CA2139465A1

CA2139465A1 - Hydrazone derivatives

Info

Publication number: CA2139465A1
Application number: CA002139465A
Authority: CA
Inventors: Dieter Durr; Roger Graham Hall; Peter Maienfisch; Alfons Pascual; Manfred Boger
Original assignee: Individual
Current assignee: Novartis AG
Priority date: 1994-01-05
Filing date: 1995-01-03
Publication date: 1995-07-06
Also published as: JPH07242618A; CN1108646A; AU1004195A; KR950032106A; SG43002A1; ES2115190T3; EP0662472A1; DE59405428D1; ATE163922T1; ZA9528B; NZ270235A; EP0662472B1

Abstract

Compounds of formula

Description

Hydrazone derivatives The invention relates to compounds of formula (R1)D~O,~ R~
N ` N ~ R2 (I), R~X

wherein m is 0, 1, 2, 3 or 4, and, when m is greater than 1, the radicals Rl7 are identical or different;
n is 0, 1, 2, 3, 4 or 5, and, when n is greater than 1, the radicals Rl are identical or different;
Rl and Rl7 are each independently of the other halogen, C~-C8aLkyl, halo-C~-C8aL~yl, phenoxy, phenylthio, halo-Cl-C8alkylthio, phenyl, Cl-C8aL~ylthio, Cl-C8aL~yl-carbonyl, OSO2R4, SO2NRl3Rl4 or P(=Y)R22R23;
either X is S, R2 is R2l or H and R3 is R3l, -NRsR6 or -OR2, or X is O, R2 is R2l and R3 is R3l, or X is O, R2 is H and R3 is -R80Rg~ -R80CORg~ -R8NRloRll or -R8Rl2, or X and R3 together are Rl8;
Y isOorS;
R4 isC1-C8alkyl,halo-Cl-C8aIkyl or halo-Cl-C8alkoxy;
R2, is C~-C8alkyl, C3-C6cycloalkyl, halo-Cl-C8alkyl, Cl-C4alkoxy-Cl-C4aIkyl, Cl-C4-alkylthio-Cl-C4alkyl, Rl3Rl4N-Cl-C4alkyl, C2-C8alkenyl, C2-C8alkynyl, Cl-C4acyl,CH=C(CN)2, or phenyl which is unsubstituted or substituted by from one to five substituents selected from the group consisting of halogen, Cl-C4alkyl, C2-Cs-alkenyl, halo-Cl-C4alkyl, Cl-C4alkoxy, SO2NRl3Rl4, halo-Cl-C4alkoxy, Cl-C4-alkylthio, Cl-C4alkoxy-Cl-C4alkoxy, halo-Cl-C4alkylthio, NRl3Rl4, -NO2 and -CN;
R3~ is H, C~-C8alkyl, C3-C6cycloalkyl, C3-C6cycloalkyl-Cl-C3alkyl, halo-Cl-C8alkyl, halo-C3-C6cycloalkyl-Cl-C3alkyl, C2-C8alkenyl, C2-C8alkynyl, halo-C2-C8alkenyl, -COOR7,-SR2,-R80R9,-R80COR9,-RxNRloRll,-RxR I 2~ -R8SR9,-RXSCSR9, or phenyl whicll is unsubsliluled or sub~Lilule(l by Irom one lo live subslilu~nLs ~;eleclc(l l`lOIn lh~ g~ P COnSjSLjl1g 01 h~IIOgCn~ CJ C4~1kYI, C2 C~.~lk~nYI, h~IIO C~ C4.11kYI, h,llo-CI-C,~alkoxy, h,llo-CI-C4,llkyllhio, SO2NR,3R,,,, Cl-C,1alkoxy, -N()2 and -CN;

an unsubstituted or substituted, saturated or unsaturated, five- or six-memberedheterocyclic or heterobicyclic ring containing from one to three hetero atoms selected from the group O, N and S, the substituents being selected from the group consisting of halogen, C1-C4alkyl, halo-C1-C4alkyl and C1-C4alkoxy;
Rs and R6 are each independently of the other H, C1-C8alkyl, halo-C1-C8alkyl, C2-Csalkenyl, Cl-C4alkoxy, C2-Csalkeneoxy or-NRl3Rl4;
R7 is H, C~-C8alkyl, halo-Cl-C8alkyl or C2-C8aLkenyl;
R8 is (CR1sR16)p, wherein p is 1, 2, 3 or 4;
Rg is C1-C8aIkyl, halo-C1-C11alkyl, C3-C6cycloalkyl, C2-C8alkenyl, halo-C2-C11-alkenyl, C2-C8alkynyl, NR1oR11, OR1o, benzyl, or phenyl which is unsubstituted or substituted by from one to five substituents selected from the group consisting of halogen, C1-C4alkyl, C2-Csalkenyl, halo-C1-C4alkyl, C1-C4alkoxy, -NO2 and -CN;
R1o and R11 are each independently of the other C1-C8alkyl, C2-C8alkenyl or C1-C8-alkoxy-Cl-C8alkyl;
R12 is an unsubstituted or substituted, saturated or unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing from one to three hetero atoms selected from the group O, N and S, the substituents being selected from the group consisting of halogen, C1-C4alkyl, halo-C1-C4alkyl and C1-C4alkoxy;
R13 and R14 are each independently of the other H or C1-C8alkyl;
R1s and R16 are each independently of the other H, C1-C8alkyl, or phenyl which is unsubstituted or substituted by from one to five substituents selected from the group consisting of halogen, Cl-C4alkyl, C2-Csalkenyl, halo-C1-C4aLkyl, Cl-C4alkoxy, -NO2 and -CN;
Rl8 is NC(Rlg)=C(Rlg)S, NC(Rlg)=C(Rlg)O, NC(Rl9)2C(Rl9)2S, NC(Rl9)2C(Rl9)20, NC(R19)=C(R1g)C(R19)=N or NC(R19)=NC(Rl9)=N;
R19 is H, C1-C4alkyl, halogen or halo-C1-C4alkyl;
R22 is C1-C4alkyl, C1-C4alkoxy or NR13R14; and R23 is C1-C4alkyl, C1-C4alkoxy, C3-C4alkylthio or NR13R14, with the proviso that, in the compounds of formula I, R2 is other than H when either m is 0, n is 1, R1 is 4-Cl, R3 is -N(OCH3)CH3, R4 is CF3 and X is O, or when m is 0, n is 2, R
is 3,4-dichloro, R3 is -N(OCH3)CH3, R4 is CF3 and X is O, or when m is 0, n is 1, R1 is 4-CI, R3 is -NHNH2, R4 is CF3 and X is O, and, as the case may be, tautomers thereof, in each case in free form or in salt l`orm;
to a process for the preparation ol` and to the use of those compounds and tautomers, to pesticidal compositions in which Lhe active ingredienl has been selected from those compounds and laulomers, in e~ch case in free form or in the form of an agrochemically 2139~65 acceptable salt, and to a process for the preparation of and to the use of thosecompositions.

Certain hydrazone derivatives are proposed in the literature as insecticidally active ingre-dients in pesticides. The biological properties of those known compounds are not, however, entirely satisfactory in the area of pest control and, therefore, there is a need to provide further compounds having pesticidal properties, especially for the control of insects, ectoparasites and representatives of the order Acarina. This problem is solved according to the invention by the provision of the present compounds I.

Some of the compounds I may be in the form of tautomers. If, for example, R2 is H, corresponding compounds I, that is to say those having a -N(H)-C(R3)=X partial structure, may be in equilibrium with the respective tautomers having a -N=C(R3)-XH partialstructure. Accordingly, hereinafter there is to be understood by compounds I, where applopliate, also corresponding tautomers, even if the latter are not specifically mentioned in every case.

The compounds I and, as the case may be, their tautomers may be in the form of salts.
Compounds I having 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.
sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, C1-C4alkanecarboxylic acids, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, for example halo-substituted, C1-C4alkane- or aryl-sulfonic acids, e.g.
methane- or p-toluene-sulfonic acid. Compounds I having at least one acid group may furthermore form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal salts and ~lk~line 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. ethylamine, diethyl-amine, triethylamine or dimethylpropylamine, or a mono-, di- or tri-hydroxy-lower alkyl-amine, e.g. mono-, di- or tri-ethanolamine. Furthermore, corresponding internal salts may also be formed. Within the scope of the invention, agrochemically advantageous salts are preferred; also included, however, are salts that have disadvantages for agrochemical applications, for example salts that are toxic to bees and ~o t`ish, which can be used, for 213g465 example, for the isolation and purification of free compounds I or their agrochemically acceptable salts. In view of the close relationship between the compounds I in free form and in the form of their salts, hereinbefore and hereinafter any reference to the free compounds I or their salts is to be understood as including also the corresponding salts or the free compounds I, respectively, where appropriate and expedient. The same applies to tautomers of compounds I and their salts.

Unless defined otherwise, the general definitions used hereinbefore and hereinafter have the meanings given below.

Halogen - as a group per se and as a structural unit of other groups and compounds, such as of haloalkyl, halocyeloalkyl and haloaLkenyl, - is fluorine, chlorine, bromine or iodine, espeeially fluorine, ehlorine or bromine, more espeeially fluorine or ehlorine.

Unless defined otherwise, groups and eompounds eont:~ining earbon each eontain from 1 up to and ineluding 8, preferably from 1 up to and including 4, especially 1 or 2, earbon atoms.

C3-C6eyeloalkyl is cyelopropyl, cyclobutyl, eyelopentyl or eyelohexyl.

Alkyl - as a group per se and as a structural unit of other groups and eompounds, sueh as of haloalkyl, alkoxy and alkylthio, - is, duly taking into aecount the number of carbon atoms contained in the group or eompound in question, either straight-ehained, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or oetyl, or branehed, e.g. isopropyl, isobutyl, see-butyl, tert-butyl, isopentyl, neopentyl or isooctyl.

Halo-substituted earbon-containing groups and compounds, such as haloalkyl, halocyclo-alkyl or haloaL~enyl, may be partially halogenated or perhalogenated, and, in the case of multiple halogenation, the halogen substituents may be identical or different. Examples of haloalkyl - as a group per se and as a structural unit of other groups and eompounds, sueh as of haloeycloalkylalkyl and haloalkenyl, - are methyl substituted by from one to three fluorine, chlorine and/or bromine atoms, such as CHF2 or CF3; ethyl substituted by from one to five fluorine, chlorine and/or bromine atoms, such as CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2, CF2CHF2, CF2CFCI2, CF2CHBr2, CF2CHClF, CF2CHBrF or CClFCHClF;
propyl or isopropyl substituted by from one to seven fluorine, chlorine and/or bromine atoms, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; and butyl or one of its isomers substituted by from one to nine fluorine, chlorine and/or bromine atoms, such as CF(CF3)CHFCF3 or CH2(CF2)2CF3.

Acyl groups may be formyl, acetyl, propionyl, butyryl or isobutyryl.

Examples of saturated heterocyclic rings are pyrrolidinyl, piperidyl and morpholinyl, and examples of unsaturated heterocyclic and heterobicyclic rings are thienyl, pyrryl, imid-azolyl, pyrazolyl, triazolyl, thiazolyl, isothiazolyl, pyridyl, indolyl, benzo[b]thienyl and benzo[b]furyl.

Preferred embodiments within the scope of the invention, taking into account the proviso mentioned above, are:

(1) A compound of formula I wherein m is 0, 1 or 2, preferably 0 or 1, especially 0, and, when m is greater than 1, the radicals R17 are identical or different, or, as the case may be, a tautomer thereof;

(2) A compound of formula I wherein n is 1,20r3, preferably 1 or 2, especially 1, and, when n is greater than 1, the radicals Rl are identical or different, or, as the case may be, a tautomer thereof;

(3) A compound of formula I wherein Rl is halogen, Cl-C4alkyl or halo-C1-C4alkyl, preferably halogen, especially fluorine, chlorine or bromine, or, as the case may be, a tautomer thereof;

(4) A compound of formula I wherein either X is S, R2 is R2l and R3 is R31, -NRsR6 or -OR2, especially X is S, R2 is R2~ and R3 is R3~;
orXisO,R2isR2l andR3isR3~;
or X is 0, R2 is H and R3 is -R80Rg, -R80COR9, -R8NRIoRl l or -R8Rl2, especially X is 0, R2 is H and R3 is -R80R~;

213g465 (5) A compound of formula I wherein R2l is Cl-C4alkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4aLkynyl, Cl-C2acyl or phenyl, preferably Cl-C4aLkyl, C3-C6cycloalkyl, Cl-C4acyl or phenyl, especially Cl-C4alkyl, formyl or acetyl;
or, as the case may be, a tautomer thereof;

(6) A compound of formula I wherein R3l is H, Cl-C6alkyl, C3-C6cycloalkyl, C3-C6cycloaL~ylmethyl, halo-Cl-C4aL~yl, halo-C3-C6cycloaLkylmethyl, C2-C4aLkenyl, C2-C4aLkynyl, halo-C2-C4aLkenyl, -COOR7, -SR2, -R80Rg, -R80CORg, -R8NRloRll, -R8Rl2, -R8SRg, -R8SCSRg, phenyl or an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic orheterobicyclic ring containing from one to three hetero atoms selected from the group O, N and S, the substituents being selected from the group consisting of halogen, Cl-C4aLkyl and Cl-C4aLkoxy, preferably H, Cl-C6alkyl, C3-C6cycloaL~yl, halo-Cl-C3aL~yl, halo-C3-C6cycloaL~ylmethyl, C2-C4alkenyl, halogen, -COOR7, -SR2, -R80Rg, -R80CORg, -R8NRloRll, -R8Rl2, phenyl or an unsubstituted or substituted, unsaturated, five- or six-membered hetero-cyclic or heterobicyclic ring containing from one to three hetero atoms selected from the group O, N and S, the substituents being selected from the group halogen;
especially H, Cl-C4aLkyl, C3-C6cycloaL~yl, halo-Cl-C2aLkyl, halocyclopropylmethyl, C2-C4aLkenyl, fluorine, chlorine, -SR2, -R80CORg~ -R8Rl2 or an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing N or S, the substituents being selected from the group fluorine and chlorine, or, as the case may be, a tautomer thereof;

(7) A compound of formula I wherein R4 is Cl-C4alkyl or halo-Cl-C4alkyl, preferably halo-Cl-C4alkyl, especially halo-Cl-C2alkyl, most especially trifluoromethyl, or, as the case may be, a tautomer thereof;

(8) A compound of formula I wherein Rs and R6 are each independently of the other H, Cl-C4alkyl, halo-Cl-C4alkyl, 21~9165 C2-C4alkenyl, Cl-C3alkoxy, C2-C3alkeneoxy or -NRl3Rl4, preferably H, Cl-C2alkyl, halo-Cl-C2alkyl, C2-C3alkenyl, Cl-C2alkoxy, C2-C3aLkeneoxy or -NRl3Rl4.
especially H, Cl-C2alkyl, C2-C3alkenyl, Cl-C2alkoxy, C2-C3alkeneoxy or -NRl3Rl4,or, as the case may be, a tautomer thereof;

(9) A compound of formula I wherein R7 is Cl-C4alkyl, halo-Cl-C4alkyl or C2-C4alkenyl, preferably Cl-C2alkyl or halo-Cl-C2alkyl, especially methyl or ethyl, or, as the case may be, a tautomer thereof;

(10) A compound of formula I wherein R8 is (CRl5Rl6)p, wherein p is 1, 2 or 3, preferably 1 or 2, especially 1, or, as the case may be, a tautomer thereof;

(11) A compound of formula I wherein Rg is Cl-C4aIkyl, halo-Cl-Cllalkyl, C3-C6cycloalkyl, C2-C4aLkenyl, halo-C2-Cllalkenyl, C2-C4alkynyl, NRloRll, ORlo, benzyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting ofhalogen, Cl-C2alkyl, halo-Cl-C2alkyl, C~-C3alkoxy, -NO2 and -CN;
preferably C~-C4alkyl, halo-Cg-Cllalkyl, C3-C5cycloalkyl, C2-C3alkenyl, halo-C8-Cllalkenyl, C2-C3alkynyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of fluorine, chlorine, methyl, Cl-C2alkoxY and -NO2;
especially Cl-C4alkyl, halo-C8-Cllalkyl, cyclopropyl, vinyl, halo-C8-Cllalkenyl, ethynyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of chlorine, methyl, methoxy and -NO2;
or, as the case may be, a tautomer thereof;

(12) A compound of formula I wherein Rlo and Rl 1 are each independently of the other Cl-C4alkyl, C2-C4alkenyl or Cl-C4alkoxy-Cl -C4alkyl, preferably Cl-C2alkyl, C2-C3alkenyl or C~-C2alkoxy-CI-C2alkyl, 213g~65 especially methyl, allyl or methoxyethyl, or, as the case may be, a tautomer thereof;

(13) A compound of formula I wherein R12 is an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing from one to three hetero atoms selected from the group 0, N and S, the substituents being selected from the group consisting of halogen, C1-C4aLkyl and Cl-C4alkoxy;
preferably an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing from one to three hetero atoms selected from the group 0, N and S, especially an unsubstituted, unsaturated, five-membered heterocyclic ring containing from one to three hetero atoms selected from the group N and S, most especially imidazolyl, pyrazolyl or triazolyl, or, as the case may be, a tautomer thereof;

(14) A compound of formula I wherein R13 and R14 are each independently of the other H or C1-C4alkyl, preferably H or C1-C2aLkyl, especially H or methyl, or, as the case may be, a tautomer thereof;

(15) A compound of formula I wherein Rls and Rl6 are each independently of the other H, C1-C4aLkyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of halogen, Cl-C2alkyl, C2-C3alkenyl, halo-Cl-C3alkyl, Cl-C2aL~oxy, -NO2 and -CN;
preferably H, Cl-C2alkyl or phenyl, especially H, methyl or phenyl, or, as the case may be, a tautomer thereof;

(16) A compound of formula I wherein Rl7 is halogen or Cl-C4alkyl, preferably chlorine or methyl, or, as the case may be, a taulonler lhereol;

213g465 (17) A compound of formula I wherein Rl8 is NC(Rlg)=C(Rlg)S~ NC(R19)=C(Rl9)O, NC(R19)=C(R1g)C(R1g)=N or N(Rl9)=Nc(Rl9)=
preferably NC(Rlg)=C(Rlg)S~ NC(Rlg)=C(Rl9)O or NC(Rlg)=C(Rlg)C(Rlg)=N~
especially NC(Rlg)=C(Rlg)S or NC(Rlg)=C(Rl9)O, or, as the case may be, a tautomer thereof;

(18) A compound of formula I wherein m ~s0, n lsl, Rl is fluorine, chlorine or bromine, R2 is Cl-C4aL~yl, C3-C6cycloaL~yl, Cl-C4acyl or phenyl, R3 is H, Cl-C6aL~yl, C3-C6cycloaLkyl, halo-Cl-C3aL~yl, halo-C3-C6cycloaL~ylmethyl, C2-C4aL~enyl, -COOR7, -SR2, -R8ORg, -R8OCORg, -R8NRloRll~ -R8R12, phenyl or an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing from one to three hetero atoms selected from the group O, N and S, the substituents being selected from the group halogen, R4 is Cl-C4aL~yl or halo-Cl-C4aL~yl, R7 is Cl-C2aL~yl or halo-Cl-C2aLI~yl, R8 iS CRl5Rl6~
Rg is Cl-C4aL~yl, halo-C8-Cllalkyl, C3-Cscycloalkyl, C2-C3aL~enyl, halo-C8-CllaL~enyl, C2-C3aL~ynyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of fluorine, chlorine, methyl, Cl-C2alkoxY and -NO2;
R1o and R11 are each independently of the other methyl, allyl or methoxyethyl, R12 is an unsubstituted, unsaturated, five-membered heterocyclic ring containing from one to three hetero atoms selected from the group N and S, and Rls and Rl6 are each independently of the other H, methyl or phenyl, or, as the case may be, a tautomer thereof;

(19) A compound of formula I wherein m is0, n is 1, Rl is fluorine, chlorine or bromine, R2 is Cl-C4alkyl, tormyl or acetyl, R3 is H, Cl-C6alkyl, C3-C6cycloalkyl, halo-Cl-C3alkyl, haJo-C3-C6cycloalkylmethyl, 2139~65 C2-C4alkenyl, -COOR7, -SR2, -R8ORg, -R8OCORg, -R8NR1oR11, -R8R12, phenyl or an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing from one to three hetero atoms selected from the group O, N and S, the substituents being selected from the group halogen, R4 is halo-Cl-C2alkyl, R7 is methyl or ethyl, R8 iS CRlsRl6~
Rg is cl-c4alkyL halo-C8-CllalkyL cyclopropyl, vinyl, halo-C8-C1laIkenyl, ethynyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of chlorine, methyl, methoxy and -NO2;
Rlo and R1 1 are each independently of the other methyl, allyl or methoxyethyl, Rl2 is an unsubstituted, unsaturated, five-membered heterocyclic ring containing from one to three hetero atoms selected from the group N and S, and R1s and R16 are each independently of the other H, methyl or phenyl, or, as the case may be, a tautomer thereof;

(20) A compound of formula I wherein m is0, n is 1, R1 is fluorine, chlorine or bromine, R2 is C1-C4aIkyl, formyl or acetyl, R3 is H, Cl-C4alkyl, C3-C6cycloaLkyl, halo-C1-C2aLkyl, halocyclopropylmethyl, C2-C4aIkenyl,-COOR7, -SR2, -R8-OCOR9, -R8-R12 or an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing N or S, the substituents being selected from the group fluorine and chlorine;
R4 is trifluoromethyl, R7 is methyl or ethyl, R8 iS CRlsRl67 Rg is cl-c4alkyl7halo-c8-cllalkyl7 cyclopropyl, vinyl, halo-C8-C11alkenyl, ethynyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of chlorine, methyl, methoxy and -NO2;
Rl2 is an unsubstituted, unsaturated, five-membered heterocyclic ring containing from one to three hetero atoms selected from the group N and S, and Rls and R~, are each independently of the other H, methyl or phenyl, or, as Ihe case may be, a tauLomer thereol;

(21) A compound of formula I wherein m is0, n is 1, Rl is fluorine, chlorine or bromine, R2 is Cl-C4aLkyl, formyl or acetyl, R3 is H, Cl-C4aIkyl, C3-C6cycloalkyl, halo-Cl-C2alkyl, halocyclopropylmethyl, C2-C4alkenyl, -COOR7, -SR2, -R8-OCORg, -R8-Rl2 or an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing N or S, the substituents being selected from the group fluorine and chlorine;
R4 is trifluoromethyl, R7 is methyl or ethyl, R8 is CH2, C(methyl)2 or CH(phenyl), Rg is Cl-C4aLkyl, halo-C8-Cllalkyl, cyclopropyl, vinyl, halo-C8-Cllalkenyl, ethynyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of chlorine, methyl, methoxy and -NO2; and Rl2 is an unsubstituted, unsaturated, five-membered heterocyclic ring containing from one to three hetero atoms selected from the group N and S, or, as the case may be, a tautomer thereof.

Especially preferred within the scope of the invention are the compounds of formula I
listed in Table 1 and, as the case may be, the tautomers thereof, and, most especially, the compounds of formula I mentioned in Examples P2, P3, P5 to P13, P15, P16 and P18 and, as the case may be, the tautomers thereof.

Specifically preferred within the scope of the invention is 4-chloro-4'-trifluoromethane-sulfonyloxybenzophenone-N-formyl-N-methylhydrazone (compound 1 in Table 1).

The invention further relates to a process for the preparation of the compounds of formula I and, as the case may be, their tautomers, taking into account the proviso mentioned above, in each case in free form or in salt form, in which process, for example, a) a compound of formula (R1)n~O,,S'O~ ~4 N (R17)m (II), NH

which is known or can be prepared analogously to corresponding known compounds and wherein m, n, Rl, R2, R4 and Rl7 are as defined for formula I, or, as the case may be, a tautomer thereof, in free form or in salt form, is reacted with phosgene or thiophosgene, preferably in the presence of a base, and the intermediate, which is optionally isolated, is reacted, if desired in the presence of a base, with a compound of formula YlH, wherein Y
is -NRsR6, -OR2 or -SR2 and R2, Rs and R6 are as defined for formula I, or with a salt thereof, or b) for the preparation of a compound of formula I wherein X is 0, a compound of formula II is reacted, if desired in the presence of a base, with a compound of formula R3COY2, wherein R3 is as defined for formula I with the exception of the meanings -OR2 and -SR2, and Y2 is a leaving group, or c) for the preparation of a compound of formula I wherein X is S, a compound of formula II is reacted with a compound of formula Y3-N=C=S, wherein Y3 is H, Cl-C8alkyl, halo-Cl-C8alkyl or C2-Csalkenyl, preferably H or Cl-C8alkyl, to form compounds of formula I
wherein X is S, or d) for the preparation of a compound of formula I wherein X is S and R3 is -SR, wherein R
is Cl-C8alkyl, C3-C6cycloalkyl, C2-C8alkenyl or C2-C8alkynyl, preferably Cl-C8alkyl or C3-C6cycloalkyl, especially Cl-C8alkyl, a compound of formula II is reacted, if desired in the presence of a base, with CS2, and the intermediate, which is optionally isolated, is reacted, if desired in the presence of a base, with a compound of forrnula RY4, wherein R
is as defined above and Y4 is a leaving group, or e) for the preparation of a compound of formula I wherein X is 0, a compound of formula II is reacted, if desired in the presence of a base, with a compound of formula ClR8COYs, wherein R8 is as defined for formula I and Ys is a leaving group, and the resulting inter-mediate is reacted, if desired in the presence of a base, optionally in the presence of an alkali melal halide, such as in the presence of sodium iodide, wi~h a compound of formula RgCOOH~ HNRloRll or Rl2, wherein Rg, Rlo, Rll and Rl2 are as defined for formula I, or f) for the preparation of a compound of formula I wherein X is S, a compound of formula (R1)~o"S'OR~
Nl R (Rl 7)m (III), R~O
which is known or can be prepared analogously to corresponding known compounds, for example in accordance with Variant b), and wherein m, n, Rl, R2, R3, R4 and Rl7 are as defined for formula I, is reacted with P2Ss, or g) for the preparation of a compound of formula I wherein X is S and R2 is H, a compound of formula ~,~Oo,,S~OR4 N ~ (R17) m (IV), N
Cl R3 which is known or can be prepared analogously to corresponding known compounds and wherein m, n, Rl, R3, R4 and Rl7 are as defined for formula I, is reacted, if desired in the presence of a base, with H2S, or h) a compound of formula I wherein R2 is H is reacted, if desired in the presence of a base, with a compound of formula R2Y6, wherein R2 is as defined for formula I with the excep-tion of the meaning H, and Y6 is a leaving group, or i) a compound of formula (R 1 )n~ o"S~OR4 (V), O (R17) m which is known or can be prepared analo~ously lo correspondin~ known compounds and , wherein m, n, Rl, R4 and Rl7 are as defined for formula I, is reacted, if desired in the presence of an acid catalyst, if desired in the presence of a water-binding agent, with a compound of formula N ~ (VI), which is known or can be prepared analogously to corresponding known compounds and wherein R2, R3 and X are as defined for formula I, or with a salt thereof and/or, as the case may be, with a tautomer thereof, and in each case, if desired, a compound of formula I or a tautomer thereof obtainable according to the process or by other means, in each case in free form or in salt form, is converted into a different compound of formula I or a tautomer thereof, a mixture of isomers obtainable according to the process is separated and the desired isomer is isolated and/or a free compound of formula I or a tautomer thereof obtainable according to the process is converted into a salt, or a salt of a compound of formula I or of a tautomer thereof obtainable according to the process is converted into the free compound of formula I or a tautomer thereof or into a different salt.

The remarks made above regarding tautomers and salts of compounds I apply analogously to starting materials mentioned hereinbefore and hereinafter with regard to their tautomers and salts.

The reactions described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or, customarily, in the presence of a suitable solvent or diluent or of a mixture thereof, the reactions being performed as necessary with cooling, at room temperature or with heating, for example in a temperature range of approximately from -80C to the boiling temperature of the reaction medium, preferably from approxi-mately -20C to approximately +150C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Especially advantageous reaction conditions are to be found in the Examples.

The starting materials mentioned hereinbefore and hereinafter which are used for the preparation of the compounds I and, as the case may be, their tautomers, in each case in free form or in salt form, are known or can be prepared by methods known per se, for example in accordance with the details given below.

Variant a):
Suitable bases for facilitating the reaction are, for example, alkylamines, alkylene-mines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, and basic heterocycles. There may be mentioned by way of example triethylamine, diiso-propylethylamine, triethylenediamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethyl-aniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reactants can be reacted with each other as such, that is to say without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro-carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro-benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri-chloromethane, 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone;
amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacet-amide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.

The reaction is advantageously carried out in a temperature range of from approximately -30C to approximately +100C, preferably from approximately -20C to approximately +20C.

In a preferred form of Variant a), a compound II is reacted with phosgene at from -20 to 0, preferably -10, in an aromatic hydrocarbon, preferably in toluene, and in the presence of a sulfonic acid as catalys~, preferably in the presence of triethylamine, and the product is isolated and further reacted with YIH.

Variant b):
Suitable leaving groups are, ror example, halogens, Cl-Cgalkoxy or Cl-C8alkylcarboxy, 2139g65 preferably halogens, especially chlorine.

Suitable bases for facilitating the reaction are, for example, alkylamines, aLkylene-1iamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, and basic heterocycles. There may be mentioned by way of example triethylamine, diiso-propylethylamine, triethylenelliamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethyl-aniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reactants can be reacted with each other as such, that is to say without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro-carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro-benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri-chloromethane, 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone;
amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacet-amide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.

The reaction is advantageously carried out in a temperature range of from approximately -30C to approximately +100C, preferably from approximately -10C to approximately +20C.

In a preferred form of Variant b), a compound II is reacted with one of the mentioned acylating agents at from -20 to 0, preferably 0, in an ether, preferably in diethyl ether.

Variant c):
The reac~ants can be reacled with each other as such, that is to say without the addition of a solvent or diluen~ r ex~mple in Ihe melt. In most cases, however, the addilion ol` an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro-carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro-benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri-chloromethane, 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone;
alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-di-methylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide.

The reaction is advantageously carried out in a temperature range of from approximately -30C to approximately +100C, preferably from approximately -10C to approximately +20C.

Variant d):
Suitable leaving groups are, for example, halogens or C1-C8alkylsulfates, preferably halogens, especially bromine or iodine, most especially iodine.

Suitable bases for facilitating the reaction are, for example, alkali metal or ~lk~line earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbo-cyclic amines. There may be mentioned by way of example sodium hydroxide, hydride, amide, methanolate, acetate or carbonate, potassium tert-butanolate, hydroxide, carbonate or hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylene(li~mine, 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). Especially suitable bases are alkali metal or alkaline earth metal hydrides, most especially alkali metal hydrides.

The re~ctants can be reacted with each other as such, tha~ is lo say wilhoul the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro-carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro-benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri-chloromethane, 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone;
amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethyl-acetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.

The reaction is advantageously carried out in a temperature range of from approximately -30C to approximately +100C, preferably from approximately -10C to approximately +20C.

In a preferred form of Variant d), a compound II is reacted at from -20 to 0, preferably 0, with CS2 in the presence of an alkali metal hydride, preferably sodium hydride, in a carboxylic acid amide, preferably in dimethylformamide, and then, without isolation of the intermediate, with one of the mentioned alkylating agents.

Variant e):
Suitable leaving groups are, for example, halogens or C1-C8alkoxy, preferably halogens, especially chlorine.

Suitable bases for facilitating the reaction are, for example, alkylamines, alkylene-diamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, and basic heterocycles. There may be mentioned by way of example triethylamine, diiso-propylethylamine, triethylenediamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethyl-aniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine and l,5-diazabicyclo[5.4.0lundec-5-ene (DBU).

The reactants can be reacted with each other as such, that is to say without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro-carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro-benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri-chloromethane, 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone;
amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethyl-acetamide, N-methylpyrrolidone or hexamethylphosphoric acid triarnide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.

The reaction is advantageously carried out in a temperature range of from approximately -30C to approximately +100C, preferably from approximately 0C to approximately +90C.

In a preferred form of Variant e), a compound II is reacted, at from -20 to 20, preferably 20, in the presence of a base, preferably pyridine, in a halogen-containing hydrocarbon, preferably in methylene chloride, with one of the acylating agents mentioned in Variant e) and then with one of the nucleophilic reagents mentioned in Variant d).

Variant f):
The reactants can be reacted with each other as such, that is to say without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro-carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro-benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri-chloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene;
ethers, such as dielhyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl e~her, ethylene glycol monomethyl ether, ethylene glycol monoe~hyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetrahydrofuran or dioxane; and sulfoxides, such as dimethyl sulfoxide.

The reaction is advantageously carried out in a temperature range of from approximately -30C to approximately +100C, preferably from approximately -10C to approximately +20C.

In a preferred form of Variant f), a compound II is reacted at from -20 to 0, preferably 0, with CS2 in the presence of a base, preferably sodium hydride, in a carboxylic acid amide, preferably in dimethylformamide, and then with an alkylating agent.

Variant ~):
Suitable bases for facilitating the reaction are, for example, alkylamines, aIkylene-minçs, unsubstituted or N-aIkylated, saturated or unsaturated cycloaLkyl~mines, and basic heterocycles. There may be mentioned by way of example triethylamine, diiso-propylethylarnine, triethylene(li~minç, N-cyclohexyl-N,N-dimethylamine, N,N-diethyl-aniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reactants can be reacted with each other as such, that is to say without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro-carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro-benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri-chloromethane, 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone;
amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethyl-acetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve a~s solvents or diluents.

The reaction is advantageously carried out in a temperature range of from approximately -30C to approximately +100C, preferably from approximately 0C to approximately +SOC.

In a preferred form of Variant g), a compound IV is reacted with H2S at from -20 to 20, preferably 20, in the presence of a base, preferably triethylamine, in an ether, preferably in tetrahydrofuran.

Variant h):
Suitable leaving groups are, for example, halogens or C1-C8alkylsulfates, preferably halogens, especially bromine or iodine, most especially iodine.

Suitable bases for facilitating the reaction are, for example, alkali metal or :llk~line earth metal hydroxides, hydrides, amides, aLkanolates, acetates, carbonates, diaLkylamides or aLkylsilylamides, alkylamines, alkylenedi~minP.s, unsubstituted or N-alkylated, saturated or unsaturated cycloaL~yl~minPs, basic heterocycles, ammonium hydroxides and carbo-cyclic amines. There may be mentioned by way of example sodium hydroxide, hydride, amide, methanolate, acetate or carbonate, potassium tert-butanolate, hydroxide, carbonate or hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylene~ minP., 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).

The reactants can be reacted with each other as such, that is to say without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro-carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro-benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri-chloromethane, 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone;
alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, e~hylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-di-methylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases used in excess, such as triethyl-amine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.

The reaction is advantageously carried out in a temperature range of from approximately -30C to approximately +100C, preferably from approximately 0C to approximately +90C.

Variant i):
Suitable acid catalysts for facilitating the reaction are, for example, sulfonic acids, such as methane- or p-toluene-sulfonic acid, camphor-10-sulfonic acid, pyridinio-p-toluene-sulfonate, including the acidic ion-exchange resins with sulfo groups, Lewis acids, such as boron trifluoride diethyl ether or dimethyl ether complexes, and mineral acids, such as sulfuric acid or phosphoric acid.

Suitable water-binding agents for facilitating the removal of water are, for example, carbodiimides, such as N,N'-dicyclohexylcarbodiimide, or l-alkyl-2-halo-pyridinium salts, such as l-methyl-2-chloro-pyridinium iodide.

The reactants can be reacted with each other as such, that is to say without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydro-carbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichloro-benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri-chloromethane, 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone;
alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-di-methylacetamide, N-melhylpyrrolidone or hexamethylphosphoric acid lriamide; nitriles"

such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of an acid catalyst, acids used in excess, for example strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, Cl-C4alkanecarboxylic acids, for example formic acid, acetic acid or propionic acid, may also serve as solvents or diluents.

The reaction is advantageously carried out in a temperature range of from approximately -30C to approximately +100C, preferably from approximately 0C to approximately +90C.

Salts of compounds I can be prepared in a manner known per se. For example, acidaddition salts of compounds I are obtained by treatment with a suitable acid or a suitable ion-exchange reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion-exchange reagent.

Salts of compounds I can be converted into free compounds I in customary manner: acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion-exchange reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion-exchange reagent.

Salts of compounds I can be converted into different salts of compounds I in a manner known per se: acid addition salts, for example, can be converted into different acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydro-chloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt being formed, for example silver chloride, is insoluble and therefore separates from the reaction mixture.

Depending upon the procedure and the reaction conditions, compounds I having salt-forming properties can be obtained in free form or in the form of salts.

The compounds I, II, III and IV may be in the form of one of the possible isomers or in the form of a mixture thereof; for example, depending upon the number and the absolute and relative contiguration of the asymmetric carbon atoms, they may be in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; lhe invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood hereinbefore and hereinafter, even if stereochemical details are not specifically mentioned in every case.

Mixtures of diastereoisomers and mixtures of racemates of compounds I, II, III and IV that are obtainable in accordance with the process - depending upon the starting materials and procedures chosen, - or by other means, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physico-chemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.

Mixtures of enantiomers, such as racemates, accordingly obtainable can be separated into the optical antipodes by known methods, for example by recryst~llic~tion from anoptically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable micro-org~nicm.s, by cleavage with specific immobilised enzymes, or via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed.

Apart from by the separation of corresponding mixtures of isomers, it is possible according to the invention to obtain pure diastereoisomers or enantiomers also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process of the invention with starting materials having correspondingly suitable stereochemistry.

Advantageously, the biologically more active isomer, for example enantiomer, or mixture of isomers, for example mixture of enantiomers, will be isolated or synthesised, insofar as the individual components have differing biological activity.

The compounds I, II, III and IV can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents that have been used, where appropriate, for the crystallisation of compounds that are in solid form.

The invention relates to all those forms of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the fornl ol` a derivative or a salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.

2139~65 The starting materials and intermediates used in the process of the present invention are preferably those which result in the compounds I described at the beginning as being especially valuable.

The invention relates especially to the preparation processes described in Examples P1 to P17.

The invention relates also to those starting materials and intermediates used according to the invention for the preparation of the compounds I or the salts thereof, in each case in free form or in salt form, that are novel, to the use thereof and to processes for the preparation thereof.

The compounds I according to the invention are valuable active ingredients in the area of pest control while being well tolerated by warm-blooded ~nim~ls, fish and plants. In particular, the compounds according to the invention are effective against insects of the type occurring on useful plants and ornamentals in agriculture and in horticulture, especially in cotton, vegetable or fruit crops, and in forestry. The compounds according to the invention are especially suitable for the control of insects in fruit and vegetable crops, especially of phytopathogenic insects, such as Spodoptera littoralis, Heliothis virescens, Diabrotica balteata and Crocidolomia binotalis. Further areas of use of the compounds according to the invention are the protection of stored goods and material stocks, and also in the hygiene sector, especially the protection of domestic ~nim~l~ and productive livestock. The compounds of the invention are effective against all or individual development stages of normally sensitive and also resistant types of pest. Their action may manifest itself, for example, in mortality of the pests, which occurs immediately or only at a later date, for example during moulting, or in reduced oviposition and/or a reduced hatching rate.

The above-mentioned pests include:
of the order Lepidoptera, for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argill~ce~e, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp.,Crocidolomia binotalis, Cryptophlebi~ leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
of the order Coleoptera, for example Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemline~t~, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.;
of the order Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp.,Periplaneta spp. and Schistocerca spp.;
of the order Isoptera, for example Reticulitermes spp.;
of the order Psocoptera, for example Liposcelis spp.;
of the order Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;
of the order Mallophaga, for example D~m~linea spp. and Trichodectes spp.;
of the order Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii;
of the order Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;
of the order Homoptera, for example 2139~65 -Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseu~la~ pis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;
of the order Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp.
and Vespa spp.;
of the order Diptera, for example Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;
of the order Siphonaptera, for example Ceratophyllus spp. and Xenopsylla cheopis and of the order Thysanura, for example Lepisma saccharina.

The good pesticidal activity of the compounds of the invention corresponds to a mortality of at least 50 to 60 % of the mentioned pests.

The activity of the compounds according to the invention and of the compositionscomprising them can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides. Examples of suitable additives are representatives of the following classes of compounds: organophosphorus compounds, nitrophenols andderivatives thereof, t`ormamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.

The compounds according lo the invention are used in unmodified form or, prel`erably, together with the adjuvants customarily employed in formulation technology and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures comprising thecompound (active ingredient) of the invention or a combination thereof with other insecticides, and, where appropriate, solid or liquid adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with the adjuvants, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably alkylbenzene fractions containing 8 to 12 carbon atoms, such as xylene mixtures or alkylated naphthalenes, aliphatic or cycloaliphatic hydrocarbons, such as cyclohexane, paraffins or tetrahydronaphthalene, alcohols, such as ethanol, propanol or butanol, glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetanol alcohol, strongly polar solvents, such N-methyl-2-pyrrolidone, dimethyl sulfoxide or N,N-di-methylformamide, water and vegetable oils or epoxidised vegetable oils, such as rape oil, castor oil, coconut oil or soybean oil or epoxidised rape oil, castor oil, coconut oil or soybean oil; and, where appropriate, silicone oils.

The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand. ln addition, a great number of granulated materials of inorganic or organic nature can be used, especially dolomite or pulverised plant residues.

Depending upon the nature of the compound of the invention or of the combination of that compound with olher inseclicide~ which is lo be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo-aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydro-carbon moiety and 6 to 18 carbon atoms in the aLkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are water-soluble adducts of polyethylene oxide with poly-propylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Repre-sentative examples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxy-ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quatern~ry ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethyl-ammonium chloride and benzyldi(2-chloroethyl)ethylammonium bromide.

Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants. Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil; mention may also be made of fatty acid methyltaurin salts. More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a C8-C22alkyl radical, which also includes the alkyl moiety of acyl radicals; there may be mentioned by way of example the sodium or calcium salt of ligno-213gl65 sulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated or sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximate ly 8 to 22 carbon atoms. Examples of aL~cylarylsulfonates are the sodium, calcium or triethanol-ammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corres-ponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.

The surfactants listed above are to be regarded merely as examples; many more surfactants customarily employed in formulation technology and suitable for use according to the invention are described in the relevant literature.

The pesticidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of the invention or of a combination of that compound with other insecticides, and 1 to 99.9 %, preferably 5 to 99.9 %, of a solid or liquid adjuvant, it generally being possible for 0 to 25 %, preferably 0.1 to 20 %, of the composition to be surfactants (percentages are by weight in each case). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations which have considerably lower active ingredient concentrations. Typical concentration rates are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, active ingredient. The application rates per hectare are generally from 1 to 1000 g of active ingredient per hectare, preferably from 25 to 500 g/ha.

Preferred formulations have especially the following composition (throughout, percentages are by weight):

Emulsifiable concentrates:
active ingredient: 1 to 90 %, preferably 5 to 20 %
surfactant: 1 to 30 %, preferably 10 to 20 %
liquid carrier: 5 to 94 %, preferably 70 to 85 %

Dusts:
active ingredient: 0.1 to 10 %, preferably ().1 ~o 1 /0 solid carrier: ')').9 to 90 %, preferably 99.9 lo 99 %

2139 16~

Suspension concentrates:
active ingredient: 5 to 75 %, preferably 10 to 50 %
water: 94 to 24 %, preferably 88 to 30 %
surfactant: 1 to 40 %, preferably 2 to 30 %

Wettable powders:
active ingredient: 0.5 to 90 %, preferably 1 to 80 %
surfactant: 0.5 to 20 %, preferably 1 to 15 %
solid carrier: S to 95 %, preferably 15 to 90 %

Granules:
active ingredient: 0.5 to 30 %, preferably 3 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The compositions may also comprise other adjuvants, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rape oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.

The following Examples serve to illustrate the invention. They do not limit the invention.
Temperatures are given in degrees Celsius.

Preparation Examples General Remarks The compounds are obtained as isomeric mixtures usually in the form of viscous oils.
They can be purified by column chromatography. NMR spectra and elemental analyses confirm the required structures.

Example P1: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-methylhydrazone 180 g of 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone are heated under reflux in 600 ml of absolute alcohol with 29.6 g of glacial acetic acid and 31.8 g of methyl-hydrazine for one day. The solution is then concentrated by evaporation in vacuo, and the residue is taken up in approximately 150 ml of toluene and again concentrated by evapora-tion. The oil which remains is taken up in hexane/ethyl acetate '): l and the solution is 2139~65 stirred over magnesium sulfate and sodium bicarbonate for approximately 30 minutes.
The salts are removed by filtration and the filtrate is concentrated by evaporation in vacuo.
The title compound remains behind in the form of a yellow oil.

Example P2: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-formyl-N-methyl-hydrazone (compound 1.1 in Table 1) With the exclusion of moisture, 150 g of sodium formate are introduced into approxi-mately 125 ml of ether with stirring, and 147 g (1.87 mol) of acetyl chloride are added dropwise thereto at a reaction temperature of 0C. The reaction mixture is then stirred for several hours at room temperature, sodium chloride is removed by filtration, and the residue is washed with dry ether to yield a solution of approximately 1.87 mol of forrnyl acetate in ether.

A portion of that solution, containing 0.49 mol of formyl acetate, is added dropwise to a solution of 184 g of the hydrazone from Example P1 in 200 ml of ether. The reaction is complete after a few hours. Ice-water is added, the organic layer is collected, washed once more with water, dried over magnesium sulfate and filtered, and the f1ltrate is concentrated by evaporation and purified by column chromatography on silica gel using ethyl acetate/hexane 1:9 as eluant. The product is obtained as an isomeric mixture in the form of an oily-waxy mass.

Example P3: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-acetyl-N-formyl-hydrazone (compound 1.2 in Table 1) 4.05 g of 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-formylhydrazone are stirred in 30 ml of dry tetrahydrofuran with 0.7 ml of acetyl chloride and 1.4 ml of triethyl-amine and, after 20 hours, the reaction solution is concentrated by evaporation and the residue is chromatographed on a column of silica gel using ethyl acetate/hexane 1:5 as eluant. The title compound is obtained as an isomeric mixture having a melting point of 1 37- 142C.

Example P4: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-chlorocarbonyl-N-methylhydrazone At -10C, a solution of 40.5 g of the hydrazone from Example P1 and 10.1 g of triethyl-amine in 100 ml of ethyl acetate are added dropwise to 57 ml of 0.1 lM phosgene solution in toluene. After approximately 1 hour, the reaction solution is filtered and washed with a small amount of ethyl acetate, the filtrate is concentrated by evaporation iM vacuo, and the residue is purified on a column of silica gel using ethyl acetate/hexane 1:9 as eluant. The product is obtained in the form of a sticky crystalline mass.

Example PS: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-methyl-N-methyl-aminocarbonylhydrazone (compound 1.3 in Table 1) 0.025 mol of methylamine (33 % in absolute alcohol) is added all at once to 0.01 mol of the carbamoyl chloride from Example P4 in the form of a crude solution in ethyl acetate.
After lS minutes, the reaction mixture is poured onto ice-water, and the organic layer is separated off and, after being dried over m~gne~ium sulfate, is concentrated by evapora-tion in vacuo. Purification by column chromatography on silica gel using ethyl acetate/-hexane (1:2) as eluant yields the title compound having a melting point of 112-116C.

Example P6: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-methyl-N-thio-methylcarbonylhydrazone (compound 1.4 in Table 1) 0.02 mol of the carbamoyl chloride from Example P4 in ethyl acetate solution is stirred overnight with 1.5 g of sodium methylmercaptide; working-up yields the title compound in the form of a viscous yellowish oil.

Example P7: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-methylthiomethyl-carbonylhydrazone (compound 1.126 in Table 1) 0.065 mol of a solution of triethylammonium hydrogen sulf1de in tetrahydrofuran (prepared beforehand by passing 34 g of hydrogen sulfide into a solution of 101 g of triethylamine in tetrahydrofuran) is added to 2.55 g of 4-chloro-4'-trifluoromethane-sulfonyloxybenzophenone-N-(l-chloro)-ethylidenehydrazone in 20 ml of tetrahydrofuran.
The reaction mixture is then stirred for a few hours and is concentrated by evaporation, and the residue is chromatographed on silica gel using ethyl acetate/hexane 1 :9 as eluant, to yield an isomeric mixture of the title compound in the form of a thick yellowish oil.

Example P8: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N,N-dimethylamino-thiocarbonyl-N-methylhydrazone (compound 1.127 in Table 1) Analogously to Example P4, but using thiophosgene instead of phosgene, a yellow solution of 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-methyl-N-chloro-thiocarbamoylhydrazone in ethyl acetate is prepared. To an aliquot of that solution, containing 0.023 mul of the thiocarbamoyl chloride, there are added 6.5 g of 33 %
dimethylamine solution in absolute alcohol. Alter three hours, ice-water is added and the organic layer is separated oll, dried and concentrated by evaporation. The residue is 213g46S

purified on a column of silica gel using ethyl acetate/hexane 1 :9 as eluant. The title compound is obtained in the form of a viscous yellow oil.

Example P9: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-methyl-N-thio-formylhydrazone (compound 1.128 in Table 1) 3.6 g of the compound from Example P2 are stirred with 1.9 g of phosphorus pentasulfide in 30 ml of toluene for 20 hours. For working up, ice-water and sodium bicarbonate are added, extraction is carried out with ethyl acetate, the organic phase is dried and concen-trated by evaporation in vacuo and the residue is chromatographed using ethyl acetate/-hexane 1:9. The title compound is obtained in the form of an orange-coloured oil.

Example P 10: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-methyl-N-methylthiothiocarbonylhydrazone (compound 1.129 in Table 1) 7.1 g of the compound from Example P1 are introduced into a mixture of 25 ml of dry dimethylformamide and 1.3 ml of carbon disulfide. At 0C, 0.6 g of sodium hydride (80 %
dispersion in oil) is added. After approximately 30 minutes, 1.3 ml of methyl iodide are added. After two hours, ice-water is added and extraction is carried out with ether. The organic phases are combined, dried and concentrated by evaporation, to yield a viscous oil which is purified on a column of silica gel using ethyl acetate/hexane 1 :9. The title compound is obtained as an isomeric mixture having a melting point of 94-99C.

Example P11: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-aminothio-carbonylhydrazone (compound 1.130 in Table 1) 15 g of 4-chloro-4'-trifluoromethanesulfonyloxybenzophenonehydrazone are stirred with 3.5 g of ammonium thiocyanate in 100 ml of alcohol, and added dropwise to 4.5 g of methanesulfonic acid. The reaction mixture is then stirred for several hours until the starting material can no longer be detected in a thin-layer chromatogram. The product is precipitated by the addition of water. It is isolated by filtration, dried and recrystallised from ethyl acetate/hexane to yield the title compound having a melting point of 94-96C.

Example P12: 4-fluoro-4'-trifluoromethanesulfonyloxybenzophenone-N-isobutylidene-carbonyl-N-methylbenzophenone (compound 1.12 in Table 1) 1.28 g of N-ethyl-diisopropylamine and 1.47 g of 3,3-dimethylacrylic acid chloride are added in succession to a solution of 3.38 g of 4-fluoro-4'-trifluoromethanesulfonyloxy-benzophenone-N-methylhydrazone (prepared analogously to the method described in Example Pl) in 50 ml of tetrahydrofuran, and the reaction mixture is stirred at room temperature for 15 hours. It is then concentrated by evaporation in vac~o. The residue is partitioned between dichloromethane and water. The organic phase is dried over sodium sulfate, filtered and concentrated by evaporation. The crude product is chromatographed on silica gel using hexane/ethyl acetate 10:1 to yield the title compound in the form of a yellow oil.

Example P13: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-methyl-N-(N'-methoxy-N'-methyl)aminocarbonylhydrazone (compound 1.5 in Table 1) 0.91 g of triethylamine and 1.1 g of N-methyl-N-methoxycarbamoyl chloride are added in succession to a solution of 3.2 g of 4-chloro-4'-trifluoromethanesulfonyloxybenzo-phenone-N-methylhydrazone in 50 ml of toluene. After refluxing for 2 hours, the reaction mixture is cooled and concentrated by evaporation in vacuo. The residue is partitioned between ethyl acetate and water. The organic phase is dried over sodium sulfate, filtered and concentrated by evaporation. The crude product is chromatographed on silica gel using ethyl acetate/hexane 1:5 to yield the title compound in the form of a brownish oil.

Example P14: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-chloromethyl-carbonylhydrazone 7.2 g of chloroacetyl chloride are added dropwise over a period of 30 minutes to a solution of 22 g of 4-chloro-4'-trifluoromethanesulfonyloxybenzophenonehydrazone and 5.5 g of pyridine in 100 ml of methylene chloride. The reaction mixture is stirred at room temp-erature for 16 hours, then poured onto 100 ml of water and extracted with 200 ml of methylene chloride. The organic phase is washed with saturated sodium chloride solution, dried with m~gn~ium sulfate and concentrated by evaporation. The resulting crudeproduct is purif1ed by chromatography on silica gel using hexane/ethyl acetate 3:1 to yield the title compound in the form of a solid having a melting point of 123-125C.

Example P15: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-(6-chloro-6,6-difluoro-2-oxa-3-oxohexanecarbonyl)hydrazone (compound 1.78 in Table 1) A mixture of 3 g of the product from Example P14, 0.1 g of sodium iodide, 1.0 g of 4-chloro-4,4-difluorobutyric acid and 0.67 g of triethylamine in 10 ml of DMF is heated at 90C for 16 hours. The reaction mixture is then poured onto water and extracted with 100 ml of ethyl acetate. The organic phase is washed with saturated sodium chloride solution, dried with magnesium sull`ate and concentrated by evaporation. The resulting crude product is purified by chromatography on silica gel using methylene chloride/2 %
methanol to yield the li~le compound in the form of an amorphous solid.

2l3g~6~

Example P16: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-(acetoxy-methylenecarbonyl)hydrazone (compound 1.77 in Table 1) A mixture of 4 g of the product from Example P14, 0.13 g of sodium iodide and 0.72 g of sodium acetate in 10 ml of DMF is heated at 50C for 5 hours. The reaction mixture is then poured onto water and extracted with 100 ml of ethyl acetate. The organic phase is washed with saturated sodium chloride solution, dried with magnesium sulfate andconcentrated by evaporation. The resulting residue is purified by chromatography on silica gel using hexane/ethyl acetate 1:1 to yield the title compound in the form of an amorphous solid.

Example P17: 4-chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-(l-imidazolyl)-methylenecarbonylhydrazone (compound 1.80 in Table 1) A mixture of 3 g of the product from Example P14, 0.1 g of sodium iodide, 0.45 g of imidazole and 0.66 g of triethylamine in 10 ml of DMF is heated at 50C for 10 hours.
The reaction mixture is then poured onto water and extracted with 100 ml of ethyl acetate.
The organic phase is washed with saturated sodium chloride solution, dried with m~gnPsium sulfate and concentrated by evaporation. The resulting crude product is purified by chromatography on silica gel using methylene chloride/methanol (1 %) to yield the title compound in the form of an amorphous solid.

Example P18:
In a manner analogous to that described in Examples P2, P3, P5 to P13 and P15 to P17, it is also possible to prepare the other compounds listed in Tables 1 to 4. In the column "physic. data" of those Tables, the numbers indicate the melting point.

- 213946~ - 37 -Table 1 R~ oO~S/~ CF3 `N' 2 R~X
R R physic. data comp. no. X R1 2 3 1.1 0 Cl CH3 H oil/wax 1.2 O Cl CHO CH3 137- 142 1.3 O C1 CH3 NHCH3 112-116 1.4 O C1 CH3 SCH3 oil 1.5 O Cl CH3 N(OCH3)CH3 resin 1.6 O F CH3 N(OCH3)CH3 resin 1.7 O C1 CH3 N(OC2Hs)CH3 resin 1.8 O Cl CH3 N(OC2Hs)C2H5 oil 1.9 O F CH3 CH3 resin 1.10 F CH3 C2Hs 88-91 1.11 O F CH3 i-C3H7 resm 1.12 O F CH3 CH=C(CH3)2 res1n 1.13 o F CH3 cyclo-C3Hs 72-76 1.14 o C1 CH3 cyclo-C3Hs 80-82 1.15 O Cl CH3 NHOC2Hs oil 1.16 Cl CH3 NHOCH2CH=cH2 oil 1.17 O Cl CH3 NHOCH2C(CH3)=cH2 oil 1.18 O Cl CH3 CH2-cyclo-c3H3F2(2~2) resin 1.19 O Cl CHO CF3 108- 110 1.20 O F CH3 CH2-cyclo-c3H3F2(272) resin 1.21 O Cl CH3 NH2 118-126 1.22 O Cl CH3 CH3 80-82 1.23 O Cl CH3 Cl oil 1.24 o Br CH3 C2H5 1 25 O Br CH3 CH3 94-1050 1.26 O Br CH3 n-c3H7 113-115 1.27 o Br CH3 i-C3H7 honey 1.28 O Br CH3 CH(CH3)C2Hs oil 1.29 O Br CH3 cyclohexyl resin 1.30 O Br CH3 t-C4Hg resin 1.31 O Br CH3 n-c3H7 resin 1.32 O Br CH3 cyclo-C3H5 92-103 1.33 O Cl CH3 thien-2-yl amorphous 1.34 O Cl CH3 thien-3-yl resm 1.35 O Cl CH3 5-chlorothien-2-yl resm 1.36 O Cl CH3 3-chlorothien-2-yl 1.37 O Cl CH3 benzo[b]thien-2-yl 1.38 O Cl CH3 5-chlorobenzo[b]thien-2-yl 1.39 O Cl CH3 3-ehlorobenzo[b]thien-2-yl amorphous 1.40 O Cl CH3 pyrid-2-yl 1.41 O Cl CH3 pyrid-3-yl 1.42 O Cl CH3 pyrid-4-yl 1.43 O Cl CH3 6-ehloropyrid-3-yl 1.44 O Br CH3 thien-2-yl amorphous 1.45 O Br CH3 thien-3-yl resin 1.46 O Br CH3 5-ehlorothien-2-yl amorphous 1.47 O Br CH3 3-ehlorothien-2-yl amorphous 1.48 O Br CH3 benzo[b]thien-2-yl amorphous 1.49 O Br CH3 5-ehlorobenzo[b]thien-2-yl 1.50 O Br CH3 3-chlorobenzo[b]thien-2-yl amorphous 1.51 O Br CH3 pyrid-2-yl 1.52 O Br CH3 pyrid-3-yl 1.53 O Br CH3 pyrid-4-yl 1.54 O Br CH3 6-ehloropyrid-3-yl 1.55 O Cl CH3 CF3 1.56 O Cl CH3 SC2Hs 1.57 O Cl CH3 N(CH3)2 1.58 O Cl CH3 NHNH2 1.59 O Cl CH3 N(CH3)NH2 1.60 O Cl CH3 NHN(CH3)2 1.61 O Cl C2H5 H oil 213946~

1.62 O C1 C2H5 CH3 50-60 1.63 Cl C2H5 C2H5 1.64 C1 C2H5 NH2 1.65 Cl C2H5 SCH3 1.66 O Cl C2Hs SC2Hs 1.67 C1 C2Hs NHNH2 1.68 O C1 C2Hs N(CH3)2 1.69 O C1 C2Hs NHCH3 1.70 O C1 n-C4Hg H
1.71 O C1 n-C4Hg CH3 1.72 O C1 n-C4Hg SCH3 1.73 O C1 n-C4Hg NH2 1.74 O C1 CHO C2Hs 1.75 O Cl CHO n-c3H7 1.76 O Cl CHO i-C3H7 1.77 O Cl H CH2OCOCH3 50-60 1.78 O Cl H CH2OCOCH2CH2CF2Cl amorphous 1.79 O Cl H CH2OCO(CH2)10CF2cl resin 1.80 O Cl H CH2- 1-imidazolyl 75-85 1.81 O Cl H CH(C6Hs)OCOCH3 1.82 O Cl H C(CH3)2OCOCH3 1.83 Cl H CH2OCOC6Hs 1.84 Cl H CH2OCOCH2C6Hs 1.85 Cl H CH2OCOC6H4Cl(4) 1.86 O Cl H CH2OCOC6H4OCH3(4) 1.87 O Cl H CH2ococ6H4No2(4) 1.88 O Cl H CH2OCO(CH2)8CH=CHCF2Cl resin 1.89 O Cl H CH2OCO(CH2)3CH=cF2 1.90 Cl H CH2OCO(CH2)9CH=cF2 1.91 O Cl H CH2OCO-t-C4Hg 1.92 O Cl H CH2OCO-cyclo-C3Hs 1.93 O Cl H CH2OCOCH=CH2 1.94 O Cl H CH2OCOC-CH
1.95 O Cl H CH2- 1 -pyrazolyl 1.96 O Cl H CH2-1-(1,2,4)triazolyl 64-68 1.97 C) Cl CH3 CH2C)COCH3 213gg65 1.98 O Cl CH3 CH2OCOCH2CH2CF2Cl 1.99 O Cl CH3 CH2oco(cH2)locF2cl 1.100 O Cl CH3 CH2-1-imidazolyl 123-125 1.101 O Cl CH3 CH2OCOc6Hs 145-147 1.102 O Cl CH3 CH2OCOCH2c6H5 resm 1.103 O Cl CH3 CH2OCO(CH2)8CH=CHCF2Cl 1.104 O Cl CH3 CH2OCO(CH2)3CH=cF2 1.105 O Cl CH3 CH2OCO(CH2)9CH=cF2 1.106 O Cl CH3 CH2OCO-t-C4Hg 1.107 O Cl CH3 CH2OCO-cyclo-C3H5 1.108 O Cl CH3 CH2OCOCH=CH2 1.109 O Cl CH3 CH2OCOC_CH
1.110 O F H CH2OCOCH3 1.111 O F CH3 CH2OCOCH3 1.112 O F H CH2OCOCH2CH2CF2Cl 1.113 O F CH3 CH2OCOCH2CH2CF2C1 1.114 O F H CH2OCOC6Hs 1.115 O F CH3 CH2OCOC6Hs 1.116 O F H CH2OCO(CH2)3CH=cF2 1.117 O F CH3 CH2OCO(CH2)3CH=cF2 1.118 O F H CH2OCO-cyclo-C3Hs 1.119 O F CH3 CH2OCO-cyclo-C3Hs 1.120 O F H CH2OCOCH=CH2 1.121 O F CH3 CH2OCOCH=CH2 1.122 O F H CH2OCOC_CH
1.123 O F CH3 CH2OCOC-=CH
1.124 O Br H CH2OCOCH3 1.125 O Br CH3 CH2OCOCH3 1.126 S Cl H CH3 oiVresin 1.127 S Cl CH3 N(CH3)2 oil 1.128 S Cl CH3 H oil 1.129 S Cl CH3 SCH3 94-99 1.130 S Cl H NH2 94-96 1.131 S Cl H N(CH3)2 154-157 1.132 S Cl H H 110-112 1.133 S Cl CH~ NHCH3 2()1-203 2139~65 1.134 S Cl H SCH3 oil 1.135 S Cl CH3 N(OCH3)CH3 1.136 S Cl CH3 OCH3 1.137 S Cl CH3 OC2Hs 1.138 S Cl CH3 CH3 1.139 S Cl C2Hs SCH3 1.140 S Cl C2Hs NHCH3 1.141 S Cl C2Hs NH2 1.142 S Cl C2Hs N(CH3)2 1.143 S Cl C2Hs OCH3 1.144 S Cl n-C3H7 NHCH3 1.145 S Cl n-C3H7 NH2 1.146 S Cl n-C3H7 OCH3 1.147 S Cl COCH3 CH3 1.148 S Cl COCH3 C2H5 1.149 S Cl COCH3 CF3 1.150 S Cl COCH3 COOCH3 1.151 S Cl H NHCH3 165-170 1.152 S Br H H
1.153 S Br H CH3 1.154 S Br H SCH3 1.155 S Br H NHCH3 1.156 S Br H N(OCH3)CH3 1.157 S Br CH3 H
1.158 S Br CH3 CH3 1.159 S Br CH3 SCH3 1.160 S Br CH3 NHCH3 1.161 S Br CH3 N(ocH3)cH3 1.162 S Br COCH3 CH3 1.163 S Br COCH3 COOCH3 1.164 O Br i-C3H7 CH3 resin 1.165 O Cl C2Hs CF3 oil 1.166 O Cl CH3 CH2Cl 59-61 1.167 O Cl n-C3H7 H oil 1.168 O Cl n-C3H7 CH3 oil l . l 69 O Cl CH3 CH2OCOC6H4NO2(P) 64-70 2139~65 1.170 O Cl CH3 CH2OCOC6H4Cl(p) resin 1.171 O Cl CH3 CH2OCOC6H4OCH3(p) 59-63 1.172 O Cl CH3 CH2-4-morpholinyl resin 1.173 O Cl H CH2OCO(CH2)scH=cH2 resin 1.174 S Cl CH3 NH2 118-125 1.175 O Cl CH3 CH2COOCH3 resin 1.176 O Cl CH3 COOC2Hs resin 1.177 O Cl CH3 C(CH3)2OCOCH3 135-137 1.178 O Cl CH3 CH2OcH2c6Hs resin 1.179 o Cl CH3 (CH2)3cOoc2Hs resin 1.180 O Cl CH3 CH2-cyclo-c6Hll resin 1.181 O Cl CH3 CH2-cyclo-CsHg resin 1.182 O Cl CH3 CH(C6H5)OCOCH3 resin 1.183 O Cl COCH3 CH3 resin 1.184 O Cl COCH3 CF3 resin 1.185 O Cl COCH3 cyclo-C3H7 resin 1.186 O Cl i-C3H7 H resin 1.187 O Cl COCF3 CF3 resin 1.188 O Cl H CH(C2Hs)SC6Hs 133-135 1.189 O Cl H CH2SCSN(CH3)2 amorphous 1.190 O Cl H CH2SCSO-i-C3H7 amorphous 1.191 O Cl COC2Hs CH3 resin 1.192 O Cl H CH2SCSOC2Hs resin 1.193 O Cl H CH2SCSN(CH3)OCH3 resin 1.194 O Br CH3 H 85-91 1.195 O Cl CH3 OCH3 oil 1.196 O Cl CH3 OC2Hs oil 1.197 O Cl CH3 O-t-C4Hg oil 1.198 O Cl C2Hs OC2Hs oil 1.199 S Cl CH3 CH2SC(=S)N(cH3)2 106-110 1.200 S Cl CH3 CH2SC(=S)-4-morpholinyl amorphous 1.201 S Cl CH3 CH2SC(=S)-l-pyrryl amorphous 1.202 O Cl CH3 CH2SC(=S)OCH3 amorphous 1.203 O Cl CH~s CH2SC(=S)-i-OC3H7 resin 1.2()4 O Cl H CH2OCO(CH2)sCH=CF2 resin Table 2 R~X
comp. no. X R1 R2 R3 Rl7 physic. data 2.01 O Cl CH3 H 3-Br oil 2.02 O Cl CH3 CH3 3-Br 97 ggo 2.03 Cl CH3 c-C3Hs 3-Br oil 2.04 Cl CH3 CF3 3-Br 107-109 2.05 O C1 C2Hs H 3-Br 65-68 2.06 O Cl C2Hs CF3 3-Br oil 2.07 O Cl C2Hs CH3 3-Br oil 2.08A1 O Cl CH3 C6H4C1(4) 3-C1 83-85 2.09B1 O Cl CH3 C6H4Cl(4) 3-C1 130-133 2.10 O Cl CH3 CF3 3-C1 96-98 2.11 O Cl i-C3H7 CH3 3-Br oil 2.12 O Cl CH3 H 3-Cl resin 1 A and B denote isomers 2139~6S

Table 3 R~ oo,S"OcH3 `N' 2 R~X

comp. no. X Rl R2 R3 Rl7 physic. data 3.01 O Cl CH3 H H 116-117 3.02 O Cl CH3 CH3 H resin 3.03 O F CH3 N(OCH3)CH3 H resin 3.04 O Br CH3 CH3 H wax 3.05Al O Br CH3 i-C3H7 H wax 3.05Bl O Br CH3 i-C3H7 H wax 3.06 O F CH3 H H 129-130 3.07 O F CH3 CH3 H resin 3.08 O Cl CH3 CH3 3-Cl resin 3.09 O Cl CH3 H 3-C1 118-120 3.10 O F CH3 H 3-C1 129-131 3.11Al O Cl CH3 (CH3)3CH=CF2 3-CH2CH=CH2 resin 3.11Bl O Cl CH3 (CH3)3CH=CF2 3-CH2CH=CH2 resin 3.12 O Cl CH3 CH3 3-CH2CH=CH2 glass-like 3.13 O Cl CH3 CH2-t-C4Hg 3-CH2CH=CH2 resin 3.14 O Br CH3 n-C3H7 H 101-107 3.15 O Br CH3 c-C3H5 H 83-91 3.16 O Br CH3 C2Hs H resin 3.17 O Br CH3 CH2Cl H resin 3.18 O Br CH3 i-C4Hg H 97-103 I A and B denote isomers , 2139965 Table 4 R1~00"S~,CF3 ` N ' 2 ZJ~N
\~4 comp. no. Z R1 R2 R19 physic. data 4.01 S Cl CH3 4-CH3 resin 4.02 S Cl CH3 S-CH3 4.03 S Cl CH3 4-Cl 4.04 S Cl CH3 5-Cl 4.05 S Cl CH3 4-CF3 4.06 S Cl CH3 5-CF3 4.07 S Cl H 4-Cl 4.08 S Cl H 5-Cl 4.09 S Cl H 4-CF3 4.10 S Cl H S-CF3 4.11 O Cl CH3 4-CH3 4.12 O Cl CH3 5-CH3 4.13 O Cl CH3 4-Cl 4.14 O Cl CH3 5-Cl 4.15 O Cl CH3 4-CF3 4.16 O Cl CH3 5-CF3 4.17 O Cl H 4-CF3 4.18 O Cl H 5-CF3 4.19 S Br CH3 4-CH3 4.20 S Br CH3 5-CH3 4.21 S Br CH3 4-CI
4.22 S Br CH3 5-CI
4.23 S Br CH~ 4-CF3 213ss65 4.24 S Br CH3 S-CF3 4.25 S Br H 4-Cl 4.26 S Br H S-Cl 4.27 S Br H 4-CF3 4.28 S Br H S-CF3 4.29 0 Br CH3 4-CH3 4.30 0 Br CH3 S-CH3 4.31 0 Br CH3 4-Cl 4.32 0 Br CH3 S-Cl 4.33 0 Br CH3 4-CF3 4.34 0 Br CH3 S-CF3 4.35 0 Br H 4-CF3 4.36 0 Br H S-CF3 4.37 S F CH3 4-CH3 4.38 S F CH3 S-CH3 4.39 S F CH3 4-Cl 4.40 S F CH3 S-Cl 4.41 S F CH3 4-CF3 4.42 S F CH3 S-CF3 4.43 S F H 4-Cl 4.44 S F H S-Cl 4.45 S F H 4-CF3 4.46 S F H S-CF3 4.47 0 F CH3 4-CH3 4.48 0 F CH3 5-CH3 4.49 0 F CH3 4-Cl 4.50 0 F CH3 S-Cl 4.51 0 F CH3 4-CF3 4.52 0 F CH3 S-CF3 4.53 0 F H 4-CF3 4.54 0 F H 5-CF3 2139~65 Formulation Examples (throughout, percentages are by weight) Example Fl: Emulsifiable concentrates a) b) c) active ingredient 25% 40% 50%
calcium dodecylbenzenesulfonate 5% 8% 6%
castor oil polyethylene glycol ether (36 mol of ethylene oxide) s%
tributylphenol polyethylene glycol ether (30 mol of ethylene oxide) - 12% 4%
cyclohexanone - 15% 20%
xylene mixture 65% 25% 20%

The finely ground active ingredient is mixed with the adjuvants, giving an emulsifiable concentrate from which emulsions of any desired concentration can be prepared bydilution with water.

ExampleF2: Solutions a) b) c) d) active ingredient 80% 10% 5% 95%
ethylene glycol monomethyl ether 20% - - -polyethylene glycol (mol. wt. 400) 70%
N-methylpyrrolid-2-one - 20% -epoxidisedcoconutoil - - 1% 5%
petroleum fraction (boiling range: 160-190) - - 94% -The finely ground active ingredient is mixed with the adjuvants, giving a solution that is suitable for application in the form of microdrops.

ExampleF3: Granules a) b) c) d) active ingredient 5% 10% 8% 21%
kaolin 94% - 79% 54%
highly dispersed silicic acid 1% - 13% 7%
attapulgile - 90% - 18%

The aclive ingredienl is dissolved in dichloromethane, the solu~ion is sprayed onto the 213996s carrier mixture, and the solvent is evaporated off in vacuo.

ExampleF4: Dusts a) b) active ingredient 2% 5%
highly dispersed silicic acid 1% 5%
talcum 97%
kaolin 90%

Ready-for-use dusts are obtained by mixing the active ingredient with the carriers.

Example F5: Wettable powders a) b) c) active ingredient 25% 50% 75%
sodium lignosulfonate 5% 5%
sodium lauryl sulfate 3% - s%
sodium diisobutylnaphthalenesulfonate - 6% 10%
octylphenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2%
highly dispersed silicic acid 5% 10% 10%
kaolin 62% 27% -The active ingredient is mixed with the adjuvants and the mixture is ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F6: Emulsifiable concentrate active ingredient 10%
octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3%
calcium dodecylbenzenesulfonate 3%
castor oil polyethylene glycol ether (36 mol of ethylene oxide) 4%
cyclohexanone 30%
xylene mixture 50%

The finely ground active ingredient is mixed with the adjuvants, giving an emulsifiable concen~rate trom which emulsions ol ~ny desired concentration can be prepared by 2139~6S

dilution with water.

Example F7: Dusts a) b) activeingredient 5% 8%
talcum 95%
kaolin - 92%

Ready-for-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

Example F8: Extruder granules active ingredient 10%
sodium lignosulfonate 2%
carboxymethylcellulose 1%
kaolin 87%

The active ingredient is mixed with the adjuvants, and the mixture is ground, moistened with water, extruded and granulated, and the granules are then dried in a stream of air.

Example F9: Coated granules active ingredient 3%
polyethylene glycol (mol. wt. 200) 3%
kaolin 94%

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol, affording non-dusty coated granules.

Example F10: Suspension concentrate active ingredient 40%
ethylene glycol 10%
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6%
sodium lignosulfonate 10~
carboxymethylcellulose l %
aqueous formaldehyde solution (37%) 0.2%
aqueous silicone oil eMulsion (75%) ().X/

- 2l3996~

water 32%

The finely ground active ingredient is mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biolo~ical Examples Example B 1: Action against Diabrotica balteata Maize seedlings are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the maize seedlings are populated with 10 Diabrotica balteata larvae in the second stage and then placed in a plastics container.
6 days later, the percentage reduction in the population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.

Compounds of Tables 1 to 4 exhibit good activity in this test. In particular, compounds 1.3,1.5,1.7tol.11,1.13,1.15,1.17,1.19,1.21tol.23,1.77tol.79,1.134,1.151,1.174 to 1.177, 1.179, 1.183 to 1.189, 1.191, 1.193 to 1.196, 1.198, 2.01, 2.04 to 2.07, 2.11, 2.12, 3.01 to 3.08, 3.10, 3.15, 3.16 and 4.01 are more than 80 % effective.

Example B2: Action against Heliothis virescens Young soybean plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 Heliothis virescens caterpillars in the first stage and then placed in a plastics container.
6 days later, the percentage reduction in the population and the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.

Compounds of Tables 1 to 4 exhibit good activity in this test. In particular, compounds 1.1 to 1.3, 1.5 to 1.22, 1.77 to 1.80, 1.126 to 1.129, 1.132 to 1.134, 1.151, 1.176 to 1.178, 1.183, 1.195, 1.196, 1.198, 2.11, 3.01, 3.02, 3.04 to 3.07, 3.15, 3.16 and 4.01 are more than 80 % effective.

Example B3: Action against Heliothis virescens (ovicidal) Egg deposits of Heliothis virescens on filter paper are immersed for a shorl time in an aqueous ace~one solu~ion comprising 400 ppm of test compound. After ~he le~,l solution has dried, the eggs are incubated in petri dishes. After 6 days, the percentage of eggs that have hatched is evaluated in comparison with untreated controls (% reduction in the hatching rate).

Compounds of Tables 1 to 4 exhibit good activity in this test. In particular, compounds l.ltol.3,1.5tol.11,1.13tol.22,1.77tol.80,1.126tol.129,1.132tol.134,1.151, 1.176 to 1.178, 1.183, 1.195 to 1.198, 2.01, 2.04 to 2.06, 2.09, 2.11, 2.12, 3.01, 3.02, 3.04, 3.06, 3.07, 3.15, 3.16 and 4.01 are more than 80 % effective.

Example B4: Action a~ainst Plutella xylostella Young cabbage plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cabbage plants are populated with 10 Plutella xylostella caterpillars in the third stage and then placed in a plastics container.
3 days later, the percentage reduction in the population and the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.

Compounds of Tables 1 to 4 exhibit good activity in this test. In particular, compounds 1.1 tol.3,1.5tol.11,1.13tol.22,1.77tol.80,1.126tol.129,1.132tol.134,1.175to 1.178, 1.183, 1.195, 1.196, 1.198, 2.11, 3.01, 3.02, 3.04 to 3.06, 3.14 to 3.16 and 4.01 are more than 80 % effective.

Example B5: Action against Spodoptera littoralis Young soybean plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 Spodoptera littoralis caterpillars in the third stage and then placed in a plastics container.
3 days later, the percentage reduction in the population and the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.

Compounds of Tables 1 to 4 exhibit good activity in this test. In particular, compounds 1.1 to 1.22, 1.77 to 1.80, 1.126 to 1.129, 1.132, 1.134, 1.175 to 1.178, 1.183, 1.195 to 1.198, 2.11, 3.01, 3.02, 3.04 to 3.07, 3.14 to 3.16 and 4.01 are more than 80 % effective.

Example B6: Al;tion a~ains~ Boophilus microplus Adult female ticks which have sucked themselves full are attached to a PVC board and 213g~6~
-covered with a cottonwool ball, and 10 ml of aqueous test solution comprising 125 ppm of active ingredient are poured over the ticks. The cotton wool ball is removed, and the ticks are incubated for 4 weeks for oviposition. The action becomes apparent either, in the case of the female, in the form of mortality or sterility or, in the case of the eggs, in the form of an ovicidal action.

Compounds of Tables 1 to 4 exhibit good activity in this test. In particular, compound 1.204 is more than 80 % effective.

Example B7: Action against Blattella germanica A solution (0.1 %) of the active ingredient in acetone is placed into a Petri dish in such an amount that this corresponds to an application rate of 1 g/m2. When the solvent has evaporated, 10 nymphs of Blattella germanica (last nymphal stage) are placed in the dish and exposed to the action of the test substance over 2 hours. The nymphs are then anaesthetised using CO2, transferred to a fresh Petri dish and kept in the dark at 25 and circa 70 % atmospheric humidity. After 48 hours, the insecticidal action is determined by calculating the destruction rate.

In this test, compounds of Tables 1 to 4 exhibit good activity. In particular, compounds 1.61, 1.186 and 3.03 are more than 80 % effective.

Example B8: Action against Musca domestica A sugar lump is treated with such an amount of test substance that the concentration of test substance in the sugar is 250 ppm after drying overnight. The lump which has been treated in this manner is placed on an aluminium dish together with a wet cotton wool ball and 10 adults of an OP-resistant strain of Musca domestica. The dish is covered with a glass beaker and incubated at 25. The mortality rate is determined after 24 hours.

In this test, compounds of Tables 1 to 4 exhibit good activity. In particular, compounds 1.61, 1.186 and 3.03 are more than 80 % effective.

Claims

1. A compound of formula (I), wherein m is 0, 1, 2, 3 or 4, and, when m is greater than 1, the radicals R17 are identical or different;
n is 0, 1, 2, 3, 4 or 5, and, when n is greater than 1, the radicals R1 are identical or different;
R1 and R17 are each independently of the other halogen, C1-C8alkyl, halo-C1-C8alkyl, phenoxy, phenylthio, halo-C1-C8alkylthio, phenyl, C1-C8alkylthio, C1-C8alkyl-carbonyl, OSO2R4, SO2NR13R14 or P(=Y)R22R23;
either X is S, R2 is R21 or H and R3 is R31, -NRSR6 or -OR2, or X is O, R2 is R21 and R3 is R31, or X is O, R2 is H and R3 is -R8OR9, -R8OCOR9, -R8NR10R11 or -R8R12, or X and R3 together are R18;
Y is O or S;
R4 is C1-C8alkyl, halo-C1-C8alkyl or halo-C1-C8alkoxy;
R21 is C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4-alkylthio-C1-C4alkyl, R13R14N-C1-C4alkyl, C2-C8alkenyl, C2-C8alkynyl, C1-C4acyl,CH=C(CN)2, or phenyl which is unsubstituted or substituted by from one to five substituents selected from the group consisting of halogen, C1-C4alkyl, C2-C5-alkenyl, halo-C1-C4alkyl, C1-C4alkoxy, SO2NR13R14, halo-C1-C4alkoxy, C1-C4-alkylthio, C1-C4alkoxy-C1-C4alkoxy, halo-C1-C4alkylthio, NR13R14, -NO2 and -CN;
R31 is H, C1-C8alkyl, C3-C6cycloalkyl, C3-C6cycloalkyl-C1-C3alkyl, halo-C1-C8alkyl, halo-C3-C6cycloalkyl-C1-C3alkyl, C2-C8alkenyl, C2-C8alkynyl, halo-C2-C8alkenyl, -COOR7, -SR2, -R8OR9, -R8OCOR9, -R8NR10R11, -R8R12, -R8SR9, -R8SCSR9, or phenyl which is unsubstituted or substituted by from one to five substituents selected from the group consisting of halogen, C1-C4alkyl, C2-C5alkenyl, halo-C1-C4alkyl,halo-C1-C4alkoxy, halo-C1-C4alkylthio, SO2NR13R14, C1-C4alkoxy, -NO2 and -CN;

an unsubstituted or substituted, saturated or unsaturated, five- or six-memberedheterocyclic or heterobicyclic ring containing from one to three hetero atoms selected from the group O, N and S, the substituents being selected from the group consisting of halogen, C1-C4alkyl, halo-C1-C4alkyl and C1-C4alkoxy;
R5 and R6 are each independently of the other H, C1-C8alkyl, halo-C1-C8alkyl, C2-C5-alkenyl, C1-C4alkoxy, C2-C5alkeneoxy or -NR13R14;
R7 is H, C1-C8alkyl, halo-C1-C8alkyl or C2-C8alkenyl;
R8 is (CR15R16)p, wherein p is 1, 2, 3 or 4;
R9 is C1-C8alkyl, halo-C1-C11alkyl, C3-C6cycloalkyl, C2-C8alkenyl, halo-C2-C11alkenyl, C2-C8alkynyl, NR10R11, OR10, benzyl, or phenyl which is unsubstituted or substituted by from one to five substituents selected from the group consisting of halogen, C1-C4alkyl, C2-C5alkenyl, halo-C1-C4alkyl, C1-C4alkoxy, -NO2 and -CN;
R10 and R11 are each independently of the other C1-C8alkyl, C2-C8alkenyl or C1-C8alkoxy-C1-C8alkyl;
R12 is an unsubstituted or substituted, saturated or unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing from one to three hetero atoms selected from the group O, N and S, the substituents being selected from the group consisting of halogen, C1-C4alkyl, halo-C1-C4alkyl and C1-C4alkoxy;
R13 and R14 are each independently of the other H or C1-C8alkyl;
R15 and R16 are each independently of the other H, C1-C8alkyl, or phenyl which is unsubstituted or substituted by from one to five substituents selected from the group consisting of halogen, C1-C4alkyl, C2-C5alkenyl, halo-C1-C4alkyl, C1-C4alkoxy, -NO2 and -CN;
R18 is NC(R19)=C(R19)S, NC(R19)=C(R19)O, NC(R19)2C(R19)2S, NC(R19)2C(R19)2O, NC(R19)=C(R19)C(R19)=N or NC(R19)=NC(R19)=N;
R19 is H, C1-C4alkyl, halogen or halo-C1-C4alkyl;
R22 is C1-C4alkyl, C1-C4alkoxy or NR13R14; and R23 is C1-C4alkyl, C1-C4alkoxy, C3-C4alkylthio or NR13R14, with the proviso that, in the compounds of formula 1, R2 is other than H when either m is 0, n is 1, R1 is 4-Cl, R3 is -N(OCH3)CH3, R4 is CF3 and X is O, or when m is 0, n is 2, R1 is 3,4-dichloro, R3 is -N(OCH3)CH3, R4 is CF3 and X is O, or when m is 0, n is 1, R1 is 4-C1, R3 is -NHNH2, R4 is CF3 and X is O, or, as the case may be, a tautomer thereof, in each case in free form or in salt form.

2. A compound according to claim 1 of formula I, wherein m is0or 1, or, as the case may be, a tautomer thereof.

3. A compound according to claim 1 of formula I, wherein m is 0;
n is 1;
R1 is fluorine, chlorine or bromine;
R2 is C1-C4alkyl, formyl or acetyl;
R3 is H, C1-C4alkyl, C3-C6cycloalkyl, halo-C1-C2alkyl, halocyclopropylmethyl, C2-C4-alkenyl, -COOR7, -SR2, -R8-OCOR9, -R8-R12 or an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing N
or S, the substituents being selected from the group fluorine and chlorine;
R4 is trifluoromethyl;
R7 is methyl or ethyl;
R8 is CR15R16;
R9 is C1-C4alkyl, halo-C8-C11alkyl, cyclopropyl, vinyl, halo-C8-C11alkenyl, ethynyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of chlorine, methyl, methoxy and -NO2;
R12 is an unsubstituted, unsaturated, five-membered heterocyclic ring containing from one to three hetero atoms selected from the group N and S; and R15 and R16 are each independently of the other H, methyl or phenyl, or, as the case may be, a tautomer thereof.

4. A compound according to claim 1 of formula I, wherein m is 0;
n is 1;
R1 is fluorine, chlorine or bromine;
R2 is C1-C4alkyl, formyl or acetyl;
R3 is H, C1-C4alkyl, C3-C6cycloalkyl, halo-C1-C2alkyl, halocyclopropylmethyl, C2-C4-alkenyl, -COOR7, -SR2, -R8-OCORg, -R8-R12 or an unsubstituted or substituted, unsaturated, five- or six-membered heterocyclic or heterobicyclic ring containing N
or S, the substituents being selected from the group fluorine and chlorine;
R4 is trifluoromethyl;
R7 is methyl or ethyl;
R8 is CH2, C(methyl)2 or CH(phenyl);
R9 is C1-C4alkyl, halo-C8,-C11alkyl, cyclopropyl, vinyl, halo-C8-C11alkenyl, ethynyl or unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of chlorine, methyl, methoxy and -NO2; and R12 is an unsubstituted, unsaturated, five-membered heterocyclic ring containing from one to three hetero atoms selected from the group N and S, or, as the case may be, a tautomer thereof.

5. 4-Chloro-4'-trifluoromethanesulfonyloxybenzophenone-N-formyl-N-methylhydrazone according to claim 1.

6. A process for the preparation of a compound according to claim 1 of formula I or, as the case may be, a tautomer thereof, in each case in free form or in salt form, taking into account the proviso mentioned above, in which process a) a compound of formula (II) which is known or can be prepared analogously to corresponding known compounds and wherein m, n, R1, R2, R4 and R17 are as defined for formula I, or, as the case may be, a tautomer thereof, in free form or in salt form, is reacted with phosgene or thiophosgene, preferably in the presence of a base, and the intermediate, which is optionally isolated, is reacted, if desired in the presence of a base, with a compound of formula Y1H, wherein Y
is -NR5R6, -OR2 or -SR2 and R2, R5 and R6 are as defined for formula I, or with a salt thereof, or b) for the preparation of a compound of formula I wherein X is O, a compound of formula II is reacted, if desired in the presence of a base, with a compound of formula R3COY2, wherein R3 is as defined for formula I with the exception of the meanings -OR2 and -SR2, and Y2 is a leaving group, or c) for the preparation of a compound of formula I wherein X is S, a compound of formula II is reacted with a compound of formula Y3-N=C=S, wherein Y3 is H, C1-C8alkyl, halo-C1-C8alkyl or C2-C5alkenyl, preferably H or C1-C8alkyl, to form compounds of formula I wherein X is S, or d) for the preparation of a compound of formula I wherein X is S and R3 is -SR, wherein R
is C1-C8alkyl, C3-C6cycloalkyl, C2-C8alkenyl or C2-C8alkynyl, preferably C1-C8alkyl or C3-C6cycloalkyl, especially C1-C8alkyl, a compound of formula II is reacted, if desired in the presence of a base, with CS2, and the intermediate, which is optionally isolated, is reacted, if desired in the presence of a base, with a compound of formula RY4, wherein R
is as defined above and Y4 is a leaving group, or e) for the preparation of a compound of formula I wherein X is O, a compound of formula II is reacted, if desired in the presence of a base, with a compound of formula C1R8COY5, wherein R8 is as defined for formula I and Y5 is a leaving group, and the resulting inter-mediate is reacted, if desired in the presence of a base, optionally in the presence of an alkali metal halide, such as in the presence of sodium iodide, with a compound of formula R9COOH, HNR10R11 or R12, wherein R9, R10, R11 and R12 are as defined for formula I, or f) for the preparation of a compound of formula I wherein X is S, a compound of formula (III), which is known or can be prepared analogously to corresponding known compounds, for example in accordance with Variant b), and wherein m, n, R1, R2, R3, R4 and R17 are as defined for formula I, is reacted with P2S5, or g) for the preparation of a compound of formula I wherein X is S and R2 is H, a compound of formula (IV), which is known or can be prepared analogously to corresponding known compounds and wherein m, n, R1, R3, R4 and R17 are as defined for formula I, is reacted, if desired in the presence of a base, with H2S, or h) a compound of formula I wherein R2 is H is reacted, if desired in the presence of a base, with a compound of formula R2Y6, wherein R2 is as defined for formula I with the excep-tion of the meaning H, and Y6 is a leaving group, or i) a compound of formula (V), which is known or can be prepared analogously to corresponding known compounds and wherein m, n, R1, R4 and R17 are as defined for formula I, is reacted, if desired in the presence of an acid catalyst, if desired in the presence of a water-binding agent, with a compound of formula (VI), which is known or can be prepared analogously to corresponding known compounds and wherein R2, R3 and X are as defined for formula I, or with a salt thereof and/or, as the case may be, with a tautomer thereof, and in each case, if desired, a compound of formula I obtainable according to the process or by other means, or a tautomer thereof, in each case in free form or in salt form, is converted into a different compound of formula I or a tautomer thereof, a mixture of isomers obtainable according to the process is separated and the desired isomer is isolated and/or a free compound of formula I obtainable according to the process, or a tautomer thereof, is converted into a salt, or a salt of a compound of formula I or of a tautomer thereof obtainable according to the process is converted into the free compound of formula I or a tautomer thereof or into a different salt.

7. A pesticidal composition which comprises at least one compound according to claim 1 of formula I or, as the case may be, a tautomer thereof, in each case in free form or in the form of an agrochemically acceptable salt, as active ingredient and, where appropriate, at least one adjuvant.

8. A process for the preparation of a composition according to claim 7 comprising at least one adjuvant, which process comprises homogeneously mixing and/or grinding the active ingredient with the adjuvant(s).

9. The use of a compound according to claim 1 of formula I or, as the case may be, a tautomer thereof, in each case in free form or in the form of an agrochemically acceptable salt, in the preparation of a composition according to claim 7.

10. The use of a composition according to claim 7 in the control of pests.

11. The use according to claim 10 in the protection of plant propagation material.

12. A method of controlling pests, which comprises applying to the pests or their habitat a composition according to claim 7.

13. A method according to claim 12 for the protection of plant propagation material, which comprises treating the propagation material or the planting site of the propagation material.

14. Plant propagation material treated in accordance with the method described in claim 13.