SK138396A3 - Perhaloalkoxybenzenophenone hydrazones, their preparation method, pesticides containing them and their use - Google Patents

Abstract

Compounds of formula (I) in which X is (a) or (b), n is 0, 1, 2, 3, 4 or 5, where if n is greater than 1, the radicals R2 are identical or different; o is 0, 1, 2, 3 or 4, where if o is greater than 1, the radicals R3 are identical or different; R1 is perhalo-C1-C4alkoxy; R2 is halogen, C1-C8alkyl, halo-C1-C8alkyl, C1-C8alkoxy, halo-C1-C8alkoxy, C1-C8alkylthio, halo-C1-C8alkylthio, C1-C8alkylsulfynyl, halo-C1-C8alkylsulfynyl, C1-C8alkylsulfonyl, halo-C1-C8alkylsulfonyl, CN or phenyl; R3 is halogen, C1-C8alkyl, halo-C1-C8alkyl or halo-C1-C8alkoxy; R4 is H, halogen, C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkoxy, C1-C8alkoxy-C1-C8alkyl, C1-C8alkoxy-C1-C8alkoxy, C1-C8alkylthio or NR8R9; R5 is C1-C8alkyl, NR10R11, OR20, SR20 or SO2R20; R6 is H, C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkenyl, C1-C8alkynyl, C1-C8acyl or phenyl; R7 is H, an unsubstituted or substituted C1-C8alkyl, C3-C6cycloakyl, C3-C6cycloalkyl-C1-C8alkyl, C1-C8alkenyl, C1-C8alkynyl, C3-C6cycloalkenyl, C3-C6cycloalkenyl-C1-C8alkyl or C3-C6cycloalkyl-C1-C8alkenyl group, it being possible for the substituents to be selected from the group consisting of halogen, C1-C8alkyl, halo-C1-C8alkyl, C1-C8alkoxy, halo-C1-C8alkoxy, C1-C8alkyl-S(O)p, it being possible for p to be 0, 1 or 2, C1-C8alkoxycarbonyl, di(C1-C8alkyl)amino and C1-C8alkanoyloxy; an unsubstituted or substituted phenyl or heteroaryl group, it being possible for the substituents to be selected from the group consisting of C1-C6alkyl and halogen; C1-C8alkoxy, NR16R17, COOR6 or SR6; R8 and R9 independently of one another are H, C1-C8alkyl or OH; R10 is H, C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, halo-C1-C8alkoxy-C1-C8alkyl, phenyl, OR12, S(O)mR13, m being 0, 1 or 2, or NR14R15; R11 is H, C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkoxy-C1-C8alkyl, allyl, C1-C8alkylallyl, haloallyl or propargyl; R12 is H, C1-C8alkyl, halo-C1-C8alkyl, C1-C8alkoxy-C1-C8alkyl, C3-C6cycloalkyl, C2-C8alkenyl, halo-C2-C8alkenyl or propargyl; R13 is H, C1-C8alkyl, halogen-C1-C8alkyl, phenyl or NR14R15; R14 and R15 independently of one another are H, C1-C8alkyl, halo-C1-C8alkyl, phenyl, C1-C8alkylamido, di(C1-C8alkyl)amido or NH2; R16 and R17 independently of one another are H, C1-C8alkyl, halo-C1-C8alkyl, C2-C8alkenyl, C1-C8alkoxy or NH2; R18 is S(O)mR19, m being 0, 1 or 2, NO2 or CN; R19 is C1-C8alkyl, halo-C1-C8alkyl, C3-C6cycloalkyl, phenyl, benzyl or NR14R15; R20 is C1-C8alkyl, halo-C1-C8alkyl or C3-C6cycloalkyl; Y is O, S, NR18 or CHC(O)R21; and R21 is H, C1-C8alkyl, halo-C1-C8alkyl, C1-C8alkoxy or phenyl, and if appropriate, E/Z isomers and tautomers thereof, in each case in free form or in salt form, can be used as agrochemical active ingredients and may be prepared in a manner known per se.

Description

Perhaloalkoxybenzophenone hydrazones, process for their preparation, pesticidal compositions containing them and their use

Technical field

The present invention relates to novel perhalogenkoxybenzophenone hydrazones, their E / Z isomers and tautomers, in free or salt form, to a process for the preparation and use of these compounds and tautomers, pesticides, the active ingredients of which are those compounds and tautomers, in free form or in the form of an agrochemically usable salt, and a process for the preparation and use of these compositions.

BACKGROUND OF THE INVENTION

Some hydrazone derivatives have been suggested in the literature as insecticidally active ingredients in pesticides. However, the biological properties of these known compounds are not entirely satisfactory in the field of pest control, and it is therefore necessary to find other compounds with pesticidal properties, in particular for insect control. This object was achieved by finding the compounds of the formula I according to the invention.

SUMMARY OF THE INVENTION

Accordingly, the invention provides a compound of formula I (R ²⁾

N

R ¹ (I)

(R) o in which

F.

X is a group of formula or

r.

n is 0, 1, 2, 3, 4 or 5, and when n is greater than 1, the radicals R ^{2 are the} same or different, o is 0, 1, 2, 3 or 4, wherein v when o is greater than 1, the radicals R ^{3 are the} same or different,

I

R ¹ is C 1 -C 4 perhaloalkoxy,

R ² is halogen, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 alkoxy, C 1 -C 8 haloalkoxy, C 1 -C 8 alkylthio, haloalkylthio (C 1 -C 8) alkyl, (C 1 -C 8) alkylsulfinyl, (C 1 -C 8) haloalkylsulfinyl, (C 1 -C 8) alkylsulfonyl, (C 1 -C 8) haloalkylsulfonyl, cyano or phenyl group,

R ³ represents a hydrogen atom, alkyl group having up to 8 carbon atoms, haloalkyl of 1 to 8 carbon atoms or C 1 -C 8 alkyl,

R ⁴ represents a hydrogen atom, a halogen atom, a C 1 -C 8 alkyl group, a C 3 -C 6 cycloalkyl group, a C 1 -C 8 haloalkyl group, a C 1 -C 8 alkoxy group, a C 1 -C 8 alkoxyalkyl group carbon atoms in the alkoxy moiety and 1 to 8 carbon atoms in the alkyl moiety, alkoxyalkoxy of 1 to 8 carbon atoms in each alkoxy moiety, alkylthio of 1 to 8 carbon atoms, or NR ^and R ⁹ ,

^R is alkyl of 1 to 8 carbon atoms, NR ⁱ R ^{1o: l, 2} 0R ° or ² ° SR or SO ² R ² ',

R ^p is H, alkyl of 1 to 8 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, haloalkyl of 1 to 8 carbon atoms, alkenyl of 1-8 carbon atoms, alkynyl of 1-8 carbon atoms , C 1 -C 8 acyl or phenyl

R ⁷ represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkylalkyl group having 3 to 6 carbon atoms in the cycloalkyl portion and 1 to 8 carbon atoms in the alkyl portion, alkenyl group (C 1 -C 8) alkynyl, (C 1 -C 8) alkynyl, (C 3 -C 6) cycloalkenyl, (C 3 -C 6) cycloalkenyl (C 1 -C 8) cycloalkenyl or C 3 -C 3 cycloalkylalkenyl The substituents may be selected from the group consisting of halogen atoms, (C 1 -C 8) alkyl groups, (C 1 -C 8) haloalkyl, (C 1 -C 8) alkoxy groups. C-C,, C,-C halhaloalkoxy, alkyl-S (O) ^p groups C 1 -C 8, wherein p may be 0, 1 or 2, C 1 -C 8 alkoxycarbonyl in the alkoxy moiety, C 1 -C 8 dialkylamino in each alkyl moiety, and C 1 -C 8 alkanoyloxy groups or unsubstituted or substituted phenyl or heteroaryl, wherein the substituents may be selected from the group consisting of alkyl of 1 to 6 carbon atoms and halogen atoms, or alkoxy of 1 to 8 carbon atoms, NR ¹⁶ R ¹⁷ , COOR ⁶ or SR ^6, the symbols ^R and R ³ independently of one another are hydrogen, alkyl having 1 to 8 carbon atoms or hydroxyl,

R ¹⁰ represents a hydrogen atom, a C 1 -C 8 alkyl group, a C 3 -C 6 cycloalkyl group, a C 1 -C 8 haloalkyl group, a C 1 -C 8 haloalkoxyalkyl group and a C 1 -C 8 carbon atom; in the alkyl moiety, a phenyl group, an OR ¹² group, S (O) ^m R ¹³ , wherein m is 0, 1 or 2, or NR ¹⁴ R ¹⁵ ,

R ¹¹ is H, alkyl of 1 to 8 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, haloalkyl of 1 to 8 carbon atoms, alkoxyalkyl of 1 to 8 carbon atoms in the alkoxy part and 1 to 8 carbon atoms in the alkyl moiety, an allyl group, an alkyl moiety having 1 to 8 carbon atoms in the alkyl moiety, a haloallyl group or a propargyl group,

R ¹² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 1 to 8 carbon atoms in the alkoxy moiety and 1 to 8 carbon atoms in the alkyl moiety, a cycloalkyl group having 3 (C 6 -C 6), (C 2 -C 8) alkenyl, (C 2 -C 8) haloalkenyl, or propargyl;

R ¹³ represents a hydrogen atom, a C 1 -C 8 alkyl group, a C 1 -C 8 haloalkyl group, a phenyl group or a NR ^{X 4} R ^{XS group} , R ¹⁴ and R ^x are each independently hydrogen, alkyl with C 1 -C 8 haloalkyl, C 1 -C 8 haloalkyl, phenyl, C 1 -C 8 alkylamido, C 1 -C 8 dialkylamido or amino, R ^xe and R ¹⁷ independently are each hydrogen, C1-C8alkyl, C1-C8haloalkyl, C2-C8alkenyl, C1-C8alkoxy or amino,

R ^xs is S (O) ^m R ¹⁹ , wherein m is 0, 1 or 2, nitro or cyano,

R ¹⁹ represents an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a benzyl group or an NR ^X4 R ^{XS group} ,

R ² is C 1 -C 8 alkyl, C 1 -C 8 haloalkyl or C 3 -C 6 cycloalkyl,

Y represents an oxygen atom, a sulfur atom, an NR ¹ ® group, or

CHC (O) R ^2X , a

R ^2X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a phenyl group, provided that in compounds of formula I in which X represents -N = C (R ⁴⁾ R ^p, R ¹ represents

_OCF3, o is 0, n is 1, R ⁴ is methyl and ^R is -N _{(CH3) OCH3,} ^R2 is not F or Cl, and the E / Z-isomers and tautomers , in free or salt form.

The compounds of formula I may exist as E / Z isomers, for example in the following two isomeric forms.

Accordingly, it will be appreciated that the term " compounds of formula I " hereinafter, where appropriate, means the respective E / Z-isomers, although these are not specifically mentioned in each case.

Some of the compounds of formula (I) may exist as tautomers, for example when R ⁶ is hydrogen, the corresponding compounds of formula (I) may be corresponding to those in which X is -N (H) -C (R ⁷ ) = Y, in equilibrium with the corresponding tautomers containing the moiety -N = C (R ⁷ ) -YH. Accordingly, it is to be understood that the term " compounds of formula I " where appropriate means corresponding tautomers, although these tautomers are not specifically mentioned in each case.

The compounds of the formula I and optionally their E / Z-isomers and tautomers may exist in the form of salts. Compounds of formula I having at least one basic center can, for example, form acid addition salts. These acid addition salts are formed, for example, with strong inorganic acids, such as mineral acids, for example sulfuric, acid, phosphoric or hydrohalic acids, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halosubstituted, alkanecarboxylic acids with 1 to 4 carbon atoms in the alkane moiety, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic acid, malonic acid, maleic acid, fumaric or phthalic acid, hydroxycarboxylic acids, e.g. ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid , or such as benzoic acid, or with organic sulfonic acids such as unsubstituted or substituted, for example, halo-substituted, C 1 -C 4 alkanesulfonic acids or arylsulfonic acids, for example methane- or p-toluenesulfonic acid. Compounds of formula I containing at least one acidic group may further form salts with bases. Examples of suitable base salts include metal salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or organic amines such as morpholine, piperidine, pyrrolidine, mono- , di- or tri (lower alkylamines), for example ethyl, diethyl, triethyl or dimethylpropylamine, or mono-, di- or trihydroxy (lower) alkylamines, for example mono-, di- or triethanolamine. internal salts Agrochemically preferred salts are preferred within the scope of the invention However, salts which are disadvantageous for agrochemical purposes, for example salts toxic to bees or fish, and which are used, for example, to isolate or purify the free compounds of formula I or their agrochemically usable salts are also included in the invention because of the close relationship between the compounds The compounds of formula (I) in free form and salts thereof, as used hereinabove and below, with the compounds of formula (I) in free form, or salts thereof, where appropriate, likewise also mean corresponding salts or compounds of formula (I) in free form. The same applies correspondingly also to the E / 2-isomers and tautomers of the compounds of the formula I and their salts.

Unless otherwise stated, the general terms used hereinbefore and hereinafter have the following meanings.

Halogen - as such and as a structural element of other groups and compounds, such as haloalkyl, haloalkoxy, haloalkoxyalkyl and haloalkenyl groups - is a fluorine, chlorine, bromine or iodine atom, in particular fluorine, chlorine or bromine.

Unless otherwise defined, the carbon groups and compounds in each case contain at least 1 but at most 8 carbon atoms, preferably at least 1 but at most 4 carbon atoms, in particular 1 or 2 carbon atoms.

C 3 -C 6 cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkyl - as such and as a structural element of other groups and compounds, such as haloalkyl, alkoxy, alkoxyalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl - is, in any case, taking into account the number of carbon atoms present in each individual case in a particular group or compound, either a straight chain group, i a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group, or a branched group such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isooctyl.

Halo-substituted carbon groups and compounds such as haloalkyl, haloalkoxy or haloalkenyl groups may be partially halogenated or perhalogenated, wherein the halogen atoms as substituents may be the same or different in the case of polyhalogenations. Examples of haloalkyl groups - as such and as structural elements of other groups and compounds such as halocycloalkylalkyl and haloalkenyl groups - include a methyl group which is mono- to trisubstituted by fluorine, chlorine and / or bromine, such as CHF ₂ or CF ₃ , an ethyl group that is mono- to pentasubstituted with fluorine, chlorine and / or bromine, such as CH ₂ CF ₃ , CF ₂ CF ₃ , CF ₂ CCl ₃ , CF ₂ CHCl ₂ , CF CHF, CF CFC 1, CF CHBr, CF CHClF, CF CHBrF or CClFCHClF, a propyl or isopropyl group which is mono- to heptasubstituted with fluorine, chlorine and / or bromine, such as CH CHBrCH Br, CF CHFCF, CH CF CF 4 or CH (CF), and butyl or one of its isomers, mono- to nonasubstituted with fluorine, chlorine and / or bromine, such as CF (CF) CHFCF or CH (CF) CF.

The acyl group may be a formyl, acetyl propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl, heptanoyl or octanoyl group, an aroyl group, for example benzoyl group, or a heteroaroyl group, for example thienoyl group.

Examples of heteroaryl radicals include thienyl, pyryl, imidazolyl, pyrazolyl, triazolyl, thiazolyl, isothiazolyl, pyridyl, indolyl, benzo [b] thienyl and benzo [b] furyl groups.

Taking into account the above condition, preferred embodiments are within the scope of the invention:

(1) compounds of the formula I in which n has a value of 0, 1, 2, 3 or 4, preferably 1, 2 or 3, in particular 1 or 2, especially 1, where n is greater than 1, the radicals R ^and the same or different, or, where applicable, their E / Z isomers or tautomers thereof, (2) a compound of formula I in which p = 0, 1, 2 or 3, preferably 0, 1 or 2, in particular 0 or 1, in particular 0, where in the case of p having a value greater than 1, the radicals R ^{3 are the} same or different or, where appropriate, their E / Z isomers or tautomers, (3) compounds of the formula I in which R ¹ is C 1 -C 3 perhaloalkoxy, preferably C 1 -C 2 perhaloalkoxy, in particular perhalomethoxy, or, where appropriate, their E / Z isomers or tautomers (4) compounds of formula I wherein R ² is halo, alkyl (C 1 -C 6), (C 1 -C 6) haloalkyl, (C 1 -C 6) alkoxy or (C 1 -C 6) haloalkoxy, preferably halogen, (C 1 -C 4) -alkyl, (C 1 -C 4) -alkyl; C 1 -C 4 or C 1 -C 4 haloalkoxy, in particular halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or C 1 -C 2 haloalkoxy, in particular halogen, methyl , a halomethyl or halomethoxy group or, where appropriate, their E / Z isomers or tautomers, (5) compounds of the formula I in which R ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 atoms C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy, preferably hydrogen a, halogen, C 1 -C 2 alkyl or C 1 -C 2 haloalkyl, in particular hydrogen, halogen or methyl, in particular hydrogen, chlorine or fluorine, or where appropriate, their E / Z-isomers or tautomers, (6) compounds of the formula I in which R ⁴ represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group, a C 3 -C 6 cycloalkyl group, a C 1 haloalkyl group (C 1 -C 4) alkoxy, (C 1 -C 4) alkoxy, (C 1 -C 4) alkoxyalkyl (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkoxy, (C 1 -C 4) alkylthio group C 4 -C ⁸ or NR ⁸ R ⁹ , preferably a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a C 3 -C 6 cycloalkyl group C 1 -C 2 -halogenoalkyl or C 1 -C 2 -alkoxy, in particular hydrogen or C 1 -C 4 -alkyl, or, where appropriate, their E / Z-isomers or tautomers, (7) a compound of formula I, wherein ^R is alkyl of 1 to 4 carbon atoms, NR ^{1 O R1: L,} oR ² ', SR ² ° or SO ₂ R ² °, preferably NR ^{1 O R1 L} and 0R ^{of O,} in particular NR ^{1 O} R ¹³ ·, or, where applicable, their E / Z isomers or tautomers thereof, (8) a compound of formula I, wherein R ⁶ is H, alkyl (C 1 -C 6) cycloalkyl, (C 3 -C 6) cycloalkyl, (C 1 -C 6) alkenyl, (C 1 -C 6) alkynyl or (C 1 -C 6) acyl, preferably hydrogen, (C 1 -C 6) alkyl C 1 -C 4 -cycloalkyl having 3 to 6 carbon atoms (9) a compound of formula (I), or, where appropriate, their E / Z isomers or tautomers; wherein R ⁷ represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkylalkyl group having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alkyl moiety , (C1-C6) alkenyl or (C1-C6) alkynyl, the substituents of which may be selected from halogen atoms, (C1-C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy groups. C 1 -C 4 halogen, C 1 -C 4 haloalkoxy, C 1 -C 4 alkyl-S (O) 2 groups, wherein p may have 1 to 4 carbon atoms; 0, 1 or 2, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 dialkylamino and C 1 -C 4 alkanoyloxy, or phenyl or heteroaryl, unsubstituted or mono- or mono- or polysubstituted with substituents selected from the group consisting of C 1 -C 4 alkyl and halogen atoms, or C 1 -C 4 alkoxy, NR ¹⁶ R ¹⁷ , COOR ⁶ or SR ⁶ , preferably hydrogen, unsubstituted or substituted C 1-6 alkyl C 1 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl, wherein the substituents may be selected from halogen atoms, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy groups. , (C1 -C2) haloalkoxy, (C1 -C2) alkyl-S (O) - and t carbon atoms, wherein p may be 0, 1 or 2, C 1 -C 2 alkoxycarbonyl, C 1 -C 2 dialkylamino and C 1 -C 2 alkanoyloxy, or phenyl or heteroaryl , unsubstituted or mono- or bi polysubstituted by substituents selected from alkyl groups having 1 to 2 carbon atoms and halogen atoms, or C 1 -C 2, NR ¹⁶ R ^{1 '7} or SR ^6, especially hydrogen, unsubstituted or substituted (C 1 -C 6) alkyl or (C 3 -C 6) cycloalkyl, wherein the substituents may be selected from halogen atoms, (C 1 -C 2) alkyl and (C 1 -C 2) alkoxy, or phenyl or phenyl; heteroaryl, unsubstituted or substituted by halogen, or alkoxys purchased with 1 to 2 carbon atoms, NR ^xe R ^{x '7} or SR ^e, in particular alkyl of 1 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, or phenyl or heteroaryl, unsubstituted or substituted by halogen, or C 1 -C 2, or NR ^{X 6} R ^X7, or, where applicable, their E / Z isomers or tautomers thereof, (10) a compound of formula I, wherein ^R is H or alkyl of 1 up to 6 carbon atoms, preferably a hydrogen atom or a C1-C4 alkyl group, in particular a hydrogen atom or a methyl group, or, where appropriate, their E / Z isomers or tautomers, (11) a compound of the formula I in which R @ 6 represents a hydrogen atom or a C1 -C6 alkyl group, preferably a hydrogen atom or a C1 -C4 alkyl group, in particular a hydrogen atom or a methyl group (12) compounds of the formula I in which R ¹⁰ represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 3 -C 3 cycloalkyl group, or, where appropriate, their E / Z isomers or tautomers; 6 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms, phenyl, oR ^12, s (0) R ^13, wherein m is 0 or 2, or a group m

NR ^X4 R ^XS , preferably hydrogen, C 1 -C 2 alkyl, phenyl or OR ^{X 2} , in particular hydrogen, C 1 -C 2 alkyl or OR ¹² , or where appropriate , their E / Z-isomers or tautomers, (13) compounds of formula I in which R ^xx represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 3 -C 6 cycloalkyl group, a C 1 -C 4 haloalkyl group C1 -C4 alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms. alkyl, allyl, C 1 -C 4 alkylallyl, haloallyl or propargyl, preferably hydrogen, C 1 -C 2 alkyl, C 3 -C 6 cycloalkyl, allyl or alkylallyl (C 1 -C 4) -alkyl, in particular hydrogen or C 1 -C 2 -alkyl or, where appropriate, their E / Z-isomers or tautomers, (14) compounds of formula (I), wherein R ¹² represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 haloalkyl group, a C 1 -C 4 alkoxyalkyl group and a C 1 -C 4 alkyl group, a cycloalkyl group containing from 1 to 4 carbon atoms; C 3 -C 6 alkenyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl or propargyl a radical of hydrogen, C1 -C4 alkyl, C3 -C6 cycloalkyl, C2 -C4 alkenyl or propargyl, especially hydrogen, C1 -C2 alkyl or cycloalkyl; a group having from 3 to 6 carbon atoms or, where appropriate, their E / Z-isomers or tautomers, (15) compounds of the formula I in which R ³ - ³ represents a hydrogen atom, an alkyl group having from 1 to 4 C 1 -C 4 haloalkyl, phenyl or NR ^{X 4} R ^{1 S} , preferably C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or phenyl, in particular C 1 -C 2 alkyl. (16) compounds of the general formula I, in which the carbon atoms or haloalkyl group having 1 to 2 carbon atoms or, where appropriate, their E / Z isomers or tautomers; R ¹⁴ is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, phenyl, C 1 -C 8 alkylamido, C 1 -C 4 dialkylamido in each alkyl moiety or an amino group, preferably a hydrogen atom, a C1 -C2 alkyl group or a phenyl group, in particular a C1 -C2 alkyl group or a phenyl group or, where appropriate, their E / Z isomers or tautomers, ( (17) compounds of the formula I in which R @ 1 ^S represents a hydrogen atom, a C1 -C4 alkyl group, a C1 -C4 haloalkyl group, a phenyl group, a C1 -C8 alkylamido group, an alkyl radical having 1 to 8 carbon atoms; up to 4 carbon atoms in each alkyl moiety or amino group, preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms or a phenyl group ECS group, especially alkyl having 1 to 2 carbon atoms or phenyl, or, where applicable, their E / Z isomers or tautomers thereof, (18) a compound of formula I in which R ^s is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 8 alkoxy, preferably hydrogen or C 1 -C 4 alkyl, in particular C 1 -C 2 alkyl, or where appropriate, their E / Z-isomers or tautomers, (19) compounds of the formula I in which R ^1-7 represents a hydrogen atom, a C 1 -C 4 alkyl group, a halo16-C 1 -C 4 alkyl group Or (C 1 -C 8) alkoxy, preferably hydrogen or C 1 -C 4 alkyl, in particular C 1 -C 2 alkyl, or, where appropriate, their E / Z isomers or tautomers thereof, (20) a compound of formula I, wherein R ¹ ® is SO ^ R ^19, nitro or cyano, preferably SO ^ R ¹⁹ or, where applicable, their E / Zisomers or tautomers, (21) compounds of formula I wherein R ¹⁹ is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, phenyl, benzyl or NR ¹⁴ R ^{1 s,} preferably C1-C2 alkyl, phenyl, benzyl or NR ¹⁴ R ^{1 s,} in particular alkyl of 1 to 2 carbon atoms or benzyl, or, where appropriate, their E / Z-isomers or tautomers, (22) compounds of the general formula I in which R ² ° represents a C 1 -C 4 alkyl group, a C 1 -C 4 haloalkyl group or a cycloalkyl group a C 3 -C 6 alkyl group, preferably a C 1 -C 2 alkyl group or a C 3 -C 6 cycloalkyl group, in particular a C 1 -C 2 alkyl group or, where appropriate, an E / Z thereof - isomers or tautomers, (23) compounds of the formula I in which Y represents an oxygen atom, a sulfur atom, an NR ¹ ® group, preferably an oxygen atom or an NR ¹ ® group, in particular an oxygen atom, or where appropriate, their E / Z-isomers or tautomers, (24) compounds of formula I wherein R ^2X is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy , preferably C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or C 1 -C 2 alkoxy, in particular methyl, trifluoromethyl, methoxy or ethoxy, and or, where appropriate, their E / Z isomers or tautomers, (25) compounds of the formula I in which 1 has a greater workshop value, or 3, where n has 1 as the radicals R @ ^{2 are} identical or, in the case where o is equal to or greater than 3, the radicals R @ ^x have a value of 0, 1 or 2, and greater than 1, the radicals R @ ³ are 1-perhalogenoalkoxy;

R ² is halogen, alkyl having 1 to 6 carbon atoms, halo-C 1 -C 6 alkyl or C 1 -C 6 alkyl,

R ³ is H, halogen, alkyl having 1 to 2 carbon atoms or haloalkyl having 1 to 2 carbon atoms,

R ⁴ represents a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a C 3 -C 6 cycloalkyl group, a C 1 -C 2 haloalkyl group or a C 1 -C 2 alkoxy group,

^R is alkyl of 1 to 4 carbon atoms, NR R ^{XO XX,} 0R ² °, ² °, or SR So_Re ² °,

R ⁶ represents a hydrogen atom, a C 1-6 alkyl group, a C 3-6 cycloalkyl group, a C 1-6 alkenyl group, a C 1-6 alkynyl group or a C 1-6 acyl group .

R ⁷ represents a hydrogen atom, an unsubstituted or substituted C 1 -C 6 alkyl group or a C 3 -C 6 cycloalkyl group, which substituents may be selected from halogen atoms, C 1 -C 2 alkyl groups, haloalkyl groups having from 1 to 6 carbon atoms; C 1 -C 2 alkoxy, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkyl-S (O) 2, where p may be 0, 1 or 2, alkoxycarbonyl C 1 -C 2 alkoxy, C 1 -C 2 dialkylamino and C 1 -C 2 alkanoyloxy, or phenyl or heteroaryl, unsubstituted or mono- or polysubstituted with substituents selected from C 1 alkyl groups up to 2 carbon atoms and halogen atoms or an alkoxy group having 1 to 2 carbon atoms; NR ^X ® R ^X ' ⁷ or SR ®

R ¹⁰ represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 3 -C 6 cycloalkyl group, a C 1 -C 4 haloalkyl group, a phenyl group, an OR ¹² group, SiO 4 R ¹³ with m being 0 or 2, or NR ¹⁴ R ^xs ,

R ^xx represents hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 4 alkoxyalkyl an alkyl moiety, an allyl group, a (C 1 -C 4) alkylallyl group, a haloallyl group or a propargyl group,

R ¹² represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 haloalkyl group, a C 1 -C 4 alkoxyalkyl group and a C 1 -C 4 alkyl group, a C 3 -C 4 cycloalkyl group (C 6 -C 6), (C 2 -C 4) alkenyl, (C 2 -C 4) haloalkenyl, or propargyl;

R ^{X 3} is a hydrogen atom, alkyl group having up to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, phenyl or NR ^{X 4} R ^X; R ⁴ and R ^X are each independently hydrogen, alkyl of 1 C 1 -C 4 haloalkyl, C 1 -C 4 haloalkyl, phenyl, C 1 -C 8 alkylamido, C 1 -C 4 dialkylamido in each alkyl moiety or amino, R ^x S and R ¹⁷ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 8 carbon atoms,

R ^X is SO ^ R ^19, nitro or cyano,

R ¹⁹ represents a C 1 -C 2 alkyl, phenyl, benzyl or NR ^{X 4} R ^{XS group} ,

R ² represents C 1 -C 2 alkyl or C 3 -C 6 cycloalkyl, and

Y represents an oxygen atom, a sulfur atom or an NR ^xe group or, where appropriate, their E / Z isomers or tautomers, (26) compounds of the formula I in which n is 1 or 2, where in the case of that n has a value greater than 1, the radicals R ^{2 are the} same or different, o being 0 or 1,

^R1 is perhaloalkoxy C 1 -C 2,

R ² is halogen, C1 -C4 alkyl, halo-C 1 -C 4 alkyl or C 1 -C 4 alkyl,

R ³ is H, halogen or methyl,

R ⁴ represents a hydrogen atom or a C 1 -C 4 alkyl group,

^R is alkyl of 1 to 4 carbon atoms, NR ¹¹ R ^{1 O,} OR ² ', SR ² ° or SO ₂ R ^2',

R ⁶ represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 3 -C 6 cycloalkyl group or a C 1 -C 6 acyl group,

R ⁷ represents a hydrogen atom, a C 1 -C 6 alkyl group, a C 3 -C 6 cycloalkyl group, an unsubstituted or substituted phenyl or heteroaryl group, wherein the substituents may be selected from halogen atoms, C 1 -C 2 alkyl groups carbon and C 1 -C 2 alkoxy or C 1 -C 2 alkoxy or NR ^{x e} R ¹⁷ ,

R ¹⁰ represents a hydrogen atom, a C 1 -C 2 alkyl group, a phenyl group or an OR ¹² group,

R ¹¹ represents a hydrogen atom, a C 1 -C 2 alkyl group, a C 3 -C 6 cycloalkyl group, an allyl group or a C 1 -C 4 alkylallyl group in the alkyl moiety,

R ¹² is H, alkyl of 1 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkenyl of 2 to 4 carbon atoms, or propargyl; R ^1G and R ¹⁷ are each independently hydrogen or (C 1 -C 4) -alkyl;

^{1 S} R is SO ₂ R ^19, nitro or cyano,

R ( ¹⁹⁾ is alkyl having 1 to 2 carbon atoms or benzyl;

R ² represents C 1 -C 2 alkyl or C 3 -C 6 cycloalkyl, and

Y represents an oxygen atom, a sulfur atom or an NR ¹ ® group or, where appropriate, their E / Z isomers or tautomers, (27) compounds of the formula I in which n is 1, o is 0 or 1,

R ¹ is perhalomethoxy,

R ² is halogen, C1 -C2 alkyl, halo-C 1 -C 2 or C 1 -C 2,

R ³ is H, Cl or F,

R ⁴ represents a hydrogen atom or a C 1 -C 4 alkyl group,

R ⁵ is NR ¹⁰ R ^{11: L} or OR ² °,

R ⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,

R ⁷ is H, alkyl group having up to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, phenyl, unsubstituted or halo-heteroaryl, C 1 -C 2 or a group NR ^s R ^17,

R ¹⁰ and R ^{1 are} each independently hydrogen, C 1 -C 2 alkyl, or OR ¹² ,

R ¹² is hydrogen, C 1 -C 2 alkyl or C 3 -C 6 cycloalkyl, R ¹⁶ and R ¹⁷ are each independently C 1 -C 2 alkyl,

R ^1S represents a group SO_R ¹⁹ ,

R ( ¹⁹⁾ is alkyl having 1 to 2 carbon atoms or benzyl;

R ²⁰ represents an alkyl group having 1 to 2 carbon atoms and

Y represents an oxygen atom or a NR ^XS group, or, where appropriate, their E / Z isomers or tautomers, (28) compounds of the formula I in which n is 1, o is 0 or 1,

R ¹ is perhalomethoxy,

R ² is halogen, methyl, halomethyl or halogénmetoxyskupinu.

R ³ is H, Cl or F,

R ⁴ represents a hydrogen atom or a C 1 -C 4 alkyl group,

^R is NR R ^{XO XX,}

R ⁶ represents a hydrogen atom or a C 1 -C 4 alkyl group,

R ⁷ is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, phenyl, unsubstituted or halo-substituted heteroaryl, C 1 -C 2 alkoxy or NR ^xe R ^{X 7} , R ^xo and R ^{xx are} each independently hydrogen, C 1 -C 2 alkyl or OR ¹² ,

R ^@ 2 is hydrogen, C1 -C2 alkyl or C3 -C6 cycloalkyl, R @ ¹⁶ and R @ ⁷ are each independently C1 -C2 alkyl,

R ^x5 represents SO _and R ^X9 ,

R ( ¹⁹⁾ is alkyl having 1 to 2 carbon atoms or benzyl;

R ²⁰ represents an alkyl group having 1 to 2 carbon atoms and

Y represents an oxygen atom or an NR ^XS group or, where appropriate, their E / Z-isomers or tautomers.

Particularly preferred compounds of formula I within the scope of the invention are those listed in Tables 1, 2 and 3, and particularly preferred compounds are those of Examples H3, H5 to H7 and H10 and, where applicable, their E / Zizomers or tautomers.

Especially preferred compounds within the scope of the invention are 4-chloro-4'-trifluoromethoxybenzophenone-N-cyclopropylcarbonylhydrazone and its E / Z-isomers (compound 1.5 in Table 1).

The invention furthermore relates to a process for the preparation of the compounds of the formula I and, where appropriate, to their E / isomers and tautomers, taking into account the aforementioned condition, always in free form or in the form of a salt, in which, for example,

(a) for the preparation of a compound of formula I in which:

Y is O, a compound of formula II

Ιβ

R is known or can be prepared in analogy to the corresponding known compounds and in which n, o, R ¹ , R ³ , R ³ and R ^{e have the} meanings defined in the case of the general formula I or, where appropriate, , its E / Z isomer or tautomer, in free form or in salt form, is reacted with a compound of formula R ⁷ COX ^X , wherein X ¹ is a leaving group, preferably a halogen atom, especially chlorine, and R ⁷ is as defined in in the case of formula I, preferably in the presence of a base;

b) for the preparation of a compound of the formula I in which Y represents an oxygen atom or a sulfur atom, a compound of the formula III

which is known or which can be prepared analogously to corresponding known compounds and in which A n, a, R ^1, R ² and R ³ are as defined for formula I, with a compound of formula IV

Y //

H ₂ N (IV) which is known or can be prepared analogously to the corresponding known compounds, in which Y represents an oxygen atom or a sulfur atom and the symbols R ® and R ⁷ have the meanings defined for formula I, in free form or in in the form of a salt, preferably in the presence of an acid;

c) for the preparation of a compound of the formula I in which Y represents a sulfur atom, a compound of the formula I in which Y represents an oxygen atom and preferably R ⁶ represents an alkyl group having 1 to 8 carbon atoms, reacted with phosphorus pentasulphide or

d) for the preparation of a compound of the formula I in which Y is a sulfur atom and R @ 6 is a hydrogen atom, a compound of the formula V

which is known or which can be prepared analogously to the corresponding known compounds and in which n, g, R ¹ , R ³ , R ³ and R ^{7 have the} meanings defined in the case of formula I or, where appropriate, the E / Z-isomer thereof, in free or salt form, is reacted with sulfane (H ₂ S), preferably in the presence of a base, or

e) reacting a compound of formula I in which R ⁶ is a hydrogen atom with a compound of formula R ^S X ² in which X ² is a leaving group such as halogen, trifluoromethylsulfonyl, toluenesulfonyl or benzenesulfonyl, preferably halogen , where appropriate in the presence of a base, or

f) for the preparation of a compound of formula I wherein Y is NR ¹ ®, the compound of formula II is reacted with a compound of formula VI

X 3 \ ₌ N (VI) _R / O ⁸ which is known or which can be prepared analogously to corresponding known compounds and in which R ⁷ and R ¹ ® as defined for formula I and X ³ is a leaving group , for example, a halogen atom or a (C 1 -C 4) alkoxy group, preferably an ethoxy group or, where appropriate, its E / Z-isomer, in free or salt form, preferably in the presence of a base or an acid, or

g) for the preparation of a compound of the formula I in which:

^R is a group NR ¹³ R ^XO -, the compound of formula II, wherein R ⁶ is H, with a compound of formula VII

OR

R ° J- (VII) / 11

R · ^R which is known or which can be prepared analogously to corresponding known compounds and in which R ^4, R ¹⁰ and R ¹¹ are as defined for formula I and R is alkyl of 1 to 4 carbon atoms, or

h) for the preparation of a compound of the general formula R ⁵ represents a group NR ^XO R ^XX , a compound of the formula I in which the general formula

(VIII) analogous to the zodpoktorá is known or which can be prepared sponding known compounds, for example reaction of a compound of formula I in which Y is oxygen and ^R is hydrogen, with phosphorus pentachloride, and in which the symbols n, o, R ^x , R ² , R ³ and R ⁴ as defined in formula I or, where appropriate, its E / Z isomer, in free form or in salt form, is reacted with a compound of formula NHR ^XO R ^XX , preferably in the presence of a base, and in each of these cases, if desired, a compound of formula I or a tautomer thereof obtainable by this process or otherwise, in free or salt form, is each another compound of formula (I) or an E / Z isomer or tautomer thereof, a mixture of isomers obtainable according to this process is resolved and the desired isomer is isolated or / and converting a compound of formula I or a tautomer or E / Z-isomer thereof in free form obtainable according to this process into a salt or a salt of a compound of formula I or a tautomer or E / Z-isomer thereof which can be obtained according to this process, converted to the free compound of formula I or a tautomer or E / Z-isomer thereof, or another salt thereof.

The invention furthermore relates to a process for the preparation of the compounds of the formula II, in each case in free form or in salt form, for example by (IX)

i) a compound of formula IX

which is known or which can be prepared analogously to corresponding known compounds and in which the symbol R ¹ is as defined for formula I, and X ⁴ is a halogen, preferably chlorine, is reacted with benzene which is mono- or polysubstituted by R ² , as defined in the case of formula (I), under conventional Friedel-Crafts reaction conditions, or

j) a compound of formula X

R ¹ ·

(X) which is known or which can be prepared in analogy to the corresponding known compounds, in which R ^{@ 1 is} as defined in formula I, is reacted with a phenylmagnesium halide which is mono- or polysubstituted by R @ ² as defined in in the case of formula I, preferably phenylmagnesium bromide, under conventional Grignard reaction conditions, or

k) a compound of formula XI

which is known or which can be prepared analogously to corresponding known compounds and in which A n, g, R ² and R ³ are as defined for formula I, with a compound of formula Br _(CF2) ^ Br, in wherein p is 1, 2, 3 or 4, preferably in the presence of a strong base, for example sodium hydride, potassium hydride or potassium tert-butoxide, or to prepare a compound of formula II wherein R ¹ is OCF _a , of formula (XI) is reacted with carbon tetrachloride in the presence of hydrogen fluoride, or for the preparation of a compound of formula (II) wherein R ¹ is OCF 2 Cl, a compound of formula (XI) is reacted with a compound of formula by treatment with hydrogen fluoride to prepare a compound of formula II wherein R ¹ is an OCF 3 group;

1) for the preparation of a compound of the formula II in which:

R ¹ is OCF _a , a compound of formula XII

(XII) which is known or which can be prepared analogously to corresponding known compounds and in which A n, o, R ² and R ³ are as defined for formula I, is reacted with hydrogen fluoride, preferably in the presence of an oxidant, preferably a 1,3-dibromo-5,5-dimethylhydantoin, and a base, preferably pyridine, or with

m) for the preparation of a compound of formula II wherein R ¹ is OCF ₃ , a compound of formula XIII (XIII)

which is known or which can be prepared analogously to corresponding known compounds and in which A n, o, R ² and R ³ are as defined for formula I and R is C 1 -C 4 alkyl, is reacted with phosphorus pentachloride and Cl _a , ^{and the} resulting product is further reacted with antimony fluoride and antimony chloride, and then hydrolyzed, further the resulting benzophenone derivative is reacted with a compound of the formula R ^e NHNH ₂ , or / and, if desired, the compound of formula (II) obtainable by this method or by another method is converted to another compound of formula (II) and / or the mixture of isomers obtainable by this method is resolved and the desired isomer is isolated.

As stated above with respect to tautomers and E / Z isomers or salts of the compounds of formula I, the same applies to the starting materials mentioned above and below.

The reactions described above and below are carried out in a manner known per se, for example in the absence or usually in the presence of a suitable solvent or diluent or a mixture thereof, the process being carried out if necessary under cooling, room temperature or heating, e.g. 80 ° C to the boiling point of the reaction mixture, preferably from about 0 ° C to about +150 ° C, and, if necessary, in a closed vessel, under pressure, under an inert gas atmosphere and / or under anhydrous conditions. Particularly preferred reaction conditions are given in the examples.

The starting materials mentioned above and used for the preparation of the compounds of the formula I and, where appropriate, their tautomers or the E / Z-isomers, in free or salt form, are known or can be prepared by means of already known methods, for example in accordance with the information below.

Variant a:

Examples of suitable bases to facilitate the reaction include alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides, and carbocyclic amines. Examples include triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylamine. and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

The reactants can be reacted as such, i. without the addition of a solvent or diluent, for example in the melt. In most cases, the addition of an inert solvent or diluent or a mixture thereof is preferred. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane 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, Ν, Ν-diethylphonamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide. When the reaction is carried out in the presence of a base, the bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or Ν, Ν-diethylaniline, may also act as a solvent or diluent.

The reaction is preferably carried out at a temperature ranging from about 0 ° C to about +100 ° C, preferably from about 10 ° C to about +40 ° C.

According to a preferred embodiment of variant a), the compound of formula II is reacted with an acyl halide at a temperature of from 10 ° C to 40 ° C, preferably at 20 ° C, in an aromatic hydrocarbon, preferably toluene, and in the presence of a base catalyst, preferably triethylamine.

Variant b:

Examples of suitable acid catalysts to facilitate the reaction include those used in catalytic amounts which have been mentioned above as suitable for the formation of acid addition salts of the compounds of formula (I).

The reactants can be reacted as such, i. 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 a mixture thereof is preferred. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane , 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 Ν, Ν-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide. When the reaction is carried out in the presence of an acid catalyst, the acids used in excess may be, for example, strong organic carboxylic acids such as unsubstituted or substituted, for example halo-substituted, C1 -C4 alkanecarboxylic acids in the alkane moiety, for example formic, acetic or propionic acid, also act as a solvent or diluent.

The reaction is preferably carried out at a temperature ranging from about 0 ° C to about +100 ° C, preferably from about 10 ° C to about +40 ° C.

Variant c:

The reactants can be reacted as such, i. 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 a mixture thereof is preferred. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane dichloroethane, trichloroethene or tetrachloroethene; 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; and sulfoxides such as dimethyl sulfoxide.

The reaction is preferably carried out at a temperature of about ^20E C to about + 120 ° C, preferably from about 40 ° C to about + 100 ° C.

Variant d:

Examples of suitable bases to facilitate the reaction include alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylamine. and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

The reactants can be reacted as such, i. 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 a mixture thereof is preferred. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane dichloroethane, trichloroethene or tetrachloroethene; 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; and sulfoxides such as dimethyl sulfoxide. When the reaction is carried out in the presence of a base, the bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or Ν, Ν-diethylaniline, may also act as a solvent or diluent.

The reaction is preferably carried out at a temperature ranging from about 0 ° C to about +100 ° C, preferably from about 10 ° C to about +40 ° C.

Variant e:

Examples of bases suitable to facilitate the reaction include alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, and carbocyclic amines. Examples which may be mentioned are triethylamine, diisopropylethylamine, triethylenediamine, N-cyclohexyl-N, N-dimethylamine and Ν, Ν-diethylaniline.

The reactants can be reacted as such, i. 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 a mixture thereof is preferred. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane dichloroethane, trichloroethene or tetrachloroethene; 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; and sulfoxides such as dimethylsulfonate. When the reaction is carried out in the presence of a base, the bases used in excess, such as triethylamine or N, N-diethylaniline, can also act as solvents or diluents.

The reaction is preferably carried out at a temperature in the range of about 0 ° C to about +100 ° C, preferably about 10 ° C to about +40 ° C.

Variant f:

Examples of bases which are suitable to facilitate the reaction include alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (Ν, Ν-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylamine. and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

Examples of acid catalysts suitable for facilitating the reaction include those used in catalytic amounts which have been mentioned above as suitable for the formation of acid addition salts of the compounds of formula (I).

The reactants can be reacted as such, i. 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 a mixture thereof is preferred. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane 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, Ν, Ν-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide. When the reaction is carried out in the presence of a base, the bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or Ν, Ν-diethylaniline, can also act as solvents or diluents. When the reaction is carried out in the presence of an acid catalyst, the acids used in excess may be, for example, strong organic carboxylic acids such as unsubstituted or substituted, for example halo-substituted, C1 -C4 alkanecarboxylic acids in the alkane moiety such as formic, acetic or propionic acid, also act as solvents or diluents.

The reaction is preferably carried out at a temperature in the range of about 20 ° C to about +100 ° C, preferably about 50 ° C to about +80 ° C.

Variant g:

The reactants can be reacted as such, i. 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 a mixture thereof is preferred. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane 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; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides such as N, N-dimethylformamide, N, N-diethylformamide, Ν, Ν-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide.

The reaction is preferably carried out at a temperature ranging from about 20 ° C to about +120 ° C, preferably from about 50 ° C to about +110 ° C.

Variant h:

Examples of bases suitable to facilitate the reaction include alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides as well as carbocyclic amines. Examples which may be mentioned are triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, Ν, Ν-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylamine. and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

The reactants can be reacted as such, i. 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 a mixture thereof is preferred. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane dichloroethane, trichloroethene or tetrachloroethene; 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; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides such as Ν, Ν-dimethylformamide, N, N-diethylformamide, Ν, Ν-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide. When the reaction is carried out in the presence of a base, the bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline, can also act as solvents or diluents.

The reaction is preferably carried out at a temperature ranging from about 20 ° C to about +120 ° C, preferably from about 50 ° C to about +110 ° C.

Salts of the compounds of the formula I can be prepared in a manner known per se. For example, acid addition salts of the compounds of Formula I are obtained by reaction with a suitable acid or a suitable ion exchange agent, and salts with bases are obtained by reaction with a suitable base or a suitable ion exchange agent.

Salts of the compounds of formula (I) can be converted in conventional manner to the compounds of formula (I) in free form, acid addition salts, for example by reaction with a suitable basic agent or a suitable ion exchange agent, and salts with bases, for example by reaction with a suitable acid or suitable ion exchange agent.

Salts of the compounds of the formula I can be converted into other salts of the compounds of the formula I by known methods, for example acid addition salts can be converted into other acid addition salts, for example by reaction of a salt with an inorganic acid such as hydrochloride with a suitable metal salt, such as sodium, barium or silver salts, acids, for example with silver acetate, in a suitable solvent in which the inorganic salt formed, for example silver chloride, is insoluble so that it is separated from the reaction mixture.

Depending on the process and reaction conditions, the compounds of the formula I which can form salts can be obtained in free form or in salt form.

The compounds of the formulas I and II may exist in the form of one of the possible isomers or in the form of a mixture thereof, for example depending on the number and absolute and relative configuration of asymmetric carbon atoms such as antipodes and / and diastereomers or mixtures of isomers such as mixtures of enantiomers. , for example, racemates, mixtures of diastereomers or mixtures of racemates. The invention relates to pure isomers as well as to all possible mixtures of isomers and is to be understood as above and below, although stereochemical details are not specifically disclosed in each individual case.

Mixtures of diastereomers and racemate mixtures of the compounds of formulas I and II obtainable by the process of the invention - depending on the choice of starting materials and processes - or by other methods, can be separated in a known manner based on the physicochemical differences of the individual components to produce pure diastereomers or racemates, for example by fractional crystallization, distillation and / or chromatography.

Mixtures of enantiomers thus obtainable, such as racemates, can be resolved by known methods to form optical antipodes, for example, by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example, by high performance liquid chromatography (HPLC) on acetylcellulose, by appropriate microorganisms, specific, immobilized enzymes, or by the formation of inclusion compounds, for example using chiral crown ethers, in which only one enantiomer is complexed.

Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of suitable mixtures of isomers, but also by means of generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process of the invention using starting materials exhibiting the appropriate suitable stereochemical properties.

If the individual components differ in their biological activity, it is advantageous to isolate or synthesize each biologically more active isomer, for example an enantiomer or a mixture of isomers, for example a mixture of enantiomers.

The compounds of the formulas I and II can also be obtained in the form of their hydrates and / or in the form containing other solvents, for example those which may need to be used for crystallization of compounds which are in solid form.

The invention relates to all those embodiments of the process wherein, starting from a compound obtainable during any stage of the process, as a starting material or intermediate, all or some of the missing steps are made or the starting material is used in the form of a derivative or a salt and / or a racemate or antipode thereof, or is formed, in particular, under reaction conditions.

In the process according to the invention, the starting materials and intermediates which are preferably used are those which give rise to the compounds of the formula I which have been described above, in particular as valuable.

In particular, the invention relates to the preparation methods described in Examples H1 to H10.

The invention also relates to starting materials and intermediates, each in free form or in salt form, which are novel and used according to the invention for the preparation of the compounds of the formula I or their salts, their use as well as the processes for their preparation.

The compounds of the formula I according to the invention are valuable preventive and / or curative active compounds in the field of pest control, even when applied at low concentrations, and their warm-blooded species, fish and plants are well tolerated and exhibit a very favorable biocidal spectrum. The active compounds according to the invention are active against all or individual stages of development of normally sensitive but also resistant animal pests, such as insects or members of the Acarina family. The insecticidal or acaricidal efficacy of the active compounds according to the invention may be apparent directly, for example from the destruction of pests, either immediately or only after a certain time, for example during stripping, or indirectly, for example from reduced egg laying and / or hatching. 50 to 60%.

The above mentioned animal pests include, for example:

from the order of the Lepidoptera (butterflies), for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp. Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia 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 bp. 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. spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp., of the genus Coleoptera (beetles), for example Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosetocnema tibialis. , Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Populus spp. Rhizopertha spp., Scar Abeidae, 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., from the order Isoptera (termites), e.g. Reticulitermes spp., from the order Psocoptera (peacocks), e.g. Liposcelis spp., from the order Anoplura (lice), e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp., from the order of the Mallophaga (oxen), for example Damalinea spp., and Trichodectes spp., from the order of the Thysanoptera (tufts), for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothripsurant. 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., from the order of the Homoptera, for example, Aleurothrixus floccosus, Aleyrodes brassicae, Aonidlola spp., Aphididae, Aphis spp., Aspidiotus spp. Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigoc spp. , Pseudulaocpis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Schizaphis spp., Schizaphis spp., Sitobion spp. from the order of the 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., Cuterebra spp., Dacus spp., Drosophann melan. , 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., from the order of the Siphonaptera (fleas), for example, Ceratophyllus spp. and Xenopsylla cheopis, from the order of the Thysanura, for example Lepisma saccharina, and from the order of the Acarina, mites, Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilusspp., Brevipalpus spp. Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora. Sarcoptes spp., Tarsonemus spp. and Tetranychus spp ..

The active compounds according to the invention are particularly suitable for controlling, i.e. control or destruction of pests of the aforementioned type, which are found mainly on plants, in particular on useful plants and ornamental plants in agriculture, horticulture and forestry, or on parts of such plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases the protective effect also applies to newly forming parts of plants.

The target crops which are suitable are in particular cereals such as wheat, barley, rye, oats, rice, maize or sorghum, beets such as sugar beet or fodder beet, fruit crops such as fruiting kernel, stone and soft fruits such as are apple, pear, plum, peach, almond, cherry or soft fruit such as strawberry, raspberry or blackberry, legumes such as beans, lentils, peas or soy, oilseeds such as oilseed rape, mustard, poppy, olives, sunflowers, coconut, castor, cocoa or groundnut, pumpkin plants such as pumpkins, cucumbers or melons, fiber plants such as cotton, flax, hemp or jute, citrus-producing plants such as oranges, lemons, grapefruits or mandarins, vegetables, such as spinach, lettuce, asparagus, kohlrabi, carrots, onions, tomatoes, potatoes or peppers, laurel plants such as avocado, cinnamon or camphor, and those tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas, rubber plants and ornamentals.

Active substances according to the invention Boophilus microplus, Nilaparvata and Tetranychus urticae on vegetables, rice lines.

They are particularly suitable for the destruction of lugens, Panonychus ulmi fruit crops and other fields of application according to the invention are the protection of stored products, warehouses and materials, and, in the field of hygiene, in particular the protection of domestic animals and livestock against pests of the above type.

Thus, the invention also relates to pesticides such as emulsifiable concentrates, suspension concentrates, direct spray solutions or solutions to be diluted, pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, dusts, granules or compositions encapsulated in polymeric substances. all of which contain at least one active ingredient according to the invention and are selected according to the intended use and the prevailing circumstances.

In these compositions, the active ingredient is used in pure form, for example, as a solid active ingredient of a given particle size, or, preferably, together with - at least one carrier or excipient commonly used in formulating such as fillers, for example solvents or solid carriers. or as surfactants.

Suitable solvents are, for example: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably C8-C12 alkylbenzene fractions, such as mixtures of xylenes, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols, as well as their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or monomethylamino or monoethyl ether of ethylene glycol, ketones such as cyclohexanone, isophorone or diacetanol alcohol, strong polar solvents such as N-methylsulfide dimethyl N, N-dimethylformamide, water, non-epoxidized or epoxidized vegetable oil 47 is such as unepoxidized or epoxidized rapeseed oil, castor oil, coconut oil or soybean oil, and silicone oils.

Solid carriers which are used, for example, for dusts and dispersible powders are generally ground natural minerals such as limestone, talc, kaolin, montmorillonite or attapulgite. High disperse silica or high disperse absorbent polymers may also be added to improve physical properties. Suitable lump adsorbent carriers for granules are porous types of materials such as pumice, brick pulp, sepiolite or bentonite, and suitable non-adsorbent carriers are limestone or sand. In addition, a wide variety of granular inorganic or organic materials can be used, especially dolomite or crushed plant residues.

Suitable surfactants are nonionic, cationic and / or anionic surfactants or surfactant mixtures having good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient used in the composition. The surfactants listed below serve only as examples, the literature describes a wide variety of other surfactants which are commonly used in the formulation of the compositions and are useful in the present invention.

Suitable nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, and these derivatives may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 atoms alkylphenols. Other preferred nonionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing from 1 to 10 carbon atoms in the alkyl chain and containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene groups.

The above compounds typically contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other suitable substances are polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are mainly quaternary ammonium salts which carry as substituents at least one alkyl radical containing 8 to 22 carbon atoms and as further substituents lower, halogenated or non-halogenated, alkyl groups, benzyl groups or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride and benzyldi- (2-chloroethyl) ethylammonium bromide.

Suitable anionic surfactants can be either water-soluble soaps or water-soluble synthetic surfactants. Suitable soaps are the alkali metal, alkaline earth metal and the substituted or unsubstituted ammonium salts of higher fatty acids (C 10 -C 22) and their substituted or unsubstituted ammonium salts, or natural mixtures of fatty acids which they can be obtained, for example, from coconut oil or tall oil. Other surfactants which may be mentioned are fatty acid methyltaurides. However, synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates, are more commonly used. Fatty sulphonates or fatty sulphates are generally in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and typically contain an alkyl group containing 8 to 22 carbon atoms, the alkyl also including alkyl radicals of acyl groups. Examples are sodium or calcium salts of lignosulfonic acid, dodecyl ester of sulfuric acid or mixtures of fatty alcohol sulfates prepared from natural fatty acids. This group also includes the salts of sulfuric acid esters and sulfonic acids of fatty alcohol and ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and a fatty acid moiety containing from about 8 to 22 carbon atoms. Alkylarylsulfonates are, for example, sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product. Suitable phosphates may also be used, for example salts of phosphoric acid ester and p-nonylphenol adduct with ethylene oxide containing 4 to 14 ethylene oxide units or phospholipids.

The compositions generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight. % of active substance and 1 to 99.9% by weight, in particular 5 to 99.9% by weight. % of at least one solid or liquid carrier or excipient, wherein, as a rule, 0 to 25% by weight, in particular 0.1 to 20% by weight. The surfactants may be formulated in the compositions. While concentrated formulations are preferred as commercial products, the end consumer generally uses dilute formulations with substantially lower concentrations of the active ingredients.

Preferred compositions preferably have the following composition (percentages given are percentages by weight):

Emulsifiable concentrates

active substance: 1 until 90 %. preferably 5 until 20% surfactant: 0 until 30 %. preferably 10 until 20% solvent: 5 until 98 % / preferably 70 until 85%

dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates:

active substance:

Water:

surfactant: wettable powders:

active ingredient surfactant: solid carrier

granules:

active substance:

solid carrier:

up to 75%, preferably 10 to 50% 94 to 24%, preferably 88 to 30% 1 to 40%, preferably 2 to 30%

0.5 to 90%, preferably 1 to 80% 0.5 to 20%, preferably 1 to 15% 5 to 99%, preferably 15 to 98%

0.5 to 30%, preferably 3 to 15% 99.5 to 70%, preferably 97 to 85%

The action of the compositions according to the invention can be substantially extended and adapted to the prevailing circumstances by the addition of other insecticidally active substances. Suitable active substances to be added are, for example, compounds from the following groups of active substances: organophosphorus compounds, nitrophenols and their derivatives, formamidines, acylureas, carbamates, pyrethroids, nitroamines and their derivatives, pyrrols, thioureas and their derivatives, chlorinated hydrocarbons Bacillus thuringiensis. The compositions of the invention may also contain other solid or liquid carriers and excipients such as stabilizers, for example, non-oxidized or epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soybean oil), antifoaming agents such as silicone oils, preservatives, agents viscosity regulators, binders and / or tackifiers, as well as fertilizers and other active ingredients to achieve special effects, such as acaricides, bactericides, fungicides, nematicides, molluscicides or selective herbicides.

The compositions according to the invention are prepared in a manner known per se, for example in the absence of carriers and excipients by grinding, sieving and / or pressing a solid active ingredient or active ingredient mixture, for example to achieve a particular particle size, and in the presence of at least one carrier or excipient e.g. and / or by grinding the active ingredient or mixture of active ingredients with the carrier or excipient (s). The invention also encompasses these methods of preparing the compositions of the invention and the use of the compounds of Formula I to prepare such compositions.

Further objects of the invention are methods of applying the compositions, i.e. methods of controlling pests of the above type, such as spraying, atomizing, dusting, coating, seed coating, spraying or watering, the particular mode of application being selected according to the desired effect and prevailing circumstances. pest control of the above type. Typical application concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm of active ingredient. The application rate per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g / ha, preferably 20 to 600 g / ha.

A preferred method of application in crop protection is application to plant leaves (foliar application), the application frequency and application rates being adapted to the risk of infestation by the pest in question. Alternatively, the active ingredient may be introduced into the plant by a root system (systemic effect) when a liquid composition is applied to the plant site or the active ingredient is applied to the locus of plants, e.g., soil, in the form of granules (soil application). . In the case of rice, such granules may be applied to a flooded rice field.

The compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruits, tubers or grains, or nurseries, against animal pests. Propagating material can be treated with this pros52 class before sowing or planting, for example seeds before sowing. Alternatively, the active compounds according to the invention can be applied to the seeds (pickling) in such a way that the seeds are either immersed in a liquid composition or coated with a solid composition. Alternatively, the composition may be applied to the sowing or planting site at the time of sowing or planting of propagating material, for example, into the sowing furrow during the sowing. The invention also encompasses these methods of treating plant propagation material and plant propagation material that has been treated in this manner.

The invention is illustrated in more detail by the following examples without limiting its scope in any way.

DETAILED DESCRIPTION OF THE INVENTION

Preparation examples

General remarks

The compounds are obtained as mixtures of isomers, in most cases in the form of viscous oils. They can be purified by column chromatography. NMR spectra and elemental analyzes confirm the reported structures of the compounds.

Example H1

4-chloro-4'-triflučrmetoxybenzofenón

To a solution of 4-chlorophenylmagnesium bromide in ether prepared from 22.9 g of 1-bromo-4-chlorobenzene and 2.88 g of magnesium turnings in 80 ml of ether was added dropwise 10.8 g of 4-trifluoromethoxybenzonitrile and the mixture was then heated to under reflux for 24 hours. After cooling, 50 ml of 50% sulfuric acid are added at 20-30 ° C. After the non-exothermic reaction was continued, stirring was continued at room temperature for 1 hour. The phases are separated and the aqueous phase is repeatedly extracted by shaking with ether. The combined organic phases are worked up using saturated sodium bicarbonate solution and saturated sodium chloride solution. The solid crude product was purified by flash chromatography eluting with ethyl acetate / hexane (1:20). 14.3 g of the title compound are obtained in crystalline form, m.p. 74-75 ° C.

Example H2

4-chloro-4'-trifluoromethoxybenzophenone hydrazone

10.0 g of 4-chloro-4'-trifluoromethoxybenzophenone, 9.70 g of hydrazine hydrate and 2 ml of acetic acid are gently refluxed in 270 ml of absolute alcohol for 10 hours. The solution is then evaporated, the residue is taken up in dichloromethane and the mixture is washed with water. Evaporation of the dry organic phase afforded 9.34 g of the title compound as white fatty crystals.

Example H3

4-Chloro-4'-trifluoromethoxybenzophenone-N-acetylhydrazone (Compound 1.1 in Table 1)

2.24 g of 4-chloro-4'-trifluoromethoxybenzophenone hydrazone, 0.52 ml of acetyl chloride and 1.04 ml of triethylamine are stirred overnight at room temperature in 40 ml of toluene. After addition of ether, the organic phase is washed with water, dried over magnesium sulphate and evaporated. The residue was stirred in cold hexane and then filtered. The title compound is obtained as a mixture of isomers as white crystals, mp 129-131 ° C.

Example H4

4-chloro-4'-trifluórmetoxybenzofenón-N-methyl hydrazone

1.50 g of 4-chloro-4'-trifluoromethoxybenzophenone hydrazone, 1.25 g of methylhydrazine and 0.4 ml of acetic acid are gently refluxed in 45 ml of ethanol for 24 hours. The mixture was evaporated, then the residue was taken up in dichloromethane and washed with water. Drying over magnesium sulfate and evaporation gave 1.48 g of the title compound as a yellow oil.

Example H5

4-Chloro-4'-trifluoromethoxybenzophenone-N-formyl-N-methylhydrazone (Compound 1.6 in Table 1)

15 g of sodium formate are added to 12.5 ml of ether with stirring and without humidity, and 14.7 g of acetyl chloride are added dropwise at 0 ° C. Stirring is continued for several hours at room temperature, the sodium chloride is filtered off and the mixture is washed with dry ether. A solution of about 14.22 g of formyl acetate in ether is obtained.

A portion of this solution, containing approximately 0.38 g of formyl acetate, was added dropwise to a solution of 1.48 g of 4-chloro-4'-trifluoromethoxybenzophenone-N-methylhydrazone in 20 ml of ether. After a few hours, the reaction is complete, the mixture is treated with ice water and the organic phase is isolated, washed again with water and dried over sodium sulfate. After evaporation, the residue is purified by flash chromatography using a 1: 3 mixture of ethyl acetate and hexane as eluent. The product is obtained as a mixture of isomers as a yellow oil-waxy substance.

Example H6

1- (4-chlorophenyl) -4-dimethylamino-1- (4-trifluoromethoxyphenyl) -2,3-diaza-1,3-pentadiene (Compound 2.1 in Table 2)

To a solution of 0.85 g of 4-chloro-4'-trifluoromethoxybenzophenone hydrazone in 15 ml of toluene was added 0.66 g of N, N-dimethylacetamide dimethyl acetal. The mixture was then heated at reflux for 18 hours. The mixture was cooled and the solvent was evaporated completely. The brown residue was then purified by flash chromatography using a 1: 5 mixture of ethyl acetate and hexane. The title compound is obtained as a mixture of isomers as yellow crystals, m.p. 52-54 ° C.

Example H7

5-ethanesulfonyl-1- (4-chlorophenyl) -1- (4-trifluoromethoxyphenyl) -2,3,5-triazapenta-1,3-diene or

5-Ethanesulfonyl-1- (4-chlorophenyl) -1- (4-trifluoromethoxyphenyl) -2,3,5-triazapenta-1,4-diene (Compound 3.1 in Table 3)

To a solution of 0.85 g of 4-chloro-4'-trifluoromethoxybenzophenone hydrazone in 15 ml of toluene was added 0.75 g of 1-ethanesulfonyl-1-aza-3-oxa-1-pentene and 0.85 g of N-ethyldiisopropylamine. The mixture was heated to reflux with stirring for 20 hours. The mixture was cooled, then the solvent was completely evaporated and the residue was purified by flash chromatography using a 1: 2 mixture of ethyl acetate and hexane as eluent. The title compound is obtained as a mixture of isomers as a yellow wax.

Example H8

4-bromodifluoromethoxy-4'-chlorobenzophenone

To a stirred solution of 25 g 4-chloro-4'-hydroxybenzophenone in 150 ml of dimethylformamide at a temperature of 25-30 ^and C in three equal portions was added 2.58 g of 80% sodium hydride in oil. 27 g of dibromodifluoromethane are then added dropwise at 25 ° C and the mixture is stirred for 16 hours at room temperature. The reaction mixture is then poured into 800 ml of water and extracted three times using 300 ml of ethyl acetate each time. The organic phase is evaporated and the residue is purified by silica gel column chromatography using a 20: 1 mixture of hexane and ethyl acetate as eluent. White crystals having a melting point of 52-55 ° C are obtained.

Example H9

4-bromodifluoromethoxy-4'-chlórbenzofenónhydrazón

7.15 g of 4-bromodifluoromethoxy-4'-chlorobenzophenone, 5.45 g of hydrazine hydrate and 1.5 ml of glacial acetic acid are stirred for 6 hours at 60 DEG C. in 150 ml of ethanol. The reaction mixture was concentrated and the concentrate was extracted using water and ethyl acetate. The organic phase is evaporated and the residue is purified by silica gel column chromatography using a 7: 1 mixture of hexane and ethyl acetate as eluent. Yellowish crystals melting at 45-49 ° C are obtained.

Example H10

4-bromodifluoromethoxy-4'-chlorobenzophenone-N-acetylhydrazone (compound 1.27 in Table 1)

To a solution of 1.0 g of 4-bromodifluoromethoxy-4'-chlorobenzophenone hydrazone and 0.23 g of acetyl chloride in 20 ml of tetrahydrofuran at 20-25 ° C was added dropwise 0.30 g of triethylamine and the mixture was stirred for 90 minutes at room temperature. temperature. The reaction mixture was concentrated and the concentrate was extracted using water and ethyl acetate. The organic phase was evaporated and the residue was purified by silica gel column chromatography using a 3: 1 mixture of hexane and ethyl acetate as eluent. The product is melted at 118-120 ° C.

Example Hli

Other compounds listed in Tables 1, 2, 3 and 5 can also be prepared analogously to the methods described in Examples H3, H6, H7 and H10. The compounds listed in Table 4 can be prepared analogously to the methods described in Examples H2 and H9. The values in the physical data column in these tables represent the melting point in ° C.

Table 1

no. T R Λ 3 R R ⁶ 7 R physical data 1.1 ocf ₃ 4-Cl H H ch ₃ 129-31 [deg.] C 1.2 ocf ₂ cf ₂ b- 4-Cl H H ch ₃ Mp 128-43 ° C 1.3 ocf ₃ 4-Cl H H t-c ₃ h ₇ 121-3 ° C 1.4 ocf ₃ 4-Cl H H CôHs wax 1.5 ocf ₃ 4-Cl H H cC ₃ H ₅ Mp 155-60 ° C 1.6 ocf ₃ 4-Cl H CH ₃ H oil / wax 1.7 ocf ₃ 4-Cl H H cC ₆ H _n Mp 158-64 ° C 1.8 ocf ₃ 4-Cl H H nC ₃ H ₇ Mp 136-8 ° C 1.9 ocf ₃ 4-Cl H ch ₃ ch ₃ amor- FNA 1.10 ocf ₃ 4-Cl H ch ₃ 1-C ₃ H ₇ amor- FNA 1.11 ocf ₃ . 4-Cl H ch ₃ CôHs resin 1.12 ocf ₃ 4-Cl H ch ₃ cC ₃ H ₅ resin 1.13 OCF ₂ CF ₂ Br 4-F H ch ₃ ch ₃ resin 1.14 OCF ₂ CF ₂ Br 4-Cl H ch ₃ ch ₃ oil 1.15 ocf ₃ 4-Cl H H 3-Thienyl 118-33 ° C 1.16 ocf ₃ 4-Cl H H 2-Thienyl 160-2 ° C 1.17 ocf ₃ 4-Cl H H 5-C1-2- thienyl Mp 159-62 ° C 1.18 ocf ₃ 4-Cl H 5-0-2- thienoyl 5-C1-2- thienyl amorphous

Continuation of Table 1

1.19 ocf ₃ 4-C1 H 1.20 ocf ₃ 4-C1 H 1.21 ocf ₃ 4-C1 H 1.22 ocf ₃ 4-C1 The 1.23 OCF ₂ CF ₂ Br 4-C1 H 1.24 OCF ₂ Br 4-C1 The 1.25 OCF ₂ Br 4-C1 H 1.26 OCF ₂ Br 4-C1 H 1.27 OCF ₂ Br 4-C1 H 1.28 OCF ₂ Br 4-C1 H 1.29 OCF ₂ Br 4-C1 H 1.30 ocf ₃ 4-C1 H 1.31 OCF ₂ CF ₂ Br 4-F H 1:32 OCF ₂ Br 4-F H 1:33 OCF ₂ Br 4-F The 1:34 ocf ₃ 4-C1 H 1:35 ocf ₃ 4-C1 The

1:36 ocf ₃ 4-C1 H 1:37 ocf ₃ 4-C1 H 1:38 ocf ₂ ci • 4-Br H 1:39 ocf ₂ ci 4-Br H 1:40 ocf ₂ ci 4-Br H 1:41 OCF ₂ Br 4-Br H 1:42 OCF ₃ 4-F . H 1:43 ocf ₃ 4-tC ₄ H ₉ H 1:44 ocf ₃ 4-OCF ₃ H 1:45 ocf ₃ 4-OCF ₃ H

H 3-Cl-2 thienyl 187-9 ° H [b] - thien-2-yl 178-80 H 3-Cl-benzoC'o] - thien-2-yl 213-5 ° ch ₃ 2-thienyl amor- FNA ch ₃ H resin ch ₃ . ch ₃ resin ch ₃ H resin H c ₂ h ₅ 119-30 H ch ₃ 118-20 ch ₃ cC ₃ H ₅ resin ch ₃ C ₂ K ₅ resin CK ₃ 3-thienyl amor- FNA ch ₃ H resin H C ₂ K ₅ 110-21 H ch ₃ 118-28 ch ₃ 5-C1-2- amor- thienyl FNA ch ₃ 3-Cl-benzo [B] thien amor- 2-yl FNA ch ₃ 3-C1-2- amor- thienyl FNA ch ₃ . [b] - amor- thien-2-yl FNA c ₂ h ₅ ch ₃ c ₂ h ₅ c ₂ h ₅ ch ₃ C-C3H5 ch ₃ H H ch ₃ H ch ₃ H ch ₃ ch ₃ H

Continuation of Table 1

1:46 ocf ₃ 3,4-Cl H 1:47 ocf ₃ 2,4-CU H 1:48 ocf ₃ 3-Cl H 1:49 ocf ₃ . 2,5-Cl ₂ H 1:50 ocf ₃ 3,5-Cl ₂ H 1:51 ocf ₃ 2-F.4-Cl H 1:52 ocf ₃ 2-Br The 1:53 ocf ₃ 3-CH ₃ , 4-Cl H 1:54 ocf ₃ 3-CF ₃ , 4-Cl H 1:55 ocf ₃ 3,5- (CF ₃ ) ₂ H 1:56 ocf ₃ 2-Cl, 5-CF ₃ H 1:57 ocf ₃ 4-Br H 1:53 OCF- 4-Br The 1:59 ocf ₃ 4-Br H 1.60 ocf ₃ 4-Br The 1.61 ocf ₃ 4-Br The 1.62 ocf ₃ 4-Br. H 1.63 ocf ₃ 4-Br The 1.64 ocf ₃ 4-Br The 1.65 ocf ₃ 4-Br The 1.66 ocf ₃ 4-Br H 1.67 ocf ₃ 4-Br The 1.63 ocf ₃ 4-Br H 1.69 ocf ₃ 4-Br H 1.70 ocf ₃ 4-Br H 1.71 ocf ₃ 4-Br H 1.72 ocf ₃ 4-Br H 1.73 ocf ₃ 4-Br H 1.74 ocf ₃ 4-Br H 1.75 OCF ₂ Br 4-Br H 1.76 OCF ₂ Br 4-Br H 1.77 OCF ₂ Br 4-Br H 1.78 OCF ₂ Br 4-Br H 1.79 OCF ₂ Br 4-Br H 1.80 OCF ₂ Br 4-Br H

H H ch ₃ ch ₃ c ₂ h ₅ ch ₃ ch ₃ ch ₃ cC ₃ H ₅ H ch ₃ H H ch ₃ ch ₃ c ₂ h ₅ c ₂ h ₅ ch ₃ H 1-C ₃ H ₇ nC ₃ H ₇ H H H H ch ₃ 136-40 Deň: 11 ° C H c ₂ h ₅ The cC ₃ H ₅ 164-7 C The 1-C ₃ H ₇ 136-8 C H nC ₃ H ₇ H CA 130-1 C H 2-thienyl H 3-thienyl ch ₃ H oil ch ₃ ch ₃ 85-93 C ch ₃ c ₂ h ₅ ch ₃ cC ₃ H ₅ oil ch ₃ 1-C ₃ H ₇ amor- FNA ch ₃ nC ₃ H ₇ ch ₃ c ₆ h ₅ ch ₃ 2-thienyl ch ₃ 3-thienyl H H H ch ₃ 116-8 C H cC ₃ H ₅ 140-6 C H 1-C ₃ H ₇ 110-3 C H nC ₃ H ₇ 99-108 i ° c H c ₆ h ₅

Continuation of Table 1

1.81 OCF ₂ Br 4-Br H 1.82 OCF ₂ Br 4-Br H 1.83 OCF ₂ Br 4-Br H 1.84 OCF ₂ Br 4-Br H 1.85 OCF ₂ Br 4-Br The 1.86 OCF ₂ Br 4-Br H 1.87 OCF ₂ CF ₂ Br 4-Br H 1.88 OCF ₂ CF ₂ Br 4-Br H 1.89 OCF ₂ CF ₂ Br 4-Br H 1.90 OCF ₂ CF ₂ Br 4-Br H 1.91 OCF ₂ CF ₂ Br 4-Br H 1.92 OCF ₂ CF ₂ Br 4-Br H 1.93 OCF ₂ CF ₂ Br 4-Br H 1.94 OCF ₂ CF ₂ Br 4-Br H 1.95 ocf ₃ 4-F H 1.96 ocf ₃ 4-F H 1.97 ocf ₃ 4-F H 1.98 ocf ₃ 4-F H 1.99 ocf ₃ 4-F H 1,100 ocf ₃ 4-F H 1,101 ocf ₃ 4-C1 H 1,102 ocf ₃ 4-C1 H 1.103 ocf ₃ 4-C1 H 1,104 ocf ₃ 4-Br H 1,105 ocf ₃ 4-Br H 1,106 ocf ₃ 4-Br H 1.107 OCF ₂ Br 4-F 3-C1 1,108 OCF ₂ Br 4-F 3-C1 1,109 OCF ₂ Br 4-F 3-C1 1.110 OCF ₂ Br 4-F 3-C1 1.111 ocf ₃ 4-C1 H. 1.112 ocf ₃ 4-Br H

ch ₃ H amor- FNA ch ₃ ch ₃ amor- FNA ch ₃ cC ₃ H ₅ oil ch ₃ iC ₃ K ₇ oil ch ₃ nC ₃ H ₇ oil ch ₃ CôHs H 'H H CK ₃ H iC ₃ K ₇ H C _{O O 5} ch ₃ H ch ₃ ch ₃ CK ₃ iC ₃ K ₇ ch ₃ c _ó h ₅ H H H CH ₃ H iC ₃ K ₇ ch ₃ H ch ₃ CK ₃ ch ₃ iC ₃ K ₇ c ₂ h ₅ H c ₂ h ₅ ch ₃ C ₂ H _p 1-C ₃ H ₇ c ₂ h ₅ H C ₂ H ₅ . ch ₃ c ₂ h ₅ 1-C ₃ H ₇ H ch ₃ 115-25 H c ₂ h ₅ 87-95 H cC ₃ H ₅ 133-44 H 1-C ₃ H ₇ 97-107 H (CH ₂ ) ₃ CH = cf ₂ 89-93 H (CH ₂ ) ₃ CH = cf ₂ 143-7

u o

Continuation of Table 1

1.113. OCF; 4-Cl H CH ₃ (CH ₂ ) ₃ CH = cf ₂ 1,114 OCF-3 4-Cl 3-C1 H ch ₃ 101-6 ° C 1.115 OCF ₂ 3y 4-Cl 3-C1 H t-c ₃ h ₇ 11-43 ° C 1.116 OCF ₂ 3y 4-Cl 3-C1 H c ₂ h ₅ 105-11 ° C 1,117 ocf ₃ 4-Br H CH ₃ 6-chloro- pyridin-3-yl amor- FNA 1.11S ocf ₃ 4-Br H ch ₃ 5-chloro- thien-2-yl Mp 109-12 ° C 1.119 OCF ₂ 3y 4-Cl 3-C1 H CH ₂ C1 amor- FNA 1.120 OCF ₂ 3y 4-Cl 3-C1 H cC ₃ H ₅ 129-34 [deg.] C 1,121 OCF ₂ 3: 4-Cl 3-C1 ch ₃ c ₂ h ₅ resin 1.122 OCF ₂ 3y 4-Cl 3-C1 ch ₃ ch ₃ resin 1,123 OCF ₂ 3y 4-Cl 3-Cl ch ₃ H resin 1.124 OCF ₂ 3y 4-Cl 3-C1 ch ₃ CH ₂ C1 resin 1,125 OCF ₂ 3y 4-Cl 3-C1 H cooc ₂ h ₅ 165-9 [deg.] C 1.126 OCF ₂ 3y 4-Cl 3-C1 H cooch ₃ Mp 149-60 ° C 1,127 OCF ₂ 3y 4-Cl 3,5-Cl ₂ H ch ₃ 129-34 [deg.] C 1,128 OCF ₂ 3y 4-Cl 3,5-CI ₂ H cC ₃ H ₅ Mp 192-3 ° C 1.129 OCF ₂ 3y 4-Cl 2,5-Cl ₂ H I-C3H7 170-3 ° C 1.130 OCF? 3r 4-Cl 3,5- or ₂ H c ₂ h ₅ 143-5 ° C 1.131 OCF ₂ 3y 4-Cl 3-C1 H I-C4H9 Mp 88-96 ° C 1.132 OCF ₂ Br 4-Cl 3-C1 H nC ₃ H ₇ 87-99 ° C 1.133 ocf ₃ 4-Br H ch ₃ (CH ₂ ) ₃ CH = cf ₂ 1.134 OCF ₂ Br 4-Cl H H cC ₃ H ₅ 127-31 [deg.] C 1.135 OCF ₂ Br 4-Cl H H nC ₃ H ₇ 88-107 [deg.] C 1.136 OCF ₂ Br 4-Cl H H iC ₃ H ₇ 106-12 ° C 1,137 OCF ₂ Br 4-Br H H C ₄ H 9 Mp 119-21 ° C 1.138 OCF ₂ Br 4-Br H H c ₂ h ₅ 108-14 ° C 1.139 OCF ₂ Br 4-Br H ch ₃ 1-C4H9 resin

Continuation of Table 1

1.140 OCF ₂ Br 4-Br H CH ₃ c ₂ h ₅ amor- FNA 1,141 OCF ₂ Br 4-Cl 3-F H ch ₃ Mp 116-20 ° C 1.142 OCF ₂ Br 4-Cl 3-Br H ce ₃ . 90-6 ° C 1143 OCF ₂ Br 4-Cl 3-Br E c ₂ h ₅ 97-104 ° C 1,144 OCF ₂ Br 4-Cl 3-F H c ₂ e ₅ Mp 122-5 ° C 1.145 OCF ₂ Br 4-Cl 3-F ch ₃ E resin 1,146 OCF ₂ Br 4-Cl 3-Br ch ₃ H resin 1,147 OCF ₂ Br 4-Cl 3-Br CK ₃ ce ₃ resin 1148 OCF ₂ Br 4-Cl 3-F CK ₃ ch ₃ resin 1.149 OCF ₂ Br 4-Cl 3-C1 CEO E 1,150 OCF ₂ Br 4-Cl 3-C1 CEO ce ₃ 1151 OCF ₂ Br 4-Cl 3-C1 CEO c ₂ e ₅ 1,152 OCF ₂ Br 4-Cl 3-C1 CEO ch ₂ ci 1.153 OCF ₂ Br 4-Cl 3-C1 CEO 1-C3E-7 1,154 OCF ₂ Br 4-Cl 3-C1 CEO CF3 1,155 OCF ₂ Br 4-Cl 3-C1 CEO c, e ₅ 1,156 OCF ₂ Br 4-Cl 3-C1 ch ₃ co H 1,157 OCF ₂ Br 4-Cl 3-C1 ce ₃ co ce ₃ 1,158 OCF ₂ Br 4-Cl 3-C1 ce ₃ co c ₂ e ₅ 1.159 OCF ₂ Br 4-Cl 3-C1 ce ₃ co ce ₂ ci 1.160 OCF ₂ Br 4-Cl 3-C1 ce ₃ co 1-C ₃ E ₇ 1,161 OCF ₂ Br 4-Cl 3-C1 3 CO cf ₃ 1.162 OCF ₂ Br 4-Cl 3-C1 CE3CO 0 5 * 1,163 OCFiBr 4-Cl H E OCE3 1,164 OCF ₃ 4-CF ₃ H E N (CE ₃ ) ₂ 1.165 ocf ₃ 4-CF ₃ H E ce ₃ 1,166 OCF ₂ Br 4-Cl H iC ₃ H ₇ E oil 1.167 OCF ₂ Br 4-Cl H 1-C ₃ E ₇ ch ₃ resin 1.168 OCF ₂ Br 4-Cl H 1-C ₃ E ₇ c ₂ e ₅ resin 1.169 OCF ₂ Br 4-Cl H 1-C ₃ E ₇ nC ₃ E ₇ resin 1.170 OCF ₂ Br 4-Cl H 1-C ₃ E ₇ iC ₃ E ₇ resin 1.171 OCF ₂ Br 4-Cl H 1-C ₃ E ₇ NECH ₃ resin

Table 2

no. 1 R R ² R ³ R ⁴ R ⁵ PHYSICAL data 2.1 ocf ₃ Cl H ch ₃ N _{(CH3) 2} 52-4 ° C 2.2 OCF. Cl H ch ₃ N (OCH ₃ ) CH ₃ oil 2.3 OCF ₂ Br Cl H ch ₃ N _{(CH3) 2} 46-74 ° 2.4 ocf ₃ br H ch ₃ sch ₃ 2.5 ocf ₃ Cl H H sch ₃ 2.6 ocf ₃ F H ch ₃ N _{(CH3) 2} 2.7 ocf ₃ br H H N _{(CH3) 2} 2.3 OCF ₂ CF ₂ Br Cl H c ₂ h ₅ och ₃ 2.9 ocf ₃ Cl H c ₂ h ₃ oc ₂ h ₅ 2.10 ocf ₃ Cl H c ₂ h ₅ och ₃ 2.11 ocf ₃ Cl H nC ₃ H ₇ N _{(CH3) 2} 2.12 ocf ₃ Cl H iC ₃ H ₇ nh ₂ 2.13 ocf ₃ Cl H c ₂ h ₅ nhch ₃ 2.14 ocf ₃ ocf ₃ H ch ₃ oc ₂ h ₅ 2.15 ocf ₃ ocf ₃ H H Sat ₂ ch ₃ 2.16 ocf ₃ br H ch ₃ N _{(CH3) 2} amor- FNA 2.17 OCF ₂ Br Cl 3-C1 ch ₃ N _{(CH3) 2} resin 2.18 OCF ₂ Br Cl 3,5-Cl ₂ ch ₃ N _{(CH3) 2} resin 2.19 OCF ₂ Br br H ch ₃ N _{(CH3) 2} resin 2.20 OCF ₂ CF ₂ Br Cl H ch ₃ N (C ₂ H ₅ ) ₂ 2.21 OCF ₂ Br Cl H . ch ₃ N _{(CH3) 2} 2.22 OCF ₂ Br F H ch ₃ N _{(CH3) 2} 2.23 OCF ₂ Br Cl 3-F ch ₃ N _{(CH3) 2} resin 2.24 OCF ₂ Br Cl 3-Br ch ₃ N _{(CH3) 2} resin

Table 3

no. E ² R ³ R ⁶ R ⁷ R ¹⁸ physical data 3.1 ocf ₃ Cl H H H SO ₂ C ₂ H ₅ wax 3.2 ocf ₃ Cl H H ' H Sat ₂ ch ₂ c ₆ h ₅ wax Λ Λ J.J. ocf ₃ Cl H H H SO ₂ C ₆ H ₅ wax 3.4 ocf ₃ Cl H ch ₃ H Sat ₂ c ₂ h ₅ 3.5 ocf ₃ br H ch ₃ ' ch ₃ Sat ₂ c ₂ h ₅ 3.6 ocf ₃ Cl Cl ch ₃ H Sat ₂ c ₂ h ₅ 3.7 OCF ₂ Br Cl H H H Sat ₂ c ₂ h ₅ 3S OCF ₂ Br br H H H Sat ₂ c ₆ h ₅ 3.9 OCF ₂ Br Cl Cl H H Sat ₂ c ₂ h ₅ 3.10 OCF ₂ Br Cl H ch ₃ H Sat ₂ c ₂ h ₅ 3.11 OCF ₂ Br Cl H ch ₃ ch ₃ Sat ₂ c ₂ h ₅ 3.12 OCF ₃ Br Cl Cl ch ₃ ch ₃ SO ₂ C ₂ H ₅

Table 4

physical data

4.1

4.2

4.3

4.4

4.5

4.6

4.7

OCF ₂ CF ₂ Br

OCF ₃

OCF ₂ Br

OCF ₃

OCF ₂ Br

OCF ₂ Br

OCF ₂ Br

Cl

Cl

Cl

br

Cl

Cl

Cl

H

H

H

H

Cl

F

Br amorphous oil

Mp 45-9 ° C

74-8 ° C oil oil oil

Table 5

R.

no. 1 2 3 6 R R R R 5.1 ocf ₂ b- CI CI The 5.2 OCF ₂ Br C1 F The 5.3 ocf ₂ b- CI br H 5.4 OCF ₂ Br C CI H 5.5 OCF ₂ Br CI F H 5.6 ocf ₂ b- 'C1 br The 5.7 OCF ₂ Br C The The 5.8 OCF, Br C H H 5.9 OCF ₂ Br Whose H ch ₃ 5.10 OCF, Br CI H ck ₃ 5.11 OCF ₂ Br CI F CK ₃ 5.12 OCF ₂ Br C1 F CH ₃ 5.13 OCF ₂ Br CI br ch ₃ 5.14 OCF ₂ Br CI br ch ₃ 5.15 OCF ₂ Br CI CI ch ₃ 5.16 OCF ₂ Br CI CI ch ₃ 5.17 OCF ₂ Br br H H 5.18 OCF ₂ Br br H H 5.19 ocf ₃ br H H 5.20 ocf ₃ CI H H

Ί 21 R R physical CFs CF ₃ oil cf ₃ cf ₃ Mp 80-96 ° C cf ₃ CF ₃ resin ch ₃ ch ₃ resin CK ₃ ch ₃ oil ch ₃ ch ₃ resin CK ₃ ch ₃ CF ₃ cf ₃ ch ₃ CK ₃ CF; cf ₃ ch ₃ ch ₃ cf ₃ cf ₃ ch ₃ ch ₃ cf ₃ cf ₃ ch ₃ ch ₃ cf ₃ CF ₃ ch ₃ . och ₃ ch ₃ oc ₂ h ₅ ch ₃ ch ₃ ch ₃ ch ₃

data

Examples of formulations of the active compounds of the formula I (the percentages given are percentages by weight)

Example F1

Emulsion concentrates

(a) (b) (c) active substance 25% calcium dodecylbenzenesulphonate 5% castor oil polyethylene glycol ether (containing 36 moles of ethylene oxide) 5% tributylphenol polyethylene glycol ether (containing 30 moles of ethylene oxide) cyclohexanone xylene mixture 65%%

calcium dodecylbenzenesulfonate cyclohexanone xylene mixture% 8%%

%%

34% 50%% 20% 20%

By mixing the finely divided active ingredient and the additives, an emulsion concentrate is obtained, from which an emulsion of any desired concentration can be prepared by dilution with water.

Example F2

solutions

a)

b)

c)

(d) active substance ethylene glycol monomethyl ether polyethylene glycol with a molecular weight of 400 N-methylpyrrolidin-2-one epoxidized coconut oil benzene fraction boiling at 160 - 190 ° C% 20%%

By mixing the finely divided active ingredient and the additives, a solution is obtained which is suitable for use as microspheres.

Example F3

granules

a) b) c) d) active substance 5% 10% 8% 21% kaolin 94% - 79% 54% highly disperse silica 1% - 13% 7% attapulgite - 90% - 18%

The active substance is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture and the solvent is evaporated off under vacuum.

Example F4

dusts

a) b)

active substance 2 % 5 % highly disperse silica 1 % 5 % talc 97 % - kaolin - 90 %

Dusts suitable for the immediate active ingredient and carriers. use is obtained by mixing- Example F5 Wettable powders a) b) C) active substance 25% 50% 75% sodium lignosulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalenesulfonate - 6% 10%

octylphenol-polyethylene glycol ether

(7-8 moles of ethylene oxide) 2 % highly disperse silica 5% 10 % 10% kaolin 62% 27 % The active ingredient is mixed with the additives and the mixture is different

in a suitable mill, wettable powders are obtained which can be diluted with water to suspensions of any desired concentration.

Example F6

Emulsion concentrate active substance 10% octylphenol-polyethylene glycol ether (containing 4-5 moles of ethylene oxide) 3% calcium dodecylbenzenesulfonate 3% polyethylene glycol ether of castor oil (containing 36 moles of ethylene oxide 4% cyclohexanone 30% xylene mixture 50%

By mixing the finely divided active ingredient and the additives, an emulsion concentrate is obtained, from which an emulsion of any desired concentration can be prepared by dilution with water.

Example F7

Powder dusts talc kaolin

(a) (b)% 8%%

%

Dusts suitable for immediate use are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill.

Example F8%

Extruded granulate active substance sodium lignosulfonate carboxymethylcellulose kaolin%

The active ingredient is mixed with the additives, the mixture is ground, moistened with water, extruded and granulated. The granulate is dried in a stream of air.

Example F9

Coated granulate active ingredient 3% polyethylene glycol with a molecular weight of 200 3% kaolin 94%

The finely divided active substance is uniformly applied to a kaolin moistened with polyethylene glycol in a mixer to obtain a dust-free coated granulate.

Example F10

Suspension concentrate active ingredient 40% ethylene glycol 10% nonylphenol-polyethylene glycol ether (containing 15 moles of ethylene oxide) sodium lignosulfonate carboxymethylcellulose 37% aqueous formaldehyde solution 75% aqueous silicone oil emulsion water% 10%%

0.2% 0.8%%

By mixing the finely divided active ingredient and the additives, a suspension concentrate is obtained, from which a suspension of any desired concentration can be prepared by dilution with water.

Biological examples

Example BI

Activity against Spodoptera littoralis caterpillars

Young soybean plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. After the spray has dried, 10 third instar of Spodoptera littoralis are placed on soybean plants and then placed in a plastic container. The test is evaluated 3 days later. The percentage of population reduction or the percentage reduction in visual damage (% efficacy) is determined by comparing the number of dead caterpillars and the fire damage on treated and untreated plants.

In this test, the compounds of Tables 1, 2, 3, 4 and 5 show good activity against Spodoptera littoralis. In particular, compounds no. 1.1, 1.3 to 1.14, 1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.76 to 1.79, 1.81 to 1.85, 1.107 to 1.111, 1.114, 1.117, 1.121 to 1.123, 1.131 to 1.133, 1.135 to 1.138, 1.140, 2.3, 2.17 and 2.19.

Example B2

Activity against Heliothis virescens

Young soybean plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. After the spray has dried, 10 first-instar Heliothis virescens are placed on the soybean plants and then placed in a plastic container. The test is evaluated 6 days later. The percent reduction in population or percent reduction in fire damage74 rom (% efficacy) is determined by comparing the number of dead caterpillars and the fire damage on treated and untreated plants.

In this test, the compounds of Tables 1, 2, 3, 4 and 5 show good activity against Heliothis virescens. In particular, compounds no. 1.1 to 1.14, 1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.76 to 1.79, 1.81 to 1.85,

1.107 to 1.112, 1.114, 1.116, 1.117, 1.120 to 1.123, 1.125, 1.131 to 1.133, 1.135 to 1.138, 1.140, .2.1 to 2.3, 2.16,

2.17, 2.19, 4.1 and 4.4.

Example B3

Ovicidal activity against Heliothis virescens

The eggs of Heliothis virescens on filter paper are briefly immersed in a test solution containing 400 ppm of the test compound in a mixture of acetone and water. Once the test solution has dried, the eggs are incubated in Petri dishes. After 6 days, the percentage of egg hatching compared to untreated controls (% hatch reduction) is evaluated.

In this test, the compounds of Tables 1, 2, 3, 4 and 5 show good activity against Heliothis virescens. In particular, compounds no. 1.1 to 1.14, 1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.76 to 1.79, 1.81 to 1.85,

1.107 to 1.112, 1.114 to 1.117, 1.120 to 1.123, 1.125, 1.126, 1.131 to 1.133, 1.135 to 1.138, 1.140, 2.1 to 2.3, 2.16,

2.17, 2.19, 3.2, 3.3, 4.1, 4.2, 4.4 and 4.5.

Example B4

Activity against larvae of Diabrotica balteata

Germinated maize plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. After the spray has dried, 10 second-instar Diabrotica balteata larvae are seeded on the germ maize plants and then placed in a plastic container. O evaluates. Percent reduction in population by comparing the number of dead larvae on plants.

days later, the test you (% efficacy) is determined treated and untreated

In this test, the compounds of Tables 1, 2, 3, 4 and 5 show good activity against Diabrotica balteata. In particular, compounds no. 1.1, 1.2, 1.4, 1.6, 1.58, 1.61, 1.66, 1.67, 1.76 to 1.79, 1.81 to 1.84, 1.107, 1.108, 1.111, 1.112, 1.114, 1.121, 1.122, 1.125, 1.132, 1.133, 1.137, 1.138, 1.140, 2.2, 2.3, 2.17, 2.19, 4.2, 4.4 and 4.5.

Example B5

Efficacy against Plutella xylostella

The young cabbage plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. After the spray has dried, 10 third plutella plutella xylostella are placed on the cabbage plants and then placed in a plastic container. The test is evaluated 3 days later. The percentage of population reduction or the percentage of reduction in fire damage (% efficacy) is determined by comparing the number of dead caterpillars and the fire damage on the treated and untreated plants.

In this test, the compounds of Tables 1, 2, 3, 4 and 5 show good activity against Plutella xylostella. In particular, compounds no. 1.1, 1.3 to 1.14, 1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.76 to 1.79, 1.81 to 1.85, 1.107 to 1.111, 1.114, 1.117, 1.121 to 1.123, 1.132, 1.133, 1.135 to 1.138, 1.140, 2.2, 2.3, 2.17 and 2.19.

Claims (22)

PATENT A perhaloalkoxybenzophenone hydrazone of the formula I n having a value of 0, 1, 2, 3, 4 or 5, wherein, when n is greater than 1, the radicals R ^{2 are the} same or different by o being 0, 1, 2, 3 or 4, where y when o is greater than 1, the radicals R ^{3 are the} same or different, R ^x is C 1 -C 4 perhaloalkoxy, R ² is halogen, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 alkoxy, C 1 -C 8 haloalkoxy, C 1 -C 8 alkylthio, haloalkylthio (C 1 -C 8) alkyl, (C 1 -C 8) alkylsulfinyl, (C 1 -C 8) haloalkylsulfinyl, (C 1 -C 8) alkylsulfonyl, (C 1 -C 8) haloalkylsulfonyl, cyano or phenyl group, R ³ is halogen, alkyl of 1-8 carbon atoms, haloalkyl of 1 to 8 carbon atoms or C 1 -C 8 alkyl, R ⁴ represents a hydrogen atom, a halogen atom, a C 1 -C 8 alkyl group, a C 3 -C 6 cycloalkyl group, a C 1 -C 8 haloalkyl group, a C 1 -C 8 alkoxy group, a C 1 -C 8 alkoxyalkyl group carbon atoms in the alkoxy moiety and 1 to 8 carbon atoms in the alkyl moiety, an alkoxyalkoxy group having 1 to 8 carbon atoms in each alkoxy moiety, an alkylthio group having 1 to 8 carbon atoms, or a NR ^S R ® group, R ⁵ is alkyl of 1 to 8 carbon atoms, NR R ^{XO XX,} 0R ² ° or ² ° SR or SO ₂ R ² ', R ⁶ represents a hydrogen atom, a C 1 -C 8 alkyl group, a C 3 -C 6 cycloalkyl group, a C 1 -C 8 haloalkyl group, a C 1 -C 8 alkenyl group, a C 1 -C 8 alkynyl group , C 1 -C 8 acyl or phenyl R ⁷ represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkylalkyl group having 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 8 carbon atoms in the alkyl moiety, alkenyl group (C 1 -C 8) alkynyl, (C 1 -C 8) alkynyl, (C 3 -C 6) cycloalkenyl, (C 3 -C 6) cycloalkenyl alkyl (C 1 -C 8) alkyl or (C 3 -C 6) cycloalkylalkenyl up to 6 carbon atoms in the cycloalkyl moiety and 1 to 8 carbon atoms in the alkenyl moiety, wherein the substituents may be selected from halogen atoms, alkyl groups of 1 to 8 carbon atoms, haloalkyl groups of 1 to 8 carbon atoms, alkoxy groups of 1 to 8 C-C,, Cko-C hal-haloalkoxy, alkyl-S (O) ^ (C 1 -C 8), wherein p may be 0, 1 or 2, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 dialkylamino in each alkyl moiety, and C 1 -C 8 alkanoyloxy groups, or unsubstituted or substituted phenyl or heteroaryl, wherein the substituents may be selected from alkyl of 1 to 6 carbon atoms and halogen atoms, or alkoxy of 1 to 8 carbon atoms, NR ^{X 6} R ^{X 7} , COOR ⁶ or SR ⁶ R @ ⁹ and R @ ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a hydroxyl group; R ¹⁰ is hydrogen, C 1 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 8 haloalkoxy, C 1 -C 8 haloalkoxyalkyl and C 1 -C 8 haloalkoxy; alkyl, phenyl, OR ^{X 2} , S (O) ^m R ^{X 3} , wherein m is 0, 1 or 2, or NR ^{X 4} R ^XS , R ^xx represents a hydrogen atom, a C 1 -C 8 alkyl group, a C 3 -C 6 cycloalkyl group, a C 1 -C 8 haloalkyl group, a C 1 -C 8 alkoxyalkyl group and a C 1 -C 8 alkoxy group at an alkyl time of 79, an allyl group, an alkylallyl group having 1 to 8 carbon atoms in the alkyl moiety, a haloallyl group, or a propargyl group, R ¹² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 1 to 8 carbon atoms in the alkoxy moiety and 1 to 8 carbon atoms in the alkyl moiety, a cycloalkyl group containing (C až-C,) alkenyl, (C až-C alk) alkenyl, (C až-C hal) haloalkenyl, or propargyl, R ^{X 3} is H, alkyl of 1-8 carbon atoms, haloalkyl of 1 to 8 carbon atoms, phenyl or NR ^{X 4} R ^X; R ⁴ and R ^X are each independently hydrogen, alkyl of C 1 -C 8 haloalkyl, C 1 -C 8 haloalkyl, phenyl, C 1 -C 8 alkylamido, C 1 -C 8 dialkylamido in each alkyl moiety or amino, R ^xe and R ^X7 independently are each hydrogen, C1-C8alkyl, C1-C8haloalkyl, C2-C8alkenyl, C1-C8alkoxy or amino, R ^xa represents the group S (O) R ¹⁹ , where m has a value of 0,1 m or 2, nitro or cyano, R ¹⁹ represents an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a benzyl group or an NR ^X4 R ^{XS group} , R ² is C 1 -C 8 alkyl, C 1 -C 8 haloalkyl or C 3 -C 6 cycloalkyl, Y represents an oxygen atom, a sulfur atom, a group NR ^1e or CHC (O) R ²¹ , a R ²¹ represents a hydrogen atom, a C 1 -C 8 alkyl group, a C 1 -C 8 haloalkyl group, a C 1 -C 8 alkoxy group or a phenyl group, provided that in the compounds of formula I in which X is a group -N = C (R ⁴⁾ R ^s, R ^x is OCFA, o is 0, n is 1, R ⁴ is methyl and R ^a is -N (CH 3) OCH _3, R ² does not represent F or a chlorine atom, or an E / Z isomer or tautomer thereof, in free or salt form. 2. Perhalogénalkoxybenzofenónhydrazón according to claim 1 of formula I wherein n is 1 or 2, wherein if the value of n is greater than 1, the radicals R ² identical or different, or, where applicable, an E / Z-isomer or tautomer. 3. A compound according to claim 1 having the value of 0 or 1 or, where appropriate, its E / Z isomer or tautomer. 4. A compound according to claim 1, wherein the compound is a compound of formula (I) R ¹ is C 1 -C 2 perhaloalkoxy or, where appropriate, its E / Z-isomer or tautomer. 5. A compound according to claim 1, wherein the compound is as defined in claim 1 R ² is halogen or, where applicable, an E / Z isomer or tautomer thereof. 6. Perhalogénalkoxybenzofenónhydrazón according to claim 1 of formula I wherein n is 1 or 2, wherein if the value of n is greater than 1, the radicals R ² identical or different, o is 0 or 1, R ³ is perhaloalkoxy · 1 -C 2 alkyl, R ² is halogen, C1 -C4 alkyl, halo-C 1 -C 4 alkyl or C 1 -C 4 alkyl, R ³ is H, halogen or methyl, R ⁴ represents a hydrogen atom or a C 1 -C 4 alkyl group, R ⁵ is alkyl of 1 to 4 carbon atoms, NR R ^{XO XX,} 0R ³ °, ³ ° SR or SO ^ R ^20, R @ 6 represents a hydrogen atom, a C1 -C4 alkyl group, a C3 -C6 cycloalkyl group or a C1 -C6 acyl group, R ⁷ represents a hydrogen atom, a C 1 -C 6 alkyl group, a C 3 -C 6 cycloalkyl group, an unsubstituted or substituted phenyl or heteroaryl group, the substituents selected from halogen atoms, C 1 -C 2 alkyl groups and (C 1 -C 2) alkoxy or (C 1 -C 2) alkoxy or NR ^{X 6} R ^{X 7} , R ¹⁰ represents a hydrogen atom, a C 1 -C 2 alkyl group, a phenyl group or an OR 2 ^{X 2} group, R ^xx represents a hydrogen atom, a C 1 -C 2 alkyl group, a C 3 -C 6 cycloalkyl group, an allyl group, or a C 1 -C 4 alkylallyl group in the alkyl moiety, R ( ¹³⁾ is hydrogen, (C1-C4) -alkyl, (C3-C6) -cycloalkyl, (C2-C4) -alkenyl or propargyl; R ( ^xe) and R ( ¹⁷⁾ independently of one another are hydrogen or (C 1 -C 4) -alkyl; R ^X is SO ^ R ^19, nitro or cyano, R ( ¹⁹⁾ is alkyl having 1 to 2 carbon atoms or benzyl; R ² represents C 1 -C 2 alkyl or C 3 -C 6 cycloalkyl, and Y represents an oxygen atom, a sulfur atom or an NR ¹⁸ group or, where appropriate, its E / Z isomer or tautomer. 7. A compound according to claim 1, wherein n is 1, o is 0 or 1, R ^x is perhalomethoxy, R ² is halogen, C1 -C2 alkyl, halo-C 1 -C 2 or C 1 -C 2, R ³ is H, Cl or F, R ⁴ represents a hydrogen atom or a C 1 -C 4 alkyl group; ^R is NR ¹ R ^{1 O L} or 0R ² °, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, R ⁷ is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, phenyl, unsubstituted or halo-substituted heteroaryl, C 1 -C 2 alkoxy or NR ^{X 6} R ^{X 7} , R ^xo and R ^{8 * * 11 are} each independently hydrogen, C 1 -C 2 alkyl or OR ¹² , R ¹² is hydrogen, C 1 -C 2 alkyl or C 3 -C 6 cycloalkyl, R ¹⁶ and R ^{X 7} are each independently C 1 -C 2 alkyl; R ^xa represents a group SO 2 R ¹⁹ , R ^X6 represents an alkyl group having 1 to 2 carbon atoms or a benzyl group, R ²⁰ represents an alkyl group having 1 to 2 carbon atoms, and Y represents an oxygen atom or a NR ^xa group or, where appropriate, its E / Z-isomer or tautomer. 8. A compound according to claim 1, wherein n is 1, o is 0 or 1, R ^x is perhalomethoxy, R ² is halogen, methyl, halomethyl or halogénmetoxyskupinu. R ³ is H, Cl or F, R ⁴ represents a hydrogen atom or a C 1 -C 4 alkyl group, ^R is NR R ^{XO XX,} R ^e represents a hydrogen atom or a C 1 -C 4 alkyl group, R ⁷ represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 3 -C 6 cycloalkyl group, a phenyl group, an unsubstituted or halo-substituted heteroaryl group, a C 1 -C 2 alkoxy group or a NR ^{X XS} R ^{X 7 group} , symbols R ^xo and R ^{xx are} each independently hydrogen, C 1 -C 2 alkyl or OR ¹² , R ¹² is H, alkyl of 1-2 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, the symbols R ^{1 e} and R ^'7 independently of one another are alkyl having 1 to 2 carbon atoms, R ^x ® represents the group SO ₂ R ^X ®, R ( ¹⁾ is C 1 -C 2 alkyl or benzyl, R ²⁰ represents an alkyl group having 1 to 2 carbon atoms and Y represents an oxygen atom or a NR ^xa group or, where appropriate, its E / Z-isomer or tautomer. 9. A compound according to claim 1 which is 4-chloro-4'-trifluoromethoxybenzophenone-N-cyclopropylcarbonylhydrazone or its E / Z-isomer. A process for the preparation of a perhalogenkoxybenzophenone hydrazone according to claim 1, or, where appropriate, its E / Z isomer or tautomer, in free or salt form, taking into account the above-mentioned condition, characterized in that: the a) to prepare a compound of formula I, wherein Y is oxygen, the compound of formula II, which is known or which can be prepared analogously to corresponding known compounds and in which A n, a, R ^1, R ^2, R ³ and R ^, as defined for formula I, or where appropriate, its E / Z isomer or tautomer, in free form or in salt form, is reacted with a compound of formula R ⁷ COX ¹ wherein X ¹ represents a leaving group, preferably a halogen atom, especially chlorine, and R ⁷ is as defined in the case of formula I, preferably in the presence of a base, or b) for the preparation perhalogénalkoxybenzof enónhydrazónu of formula I, wherein Y is O or (III) which is known or which can be prepared analogously to corresponding known compounds and in which A n, a, R ^1, R ² and R ³ the meanings defined in the case of the formula I are reacted with a compound of the formula IV which is known or which can be prepared analogously to the corresponding known compounds in which Y represents an oxygen atom or a sulfur atom and R ^e and R ⁷ have the meanings defined in of the formula I, in free form or in salt form, preferably in the presence of an acid, or in the presence of an acid c) for the preparation of a perhaloalkoxybenzophenone hydrazone of the formula I in which Y represents a sulfur atom, a perhaloalkoxybenzophenone hydrazone of the formula I in which Y represents an oxygen atom and R ^e is preferably an alkyl group having 1 to 8 carbon atoms; d) for the preparation of the perhalogenoalkoxybenzophenone hydrazone of the general formula I, in which Y represents a sulfur atom and R ^e represents a hydrogen atom, a compound of the general formula V R (R) π · (V) which is known or can be prepared analogously to the corresponding known compounds and in which the symbols n, p, R ¹ , R ² , R ³ and R ^{7 have the} meanings defined for formula I, or, where appropriate, its E / Z-isomer, in free form or in salt form, is reacted with a sulfane, preferably in the presence of a base, or that e) reacting a perhaloalkoxybenzophenone hydrazone of the formula I in which R ^e represents a hydrogen atom with a compound of the formula R ^e X ² in which X ² represents a leaving group, for example halogen, trifluoromethylsulfonyl, toluenesulfonyl or benzenesulfonyl, preferably halogen , where appropriate in the presence of a base or that (f) for the preparation of perhaloalkoxybenzophenone hydrazone of formula I in which Y is NR ¹ ®, the compound of formula II is reacted with a compound of formula VI \ F? ⁸ (VI) which is known or which can be prepared analogously to corresponding known compounds and in which R ⁷ and R ^X are as defined for formula I and X ³ is a leaving group, e.g. halogen or C 1 -C 4 carbon atoms, preferably ethoxy or, where appropriate, its E / Z isomer, in free or salt form, preferably in the presence of a base or an acid, or g) to prepare a compound of formula I, wherein ^R is NR R ^{XO XX,} the compound of formula II, wherein R ⁶ is H, with a compound of formula VII OR F? ^-0 R 11 'N 11 R (VII) which is known or which can be prepared analogously to the corresponding known compounds and in which R ⁴ , R ¹⁰ and R ^{11 have the} meanings defined for formula I and R represents an alkyl group having 1 to 4 carbon atoms, or that is h) to prepare a compound of formula I, wherein ^R is NR ^XO R ^XX, the compound of formula VIII, (VIII) which is known or which can be prepared analogously to corresponding known compounds, e.g., by reaction perhalogénalkoxybenzof enónhydrazónu of formula I, in which Y represents an oxygen atom and R ⁶ represents a hydrogen atom with phosphorus pentachloride and in which the symbols n, p, R ^x , R ² , R ³ and R ^{4 have the} meanings defined for formula I or, where appropriate, the E / Z-isomer thereof, in free or salt form, is reacted with a compound of the formula NHR ^XO R ^XX , preferably in the presence of a base, and in each case, if desired, the perhalogenoalkoxybenzophenone hydrazone of the formula I or a tautomer thereof, obtainable according to this process or otherwise, in free form or f converting to another perhalogenkoxybenzophenone hydrazone of formula I or an E / Z-isomer or tautomer thereof, resolving the mixture of isomers obtainable by this process and isolating the desired isomer and / or isolating the perhalogenkoxybenzophenone hydrazone of formula I or a tautomer thereof The E / Z-isomer in the free form obtainable according to the process is converted to the salt or the salt of the perhalogenoalkoxybenzophenone hydrazone of the formula I or its tautomer or its E / Z-isomer obtainable according to the process is converted to the free perhalogenoalkoxybenzophenone hydrazone. or a tautomer or E / Z-isomer thereof, or another salt thereof. 11. A pesticide comprising at least one perhaloalkoxybenzophenone hydrazone according to claim 1 of the general formula I, in free form or in the form of an agrochemically usable salt, as active ingredient and optionally at least one carrier or excipient. A composition according to claim 11 for controlling insects or members of the Acarina family. A process for the preparation of a composition according to claim 11 comprising at least one carrier or excipient, characterized in that the active ingredient is thoroughly mixed and / or ground with the carrier or excipient (s). Use of a perhalogenkoxybenzophenone hydrazone according to claim 1 of the general formula I in free form or in the form of an agrochemically usable salt for the preparation of a composition according to claim 11. Use of a composition according to claim 11 for controlling pests. Use according to claim 15 for the protection of plant propagation material. 17. A method for controlling pests, characterized in that the composition according to claim 11 is applied to the pests or to their environment. A method according to claim 17 for the protection of plant propagation material, characterized in that the propagation material or the place to which the propagation material is sown or planted is treated. Plant propagation material treated by the method of claim 18. 20. Perhalogénalkoxybenzofenónhydrazón of formula II wherein n, a, R ^1, R ^2, R ³ and R ⁶ are as defined for formula I, or, where applicable, an E / Z isomer or tautomer thereof , in free form or in salt form, provided that in the perhaloalkoxybenzophenone hydrazones of formula II wherein R ⁶ is hydrogen, o is 0, n is 0 or n is 1 and R ² is 4-n-butyl , R ^{x is} not an OCF group. A process for the preparation of a perhalogenkoxybenzophenone hydrazone according to claim 20, in free form or in salt form, characterized in that it is known or can be prepared analogously to the corresponding known compounds and in which R ^{x is} as defined in of formula I and X ⁴ represents a halogen atom, preferably chlorine, reacted with benzene which is mono- or polysubstituted with the substituent R ² as defined in formula I, under conventional Friedel-Crafts conditions, or that j) a compound of formula X s- (X) which is known or which can be prepared analogously to corresponding known compounds and in which R ^x is a symbol defined 92 and as defined for formula (I), is reacted with phenylmagnesium halide which is mono- or polysubstituted with R ² as defined for formula (I), preferably phenylmagnesium bromide, under conventional Grignard reaction conditions, or k) reacting a compound of formula XI * which is known or which can be prepared analogously to the corresponding known compounds and in which n, o, R ² * and R ^{3 have the} meanings defined for formula I, is reacted with a compound of formula Br (CF ₂ ) 4 Br in which p has a value of 1, 2, 3 or 4, preferably in the presence of a strong base such as sodium hydride, potassium hydride or potassium tert-butoxide, or that for the preparation of perhalogenoalkoxybenzophenone hydrazone R ¹ represents OCF _a compound of formula XI is reacted with carbon tetrachloride in the presence of hydrogen fluoride, or that _t to prepare a compound of formula II in which R ^x is OCF ₂ C 1, a compound * of formula XI with a compound of formula C 1 -C ₃ COCOC1 in the presence of HF and, if desired, the product Ad The reaction is then reacted with hydrogen fluoride to prepare a perhaloalkoxybenzophenone hydrazone of formula II wherein R ¹ is OCF ₃ , or 1) to prepare a compound of formula II in which R ^x is a group of OCF _and, the compound of formula XII (XII) which is known or which can be prepared analogously to corresponding known compounds and in which A n, a, R ² a R ³ as defined in formula I is reacted with hydrogen fluoride, preferably in the presence of an oxidizing agent, preferably 1,3-dibromo-5,5-dimethylhydantoin, and a base, preferably pyridine, or m) to prepare a compound of formula II in which R ^x is a group of OCF _and, the compound of formula XIII, which is known or which can be prepared analogously to corresponding known compounds and in which A R, a, R ² and R ³ defined as defined in formula (I) and R represents a (C1-C4) alkyl group, reacted with phosphorus pentachloride and Cl ₂ , and the resulting product is further reacted with antimony (III) fluoride and antimony ( _II) chloride, followed by hydrolysis, followed by the benzophenone derivative is reacted with a compound of the formula R ^e NHNH ₂ and / or, if desired, the perhalogenoalkoxybenzophenone hydrazone of the formula II obtained by this process or otherwise is converted to another perhalogenoalkoxybenzophenone hydrazone of the formula II and / or cleaves a mixture of isomers which It can be obtained according to this method and the desired isomer is isolated. Use of the perhalogenkoxybenzophenone hydrazone according to claim 20 of the general formula II, in free form or in the form of a salt, for the preparation of the perhalogenkoxybenzophenone hydrazone according to claim 1 of the general formula I.