 15% NaCI
solution. The organic phase is dried, filtered over sodium sulfate, and concentrated to dryness by evaporation on the rotary evaporator. The residue is crystallized out from toluene. This yields the title compound with a melting point of 160-161 °C.
Exam 12e H5: Preparation of 4-f1-[(2,6-dichloro-4-trifluoromethylphenyl)-N-methyl-N-methoxycarbamoylhydrazono]-2-nitriloethyl}nitrobenzene of formula WO 99137b03 PCT/EP99/003b3 -28- _ O-N N
CI
/ N~N/ /
F ~ ~ CI ~ ~ .'.O
F , " N
I
F O_ To 1.2 g 4-{1-[(2,6-dichioro-4-trifluoromethylphenyl)hydrazono]-2-nitriloethyl}nitrobenzene in 50 ml tetrahydrofuran, 0.44 g of finely pulverized potassium tert-butylate is added at room temperature. The mixture is stirred for 10 minutes, resulting in a deep red solution. 0.48 g methylmethoxycarbamoyl chloride is added and the mixture stirred for three hours. The sohrent is removed in the rotary evaporator and the residue dissolved in ethyl acetate. The ethyl acetate phase is washed with water and NaCI solution, dtyed over sodium sulfate, and concentrated to dryness by evaporation under a vacuum. The residue is chromatographed over a silica gel column with hexane : tetrahydrofuran in the ratio 5:1.
Concentration by evaporation of the fractions 6-14 yields the title compound with a melting point of 96-97°C
(compound 2.1 ).
Exam I~e 6: The other compounds listed in Tables 2 and 3 can also be prepared in a manner analogous to that described under Example H5.
Table 2: Compounds of formula N
I
/ N.N/ /
~Rsb)nx C3HsFzcyc is 2,2-difluoro-cycloprop-1-yl 4-C(NOMe)CF3 stands for the substituent 4-C(=NOCH3)CF3 No. (Ra~)~, (R~,)~2 R2 mp (C) 2.1 2,6-C!2-4-CF3 4-N02 -CON(OCH3)CH3 96-97 2.2 2,6-CI2-4-CF3 4-N02 -COSCZHS 198-i 9s 2.3 2,6-CI2-4-CF3 4-N02 -COSCH3 198-200 2.4 2,6-C12-4-CF3 4-N02 -CH20C(O)C(CH3)3 87-90 ~WO 99/37603 PCT/EP99/00363 -2g- _ N0. (R~)", (R~)~2 R2 mP (C) 2.5 2,6-CI2-4-CF3 4-N02 -CHpOCpH4OCH3 63-65 2.6 2,6-CI2-4-CF3 4-N02 -CH20CH2CH=CH2 73-74 2.7 2,6-CI2-4-CF3 4-N02 -CH20CH2C=CH 99-100 2.8 2,6-CI2-4-CF3 4-SOCF3 -H 157-158 2.9 2,6-CI2-4-CF3 4-S02CF3 -H 108-109 2.10 2,6-CI2-4-CF3 4-SCF3 -H 156 2.i 2,6-CI2-4-CF3 4-SOCF3 -CH20C2H5 Oil 2.12 2,6-CI2-4-CF3 4-S02CF3 -CHZOC2H5 Oil 2.13 2,6-CI2-4-CF3 4-SCH3 -H 147-149 2.14 2,8-CI2-4-CF3 4-S02N(CH3}2-H 201-202 2.15 2,6-CI2-4-CF3 4-S02N(CH3)2-CH20C2H5 136 2.16 2,6-CI2-4-CF3 4-SCH3 -CH20C2H5 80-81 2.17 2,6-CI2-4-CF3 4-F -H 126-128 2.18 2,6-CI2-4-CF3 4-F -CH20C2H5 Oil 2.19 2,4,6-CI3 4-SCF3 -H 126-127 2.20 2,4,6-CI3 4-SOCF3 -H 133-135 2.21 2,4,6-Ci3 4-S02CF3 -H 146-148 2.22 2,4,6-CI3 4-SCH3 -H i 13 2.23 2,4,6-CI3 4-S02CH3 -H 205-206 2.24 2,4,6-CI3 4-SOCH3 -H 216-217 2.25 2,4,6-CI3 4-SOCF3 -CH20C2H5 Oil 2.26 2,4,6-CI3 4-S02CF3 -CH20C2H5 86-88 2.27 2,4,6-CI3 4-S02CH3 -CH20C2H5 104-105 2.28 2,4,6-CI3 4-SOCH3 -CH20C2H5 Oil 2.29 2-CI-4-OCF3-6-NOz4-N02 -H 175-176 2.30 2-CI-4-OCF3-6-NOZ4-N02 -CH3 125-126 2.31 2-CI-4-OCF3-6-N024-N02 -CH20C2H5 94-95 2.32 2-CI-4-OCF3-6-N024-NOz CO2C2H5 Resin 2.33 2,6-Ci2-4-CF3 4-NH2 -CH20C2H5 142-143 2.34 2,6-CIZ-4-CF3 4-N02 -COC4H9 n 149-150 2.35 2,6-CI2-4-CF3 4-N02 -COCH(CH3)2 138-139 2.36 2,6-CI2-4-CF3 4-N02 -COCHZC(CH3~3 135-136 NO. (R3,)r,i (R~)n2 R2 mp (C) 2.37 2,6-CI2-4-CF3 4-N02 -COCH2CgH5 129-131 2.38 2,6-CI2-4-CF3 4-N02 -COC3H~ n 142-143 2.39 2,6-CI2-4-CF3 4-N02 -COCH2CH2CI 140-142 2.40 2,6-CI2-4-CF3 4-N02 -COCSHtt n 144-145 2.41 2,6-CI2-4-CF3 4-N02 -COC,oH2t Oil 2.42 2,6-CI2-4-CF3 4-N02 -COC,HtS n 85-86 2.43 2-CI-4-OCF3-6-N024-CN -H 191-193 2.44 2-CI-4-OCF3-6-NOZ4-CN -CH20C2H5 60-61 2.45 2-CI-4-OCF3-6-NHZ4-CN -CH2OC2H5 Resin 2.46 2,6-CIZ-4-CF3 4-N02 -COCH20CH3 152-153 2.47 2,6-CI2-4-CF3 4-N02 -COCH2C3H3F2cyc 154-155 2.48 2,6-CI2-4-CF3 4-NHCOCH3 -CH20CZH5 129-130 2.49 2,6-CI2-4-CF3 4-NHCOCF3 -CH20C2H5 155-156 2.50 2,6-CI2-4-CF3 4-N-Pyrrol -CH20C2H5 104-105 2.51 2-Ci-4-OCF3-6- 4-CN -CH20C2H5 136-137 2.52 2-CI-4-OCF3-6- 4-CN -CH20C2H5 86-87 2.53 2,6-CI2-4-CF3 4-SC2F5 -H 134-135 2.54 2,6-C12-4-CF3 4-SOC2F5 -H 142-143 2.55 2,6-CI2-4-CF3 4-SO2C2F5 -H 153-158 2.56 2,6-CI2-4-CF3 4-SOCZFS -CH20C2H5 Resin 2.57 2,6-C12-4-CF3 4-SOC2F5 -COCH3 Resin 2.58 2,6-CI2-4-CF3 4-SOC2F5 -C02CH3 Resin 2.59 2,6-CI2-4-CF3 4-SOC2F5 -CH3 Resin 2.60 2,6-CI2-4-CF3 4-S02C2F5 -CH20C2H5 Amorphous 2.61 2,6-CI2-4-CF3 4-S02C2F5 -COCH3 Amorphous 2.62 2,6-CI2-4-CF3 4-S02C2F5 -CH3 Solid 2.63 2,6-CI2-4-CF3 4-SOCF3 -CN Resin 2.64 2,6-CI2-4-CF3 4-SOCF3 -CH2C--CH Resin 2.65 2,6-CI2-4-CF3 4-SOCF3 -C2H5 Resin 2.66 2,6-CI2-4-CF3 4-SOCF3 -COOCH3 Resin _31 _ _ NO. (R~)~t (R~)nz R2 mp (C) 2.67 2,6-CI2-4-CF3 4-SOCF3 -COCH3 Amorphous 2.68 2,6-CI2-4-CF3 4-SOCF3 -CON(CH3)OCH3 Resin 2.69 2,6-CI2-4-CF3 4-SOCF3 -CH3 Amorphous 2.70 2,6-CI2-4-CF3 4-S02CF3 -CON(CH3)OCH3 106-107 2.71 2,6-CI2-4-CF3 4-S02CF3 -COOCH3 Amorphous 2.72 2,6-CI2-4-CF3 4-S02CF3 -CH2C~CH Resin 2.73 2,6-CI2-4-CF3 4-S02CF3 -COCH3 Amorphous 2.74 2,6-Ci2-4-CF3 4-S02CF3 -C2H5 Resin 2.75 2,6-CI2-4-CF3 4-S02CF3 -CH3 Resin 2.76 2,6-CI2-4-CF3 4-SOCF3 -CH2CH2N(C2H5)2 amorph 2.77 2,6-CI2-4-CF3 4-S02CF3 -CH2CH2N(C2H5)2 Oel 2.78 2,4,6-CI3 4-S02CF3 -CH2CH2N(C2H5)2 Oel 2.79 2,6-CI2-4-CF3 4-N02 -COCH20C(O)CH3 175-177 2.80 2,6-CI2-4-CF3 4-N02 -COCH2SCH3 Harz 2.81 2,6-CI2-4-CF3 4-N02 -CO(CH3)20C(O)CH3 149-150 2.82 2,4,6-CI3 4-SCF3 -COCH2C3H3Fzcyc 97-98 2.83 2,4,6-CI3 4-SOCF3 -COCHZC3H3Fzcyc 91-93 2.84 2,4,6-CI3 4-S02CF3 -COCH2C3H3Fzcyc 153-154 2.85 2,6-CI2-4-CF3 4-SCF3 -COCH2C3H3F2cyc 75-77 2.86 2,6-CI2-4-CF3 4-SOCF3 -C4CH2C3H3Fzcyc 114-1 i 5 2.87 2,6-C12-4-CF3 4-S02CF3 -COCH2C3H3F2cyc 154-155 2.88 2-CI-4-CFA-6-F4-N02 -COCH2C3H3F2cyc 113-114 2.89 2,6-CI2-3-F-4-CF34-N02 -COCH2C3H3F2cyc 103-104 2.90 2,4-CI2-6-CF3 4-N02 -COCH2C3H3F2cyc 174-175 2.91 2,4,6-CI3 4-N02 -COCH2C3H3F2cyc 153-154 2.92 2,4,6-CI3 4-CN -COCH2C3H3Fzcyc 134-135 2.93 2,6-CI2-4-CF3 3-CH3-4-N02 -COCH2C3H3F2cyc 138-139 2.94 2,6-CI2-4-CF3 4-C(NOMe)CF3 -CH20C2H5 Harz 2.95 2,6-CI2-4-CF3 4-C(NOMe)CF3 -H 145-146 2.96 2,4,6-CI3 4-C(NOMe)CF3 -CH20CZH5 92-93 2.97 2,4,6-CI3 4-C(NOMe)CF3 -H 134-135 2.98 2,4,6-CI3 4-CH=NOH -CH20C2H5 Oil 'WO 99/37603 PCT/EP99/003b3 _32- _ No. (R~,)", (R~)~ RZ mp (C) 2.99 2,6-CI2-4-CF34-N02 -COCH20CeH5 amorph 2.100 2,6-CI2-4-CF34-N02 -COCH20CeH4-4-N02 189-192 2.101 2,6-CI2-4-CF34-N02 -COCH20CBH4-4-F amorph 2.102 2,6-CI2-4-CF34-N02 -COCH20CgH4-4-Br 146-148 2.103 2,6-CI2-4-CF34-N02 -COCH20CgH4-4-CF3 155-158 2.104 2,6-CI2-4-CF34-N02 -COCH20CeH,-3-CF3 111-114 2.105 2,6-CI2-4-CF34-N02 -COCH20CeH4-2-F harz 2.106 2,6-CI2-4-CF34-N02 -COCH20CgH4-3-NO2 140-143 2.107 2,6-Ci2-4-CF34-N02 -COCH20CgH4-3-Br 125-12g 2.108 2,6-C12-4-CF34-N02 -COCH20CeH4-3-F 112-114 2.109 2,6-CI2-4-CF34-N02 -COCHZOCeH4-4-CI 143-147 2.110 2,6-CI2-4-CF34-N02 -COCH20CgH4-3-CH3-4.-CI163-167 2.111 2,6-CIZ-4-CF34-NOz -COCH20CeH,,-3-CI,4-F150-153 2.112 2;6-CI2-4-CF34-SON(CH3)2 -H Harz 2.113 2,6-CIr4-CF34-SOCF3 -CH20CH3 Harz 2.114 2,6-CI2-4-CF34-S02CF3 -CH20CH3 Harz 2.115 2,6-CI2-4-CF34-SOCF3 -CH(CH3)2 91-92 2.116 2,6-CI2-4-CF34-S02CF3 -CH(CH3)2 Harz 2.117 2,6-CI2-4-CF34-SOCF3 -CH20CH(CH3)2 amorph 2.118 2,6-CI2-4-CF34-S02CF3 -CH20CH(CH3)2 amorph 2.119 2,6-CI2-4-CF34-SCF2H H 152-153 2.120 2,6-CI2-4-CF34-SCF2H -COCH3 110-112 2.121 2,6-CI2-4-CF34-SOCF2H -COCH3 amorph 2.122 2,6-CI2-4-CF34-S02CF2H -COCH3 174-176 2.123 2,6-CI2-4-CF34-SCF2H -CH20C2H5 91-92 2.124 2,6-CI2-4-CF34-SOCF2H -CH20C2H5 94-96 2.125 2,6-Ci2-4-CF34-S02CF2H -CHZOC2H5 182-184 2.126 2,4,6-CI3 4-SOCF3 -COCH3 amorph 2.127 2,4,6-CI3 4-S02CF3 -COCH3 152-154 2.128 2,4,6-CI3 4-SOCF3 -COOCH3 181-183 2:129 2,4,6-CI3 4-S02CF3 -COOCH3 170-172 2.130 2,4,6-CI3 4-SOCF3 -C2H5 83-87 NO. (R~)", (R~,),~ R2 mp (C) 2.1312,4,6-CI3 4-S02CF3 -C2H5 72-74 2.1322,4,6-CI3 4-SOCF3 -CH3 80-84 2.1332,4,6-CI3 4-S02CF3 -CH3 120-124 2.1342,4,6-CI3 4-SOCF3 -CH20CH(CH3)2 Harz 2.1352,4,6-CI3 4-SOCF3 -CH(CH3)2 103-108 2.1362,4,6-CI3 4-SCF3 -CH20C2H5 84-86 2.1372,4,6-CI3 4-SCHF2 H 113-114 2.1382,4,6-CI3 4-SOCHF2 H 160-161 2.1392,4,6-CI3 4-S02CHF2 H 194-195 2.1402,4,6-Ci3 4-SCHF2 -CH20C2H5 Harz 2.1412,4,6-Ci3 4-SOCHF2 -CH20C2H5 111-113 2.1422,4,6-CI3 4-S02CHF2 -CH20C2H5 168-169 2.1432,4,6-CI3 4-SOCHF2 -COCH3 146-148 2.1442,4,6-CI3 4-S02CHF2 -COCH3 187-189 2.1452,4,6-CI3 4=SCHF2 -COCH3 97-99 2.1462,6-Ci2-4-CF3 4-SC2F5 -CHg Oel 2.1472,6-Ci2-4-CF3 4-N02 -COCH2CH2CF2C) 189-190 2.1482,4,6-CI3 4-CN -COCH2CI-12CF2CI 167-168 2.1492,6-CI2-4-CF3 3-CH3-4-N02 -COCH2CH2CF2CI 108-109 2.1502,4,6-CI3 4-N02 -COCH2CH2CF2CI 157-158 2.1512,4-CI2-6-CF3 4-N02 -COCH2CH2CF2Ci 143-144 2.1522-CI-4-CF3-6-F 4-NOZ -COCH2CH2CF2CI 152-153 2.1532,6-Cl2-3-F-4-CF34-NOZ -COCH2CHZCF2CI 126-127 2.1542,6-CI2-4-CF3 4-SCF3 -COCH2CH2CF2CI 121-122 2.1552,6-CI2-4-CF3 4-SOCF3 -COCH2CHZCF2CI 129-130 2.1562,6-CI2-4-CF3 4-S02CF3 -COCH2CH2CF2CI 165-166 2.1572,3,6-CI3-4-CF34-NOz -COCH2CH2CF2CI 128-129 2.1582,4,6-CI3 4-SCF3 -COCH2CH2CF2CI 88-89 2.1592,4,6-Ci3 4-SOCF3 -COCH2CH2CF2CI 63-65 2.1602,4,6-CI3 4-S02CF3 -COCH2CHZCF2CI 143-144 2.1612,4,6-CI3 4-SC2F5 -H 103-104 2.1622-CI-4-CF3-6-F 4-SC2F5 -H 100-101 No. (R~,)", (R~)"2 R2 mp (°C) 2.1632,3,6-CI3-4-CF34-SC2F5 -H 119-120 2.1642,6-C12-3-F-4-CF34-SC2F5 -H 101-102 2.1652,6-C!2-4-N02 4-SCzFS -H 139-140 2.1662,4-CI2-6-CF3 4-SC2F5 -H 93-94 2.1672,4,6-CI3 4-SC2F5 -CH20C2H5 Harz 2.1682,4,6-Ci3 4-SC2F5 -COOCH3 104-105 2.1692,4,6-CI3 4-SC2F5 -COCH3 102-103 2.1702,4,6-CI3 4-SC2F5 -CH3 Harz 2.1712-CI-4-CF3-6-F 4-SC2F5 -CH20C2H5 Harz 2.1722-CI-4-CFA-6-F 4-SC2F3 -COOCH3 80-81 2.1732-CI-4-CF3-6-F 4-SC2F5 -COCH3 86-87 2.1742-CI-4-CFA-6-F 4-SC2F5 -CH3 Harz 2.1752,3,6-CI3-4-CF34-SC2F5 -CH20C2H5 Harz 2.1762,3,6-CI3-4-CF34-SC2F5 -COOCH3 Harz 2.1772,3,6-CI3-4-CF34-SC2F5 -COCH3 Harz 2.1782,3,6-CI3-4-CF3.4-SC2F5 -CH3 Harz 2.1792,6-CI2-3-F-4-CF34-SC2F5 -CHZOC2H5 Harz 2.1802,6-CI2-3-F-4-CF34-SCZFS -COOCH3 Hart 2.1812,6-CI2-3-F-4-CF34-SC2F$ -COCH3 Harz 2.1822,6-CI2-3-F-4-CF34-SC2F5 -CH3 Harz 2.1832,6-CI2-4-N02 4-SC2F5 -CHZOC2H5 Harz 2.1842,6-CI2-4-N02 4-SC2F5 -COOCH3 Harz 2.1852,6-CI2-4-N02 4-SC2F5 -COCH3 92-94 2.1862,6-CI2-4-NOZ 4-SC2Fb -CH3 Harz 2.1872,4,6-CI3 4-SOC2F5 -CH20C2Hs Harz 2.1882,4,6-CI3 4-S02C2F5 -CH20C2H5 103-104 2.1892,4-C12-6-CF3 4-SCZFS -CH20CZH5 Harz 2.1902,4-CI2-6-CF3 4-SC2F5 -COOCH3 Harz 2:1912,4-CI2-6-CF3 4-SC2F5 -COCH3 Harz 2.1922,4-CI2-6-CF3 4-SC2F5 -CH3 Harz 2.1932-CI-4-CF3-6-F 4-SOC2F5 -CH20C2H5 Harz 2.1942-CI-4-CF3-6-F 4-S02C2F5 -CH20C2H5 Harz No. (R~)", (R3c)nz R2 mp (C) 2.1952,3,6-CI3-4-CF34-SOC2F5 -CH20C2H5 Harz 2.1962,3,6-CI3-4-CF34-S02C2F5 -CH20C2H5 Harz 2.1972,6-CI2-3-F-4-CF34-SOCZF5 -CH20C2H5 Harz 2.1982,6-CI2-3-F-4-CF34-S02C2F5 -CH20C2H5 Harz 2.1992,6-CI2-4-N02 4-SOC2F5 -CH20C2H5 2.2002,6-CI2-4-NOZ 4-S02CZF5 -CH20C2H5 2.2012,4-CI2-6-CF3 4-SOC2F5 -CH20C2H5 Harz 2.2022,4-CI2-6-CF3 4-S02C2F5 -CH20C2H5 108-110 2.2032,4,6-CI3 4-SOC2F5 -COOCH3 Harz 2.2042,4,6-CI3 4-S02C2F5 -COOCH3 131-133 2.2052-CI-4-CF3-6-F 4-SOC2F5 -COOCH3 Harz 2.2062-CI-4-CF3-6-F 4-S02C2F5 -COOCH3 Harz 2.2072,3,6-CI3-4-CF34-SOCZFS -COOCH3 Harz 2.2082,3,6-CI3-4-CF34-S02CZF5 -COOCH3 Harz 2.2092,6-CI2-3-F-4-CF34-SOC2F5 -COOCH3 2.2102,6-CI2-3-F-4-CF34-S02C2F5 -COOCH3 2.2112,6-Ciz-4-N02 4,-SOC2F5 -COOCH3 2.2122,6-CI2-4-N02 4-S02C2F5 -COOCH3 2.2132,3,6-CI3-4-CF34-SOC2F5 -COOCH3 2.2142,3,6-Ci3-4-CF34-S02C2F5 -COOCH3 2.2152,4,6-CI3 4-SOC2F5 -COCH3 2.2162,4,6-CI3 4-SO2C2F5 -COCH3 2.2172,4,6-CI3 4-SCF2CHFCF3 -H

2.2182,4,6-CI3 4- -H

2.2192,4,6-CI3 4- -H

2.220 2,6-CI2-4-CF3 4-SCFZCHFCF3 -H
2.221 2,6-CIZ-4-CF3 4- -H

2.222 2,6-CI2-4-CF3 4- -H

-36- _ NO. (R~)n~ (R~)r,2 R2 mp (C) 2.2232,6-(N02)2-4-CF3H -H 180-181 2.2242,6-(N02)2- H -H

4-CF3-5-C!

2.2252,6-(N02)2 H -H

2:2262,6-(N02)2-4-CF34-N02 -CH3 2.2272,6-(N02)2- 4-N02 -COOCH3 2.2282,6-(N02)2 4-N02 -CH2OC2H5 2.2292,6-(NOZ)2-4-CF34-SCF3 -CH3 2.2302,6-(N02)2- 4-SOCF3 -COOCH3 2.2312,6-(N02)2 4-SON(CH3)z -CH20C2H5 2.2322,6-(N02)2-4-CF34-S02N(CH3)2 -CH20CH(CH3)2 2.2332,6-(N02)2- 4-SCH3 -COCH2C3H3F2cyc 2.2342,6-(N02)2 4-F -COCH20CgH,,-4-F

2.2352,6-(N02)2-4-CF34-Br -CH3 2.2362,6-(N02)2- 4-SOCF3 -COOCH3 2.2372,6-(N02)2 4-F -CH20C2H5 2.2382,6-(N02)2-4-CF34-Br -CH3 2.2392,6-(N02~-4- 4-SOCF3 -COOCH

2.2402,6-(N02)2 4-F -CH20C2H5 2.2412,6-(N02)2-4-CF34-Br -CH20CH(CH3)2 2.2422,6-(N02)2- 4-SOCF3 -COCH2C3H3F2cyc 4-CF3-5-Ci 2.2432,6-(N02)2 4-SOCF3 -COCH20CeH4-4-F

-37- _ Tab"ig 3: Compounds of formula N
R II
~2 N,N A2 ~R3'a ~n~
NO. (R3a)m A2 R2 mp (~C) 3.1 2,6-Ch-4-CF3 ' j -H
3.2 2,6-CI2-4-CF3 \ j -CH20C2H~
3.3 2,6-Ch-4-CF3 ' I -H
3.4 2,6-CI2-4-CF3 \ I -CH2OC2H5 3.5 2,4,6-CI3 ' i -H
3.6 2,4,6-C13 \ I -CH2OC2H5 O
3.7 2-CI-4-CF3 o N' -H 18g / ,o_ 3.8 2,6-CI2-4-CF3 $ N' -H 169-170 / 'o 3.9 2,6-Ci2-4-CF3 $ N; _ -H 128-132 \ / o 3.10 2,6-CI2-4-CF3 ' ~N _H
3.11 2,6-CI2-4-CF3 ~ ~ -H 152-153 y Nvo O
3.12 2,6-CI2-4-CF3 ~ ~ -COCH3 192 N_O

WO 99/37603 PC'f/EP99/00363 -38- _ No. (R3a)", A2 R2 mp (C) 3.13 2,6-CI2-4-CF3 ~ ~ -CH3 108 ~r N-p 3.14 2,6-CI2-4-CF3 ~ ~ -H 172-173 ~ .r N-O

3.15 2,6-CI2-4-CF3 ~ ~ -CH20C2H5 112 ,r N_O

3.16 26-(N02)2-4-CF3 \ I -H

3.17 2~6-(N02)2-4-CF3-5-CI\ I -H

3.18 2.6-(N02)2 % i -H

3.19 26-(N02)2-4-CF3 ' i -CH3 3.20 2~6-(N02)2-4-CFs-5-CI\ I -CH3 3.21 2~6-(N02)2 o N -H
' \ /
o 3.22 2~6-(N02)2-4-CF3 o N -CH
, 3 \ / ~O-3.23 2~6-(N02)2-4-CF3-5-CIo N' o \ /

3.24 2 6-(NO2)2 O -COCH2CsH3Fzcyc ' N;
-\
/
o 3.25 26-(N02)2-4-CF3 s' H
/N

3.26 2,6-(N02)2-4-CF3-5-CIs'N
1 / ~H3 s 3.27 2.6-(N02)2 ' ~N -COCH3 2 6-(N02)2-4-CF3 s 3.28 ' 1 /N -COCH2C3H3F2cyc Table A

A.1 ) -CON(OCH3)CH3 4-CN

A.2) -CON(OCH3)CH3 4-N02 A.3) -CON(OCH3)CH3 4-CF3 A.4) -CON(OCH3)CH3 2-CI - 4-N02 A.5) -CON(OCH3)CH3 3-CH3 - 4-N02 A.6) -CON(OCH3jCH~ 4-CI

A.7) -CON(OCH3)CH3 4-CgH4-4-N02 A.8) -CON(OCH3)CH3 4-CBH4-2-N02 A.9) -CON(OCH3)CH3 4-SCF3 A.10) -CON(OCH3)CH3 4-SOCF3 A.11 -CON(OCH3)CH3 4-S02CF3 ) A.12) -CON(OCH3)CH3 2-F-4-CN

A.13) -CON(OCH3)CH3 2-F- 4-N02 A.14) -CON(OCH3)CH3 4-COCF3 A.15) -CON(OCH3)CH3 4-CHO

A.16) -CON(OCH3)CH3 4-CI-3-N02 A.17) -CON(OCH3)CH3 4-NH2 A.18) -CON(OCH3)CH3 3-CI-4-CN

A.19) -CON(OCH3)CH3 3-OCH3-4-NOZ

A.20) -CON(OCH3)CH~ 3-CI-4-NOZ

A.21 -CON(OCH3)CH3 3-F-4-N02 ) A.22) -CON(OCH3)CH3 4-CsH4-4-CN

A.23) -CON(OCH3)CH3 4-CBH4-2-CN

A.24) -C(O)NHOCH3 4-CN

A.25) -C(O)NHOCH3 4-N02 A.26) -C(O)NHOCH3 4-CF3 A.27) -C(O)NHOCH3 2-CI - 4-N02 A.28) -C(O)NHOCH3 3-CH3 - 4-N02 A.29j -C(O)NHOCH3 4-Cf A.30) -C(O)NHOCH3 4-CBH4-4-N02 WO 99!37603 PCT/EP99/00363 A.31 -C(O)NHOCH3 4-CBH,-2-N02 ) A.32) -C(O)NHOCH3 4-SCF3 A.33) -C(O)NHOCH3 4-SOCF3 A.34) -C(O)NHOCH3 4-S02CF3 A.35) -C(O)NHOCH3 2-F-4-CN

A.36) -C(O)NHOCH3 2-F- 4-N02 A.37) -C(O)NHOCH3 4-COCF3 A.38) -C(O)NHOCH3 4-CHO

A.39) -C(O)NHOCH3 4-CI- 3-N02 A.40) -C(O)NHOCH3 4-NH2 A.41 -C(O)NHOCH3 3-CI-4-CN
) A.42) -C(O)NHOCH3 3-OCH3-4-N02 A.43) -C(O)NHOCH3 3-CI-4-N02 A.44) -C(O)NHOCH3 3-F-4-N02 A.45) -C{O)NHOCH3 4-CeH4-4-CN

A.46) -C(O)NHOCH3 4-CeH,,-2-CN

A.47) -COSC2H~ 4-CN

A.48) -COSCzH5 4-N02 A.49) -COSC2H5 4-CF3 A.50) -COSCZHS 2-CI - 4-N02 A.51 -COSC2H5 3-CH3 - 4-N02 ) A.52) -COSC2H5 4-Cl A.53) -COSC2H5 4-CgH4-4-N02 A.54) -COSC2H5 4-CeH4-2-N02 A.55) -COSC2H5 4-SCF3 A.56) ~ -COSC2H5 4-SOCF3 A.57) -C~SC2H5 4-S02CF3 A.58) -COSCZHS 2-F-4-CN

A.59) -COSC2H5 2-F- 4-N02 A.60) -COSC2H5 4-COCF3 A.61 -COSC2H5 4-CHO
) A.62) -COSC2H5 4-CI-3-N02 (R3b)n2 A.63) -COSC2H5 4-NH2 A.64) -COSC2H5 3-CI-4-CN

A.65) -COSC2H5 3-OCH3-4-N02 A.66) -COSC2H5 3-CI-4-N02 A.67) -COSCZH5 3-F-4-NOZ

A.68) -COSC2H5 4-CeH,,-4-CN

A.69) -COSC2H5 4-C6H4~2-CN

A.70) -COSCH3 4-CN

A.71 ) -COSCH3 4-N02 A.72) -COSCH3 4-CF3 A.73) -COSCH3 2-CI - 4-N02 A.74) -COSCH3 3-CH3 - 4-N02 A.75) -COSCH3 4-CI

A.76) -COSCH3 4-CgH4-4-N02 A.77) -COSCH3 4-CeH4-2-N02 A.78) -COSCH3 4-SCF3 A.79) -COSCH3 4-SOCF3 A.80) -COSCH3 4-S02CF3 A.81 ) -COSCH3 2-F-4-CN

A.82) -COSCH3 2-F- 4-N02 A.83) -COSCH3 4-COCF3 A.84) -COSCH3 4-CHO

A.85) -COSCH3 4-CI- 3-N02 A.86) -COSCH3 4-NH2 A.87) -COSCH3 3-CI-4-CN

A.88) -COSCH3 3-OCH3-4-N02 A.89) -COSCH3 3-CI-4-N02 A.90) -COSCH3 3-F-4-N02 A.91 ) -COSCH3 4-CeH4-4-CN

A.92) -COSCH3 4-CaH,-2-CN

A.93) -CH20C(O)C(CH3)a 4-CN

A-94) -CHZOC(O)C(CH3)s 4-N02 {Rae)~z A.95) -CH20C(O)C(CHa)a 4-CFa A.96) -CH20C(O)C(CHa)a 2-CI - 4-N02 A.97) -CH20C(O)C(CHa)a 3-CHa - 4-NOZ

A.98) -CH20C(O)C(CHa)a 4-CI

A.99) -CH20C(O)C(CHa)a 4-CsH,-4-NOZ

A.100) -CH20C(O)C(CHa)a 4-CgH4-2-NOZ

A.101 -CH20C(O)C{CHa)a ~ 4-SCFa ) A.102) -CH20C{O)C(CHa)a 4-SOCFa A.103) -CH20C(O)C(CHa)a 4-S02CFa A.104) -CH20C(O)C(CHa)a 2-F-4-CN

A.105) -CH20C{O)C(CHa)a 2-F- 4-N02 A.106) -CH20C(O)C(CHa)a 4-COCFa A.107) -CH20C(O)C(CHa)a 4-CHO

A.108) -CH20C(O)C(CHa)a 4-CI-3-N02 A.109) -CH20C(O)C{CHa)a 4-NH2 A.110) -CH20C(O)C(CHa)a 3-Ci-4-CN

A.111 -CH20C(O)C{CHa)a 3-OCHa-4-N02 ) A.112) -CH20C(O)C(CHa)a 3-CI-4-N02 A.113) -CH20C(O)C(CHa)a 3-F-4-N02 A.114) -CH20C{O)C(CHa)a 4-CeH4-4-CN

A.115) -CH20C(O)C(CHa)a 4-CeH4-2-CN

A.116) -CH20C2H,,OCHa 4-CN

A.117) -CH20C2H,OCHa 4-N02 A.118) -CH20C2H,OCHa 4-CFa A.119) -CH20C2H40CHa 2-CI - 4-N02 A.120) -CH20C2H40CHa 3-CH3 - 4-N02 A.121 -CH20C2H40CHa 4-CI
) A.122) -CH20C2H,,OCHa 4-CBH4-4-N02 A.123) -CH2OC2H,OCHa 4-CBH<-2-N02 A.124) -CH20C2H40CHa 4-SCFa A.125) -CH20C2H,,OCHa 4-SOCFa A.126) -CH20C2H40CHa 4-S02CFa (R~)nz A.127) -CH20C2H4OCH3 2-F-4-CN

A.128) -CH20C2H40CH3 2-F- 4-N02 A.129) -CH20CZH40CH3 4-COCF3 A.130) -CH20C2H,,OCH3 4-CHO

A.131 -CH20C2H,OCH3 4-CI- 3-N02 }

A.132) -CH20C2H40CH3 4-NH2 A.133) -CH2OC2H4OCH3 3-CI-4-CN
~

A.134) -CH20C2H4OCH3 3-OCH3-4-N02 A.135} -CH20C2H40CH3 3-CI-4-NOZ

A.136) -CH2OC2H4OCH3 3-F-4-N02 A.137) -CH2OC2H4OCH3 4-CeH4-4-CN

A.138) -CH20C2H40CH3 4-CBH4-2-CN

A.139) -CH20CH2CH=CH2 4-CN

A.140) -CH20CH2CH=CH2 4-N02 A.141 -CH20CH2CH=CH2 4-CF3 }

A.142) -CH20CH2CH=CH2 2-CI - 4-N02 A.143) -CH20CH2CH=CH2 3-CH3 - 4-N02 A.144) -CH20CH2CH=CH2 4-CI

A.145} -CH20CHZCH=CHZ 4-CBH,-4-NOZ

A.146) -CH20CH2CH=CH2 4-CgH4-2-N02 A.147) -CH20CH2CH=CH2 4-SCF3 A.148) -CH20CH2CH=CH2 4-SOCF3 A.149) -CH20CH2CH=CH2 4-S02CF3 A. i 50} -CH20CH2CH=CH2 2-F-4-CN

A.151 -CH20CH2CH=CH2 2-F- 4-N02 ) A.152} -CHZOCH2CH=CH2 4-COCF3 A.153) -CH20CH2CH=CH2 4-CHO

A.154) -CH20CH2CH=CH2 4-CI-3-N02 A.155) -CH20CH2CH=CH2 4-NH2 A.156) -CH20CH2CH=CH2 3-CI-4-CN

A.157) -CH20CH2CH=CH2 3-OCH3-4-N02 A.158) -CH20CH2CH=CH2 3-CI-4-NOZ

~R~)nz A.159) -CH20CH2CH=CHz 3-F-4-NOz A.160) -CH20CH2CH=CH2 4-CeH4-4-CN

A.161 -CH20CH2CH=CHz 4-CeH4-2-CN
) A.162) -CH20CH2C--CH 4-CN

A.163) -CH20CH2C~H 4-NOz A.164) -CH20CHzCaCH 4-CF3 A.i65) -CH20CH2C_--CH 2-CI - 4-NOz A.166) -CH20CH2C=-CH 3-CH3 - 4-NOz A.167) -CH20CHzC=CH 4-CI

A.168) -CH20CH2C~CH 4-CBH4-4-NOz A.169) -CH20CH2C~H 4-CeH4-2-NOz A. i 70) -CH20CHZC---CH 4-SCF3 A.171 -CH20CH2C~CH 4-SOCF3 ) A:172) -CH20CH2C=CH 4-S02CF3 A.173) -CH20CH2C$CH 2-F-4-CN

A.174) -CH20CH2C~CH 2-F- 4-NOz A.175) -CH20CH2C~CH 4-COCF3 A.176) -CH20CH2C=-CH 4-CHO

A.177) -CH20CH2C~CH 4-CI- 3-NOz A.178) -CH20CH2C~CH 4-NHz A.179) -CH20CH2C~CH 3-CI-4-CN

A.180) -CHZOCH2C~CH 3-OCH3-4-NOz A.181 -CH20CH2C~CH 3-CI-4-NOz ) A.182) -CH20CH2C~H 3-F-4-NOz A.183) -CH20CH2C~H 4-CeH4-4-CN

A.184) -CH20CH2C~CH 4-CgH,,-2-CN

A.185) -COC,oHz, 4-CN

A.186) -COC,otiz, 4-NOz A.187) -COC,oHz, 4-CF3 A.188) -COC,oHz, 2-Cl - 4-NOz W

A.189) -COC,oH2, 3-CH3 - 4-N02 A.190) -COC,oH2, 4-CI

A.191 -COC,oH2, 4-CgH,,-4-N02 ) A. i 92) -COC,oH2, 4-CgH4-2-N02 A.193) -COC,oH2, 4-SCF3 A:194) -COC,oH2, 4-SOCF3 A.195) ' -COC,oH2, 4-S02CF3 A.196) -COC,oH2, 2-F-4-CN

A.197) -COC,oH2, 2-F- 4-N02 A.198) -COC,oH2, 4-COCF3 A.199) -COC,oH2, 4-CHO

A.200) -COC,oH2, 4-CI-3-N02 A.201 -COC,oH2, 4-NHz ) A.202) -COC,oH2, 3-CI-4-CN

A.203) -COC,oH2, 3-OCH3-4-N02 A.204) -COC,oH2, 3-CI-4-N02 A.205) -COC,oH2, 3-F-4-N02 A.206) -COC,oH2, 4-C8H4-4-CN

A.207) -COC,oHz, 4-CeH,-2-CN

A.208) -H 4-SCF3 A.209) -H 4-SOCF3 A.210) -H 4-S02CF3 A.21 i -H 4-SC2F5 ) A.212) -H 4-SOC2F5 A.213) -H 4 -S02C2F5 A.214) -H 4-SCF2H

A.215) -H 4-SOCF2H

A.216) -H 4-S02CF2H

A.217) -H 4-SCF2CI

A.218) -H 4-SOCF2CI

A.219) -H 4-S02CF2CI

A.220) -H 4-SF5 ~R~)nz A.221 -H SCF2Br ) A.222) -H SOCF2Br A.223) -H S02CF2Br A.224) -H SCF2CF2Br A.225) -H SOCF2CFZBr A.226) -H S02CF2CF2Br A.227) -CH3 4-SCF3 A.228) -CH3 4-SOCF3 A.229) -CH3 4-S02CF3 A.230) -CH3 4-SC2F5 A.231 -CH3 4-SOCZFS
) A.232) -CH3 4-S02C2F5 A.233) -CH3 4-SCF2H

A.234) -CH3 4-SOCF2H

A.235) -CH3 4-S02CF2H

A.236) -CH3 4-SCF2Ci A.237) -CH3 4-SOCF2CI

A.238) -CH3 4-S02CF2CI

A.239) -CH3 4-SF5 A.240) -CH3 SCFZBr A.241 -CH3 SOCF2Br ) A.242) -CH3 S02CF2Br A.243) -CH3 SCF2CF2Br A.244) -CH3 SOCF2CF2Br A.245) -CH3 S02CF2CFaBr A.246) -C2H5 4-SCF3 A.247) -C2H5 4-SOCF3 A.248) -C2H3 4-S02CF3 A.249) -C2H5 4-SC2F5 A.250) -C2H5 4-SOC2F5 A.251 -CzHS 4-S02C2F5 ) A.252) -C2H5 4-SCF2H

-47- _ Ra (R~n)~a A.253) -CzHS 4-SOCF2H

A.254) -C2Hs 4-SOZCF2H

A.255) -C2H5 4-SCF2C!

A.256) -C2H5 4-SOCF2CI

A.257) -C2H5 4-S02CF2CI

A.258) -C2H5 4-SF5 A.259) -C2H5 ~ SCF2Br A.260) -C2H3 SOCF28r A.261 -CZHS S02CFZBr ) A.262) -C2H5 SCF2CF2Br A.263) -C2H5 SOCF2CF2Br A.264) -CaHg SOaCF2CF2Br A.265) -CH(CH3)a 4-SCF3 A.266) -CH(CHa)a 4-SOCF3 A.267) -CH(CH3)a 4-S02CF3 A.268) -CH(CH3)a 4-SC2F5 A.269) -CH(CH3}a 4-SOC2F5 A.270) -CH(CH3)a 4-S02CZF5 A.271 -CH (CH3)a 4-SCF2H
) A.272) -CH(CH3)a 4-SOCF2H

A.273) -CH(CH3)a 4-S02CF2H

A.274) -CH(CH3)a 4-SCF2CI

A.275) -CH(CH3)a 4-SOCF2CI

A.276) ~ -CH(CH3)a 4-S02CF2CI

A.277) -CH(CH3)a 4-SF5 A.278) -CH(CH3)a SCF2Br A.279) -CH(CH3}a SOCF2Br A.280) -CH(CH3)a S02CF2Br A.281 -CH(CH3)a SCF2CF2Br ) A.282) -CH(CH3)a SOCF2CF2Br A.283} -CH(CH3)a S02CF2CF2Br A.284) -COCH3 4-SCF3 - 48 _ . _ ~R3b)n2 A.285) -COCH3 4-SOCF3 A.286) -COCH3 4-S02CF3 A.287) -COCH3 4-SC2F5 A.288) -COCH3 4-SOC2F5 A.289) -COCH3 4-S02C2F5 A.290) -COCH3 4-SCF2H

A.291 -COCH3 4-SOCF2H
) A.292) -COCH3 4-S02CF2H

A.293) -COCH3 4-SCF2CI

A.294) -COCH3 4-SOCF2CI

A.295) -COCH3 4-S02CF2CI

A.296) -COCH3 4-SF5 A.297) -COCH3 SCF2Br A.298) -COCH3 SOCF2Br A.299) -COCH3 S02CF2Br A.300) -COCH3 SCFZCF2Br A.301 -COCH3 SOCF2CF2Br ) A.302) -COCH3 S02CF2CF2Br A.303) -COC2H5 4-SCF3 A.304) -COC2H5 4-SOCF3 A.305) -COCpHS 4-S02CF3 A.306) -COC2H5 4-SC2F$

A.307) -COC2H5 4-SOCZF5 A.308) -COC2Hb 4-S02C2F5 A.309) -COC2H5 4-SCF2H

A.310) -COC2H5 4-SOCF2H

A.311 -COC2H5 4-S02CF2H
) A.312) -COC2H5 4-SCF2CI

A.313) -COC2Hb 4-SOCF2C1 A.314) -COC2H5 4-S02CF2CI

A.315) -COC2H5 4-SF5 A.316) -CO2CH3 4-SCF3 (R~)nz A.317) -COC2H5 SCF2Br A.318) -COC2H5 SOCF2Br A.319) -COC2H5 S02CF2Br A.320) -COC2H5 SCF2CF2Br A.321 -COC2H5 SOCF2CF2Br ) A.322) -C02CH3 S02CF2CF2Br A.323) -C02CH3 4-SOCF3 A.324) -C02CH3 4-S02CF3 A.325) -C02CH3 4-SC2F5 A.326) -C02CH3 4-SOC2F5 A.327) -C02CH3 4-SO2C2F5 A.328) -C02CH3 4-SCFZH

A.329) -C02CH3 4-SOCF2H

A.330) -CO2CH3 4-S02CF2H

A.331 -C02CH3 4-SCF2CI
) A.332) -COZCH3 4-SOCF2CI

A.333) -COZCH3 4-S02CF2Ci A.334) -C02CH3 4-SF5 A.335) -C02CH3 SCF2Br A.336) -C02CH3 SOCF2Br A.337) -C02CH3 S02CF2Br AW) -C~2CE"~3 SCF2CF2Br A.339) -C02CH3 SOCF2CF2Br A.340) -CO2CH3 SO2CF2CF2Br A.341 -CO2C2H5 4-SCF3 ) A.342) -C02C2H5 4-SOCF3 A.343) -CO2C2H5 4-S02CF3 A.344) -CO2C2H5 4-SC2F5 A.345) -CO2C2H5 4-SOC2F5 A.346) -CO2C2Hb 4-SO2C2F5 A.347) -CO2C2H5 4-SCF2H

-C~2C21"i5 4-SOCF2H

WO 99/3?603 p~~pgg~p0~

A.349) -CO2C2Hfi 4-S02CF2H

A.350) -CO2C2H5 4-SCF2CI

A.351 -C02C2H5 4-SOCF2CI
) A.352) -CO2C2H5 4-S02C F2CI

A.353) -CO2C2H5 4-SF5 A.354) -CO2C2H5 SCF2Br A.355) -CO2C2Hb SOCF2Br A.356) -C02C2H3 S02CF2Br A.357) -CO2C2H5 SCF2CF2Br A.358) -CO2C2H5 SOCF2CF28r A.359) -CO2C2H5 S02CF2CF2Br A.380) -CH20C2H5 4-SCF3 A.361 -CH2OC2H5 4-SOCF3 ) A.382) -CH20C2H5 4-S02CF3 A.383) -CH20C2H5 4-SC2F5 A.364) -CH20C2H5 4-SOC2F5 A.365) -CH20C2H5 4-SO2C2F5 A.366) -CH20C2H5 4-SCF2H

A.367) -CH20C2H5 4-SOCF2H

A.388) -CH20CZH3 4-S02CF2H

A.389) -CH20C2H5 4-SCF2CI

A.370) -CHzOC2H5 4-SOCF2CI

A.371 -CH20C2H5 4-S02CF2CI
) A.372) -CHpOC2H5 4-SF5 A.373) -CH20C2Hb SCF2Br A.374) -CHZOC2H5 SOCF2Br A.375) -CH2OC2H5 S02CF2Br A.376) -CH20C2H5 SCF2CF2Br A.377) -CH20C2H5 SOCF2CF2Br A.378) -CH20C2H5 S02CF2CF2Br A.379) -CH20CH3 4-SCF3 A.380) -CH20CH3 4-SOCF3 -51 - _ A.381 ) -CH20CH3 4-S02CF3 A.382) -CH20CH3 4-SC2F5 A.383) -CH20CH3 4-SOC2F5 A.384) -CH20CH3 4-S02C2F5 A.385) -CH20CH3 4-SCF2H

A.386) -CH20CH3 4-SOCF2H

A.387) -CH20CH3 4-SOZGF2H

A.388) -CH20CH3 4-SCF2CI

A.389) -CH20CH3 4-SOCF2CI

A.390) -CH20CH3 4-S02CF2CI

A.391 ) -CH20CH3 4-SF5 A.392) -CH20CH3 SCF2Br A.393) -CH20CH3 SOCF2Br A.394) -CH20CH3 S02CF2Br A.395) -CH20CH3 SCF2CF28r A.396) -CH20CH3 SOCF2CF2Br A.397) -CH20CH3 S02CF2CF2Br A.398) -CH20-n-C3H, 4-SCF3 A.399) -CH20-n-C3H, 4-SOCF3 A.400) -CH20-n-C3H, 4-S02CF3 A.401 ) -CH20-n-C3H, 4-SC2F5 A.402) -CH20-n-C3H, 4-SOC2F5 A.403) -CH20-n-C3H, 4-S02C2F5 A.404) -CH20-n-C3H, 4-SCF2H

A.405) -CH20-n-C3H, 4-SOCF2H

A.406) -CH20-n-C3H, 4-SOZCF2H

A.407) -CH20-n-C3H, 4-SCF2CI

A.408) -CH20-n-C3H, 4-SOCF2Ci A.409) -CH20-n-C3H, 4-S02CF2CI

A.410) -CH20-n-C3H, 4-SFS

A.411 ) -CH20-n-C3H, SCF2Br A.412) -CH20-n-C3H, SOCF2Br ~WO 99/37603 . PCT/EP99/00363 _52- _ A.413) -CH20-n-C3H, SOZCF2Br A.414) -CH20-n-C3H, SCF2CF2Br A.415) -CH20-n-C3H, SOCF2CF2Br A.416) -CH20-n-C3H, S02CF2CF2Br A.417) -CH2N(CH3)C02CH3 4-SCF3 A.418) -CH2N(CH3)C02CH3 4-SOCF3 A.419) -CH2N(CH3)C02CH3 4-S02CF3 ~

A.420) -CH2N(CH3)C02CH3 4-SC2F5 A.421 -CH2N(CH3)C02CH3 4-SOC2F5 ) A.422) -CH2N(CH3)C02CH3 4-S02C2F5 A.423) -CH2N(CH3)C02CH3 4-SCF2H

A.424) -CH2N(CH3)C02CH3 4-SOCF2H

A.425) -CH2N(CH3)C02CH3 4-S02CF2H

A.426) -CH2N(CH3)C02CH3 4-SCF2CI

A.427) -CH2N(CH3)COZCH3 4-SOCF2CI

A.428) -CH2N(CH3)C02CH3 4-S02CF2CI

A.429) -CH2N(CH3)C02CH3 4-SF5 A.430) -CH2N(CH3)C02CH3 SCF2Br A.431 -CH2N(CH3)C02CH3 SOCF2Br ) A.432) -CH2N(CH3)C02CH3 SOZCF2Br A.433) -CH2N(CH3)C02CH3 SCF2CF2Br A.434) -CH2N(CH3)C02CH3 SOCF2CF2Br A.435) -CHZN(CH3)C02CH3 S02CF2CF2Br A.436) -CH2N(CH3)S02CH3 4-SCF3 A:437) -CH2N(CH3)S02CH3 4-SOCF3 A.438) -CH2N(CH3)S02CH3 4-SOzCF3 A.439) -CH2N(CH3)S02CH3 4-SC2F5 A.440) -CH2N(CH3)S02CH3 4-SOCZFS

A.441 -CH2N(CH3)S02CH3 4-S02C2F5 ) A.442) -CH2N(CH3)S02CH3 4-SCF2H

A.443) -CH2N(CH3)S02CH3 4-SOCF2H

A.444) -CH2N(CH3)S02CH3 4-S02CF2H

A.445) -CH2N(CH3)SOzCH3 4-SCF2CI

A.446) -CH2N(CH3)S02CH3 4-SOCF2CI

A.447) -CHzN(CH3)S02CH3 4-S02CF2CI

A.448) -CH2N(CH3)S02CH3 4-SFS

A.449) -CH2N(CH3)S02CH3 SCFZBr A.450) -CH2N(CH3)S02CH3 SOCF2Br A.451 -CH2N(CH3)S02CH3 S02CF2Br ) A.452) -CH2N(CH3)S02CH3 SCF2CF2Br A.453) -CH2N(CH3)S02CH3 SOCFZCF2Br A.454) -CH2N(CH3)S02CH3 S02CF2CF2Br Table 4 Compounds of general formula F~ CN
/ N,Ni /
(~m ~ ~ ~ ~nz (Ib), wherein (R~,)", is 2,6-CI2-4-CF3 and R2 and (R~)~2 each correspond to a line of Table A.
abl 5:
Compounds of general formula (Ib), wherein (R~,)~, is 2,4,6-CI3 and R2 and (R~)"2 each correspond to one line of Table A.
Table 6:
Compounds of general formula (Ib), wherein (R~)~, is 2-CI-4-CF3 and R2 and (R~,)" each correspond to one line of Table A.
Table .
Compounds of general formula (Ib), wherein (R~)~, is 2,6-CI2-4-N02 and R2 and (R~,)~2 each correspond to one line of Table A.
Table 8:
Compounds of general formula (Ib), wherein (R~)~, is 2,6-CI2-4-OCF3 and R2 and (R~),~
each correspond to one line of Table A.

T, able 9 Compounds of general formula (Ib), wherein (R~)~~ is 2,6-CI2-4-F and R2 and (R~)"2 each correspond to one line of Table A.
able 10:
Compounds of general formula (Ib), wherein (R~)", is 2,6-CI2-4-Br and R2 and (R~,)"2 each correspond to one line of Table A.
Table 11:
Compounds of general formula (Ib), wherein (R~,)"1 is 2-CI-4-CF3-6-F and R2 and (Ra,)"2 each correspond to one line of Table A.
Table 12:
Compounds of general formula (Ib), wherein (R~,)", is 2,3,6-CI3-4-CF3 and R2 and (R~)"
each correspond to one line of Table A.
Ta I 1 Compounds of general formula (Ib), wherein (R~)~, is 2,6-CI2-3-F-4-CF3 and R2 and (R~)~
each correspond to one line of Table A.
Table 14:
Compounds of general formula (Ib), wherein (R~)", is 2,3-F2-4-CF3-6-CI and R2 and {R~)"
each correspond to one line of Table A.
T a 15:
Compounds of general formula (Ib), wherein (R~,)"~ is 2,6-CI-4-CN and R2 and (R~,)" each correspond to one line of Table A.
Table 16:
Compounds of general formula (Ib), wherein (R~,)", is 2,4-CI2-6-CF3 and R2 and (R~,),~ each correspond to one line of Table A.

Compounds of general formula (Ib), wherein (R~,)", is 2,6-CI2-4-SCF3 and R2 and (R~)"2 each correspond to a line of Table A.
Table 18:
Compounds of general formula (Ib), wherein (R~,)"~ is 2,6-CI2-4-SOCF3 and R2 and (R~)~2 each correspond to a line of Table A.
T 19:
Compounds of general formula (Ib), wherein (R~)", is 2,6-Ci2-4-S02CF3 and R2 and (R~)"2 each correspond to a line of Table A.

_55_ _ Tabl 0:
Compounds of general formula (Ib), wherein (R~)", is 2,6-CI2-4-S02CH3 and R2 and (R~)"2 each correspond to a line of Table A.
Table 21:
Compounds of general formula (Ib), wherein (R~)~, is 2,6-CI2-4-OCF2Br and R2 and (R~)~2 each correspond to one line of Table A.
Table 22:
Compounds.of general formula (Ib), wherein (R~,)", is 2,6-CI2-4-OCF2H and R2 and (R~),~
each correspond to one line of Table A.
Table 23:
Compounds of general formula (Ib), wherein (R~)~, is 2,6-CI2-4-C2F5 and R2 and (R~),~ each correspond to one line of Table A.
bl 24:
Compounds of general formula (Ib), wherein (R~)~, is 2,6-(N02)2-4-CF3 and R2 and (R~,),~
each correspond to one line of Table A.
le Compounds of general formula (Ib), wherein (R~,)~, is 2,6-(N02)2-4-CI and R2 and (R~),~
each correspond to one line of Table A.
T,~ble 26:
Compounds of general formula (Ib), wherein (R~)", is 2,6-CI2-4-OS02CH3 and R2 and (R~,),~
each correspond to a line of Table A.
able 2 Compounds of general formula (Ib), wherein (R~)", is 2,6-CI2-4-OS02CF3 and R2 and (R~)n2 each correspond to a line of Table A.
Table 28:
Compounds of general formula (Ib), wherein (R~)~, is 2,6-CI2-4-SFS and R2 and (R~,),~ each correspond to a line of Table A.
Examples of formulations of compounds of the invention, i.e. solutions, granulates, dusts, wettable powders, emulsifiable concentrates, coated granules, and suspension concentrates are of the types listed for instance in EP-A-580'553(Case 19164), Examples F1 to F10.

Biological Examl les Example B1: Ovicidal effect on Heiiothis virescens Eggs of Heliothis virescens deposited on filter paper are immersed briefly in a test solution comprising 400 ppm of the mixture of active ingredients to be tested in acetone/water. After the test solution has dried, the eggs are incubated in Petri dishes. After 6 days, the percentage hatching rate of the eggs is compared with that for untreated controls (%
reduction in hatching rate).
Compounds listed in Tables 3 to 5 show good activity against Heliothis virescens. In particular, compounds 2.1 to 2.5, 2.8 to 2.i3 and 3.7 show a response of more than 80%.
Example B2: Effect on Spodowtera littoralis cater,~illars Young soya plants are sprayed with an aqueous emulsion containing 400 ppm of active ingredient. After the spray deposit has dried, the soya plants are populated with 10 third-instar larvae of Spodoptera littoralis and placed in a plastic container.
Three days later they are evaluated. The percentage reduction of the population and percentage reduction in feeding damage (% response) is determined by comparing the number of dead larvae and the extent of feeding damage on the treated plants with those on the untreated plants.
The compounds of table 1 show good efficacy against Spodoptera littoralis in this test. In particular, compounds 2.1 to 2.5, 2.7 to 2.18 and 3.7 to 3.9 show a response of more than 80%.
Examlhe B3: Effect on Diabrotica balteata larvae Com seedlings are sprayed with an aqueous emulsion containing 400 ppm of active ingredient. After drying of the spray deposit, the com seedlings are inoculated with 10 second-instar larvae of Diabrotica balteata and placed in a plastic container.
Six days later they are evaluated. The percentage reduction of the population (% response) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.
The compounds of Tables 3 to 5 show good efficacy against Diabrotica balteata in this test.
In particular, compounds 2.1 to 2.4, 2.6, 2.7, 2.11, 2.25 to 2.28 and 3.9 show a response of more than 80%.

Example B4: Effect on Plutella xarlostella caterpillars Young cabbage plants are sprayed with an aqueous emulsion containing 400 ppm of active ingredient. After the spray deposit has dried, the cabbage plants are populated with 10 third-instar larvae of Plutella xylostella and placed in a plastic container.
Three days later they are evaluated. The percentage reduction of the population and percentage reduction in feeding damage (% response) is determined by comparing the number of dead larvae and the extent of feeding damage on the treated plants with those on the untreated plants.
The compounds of Tables 3 to 5 show good efficacy against Plutella xylostella in this test.
Example B5: Effect on Tebanychus urticae Young bean plants are inoculated with a mixed population of Tetranychus urticae and, one day later, are sprayed with an aqueous emulsion containing 400 ppm of active ingredient.
The plants are incubated for 6 days at 25°C and then evaluated. The percentage reduction of the population (% response) is determined by comparing the number of dead eggs, larvae, and adults on the treated plants with those on the untreated plants.
The compounds of Tables 3 to 5 show good efficacy against Tetranychus urticae in this test.
Example B6: Effect on Alphis craccivora Pea seedlings are infected with Aphis craccivora; then sprayed with an emulsion containing 400 ppm of active ingredient and incubated at 20°C. Three and six days later they are evaluated. The percentage reduction of the population (% response) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
The compounds of Tables 3 to 5 show good efficacy against Aphis craccivora in this test.
In particular, compounds 2.7, 2.22 and 3.8 show a good response of more than 80%.
Example B7: effect on MyzusJ~er~icae Pea seedlings are infected with Myzus persicae, then sprayed with an emulsion containing 400 ppm of active ingredient and incubated at 20°C. Three and six days later they are evaluated. The percentage reduction of the population (% response) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.

-58- _ The compounds of Tables 3 to 5 show good efficacy against Myzus persicae in this test. In particular, compounds 3.7 and 3.13 show a good response of more than 80%.

Claims (14)

1. Compound of formula wherein A1 and A2 are independent of one another and in each case represent a monocyclic or bicyclic aryl or heteroaryl radical, and each heteroaryl radical independently of the other having 1 up to and including 4 hetero atoms selected from the group consisting of N, O and S; and A1 is substituted where appropriate with substituent (R3a)n1, and A2 where appropriate with substituent (R3b)n2;
n1 and n2 are independently of one another 1, 2, 3 or 4, depending on the possibilities for substitution on ring system A1 and A2; and either (A) R3a and R3b independently of one another are hydrogen, halogen, C1-C6alkyl, halogen-C1-C6alkyl, C2-C4alkenyl, C2-C4alkinyl, halogen-C2-C4alkenyl, halogen-C2-C4alkinyl, C1-C6alkoxy, halogen-C1-C6-alkoxy, C2-C6alkenyloxy, C2-C6alkinyloxy, halogen-C2-C6alkenyloxy, halogen-C2-C6alkinyloxy, -OH, -SF5, -CHO, -C(=O)-C1-C6-alkyl, -C(=O)-halogen-C1-C6alkyl, -C(=O)-OC1-C6alkyl, -C(=O)-O-halogen-C1-C6alkyl, -O-C(=O)N(R6)2 (wherein both R6 substituents are independent of one another), -CN, -NO2, -S(=O)2N(R6)2 (wherein both R6 substituents are independent of one another), -S(=O)p-C1-C6alkyl, -S(=O)p halogen-C1-C6alkyl, -O-S(=O)p-C1-C6alkyl, -O-S(=O)P-halogen-C1-C6alkyl, phenyl, benzyl, phenoxy or benzyloxy, wherein each of the phenyl, benzyl, phenoxy, or benzyloxy radicals is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, NO2, C1-C6alkyl, halogen-C1-C6alkyl, C1-C6alkoxy and halogen-C1-C6alkoxy; and R2 is R2a; or, (B) R3a and R3b independently of one another as defined under (A) and at least one of the radicals R3a or R3b is -CR5=CR5R14, -NR11R12, -C(=O)CN, -C(=O)C(=O)O-C1-C6alkyl, -CR15=NOR10 or a five or six-membered heteroaryl ring, wherein the said heteroaryl ring is substituted, where appropriate, depending on the substitution possibilities on the ring, with 1 to 3 substituents selected from the group consisting of halogen, C1-C4alkyl, C1-C4haloalkyl, NO2 and CN; and R2 is R2a, or R2b; or (C) R3a has one of the meanings defined hereinbefore under (A) or (B);
R3b is hydrogen, halogen, C1-C6alkyl, halogen-C1-C6alkyl, C2-C4alkenyl, C2-C4alkinyl, halogen-C2-C4alkenyl, halogen-C2-C4alkinyl, C1-C4alkoxy, halogen-C1-C6alkoxy, C2-C6alkenyloxy, C2-C6alkinyloxy, halogen-C2-C6alkenyloxy, halogen-C2-C6alkinyloxy, -OH, -SF5, -CHO, -C(=O)-C1-C6alkyl, -C(=O)-halogen-C1-C6alkyl, -C(=O)-OC1-C6alkyl, -C(=O)-O-halogen-C1-C6alkyl, -O-C(=O)N(R5)2 (wherein the two R6 substituents are independent of one another), -CN, -NO2, phenyl, benzyl, phenoxy or benzyloxy, wherein each of the phenyl, benzyl, phenoxy, or benzyloxy radicals is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, NO2, C,-Csalkyl, halogen-C1-C6alkyl, C1-C6alkoxy and halogen-C1-C6alkoxy; -S(=O)p-C1-C6alkyl in the 4-position or -S(=O)p-halogen-C1-C6alkyl in the 4-position, with the proviso, that one of the substituents R3b is -S(=O)p-C1-C6alkyl or -S(=O)P-halogen-C1-C6alkyl; and R2a is R2b or R2b;
and in the groups (A), (B) and (C), where appropriate, R2a is -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-C6 alkenyl, -CH2O(C=O)C2-C6alkinyl, -C(=S)OC2-C6alkenyl, -C(=S)OC2-C6alkinyl, -C(=S)SC1-C6alkyl, -C(=S)SC2-C6alkenyl, -C(=S)SC2-C6alkinyl, -C(=O)SC1-C6alkyl, -C(=O)SC2-C6alkenyl, -C(=O)SC2-C6alkinyl, -C(=S)NR11R12, -C(=O)NR10OR13, -CH2OC2-C6alkenyl, -CH2OC2-C6alkinyl, -CH2OC2-C6haloalkenyl or -CH2OC2-C6haloalkinyl;
R2b is hydrogen, -OH, C1-C6alkyl, C1-C6alkoxy, C3-C6cycloalkyl, C3-C6alkenyl, C3-C6alkinyl, halogen-C1-C6alkyl, halogen-C3-C6alkenyl, halogen-C3-C6alkinyl, benzyl or benzoyl, wherein the benzyl or benzoyl radical is substituted in the aromatic ring independently of one another once to three times by substituents selected from the group consisting of halogen, -CN, NO2, C1-C6alkyl, C1-C6alkoxy, halogen-C1-C6alkyl and halogen-C1-C6alkoxy; C1-C6alkoxy-C1-C6alkyl, cyano-C1-C6alkyl, -C(=X)-R7b, -C(=X)-R7b, -OC(=O)-R7a, -C(=O)-C(=O)-R7a, -OC(=O)-R7b, -C(=O)-C(=O)-R7b, -S(=O)p N(R6)2 (wherein the two R8 substituents are independent of one another); cyano, -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 O, 1 or 2;
R5 is independently H or C1-C8alkyl;
R6 is independently H, C1-C8alkyl, C3-C6cycloalkyl, phenyl or benzyl, wherein the phenyl or benzyl group is substituted in the aromatic ring where appropriate independently of one another once to three times with substituents selected from the group consisting of halogen, -CN, NO2, C1-C6alkyl, C1-C4alkoxy, halogen-C1-C6alkyl and halogen-C1-C6alkoxy;
or two alkyl radicals R6, together with the nitrogen atom to which they are bonded, form a five to seven-membered ring, wherein a CH2 group, where appropriate, is substituted by a heteroatom selected from the group consisting of O
and S, or is substituted by NH, and wherein the five to seven-membered ring, where appropriate, is substituted once or twice with C1-C4alkyl;
R7a is C1-C6alkoxy-C1-C6alkyl, CH2CH2CF2Cl, C1-C6alkylthio-C1-C6alkyl, acyloxy-C1-C6alkyl, halogen-C3-C6cycloalkyl, C3-C6cycloalkyl-C1-C6alkyl, halogen-C3-C6-cycloalkyl-C1-C6alkyl, aryloxy-C1-C6alkyl; or phenyl, benzyl, phenoxy or aryloxy-C1-C6alkyl, which are substituted with 1 to 3 substituents selected form the group consisting of halogen, nitro, cyano, C1-C4-alkyl, halogen-C1-C4-alkyl and halogen-C1-C4-alkoxy;
R7b is H, C1-C8alkyl, C2-C8alkenyl, halo-C1-C8alkyl, halo-C2-C8alkenyl, C1-C8alkoxy, halo-C1-C6alkoxy, C3-C6cycloalkyl, phenyl, benzyl, phenoxy, benzyloxy or -N(R8)2 (in which the two R6 are independent of one another);
R8 is C1-C8alkyl, C1-C8alkoxy, halogen-C1-C8alkyl, halogen-C1-C8alkoxy, C1-C8alkylthio, phenyl, benzyl or -N(R6)2 (wherein the two R6 radicals are independent of one another);
R9 is C1-C6alkyl, halogen-C1-C4alkyl or aryl, which is unsubstituted or substituted once to three times, independently of one another, with subsituents selected from the group consisting of C1-C6alkyl, C2-C4alkenyl, C2-C4alkinyl, C1-C4alkoxy, halogen, cyano, halogen-C1-C4alkyl, halogen-C2-C4alkenyl, halogen-C2-C4alkinyl, halogen-C1-C4alkoxy and nitro;
R10 is H, C1-C6alkyl, C3-C8cycloalkyl, phenyl oder benzyl, wherein the phenyl and benzyl radicals are unsubstituted or substituted in the aromatic ring once to three times independently of one another with substituents selected from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, cyano, halogen-C1-C4alkyl, halogen-C1-C4alkoxy and nitro;
R11 and R12 are independently of one another H, C1-C6 alkyl, phenyl, -COC1-C6alkyl, -COC1-C6haloalkyl, -COphenyl, or together form a five or six-member saturated or unsaturated ring, wherein if appropriate one or more, especially one, of the CH- or CH2-groups is or are substituted by a heteroatom selected from the group consisting of O, N and S, and wherein the five or six-membered ring if appropriate is independently of each other substituted with 1 to 3 substituents selected from the group consisting of halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy, NO2 and CN; or the two substituents R11 and R12 together form a ring q is 2 or 3; and R13 is H, C1-C6alkyl, C2-C6alkenyl, C2-C6alkinyl;
R14 is hydrogen, C1-C6alkyl, halogen-C3-C6alkyl, C1-C6alkoxy, halogen-C1-C6alkoxy, C2-C6alkenyloxy, -CHO, -C(=O)-C1-C6alkyl, -C(=O)-halogen-C1-C6alkyl, -C(=O)-OC1-C6alkyl, -C(=O)-O-halogen-C1-C6alkyl, -CN, -NO2, -S(=O)2N(R6)2 (wherein the two R6 substituents are independent of one another), -S(=O)p-C1-C6alkyl, -S(=O)p-halogen-C1-C6alkyl, -O-S(=O)p-C1-C6alkyl, -O-S(=O)p-halogen-C1-C6alkyl, phenyl, benzyl, or benzyloxy wherein each of the phenyl, benzyl, or benzyloxy substituents is unsubstituted or substituted in the aromatic ring independently of one another once to five times with substituents selected from the group consisting of halogen, cyano, NO2, C1-C6alkyl, halogen-C1-C6alkyl, C1-C6alkoxy and halogen-C1-C6alkoxy; and R15 is hydrogen, C1-C6alkyl or halogen-C1-C6alkyl;
and, if appropriate, to the possible E/Z isomers, E/Z isomer mixtures and/or tautomers, in each case in free form or in the form of a salt, to a method for the preparation and use of these compounds, E/Z isomers and tautomers, pesticides, whose active ingredient is selected from these compounds, E/Z isomers and tautomers, and to a method for the preparation and use of these compositions, intermediate products, in free form or in the form of a salt, for the preparation of these compounds, and where appropriate their tautomers, in free form or in the form of a salt, and to a method for the preparation and use of these intermediate products and their tautomers.
2. A compound of formula (I) according to claim 1 in free form.
3. A compound of formula (I) according to claim 1, wherein A1 and A2 are phenyl.
4. A compound of formula (I) according to claims 1 to 3 wherein R2a is -C1-C6alkyl-NR11R12, -COC9-C20alkyl, -C1-C6alkyl-O-C1-C6alkyl-O-C1-C6alkyl, -CH2O(C= O)C1-C6alkyl, -CH2O(C=O)C2-C6 alkenyl, -CH2O(C=O)C2-6alkinyl, -C(=S)OC2-C6alkenyl, -C(=S)OC2-C6alkinyl, -C(=S)SC1-C6alkyl; -C(=S)SC2-C6alkenyl, -C(=S)SC2-C6alkinyl, -C(=O)SC1-C6alkyl, -C(=O)SC2-C6alkenyl, -C(=O)SC2-C6alkinyl, -C(=S)NR11R12, -C(=O)NR10OR13, -CH2OC2-C6alkenyl, -CH2OC2-C6alkinyl, -CH2OC2-C6haloalkenyl or -CH2OC2-C6haloalkinyl.
5. A compound of formula (I) according to claims 1 to 4, wherein n, is 2, 3, or 4 and n2 is 1 or 2.
6. A pesticidal composition comprising at least one compound of formula (I) according to claim 1 as active ingredient, either in free form or in the form of an agrochemically acceptable salt, and at least one adjuvant.
7. A method for the control of pests comprising applying a composition of claim 6 to pests or their habitat.
8. A method according to claim 7 for the control of insects and members of the order acarina.
9. A method for preparing a composition of claim 6 which contains at least one adjuvant and comprises the intimate mixing and/or grinding of the active ingredient with the adjuvant(s).
10. The use of a compound of formula (I) according to claim 1, either in free form or in the form of an agrochemically acceptable salt, for preparing a composition of claim 6.
11. The use of a composition of claim 6 for the control of pests.
12. The use of claim 11 for the protection of plant propagation material.
13. A method of claim 7 for protecting plant propagation material, comprising treatment of said propagation material or of the locus for cultivation of said propagation material.
14. Plant propagation material which is treated according to the method described in claim 13.
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