HUT75200A - Perhalogenalkoxy-benzenophenone hydrazone derivatives, intermediates, preparation thereof, and pesticide compositions containing these compounds as active ingredients, preparation and use thereof - Google Patents

Description

Perhalogenalkoxy-benzophenone hydrazone derivatives t / 7Y?

eiolf / t ftfxuk. _t hadvcaujíí ^ lc ^ t ^ f- -eded c * - fa '/ööw.-eö'pejzfi'c.'/ kZ kcMiper / ctúk ejfccf / fi + duik and -feffz & rmdfn ^ αΐχ

The present invention relates to a compound of formula (I)

in the formula

X is a group of formula (a) or (b), (a) \ _k , (b)

n is 0, 1, 2, 3, 4 or 5; if n is greater than 1, the same or different;

o is 0, 1, 3, 3 or 4; if o is greater than 1, R 4 is the same or different;

R1 is perhalogen (C1-C4) -alkoxy;

R 4 is halogen, C 1-8 alkyl, halo (C 1-8) alkyl, C 1-8 alkoxy, halogen * R

- (C 1 -C 8) alkoxy, (C 1 -C 8) alkylthio, halo (C 1 -C 8) alkylthio, (C 1 -C 8) alkylsulfinyl, halo (1-8) C 1 -C 4 alkylsulfinyl, C 1 -C 8 alkylsulfonyl, halo-C 1 -C 8 alkylsulfonyl, CN, or phenyl;

R ³ is halogen, C 1-8 alkyl, halo (C 1-8 alkyl) or halo (C 1-8 alkoxy);

R ⁴ is H, halo, C 1-8 alkyl,

C3-C6 cycloalkyl, halo (C1-C8 alkyl),

(C 1 -C 8) alkoxy, (C 1 -C 8) alkoxy (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy (C 1 -C 8) alkoxy, (C 1 -C 8) alkylthio - or NR @ R @ 4;

R 4 is C 1 -C 8 alkyl, NR 1 -Or ³ ', OR ₂ R ² , SR ₂ O or SO ₂ R ² °;

R @ 3 is hydrogen, (C1-C8) alkyl, (C3-C6) cycloalkyl, halo ((C1-C8) alkyl), (C1-C8) alkenyl, (C1-C8) alkynyl, (C1-C8) acyl- or phenyl;

R ³ is hydrogen, unsubstituted or substituted C 1 -C 8 alkyl, C 3 -C 6 cycloalkyl, (C 3 -C 6 cycloalkyl) -C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 1 -C 8 alkynyl, C3-C6 cycloalkenyl, (C3-C6 cycloalkenyl) -C1-C8 alkyl, or (C3-C6 cycloalkyl) -C1-C8 alkenyl, which may have from 1 to 8 halogen atoms. C 1 -C 8 alkyl, halo-C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halo-C 1 -C 8 alkoxy, (C 1 -C 8)

- (3) alkyl) -S (Ο) _p , wherein p is 0, 1 or 2, (C 1 -C 8) alkoxy-carbonyl, di- (C 1 -C 8) -alkylamino, and (C 1 -C 8) -alkanoyl; they may be substituted by oxy; phenyl or heteroaryl, unsubstituted or substituted with C 1-6 alkyl or halogen; C 1-8 alkoxy, NR ¹⁶ R ¹⁷ , COOR ⁶ , or SR ⁶ ;

R ⁸ and R ⁹ are each independently hydrogen, C 1-8 alkyl, or OH;

r10 is hydrogen, (C1-C8) alkyl, (C3-C6) cycloalkyl, halo (C1-C8) alkyl, halo (C1-C8) alkoxy (C1-C8) alkyl, phenyl, OR ¹² -, S (O) _m R ¹³ -, (m is 0, 1 or 2) or

NR ^ R ^ alkyl;

R ¹¹ is hydrogen, C 1-8 alkyl, C 3-6 cycloalkyl, halo (C 1-8 alkyl), (C 1-8 alkoxy) (C 1-8 alkyl), allyl, C 1-8 -alkyl-allyl, haloallyl or propargyl;

R ¹² is hydrogen, C 1-8 alkyl, halo (C 1-8 alkyl), (C 1-8 alkoxy) (C 1-8 alkyl), C 3-6 cycloalkyl, 2-8. C 1 -C 5 alkenyl, halo (C 2 -C 8) alkenyl or propargyl;

R ¹³ is hydrogen, C 1 -C 8 alkyl, halo-C 1 -C 8 alkyl, phenyl or NR ¹⁴ R ¹⁵ ;

R-L 4 and R 15 are each independently hydrogen, C 1-8 alkyl, halo (C 1-8) alkyl, phenyl, ···· · · · · · · · · · · · · · · · · · · · · · · ·

- (C 1 -C 8) alkylamido, di- (C 1 -C 8) alkylamido or NH ₂ ;

R ¹⁶ and R ¹⁷ are each independently hydrogen, 1-8

C 1-8 -alkyl, halo-C 1-8 -alkyl, 2-8 R ¹⁸ alkenyl, C1-8 alkoxy cut NH ₂ group; is S (O) _m R ¹⁹ -, - m is 0, 1 or 2 - NO ₂ - or CN- Rl9 -group; C 1-8 alkyl, halogen C 1-8 R ²⁰ alkyl), (C 3 -C 6) cycloalkyl, phenyl, benzyl or NR ⁷⁴ R ¹⁵ ; C 1-8 alkyl, halogen C 1-8 Y alkyl) or C 3-6 cycloalkyl; is O, S, NR ⁷⁸ or CHC (O) R ²¹ ; R21 and is H, (C 1 -C 8) alkyl, halo (C 1 -C 8 alkyl), (C 1 -C 8) alkoxy, or phenyl, provided that for compounds of formula (I) wherein X is is -N = C (R ⁴⁾ R ^5, R is OCF 3, 0 is 0, n is 1, ^R4 is CH3 and R5 is -N (CH 3) OCH 3, R ² and fluorine and chlorine atom other than 'meaning - E / Z isomers and tautomers, in each case in free form or in salt form; processes for the preparation of these compounds, the use of these compounds and their tautomers, pesticides having the active ingredient of these compounds and tautomers, in each case in free form or in the form of their agrochemically useful salts, and for the preparation and use of these compositions.

natkozik.

····· * ·· · · · · · · · · · · · · · · · ···

Certain hydrazone derivatives have been suggested in the literature for the pesticide insecticide. However, the biological properties of these known compounds are unsatisfactory in the field of pest control, since it is necessary to include other pesticidal compounds, in particular for insect control. This requirement is met by the compounds of formula (I) described herein. For example, the compounds may exist as E / Z isomers.

in the isomeric forms (IA) and (IB)

(IA)

(IB)

Consequently, they are compounds of formula (I)

where appropriate, the following E / Z isomers may be used, even if not specifically mentioned in each case.

Some of the compounds of formula I may exist in tautomeric forms, for example, when R ⁶ is H, the corresponding compounds of formula I are those wherein X is -N (H) -C (R ⁷ ) = Y may be in equilibrium with the tautomers of the corresponding N-C (R ⁷ ) -YH structure. Accordingly, the compounds of formula (I), where applicable, are intended to include the corresponding tautomers, unless specifically mentioned below.

• Here »

The compounds of formula (I) and, where appropriate, their E / Z isomers and tautomers may also be in the form of salts. Compounds of formula (I) having at least one basic center may form acid addition salts. These acid addition salts are, for example, with strong inorganic acids such as mineral acids such as sulfuric acid, phosphoric acid or hydrogen halide or strong organic carboxylic acids such as unsubstituted or unsubstituted C 1 -C 4 alkanoic acids such as acetic acid or acetic acid, e.g. , malonic acid, maleic acid, furmaric acid or phthalic acid, or hydroxycarboxylic acids such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid or benzoic acid or organic sulfonic acids such as unsubstituted or substituted arylsulfen for example, methanesulfonic acid or p-toluenesulfonic acid. Further, compounds of formula I having at least one acidic group may form salts with bases. Suitable bases include, but are not limited to, metal salts such as alkali metal salts or alkaline earth metal salts, or with ammonia or organic amines such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamine, e.g. salts with either dimethylpropylamine or triethyl or dimethylpropylamine or with mono-, di- or tri-hydroxy (lower alkyl) amines such as mono-, di- or triethanolamine. Also suitable internal salts.

- 7 can form. Within the scope of the invention, agricultural salts are preferred; although the invention includes salts which are disadvantageous in agriculture, such as bees and fish toxic salts which are used, for example, to isolate or purify the free compounds of formula (I) and their agriculturally useful salts.

Due to the similarity between the free compounds of formula (I) and their salts, the compounds of formula (I) and their salts above and below are to be understood by analogy to mean the corresponding salts and the free compounds of formula (I) too. The same applies to the corresponding E / Z isomers and tautomers of the compounds of formula I and their salts.

Unless otherwise defined, the general terms used above and below are defined below.

As halogen or other groups or compounds such as haloalkyl, haloalkoxy, haloalkoxyalkyl and haloalkenyl, fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, may be used.

Unless otherwise specified, the carbon-containing groups and compounds in each case contain at least one and not more than eight, preferably at least one and not more than four, in particular 1-2 carbon atoms.

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

The alkyl group alone or as a component of other groups or compounds, such as haloalkyl, alkoxy, alkoxyalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl, is in each case straight-chain in each group or compound. such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl or branched chain such as isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl or isooctyl groups.

The halogen-substituted carbon-containing groups and compounds, such as, for example, haloalkyl, haloalkoxy or haloalkenyl, may be partially halogenated or perhalogenated and the halogen substituents may be the same or different when polyhalogenated. Halogenalkyl groups, alone or as constituents of other groups or compounds such as halocycloalkylalkyl and haloalkenyl, may be methyl, mono-, di- or tri-substituted with fluorine, chlorine and / or bromine, such as CHF2 or CF. ₃ ; mono-, di-, tri-, tetra and pentasubstituted ethyl groups such as CH ₂ CF ₃ , CF ₂ CF ₃ , CF ₂ CCl ₃ , CF ₂ CHCl ₂ , CF ₂ CHF ₂ , CF with fluorine, chlorine and / or bromine. ₂ CFC1 ₂ CF ₂ CHBr _2, CF ₂ CHC1F, _CF2 CHBrF or CC1FCHC1F; propyl or isopropyl groups mono-heptasubstituted with fluorine, chlorine and / or bromine, such as CH ₂ CHBrCH ₂ Br, CF ₂ CHFCF ₃ , CH ₂ CF ₂ CF ₃ or CH (CF ₃ ) ₂ ; and a mono-, non-substituted butyl group or an isomer thereof such as CF (CF ₃ ) CHFCF ₃ or CH ₂ (CF ₂ ) ₂ CF _{3 with} fluorine, chlorine and / or bromine.

Acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl, • · • ·

9 may be heptanoyl, octanoyl, aroyl such as benzoyl or heteroaryl such as thienoyl.

Heteroaryl groups include thienyl, pyrryl, imidazolyl, pyrazolyl, triazolyl, thiazolyl, isothiazolyl, pyridyl, indolyl, benzo [b] thienyl or benzo [b] furyl.

Within the above limitations, preferred embodiments of the invention are:

(1) a compound of formula (I) wherein n is 0, 1, 2, 3 or 4, preferably 1, 2 or 3, in particular 1 or 2, especially 1, and if n is greater than one, R ² radicals same or different; or, where appropriate, their E / Z isomer or tautomeric form;

(2) a compound of formula I wherein o is 0, 1, 2 or 3, preferably 0, 1 or 2, in particular 0 or

1, particularly preferably 0, wherein when m is greater than one, the group R ² may be the same or different; or, where appropriate, their E / Z isomer or tautomeric form;

(3) a compound of formula (I) wherein:

R1 is perhalogen (C1-C3 alkoxy), preferably perhalogen (C1-C2 alkoxy), particularly preferably perhalomethoxy or, where appropriate, its E / Z isomer or tautomeric form;

(4) a compound of formula (I) wherein:

R ² is halogen, C 1-6 alkyl, halo (C 1-6 alkyl), halo (C 1-6 alkyl), C 1-6 alkoxy or halo (C 1-6 alkoxy), preferably halogen

C 1 -C 4 alkyl, halo (C 1 -C 4 alkyl) or halo (C 1 -C 4 alkoxy), especially halogen, C 1 -C 2 alkyl, halo (1) C 2 -C 2 alkyl) or halo-C 1 -C 2 alkoxy, particularly preferably halogen, methyl, halomethyl, halomethoxy; or, where appropriate, their E / Z isomer or tautomeric form;

(5) a compound of formula (I) wherein: hydrogen, halogen, (C1-C4) -alkyl, halo ((C1-C4) -alkyl) or halo ((C1-C4) -alkoxy), preferably hydrogen, halogen; C 1 -C 2 alkyl or halo (C 1 -C 2 alkyl), in particular hydrogen, halogen or methyl, particularly preferably hydrogen, chlorine or fluorine or, where appropriate, their E / Z isomer or tautomeric form;

(6) a compound of formula (I) wherein:

R ⁴ is hydrogen, halogen, C 1-6 alkyl,

C 3 -C 6 cycloalkyl, halo (C 1 -C 4 alkyl), C 1 -C 4 alkoxy, (C 1 -C 4 alkoxy) (C 1 -C 4 alkyl), (C 1 -C 4 alkoxy) - ( C 1 -C 4 alkoxy), C 1 -C 4 alkylthio or NR ⁸ R ⁶ , preferably hydrogen, halogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, halo (C 1 -C 2) alkyl) or (C 1 -C 2) alkoxy, particularly preferably hydrogen or (C 1 -C 4) alkyl, or, where appropriate, E / Z isomer or tautomeric form;

(7) a compound (I) wherein R ⁵ is C 1-4 alkyl, NR ^{4 'R 44,} OR ^2I \ SR or SO ² R ² ^ ² ^, • · · *

11 is preferably NR ¹⁰ R ^{1: 1} or OR ²⁰ , especially NRTr ¹¹ or, where appropriate, its E / Z isomer or tautomeric form;

(8) a compound (I) wherein ^R6 is hydrogen, C1-6 alkyl, C3-6 cycloalkyl, C1-6 alkenyl, C1-6 alkynyl, C1-6 acyl, preferably hydrogen, (C 1 -C 4) -alkyl, (C 3 -C 6) -cycloalkyl or (C 1 -C 6) -acyl, in particular hydrogen or (C 1 -C 4) -alkyl or, where appropriate, an E / Z isomer or tautomer thereof;

(9) a compound of formula (I) wherein R ⁷ is hydrogen, unsubstituted or substituted C 1-6 alkyl, C 3-6 cycloalkyl, (C 3-6 cycloalkyl) (C 1-4 alkyl), C 1 -C 6 alkenyl, C 1 -C 6 alkynyl substituted with C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkoxy, (C 1 -C 4 alkyl) -S (O) p where p is 0, 1 or 2, (C 1 -C 4 alkoxy) carbonyl, di (C 1 -C 4 alkyl) amino and C 1 -C 4 alkanoyl they may be oxy;

phenyl or heteroaryl, which are unsubstituted or mono- or polysubstituted with C 1-4 alkyl or halogen;

NR ¹⁶ R ¹⁷ , COOR ⁶ or SR ⁶ , preferably hydrogen, unsubstituted or substituted C 1-6 alkyl, 3-6 s Zen atom cycloalkyl group having a halogen atom, 1-2 -C alkyl, halo (1-2 -C alkyl) -, 1-2 -C alkoxy, halogen (1-2 -C alkoxy) -, 1-2 -C alkyl-S (O) p -, wherein p value is 0, 1 or 2, 1-2

They may be substituted by one of C 1 -C 6 alkoxycarbonyl, di (C 1 -C 2 alkyl) amino and C 1 -C 2 alkanoyloxy;

phenyl or heteroaryl groups which are unsubstituted or mono- or polysubstituted with C 1-2 alkyl or halo; C 1-2 alkoxy, NR ¹⁶ R ¹⁷ or SR ⁶ ; in particular hydrogen, unsubstituted or substituted (C 1 -C 6) alkyl, (C 3 -C 6) cycloalkyl, which may be substituted by halogen, (C 1 -C 2) alkyl and (C 1 -C 2) alkoxy; unsubstituted or halogen-substituted phenyl or heteroaryl; Alkoxy of ^{1 to} 2 carbon atoms, NR ¹ to ⁶ R ¹ - 1 or SR ⁶ ; particularly preferably C 1-4 alkyl, C 3-6 cycloalkyl;

unsubstituted or halogen-substituted phenyl or heteroaryl; C 1-2 alkoxy or NR 16 R 17 or, where appropriate, an E / Z isomer or tautomer thereof;

(10) a compound of formula (I) wherein ^R8 is hydrogen or C1-6 alkyl, preferably hydrogen or methyl, or E / Z isomer or tautomer thereof, where appropriate shape;

(11) a compound of formula (I) wherein R 1 is hydrogen or C 1-6 alkyl, preferably hydrogen or C 1-4 alkyl, particularly preferably hydrogen or methyl, or an E / Z isomer or tautomer thereof;

(12) a compound of Formula (I) wherein R- ¹ - ^O is hydrogen, (C 1 -C 4) alkyl, (C 3 -C 6) cycloalkyl, halo (C 1 -C 4) alkyl; ), phenyl, OR ¹² , S (O) _m R ¹³ wherein m is 0 or 2 or NR ¹⁴ R ¹⁵ , preferably hydrogen, C 1 -C 2 alkyl, phenyl or OR ¹² , especially hydrogen C 1 -C 2 alkyl or OR ¹² or, where appropriate, an E / Z isomer or tautomer thereof;

(13) a compound of Formula (I) wherein R ¹¹ is hydrogen, C 1-4 alkyl, C 3-6 cycloalkyl, halo (C 1-4 alkyl), (C 1-4 alkoxy) - C 1-4 alkyl, allyl, C 1-4 alkyl allyl, haloallyl or propargyl, preferably hydrogen, C 1-2 alkyl, C 3-6 cycloalkyl, allyl or (C1-C4) alkyl-allyl, in particular hydrogen or (C1-C2) -alkyl, or, where appropriate, an E / Z isomer or tautomer thereof;

(14) a compound of Formula (I) wherein R ¹² is hydrogen, (C 1 -C 4) alkyl, halo (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkyl. -, C3-C6 cycloalkyl, C2-C4 alkenyl, halo (C2-C4 alkenyl) or propargyl, preferably hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl,

C 2 -C 4 alkenyl or propargyl, in particular hydrogen, C 1 -C 2 alkyl or C 3 -C 6 cycloalkyl, or, where appropriate, an E / Z isomer or tautomer thereof;

(15) a compound of formula (I) wherein R ¹³ is hydrogen, C 1-4 alkyl, halo (C 1-4 alkyl), phenyl or NR ¹⁴ R ¹⁵ , preferably C 1-2 alkyl; , halogen (C 1-2 alkyl) or phenyl,

- 14 in particular C 1 -C 2 alkyl or halo-C 1 -C 2 alkyl or, where appropriate, an E / Z isomer or tautomer thereof;

(16) a compound of formula (I) wherein R is hydrogen, (C1-C4) -alkyl, halo ((C1-C4) -alkyl), phenyl, (C1-C8) -alkylamido, di (1-). C 4 alkyl) amido or NH ₂ , preferably hydrogen, C 1-2 alkyl or phenyl, especially C 1-2 alkyl or phenyl or, where appropriate, their E / Z isomer or tautomeric form;

(17) a compound of Formula (I) wherein: H is (C1-C4) alkyl, halo (C1-C4) alkyl, phenyl, (C1-C8) alkylamido, di (C1-C4) alkyl ) -amido or NH ₂ , preferably hydrogen, C 1 -C 2 alkyl or phenyl, particularly preferably C 1 -C 2 alkyl or phenyl or, where appropriate, their E / Z isomer or tautomeric form;

(18) a compound of formula (I) wherein R ¹⁶ is hydrogen, C 1-4 alkyl, halo (C 1-4 alkyl) or C 1-8 alkoxy, preferably hydrogen or C 1-4 alkyl, in particular 1-2 alkyl groups or, where appropriate, E / Z isomeric or tautomeric forms;

(19) a compound of formula (I) wherein it is hydrogen, (C1-C4) -alkyl, halo ((C1-C4) -alkyl) or (C1-C8) -alkoxy, preferably hydrogen or (C1-C4) -alkyl, especially 1 A C2-C4 alkyl group or, where appropriate, an E / Z isomer or tautomer thereof;

(20) a compound of formula (I) wherein R ¹⁸ is SO ₂ r ¹⁹ , NO ₂ or CN, preferably SO ₂ r ¹⁹ or, where appropriate, an E / Z isomer or tautomer thereof;

(21) a compound of Formula (I) wherein R ¹⁹ is C 1-4 alkyl, halo (C 1-4 alkyl), C 3-6 cycloalkyl, phenyl, benzyl, or -NR ¹⁴ R ^15; , preferably C 1-2 alkyl, phenyl, benzyl or NR ¹⁴ R ¹ · ^5, in particular C 1-2 alkyl or benzyl or where appropriate, E / Z isomer or tautomer thereof;

(22) a compound of Formula (I) wherein R ²⁰ is C 1-4 alkyl, halo (C 1-4 alkyl) or C 3-6 cycloalkyl, preferably C 1-2 alkyl or C 3-6 cycloalkyl; especially C 1 -C 2 alkyl or, where appropriate, E / Z isomeric or tautomeric forms;

(23) a compound of the formula I in which Y is O, S or NR ¹⁸ , preferably O or NR * - ⁸ , particularly preferably O or, where appropriate, E / Z isomer or tautomeric form;

(24) a compound of formula (I) wherein R ²¹ is hydrogen, C 1-4 alkyl, halo (C 1-4 alkyl) or C 1-4 alkoxy, preferably C 1-2 alkyl, halogen; C 1 -C 2 alkyl or C 1 -C 2 alkoxy, especially methyl, trifluoromethyl, methoxy or ethoxy or, where appropriate, E / Z isomer or tautomeric form;

(25) a compound of Formula (I) wherein n is 1, 2 or 3, wherein when n is greater than 1, the radicals R ² are the same or different and o is 0, 1 or 2, wherein when o is greater than 1, the radicals R ³ are the same or different, R ¹ is perhalogen (C 1-3 alkoxy), R ² is halogen, C 1-6 alkyl, halogen (1). -C 6 -alkyl) or halo-C 1 -C 6 -alkoxy, R ³ is hydrogen, halo, C 1 -C 2 alkyl or halo-C 1 -C 2 alkyl, R 1 is hydrogen, halogen , C 1-4 alkyl, C 3-6 cycloalkyl, halo (C 1-2 alkyl) or C 1-2 alkoxy, R ³ is C 1-4 alkyl, N ¹⁰ R ³³ , OR ²

SR or SC ^ R ²⁰ , R R is hydrogen, C 1-6 alkyl, C 3-6 cycloalkyl, C 1-6 alkenyl, C 1-6 alkynyl or C 1-6 acyl, R ⁷ is hydrogen, unsubstituted or substituted C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl substituted by halogen, C 1 -C 2 alkyl, halo (C 1 -C 2 alkyl), C 1 -C 2 alkoxy, halogen- C 1 -C 2 alkoxy), (C 1 -C 2 alkyl) -S (O) p and p are 0, 1 or 2, (C 1 -C 2 alkoxy) carbonyl, di (C 1 -C 2 alkyl) - amino and C 1-2 alkanoyloxy groups; and phenyl or heteroaryl, singly or multiply substituted by unsubstituted or singly or multiply substituted C1-C2 alkyl or halogen; C 1 -C 2 alkoxy, NR 1 - ⁶ - R 17 or SR ⁶ ; R 6 -θ is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, halo (C 1 -C 4 alkyl), phenyl, OR ¹² , S (O) _m R ¹³ wherein m is 0 or 2 or NR ⁴⁴ R ⁴³ , R 4 - is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, halo (C 1 -C 4 alkyl), (C 1 -C 4 alkoxy) -. (C1-C4 alkyl), allyl, (C1-C4 alkyl) allyl, haloallyl, or propargyl, R * ² is hydrogen, (C 1 -C 4) alkyl, halo (1-4); C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl, halo (C 2 -C 4 alkenyl) or propargyl, R - * - ³ is hydrogen, C1-4 alkyl, halo (C1-4 alkyl) -, phenyl, or NRl ⁴ R ⁴⁵ group and R ¹⁴ and R is hydrogen, ⁴⁵ are independently C 1-4 alkyl , halo (C1-C4 alkyl), phenyl, (C1-C8) alkylamido, di (1-4) alkyl) amino or NH2-groups are, ^R4 ® and R ⁴⁷ each independently represents hydrogen, C1-4 alkyl, halo (C1-4 alkyl) - or C 1-8 -alkoxy are, ^R43 represents SO2R ^{4 ',} NO ₂ or CN, R ⁴ ® represents C1-2 alkyl, phenyl, benzyl, or NR ^ R ^ -alkyl, R ²³ is C1-2 alkyl or C3-6 cycloalkyl, and Y is oxygen , a sulfur atom or a NR * * ³ or an E / Z isomer or a tautomer thereof, as appropriate;

(26) a compound of Formula (I) wherein n is 1 or 2, wherein when n is greater than 1, the radicals R ² are the same or different, o is 0 or 1, R ⁴ is perhalogen (C 1-2) alkoxy), R ² is halogen, C 1-4 alkyl, halo (C 1-4 alkyl) or halo (C 1-4 alkoxy), R ³ is hydrogen, ···· ·· ··· · halogen or methyl, R ⁴ is hydrogen or C 1 -C 4 alkyl, R ³ is C 1 -C 4 alkyl, NR ¹⁰ R ¹¹ , OR ²⁰ , SR ²⁰ or SO ₂ R ₂₀ , R 4 is hydrogen, C 1-4 alkyl, C 3-6 cycloalkyl or C 1-6 acyl, R ⁷ is hydrogen, C 1-6 alkyl, C 3-6 cycloalkyl, unsubstituted or halo, C 1-2 alkyl or Phenyl or heteroaryl substituted with C 1-2 alkoxy or C 1-2 alkoxy or NR ⁴³ R ⁴⁷ ; R ^{4 (7} is hydrogen, C 1 -C 2 alkyl, phenyl or OR ¹² , R ⁴¹ is hydrogen, C 1 -C 2 alkyl, C 3 -C 6 cycloalkyl, allyl or (C 1 -C 4 alkyl) allyl, R ⁴² is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl or propargyl, R ⁴ - and R ⁴⁷ are independently hydrogen or C 1 -C 4 alkyl, R ⁴⁸ is SO 2 R ⁴⁹ , NO 2 or CN, R ⁴⁹ is C 1 -C 2 alkyl or benzyl, R ²⁹ is C 1 -C 2 alkyl or C 3 -C 6 cycloalkyl, and Y is oxygen, sulfur or NR ⁴⁸ or, if appropriate, E / Z isomer or their tautomeric form;

(27) a compound (I) wherein n is 1, o is 0 or 1, R ⁴ is perhaloalkyl methoxy, ^R2 is halogen, C1-2 alkyl, halo (C1-2 alkyl) or halo (C 1 -C 2 alkoxy), R ³ is hydrogen, chloro or fluoro, R ⁴ is hydrogen or C 1 -C 4 alkyl, R ⁵ is NR ⁴⁹ R ⁴⁴ or OR ²⁸ , R ⁹ is hydrogen or C 1 -C 4 • ·

- 19 alkyl, R ⁷ is hydrogen or C 1-4 alkyl, R ⁷ is hydrogen, C 1-4 alkyl, C 3-6 cycloalkyl, phenyl, unsubstituted or halo-substituted heteroaryl, - C 1-2 alkoxy or NR ²⁶ R ⁷⁷ , R ²⁰ and R ¹¹ independently of one another are hydrogen, C 1-2 alkyl or OR ¹² , R ¹² is hydrogen, C 1-2 alkyl or C 3-6 cycloalkyl, and R ⁷ - ⁷ each independently represents a C 1 -C 2 alkyl group, R ⁸ * ⁸ represents SO ₂ R ¹⁹ , R ¹⁹ represents a C 1 -C 2 alkyl or benzyl group, R ²⁹ represents a C 1 -C 2 alkyl group, and Y represents O or NR ²⁸ in the case of E / Z isomer or tautomeric form;

(28) a compound of Formula (I) wherein n is 1, o is 0 or 1, R 1 - is perhalomethoxy, R ² is halogen, methyl, halomethyl or halomethoxy; R ² is hydrogen, chloro or fluoro, R 1 is hydrogen or C 1 -C 4 alkyl, R ² is NR- ¹ -Or ² · '-, R 4 is hydrogen or C 1 -C 4 alkyl, R ⁷ is hydrogen, C 4 -C 4 alkyl, C 3 -C 6 cycloalkyl, phenyl, unsubstituted or halo-substituted heteroaryl, C 1 -C 2 alkoxy, or NR ¹⁶ R ¹⁷ , R ²⁰ and R 6 independently of one another hydrogen, C 1-2 alkyl- or C 3 -C 6 cycloalkyl, R 1 * 2 and R ²⁷ independently of one another are C 1-2 alkyl, R ¹⁸ is SO ₂ R ²⁹ , R ¹⁹ is C 1-2 alkyl or benzyl, R ^{29 is C} 1-2 alkyl. Y is O ot or NR ²⁸ «· · · · · ·

- represents 20 groups or, where appropriate, an E / Z isomer or tautomer thereof;

Particularly preferred within the scope of the invention are the following: 1, 2 and

The compounds mentioned in Table 3, and more preferably the compounds of Examples H3, H5H7 and H10 and, where appropriate, their E / Z isomer or tautomeric form.

Particularly preferred within the scope of the invention are the 4-chloro-4'-trifluoromethoxybenzophenone-N-cyclopropylcarbonylhydrazone and the E / Z isomer (Compound 1.5 of Table 1).

The invention further relates to a process for the preparation of the compounds of formula I and their possible isomers and tautomers, subject to the above-mentioned limitations, in each case in free form or in the form of a salt, e.g.

(a) for the preparation of compounds of formula (I) in which Y is oxygen;

a compound of formula (II) which is known or may be prepared in an analogous manner to known compounds, wherein n, o, R ³ , R ² , R ³ and R 4 are the E / Z isomers given or possible in the formula (I) or their tautomeric form, either as a free compound or in the form of a salt with an R ³ COX · '· compound - wherein X ¹ represents a leaving group, preferably a halogen atom, ···· ····

- in particular 21 is chlorine and R ⁷ is as defined for formula (I) - preferably in the presence of a base, or

b) for the purpose of preparing a compound of general formula (I) in which Y is oxygen or sulfur;

(III), a compound of formula which is known or analogous gyületekkel manner adjustable and which in, p, R ¹ and R ² and R ³ is the formula (I) mecradott, (III), known ve wherein formula ^R6 Y (IV), h ₂ nr _{7 with} a compound of formula (IV) - which is known or may be prepared in an analogous manner to known compounds, wherein Y is oxygen or sulfur and R ⁷ is as defined for formula (I) and is free in the form of a compound or a salt, preferably in the presence of an acid, or

c) reacting phosphorus pentasulfide with a compound of formula I wherein Y is oxygen and R ⁶ ···· ···· is a C 1 -C 8 alkyl group to prepare compounds of formula I wherein Y is sulfur. , obsession

(d) for the preparation of compounds of formula (I):. wherein Y is sulfur and R ⁶ is hydrogen,

(V), a compound of formula (V), which is known or may be prepared in an analogous manner to known compounds, wherein n, o, R ¹ , R ² , R ³ and R ⁷ are as defined for formula (I), or reacting the possible E / Z isomer, either as the free compound or in the form of a salt, with S, preferably in the presence of a base, or

e) a compound of formula I wherein R ⁶ is hydrogen, with R ⁶ X ² wherein X ² is a leaving group such as halogen, trifluoromethylsulfonyl, toluenesulfonyl or benzenesulfonyl, preferably halogen; optionally in the presence of a base, or

f) for the preparation of compounds of the formula I in which Y is NR ^{43 of} the formula II (VI),

23 with a compound of formula VI, which may be prepared in an analogous manner to known or known compounds wherein R ⁷ and R ¹⁸ are as defined for formula I, X ⁸ is a leaving group such as halogen or With a C4 alkoxy, preferably ethoxy, or its possible E / Z isomer, preferably in the form of a free compound or a salt, in the presence of a base or an acid, or

g) (I) Compounds of formula wherein R ⁵ is NR ¹¹ R ^L0 group, a (II) compound of the formula: - wherein ^R6 is hydrogen vivid j

GUARD

ROj_ (VII), '11

a compound of formula VII, which is known or may be prepared in an analogous manner to the corresponding known compounds, wherein R ⁴ , R ¹⁰ and R ⁸ · ¹ · are as defined for formula I, R is C 1 -C 4 alkyl. , obsession

h) for the preparation of compounds of formula I wherein R ⁸ is NR 4 - R ⁸⁸ , (R ₂ ) n 4 -

(R ₃ ) o

Cl '(VIH), ···· · · · · f

- a compound of formula VIII, which can be prepared, for example, by reacting a compound of formula I wherein Y is oxygen and R ^s is hydrogen with phosphorus pentachloride, in a manner analogous to the corresponding known compounds, wherein n, o, R R ', R ² , R ² and R 4 are - or a possible E / Z isomer of formula (I), preferably in the form of a free compound or a salt, with NHR- ¹ -Qr ¹ - ² - in the presence of a base; wherever desired, the compounds of formula (I) or tautomeric form obtained by the process or by different means, in each case in the free form or in the form of a salt, may be converted into another compound of formula (I), E / Z or tautomeric form resolution and isolation of the desired isomer and / or (I ) or the E / Z isomer or tautomer or salt thereof, or the salt of the compound of formula I obtained by the process into the compound or tautomer or E / Z isomer or the free compound or tautomer of formula I or the E / Z isomer or various salts thereof.

The invention also relates to the preparation of compounds of formula II in each case in the form of a free compound or a salt which includes, for example,

(i) a compound of formula (IX) cox ₄ (IX),

which is known or may be prepared in an analogous manner to the corresponding known compounds and which has the meaning given in formula (I) is a halogen atom, preferably a chlorine atom - with the benzene derivative mono- or polysubstituted with the R ² group represented by formula (I) your normal circumstances, or

j) a compound of the formula X

Ri

CN (X), which is known or may be prepared in an analogous manner to the corresponding known compounds and wherein R ² is phenyl-magnesium halide mono- or polysubstituted by the formula I - substituted by the R ² group in the formula (I) preferably reacting with phenylmagnesium bromide under standard conditions of the Grignard reaction, or

k) a compound of formula XI: wherein R _{2 is} n

(XI), (R ₃ ) o which is known or may be prepared in an analogous manner to the corresponding known compounds, wherein n, o, R ² and R ² are as defined for formula (I) - with Br (CF ₂ ) pBr in the formula p is 1, 2, 3 or 4 - preferably a strong base,

- 26, for example, in the presence of sodium hydride, potassium hydride or potassium tert-butoxide, or to form compounds of formula II wherein R ¹ is OCF ₃ in the presence of hydrogen fluoride reacting CCl ₄ ~ away from, or to prepare (II) compounds, wherein the reaction of R ¹ is OCF ₂ C1 (XI) compound with hydrogen fluoride in the presence of CljCOCOCl-out resulting product, if desired, and further reacted with hydrogen fluoride is (II) compound is obtained, wherein R ¹ is OCF 3, or

1) for the preparation of compounds of formula II in which R 1 'is OCF 3, a compound of formula XII

which is known or may be prepared in an analogous manner to the corresponding known compounds and wherein η, o, R ² and R ² are as defined for formula (I) with hydrogen fluoride, preferably an oxidizing agent, preferably 1,3-dibromo-5,5- dimethylhydantoin in the presence of a base, preferably pyridine; or · · · ·

- 27 m) for the preparation of compounds of formula II in which R ¹ is OCF ₃ , a compound of formula XIII

(XIII) following,

- which is known or may be prepared in an analogous manner to the corresponding known compounds and wherein η, o, R ² and R ³ are as defined for formula (I) and R is C 1 -C 4 alkyl - with PClg and C and reacting the resulting product with SbFg and SbClg and subsequent hydrolysis, and the resulting benzophenone derivative is reacted sequentially with R 1 NHN converting the compounds to other compounds of the formula II and / or resolving the isomeric mixture obtained by the process and isolating the desired isomer.

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

The above and the following reactions are carried out in known manner, for example in the absence of solvent or in the presence of a conventional solvent or diluent or mixture thereof, where appropriate under refrigeration or at room temperature or heating, e.g. In the temperature range from C to the boiling point of the reaction medium, preferably from 0 ° C to about 150 ° C and, if necessary, in a sealed container under pressure, under an inert gas atmosphere and / or under anhydrous conditions. Particularly advantageous reaction conditions are found in the Examples.

The starting materials mentioned above and below and used for the preparation of the compounds of formula I, and their tautomers or E / Z isomers, respectively, in each case in the form of the free compound or salt, are known and can be prepared by known methods, for example.

(a) Variant:

Suitable bases which aid in the reaction include, by way of example, alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocyclic compounds, ammonium hydroxide and carbocyclic amines. Examples include triethylamine, di (isopropylethyl) amine, triethylene diamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

The reagents may react with each other alone, i.e. without the addition of a solvent such as a melt. However, in most cases, the addition of a neutral solvent or diluent or a mixture thereof is preferred. Examples of such solvents and diluents include aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petrol, , trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters such as ethyl acetate; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether. , tetrahydrofuran or dioxane; ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; amides such as N, N-dimethylformamide,

N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, the base may be used in an excess, such as triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline as a solvent or diluent.

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

In a preferred embodiment of variant a), a compound of formula II is reacted with an acid halide at a temperature of 10-40 ° C, preferably 20 ° C, in an aromatic solvent, preferably toluene, in the presence of a base, preferably triethylamine.

Variant (b):

By way of example, a suitable acid catalyst for the reaction includes catalytic amounts in the appropriate acid catalysts: * · · *: * ········································• ·

The acids used as listed above as acids suitable for forming the acid addition salts of the compounds of formula (I).

The reagents may react with each other alone, i.e. without the use of a solvent or diluent, e.g. However, in most cases it is an inert solvent or diluent

or these addition of a mixture thereof may be advantageous. Such solvents and examples of 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, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters such as ethyl acetate; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether,

ethylene glycol -monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones such as acetone, methyl ethyl ketone or the like

methyl isobutyl ketone; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide. If the reaction is acid

catalyst in the presence of the surplus employee acids such as strong organic carboxylic acids such as

unsubstituted and substituted C 1-4 alkanecarboxylic acids, such as halogen, such as · · 9 · ···· ··

- 31 formic, acetic or propionic acids may be used as solvents or diluents.

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

(c) variant:

The reagents may react with each other alone, i.e. without the addition of a solvent such as a melt. However, in most cases, the addition of an inert solvent or diluent or a mixture thereof is preferred. Examples of such solvents and diluents include aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, hexane, cyclohexane, hexane, cyclohexane 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 ; and sulfoxides such as dimethyl sulfoxide.

The reaction is preferably carried out at a temperature in the range of from about 20 ° C to about 120 ° C, preferably from about 40 ° C to about 100 ° C.

Variant (d):

Suitable bases which aid in the reaction include, by way of example, alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocyclic compounds, ammonium hydroxide and carbocyclic amines. Examples include triethylamine, di (isopropylethyl) amine, triethylene diamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

The reagents may react with each other alone, i.e. without the addition of a solvent such as a melt. However, in most cases, the addition of a neutral solvent or diluent or a mixture thereof is preferred. Examples of such solvents and diluents include aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, hexane, cyclohexane, hexane, cyclohexane 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 ; and sulfoxides such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, the base may be used in an excess such as triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline as a solvent or diluent.

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

- 33 ···· ···> · · *

e) Variant

Suitable bases which aid in the reaction include, by way of example, alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocyclic compounds, ammonium hydroxide and carbocyclic amines. Examples include triethylamine, diisopropylethylamine, triethylenediamine, N-cyclohexyl-N, N-dimethylamine and N, N-diethylaniline.

The reagents may react with each other alone, i.e. without the addition of a solvent such as a melt. However, in most cases, the addition of a neutral solvent or diluent or a mixture thereof is preferred. Examples of such solvents and diluents include aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, hexane, cyclohexane, hexane, cyclohexane 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 ; and sulfoxides such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, the base may be used in an excess, such as triethylamine or N, N-diethylaniline as a solvent or diluent.

• ·

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

It is carried out at a temperature of 10-40 ° C.

(f) variant

Suitable bases which aid in the reaction include, by way of example, alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocyclic compounds, ammonium hydroxide and carbocyclic amines. Examples include triethylamine, di (isopropylethyl) amine, triethylene diamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

Suitable acid catalysts for the reaction include, by way of example, the catalytic amounts of the acids listed above as suitable acids for the formation of acid addition salts of compounds of formula (I).

The reagents may react with each other alone, i.e. without the use of a solvent or diluent, e.g. However, in most cases, the addition of an inert solvent or diluent or a mixture thereof may be advantageous. Examples of such solvents and diluents include aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, hexane, cyclohexane or tetrachlorethene; esters • such as ethyl acetate; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide;

nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, the base may be used in an excess, such as triethylamine or N, N-diethylaniline as a solvent or diluent. When the reaction is carried out in the presence of an acid catalyst, the excess acids used may be, for example, strong organic carboxylic acids, such as unsubstituted or substituted C 1 -C 4 alkane carboxylic acids such as formic acid, acetic acid or propionic acid, as solvent or diluent.

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

g) variant

The reagents may react with each other alone, i.e. without the addition of a solvent such as a melt. However, in most cases, the addition of a neutral solvent or diluent or a mixture thereof is preferred. Examples of such solvents and diluents are aromatic aliphatic and ···

- 36 ···· · · · · · ·

alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachlorethane, dichloroethane, 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, N, N-dimethylacetamide,

N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile or propionitrile; sulfoxides such as dimethyl sulfoxide.

The reaction is preferably carried out at a temperature in the range of about 20 ° C to about + 120 ° C, more preferably about

It is carried out at a temperature between 50 ° C and 110 ° C.

h) variant

Suitable bases which aid in the reaction include, by way of example, alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocyclic compounds, ammonium hydroxide and carbocyclic amines. Examples include triethylamine, di (isopropylethyl) amine, triethylene diamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

· »·· ········ · ·

The reagents may react with each other alone, i.e. without the addition of a solvent such as a melt. However, in most cases, the addition of a neutral solvent or diluent or a mixture thereof is preferred. Examples of such solvents and diluents include aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, hexane, cyclohexane, hexane, cyclohexane 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 ; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, the base may be used in an excess such as triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline as a solvent or diluent.

The reaction is preferably carried out at a temperature in the range of from about 20 ° C to about + 120 ° C, more preferably in the range of about

The temperature is from 50 ° C to about 110 ° C.

Salts of the compounds of formula (I) may be prepared in known manner. For example, salts of the compounds of formula (I) may be prepared by treatment with an appropriate acid or acidic ion exchanger, and salts with a base of a compound of formula (I) by treatment with a suitable base or an appropriate ion exchanger.

Salts of the compounds of formula (I) may be converted into the free compounds of formula (I) by conventional means, for example, by treatment with an appropriate base or a suitable ion exchanger and salts thereof with a suitable acid or a suitable ion exchange reagent.

Salts of the compounds of the formula I can be converted in a conventional manner into other salts of the compounds of the formula I, for example acid addition salts, for example a salt with an inorganic acid such as a hydrochloride with a suitable metal salt such as sodium, barium or silver. with an acid salt thereof, such as silver acetate, in a suitable solvent in which the inorganic salt formed, such as silver chloride, is insoluble and thus separates from the reaction mixture.

Depending on the process and reaction conditions, the compounds of formula (I) having salt-forming properties may be prepared as free compounds or in the form of salts.

The compounds of formula (I) and (II) may exist in the form of one of the isomers which is possible or in a mixture thereof, for example depending on the number and absolute or relative configuration of the asymmetric carbon atoms, as pure isomers such as antipodes and / or diastereomers as mixtures, such as enantiomeric mixtures such as racemates, diastereomeric mixtures or racemate mixtures; The invention includes pure.

isomers as well as any possible mixture of isomers and is valid in all cases for the aforementioned isomers and the following, even if the stereochemical details are not mentioned.

The diastereomeric mixtures and the racemate mixtures of the compounds of formula (I) and (II) may be prepared according to the process.

Depending on the choice of starting material and process or otherwise, it can be isolated by known methods by differing physicochemical properties of the components to form pure diastereomers or racemates, for example by fractional crystallization, distillation and / or chromatography.

The enantiomeric mixtures thus obtained, such as racemates, can be resolved by known methods for the preparation of optical antipodes, for example by recrystallization from an optically active solvent, chromatography on chiral adsorbents such as high pressure liquid chromatography (HPLC) on acetylcellulose, cleavage, formation of inclusion compounds such as chiral crown ethers, so that only one enantiomer is present in the process.

The pure diastereomers or enantiomers of the present invention may be prepared not only by isolation of the corresponding isomers, but also by known methods of diastereoselective or enantioselective synthesis, for example by employing appropriate starting materials having stereochemical properties.

If the individual components differ in their biological properties, it is preferable in each case to isolate or synthesize the more biologically active isomer, such as an enantiomer, or a mixture of isomers, such as an enantiomeric mixture.

The compounds of formula (I) and (II) may also be prepared in the form of a hydrate and / or include other solvents, for example, which are necessary for the crystallization of the compounds in solid form.

The invention encompasses all embodiments of the process, starting with a compound obtainable by a process step as a starting material or intermediate or a starting compound used in the form of a derivative or a salt and / or racemate thereof or an antipode thereof, particularly under the reaction conditions. compounds.

The starting materials and intermediates used in the process of the present invention are those which lead to the compounds of formula (I) of outstanding, particularly valuable, value as described above.

The invention relates in particular to the production methods described in Examples H1 to H10.

The invention also encompasses starting materials and intermediates, in each case in the form of the free compound or in the form of a salt, which are novel and according to the invention (I).

between formed the preferably those, which a (I) general

for the preparation of compounds of the general formula or their salts • · ·· · ·

41, as well as for the use and preparation of these compounds.

The compounds of the formula I according to the invention are valuable active compounds for the prevention and / or treatment of pesticides, even when used in low concentrations, because they are well tolerated by warm-blooded species, fish and plants and have a very favorable biocidal spectrum. The active compounds of the present invention are effective against normal susceptible and even resistant animal pests at any or all stages of their development, such as insects or members of the Acarina order. The insecticidal or acaricidal activity of the active compounds of the invention will be evident directly, for example, from the immediate or delayed elimination of pests, such as during thawing; or indirectly, such as reduced egg-laying capacity and / or hatching rate, the efficacy corresponds to a mortality rate of 50-60%.

The above-mentioned animal pests include:

from the order of the Lepidoptera, for example

Acler spp., Adoxophyes spp., Aegeria spp., Agrotis spp. , Alabama argillaceae, Amylois spp. Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp.,

Clysia ambiguella, Cnaphalocrocis pp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea,

Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, • · · · · · 42

Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lymantria spp. Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolos flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.

Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusiani and

Yponomeuta spp .;

from the order of Coleoptera, for example

Agriotes spp., Anthonomus spp., Automeria linear, Chaetocnema tibialis, Cosmopolites spp., Curculip spp., Dermester spp.,

Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineate, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp.,

Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp.,

Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogtoderma spp. ;

from the order of Orthoptera, for example

Blatta spp., Balttella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp .; from the order of the Isoptera, for example, Reticulitermes spp .;

from the order of the Psocoptera, for example

Liposcelis spp .;

from the order of Anoplura, for example

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp .;

from the order of Mallophaga, for example

Damalinea spp. and Trichodectes spp .;

from the order of Thysanoptera, for example

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, thrips tabaci and Scirtothrips aurantii;

from the order of Heteroptera, for example

Cimex spp., Distantiella Theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Thodnius spp., Sahlbergella singularis, Scotinophara spp.

and Triatoma spp .;

from the order of Homoptera, for example

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp.,

Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigeru, Erythroneura spp., Gasc.

Lecaniura corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp.,

Pemphigus spp., Planococcus spp., Pseudaulacaspis spp.,

Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhoplasophum spp., Saissetia spp.,

Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;

from the order of Hymenoptera, for example

Acromyrmex, Atta spp., Cephus spp., Diprionidae, Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp .;

from the order of the Diptera, for example

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp. ., 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, for example

Ceratophyllus spp. and Xenopsylla cheopis;

from the Thysanura order, for example

Lepisma saccharina and Acarina, for example

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Choriptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eri.

Ixodes spp., Olyonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.

The active compounds of the invention are particularly suitable for controlling, controlling or eradicating the pests listed above, which are pests especially on plants, in particular.

- 45 are found on useful plants and ornamental plants, in agriculture, horticulture and forestry, or on parts, fruits, flowers, foliage, stems, tubers or roots of such plants, and in some cases the protective effect extends to newly developed parts of plants.

Suitable crops to be protected are in particular cereals such as wheat, barley, rye, oats, rice, maize and millet; beets such as sugar beet or fodder beet; fruits such as apple fruits, stone fruits and soft fruits such as apples, pears, plums, peaches, almonds, cherries and berries such as strawberries, raspberries or currants; legumes such as beans, lentils, peas or soybeans; oily fruits such as oilseed rape, mustard, poppy, olive, sunflower, coconut, castor, cocoa bean or peanut; pumpkins such as pumpkin, cucumber or melon; fiber plants such as cotton, flax, hemp or jute; citrus fruits such as orange, lemon, grapefruit or tangerine; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or green peppers; laurels such as avocado, cinnamon or camphor; tobacco, hazelnuts, coffee, egg fruits, sugar cane, tea, pepper, grapes, hops, banana family, natural latex plants and ornamental plants.

The active compounds of the invention are particularly suitable for use in the treatment of a

Boophilus microplus, Nilaparvata lugens, Panonychus ulmi and

For the control of Tetranychus urticae in vegetables, fruits and rice plants.

Other areas of application of the active compounds of the present invention are the protection of stored products, warehouses and materials.

- 46 and hygiene, in particular pets and the aforementioned pests.

The invention therefore also relates to at least one composition of at least one composition encapsulated in pesticides, such as emulsifiable concentrates, suspension concentrates, ready-to-use sprays, dilutable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, powders, granular or polymeric materials. includes the active ingredient of the invention and is selected according to the desired purpose and local conditions.

In such compositions, the active ingredient may be employed in pure form, for example, in a solid particle size, or preferably with at least one excipient commonly used in the art of formulation, such as fillers such as solvents or solid carriers or surfactant compounds.

Suitable solvents are, for example, unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably C 8 -C 12 alkylbenzene fractions such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexanes, alcohols, e.g. glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, isophorone or diacethanol alcohol, highly polar solvents such as N-methyl 2-on, dimethyl • ·

sulfoxide or N, N-dimethylformamide, water, epoxidized or epoxidized vegetable oils such as epoxidized or epoxidized rapeseed oil, castor oil, coconut oil or soybean oil and silicone oils.

Solid carriers which can be used, for example, for powders and dispersible powders are usually natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly dispersed silica gels or highly dispersed absorbent polymers may also be added to improve physical properties. For granules, suitable particles, adsorptive carriers are porous types such as pumice, brick, sepiolite or bentonite, and suitable non-sorptive carriers are calcite or sand. In addition, many granular materials of inorganic or organic origin can be used, in particular dolomite or shredded plant residues.

Suitable surfactants, depending on the nature of the active ingredient to be formulated, are nonionic, cationic and / or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties.

The following surfactants are provided by way of example only; many other surfactants commonly used in the art of formulation and suitable for use in the present invention are described in the literature.

Suitable nonionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated and unsaturated fatty acids and alkylphenols, which contain from 3 to 30 glycol ethers and are in the (aliphatic) hydrocarbon group. They contain 20 carbon atoms and 6 to 18 carbon atoms in the alkyl portion of the alkylphenols. Other suitable nonionic surfactants include water soluble adducts of polyethylene oxide with polypropylene glycol, ethylene diaminopolypropylene glycol, and alkyl polypropylene glycol having from 1 to 10 carbon atoms in the alkyl moiety and from 20 to 250 ethylene glycol ether propylene groups and from 10 to 100 g of ethylene glycol ether. they contain an ether group. The aforementioned compounds generally contain from 1 to 5 ethylene glycol units per propylene glycol unit. Examples include nonyl phenol polyethoxyethanol, castor oil polyglycol ethers, polypropylene polyethylene oxide adducts, tributyl phenoxy polyethoxy ethanol, polyethylene glycol and octylphenoxy polyethoxy ethanol. Other suitable materials are polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan trioleate.

Cationic surfactants, in particular quaternary ammonium salts, which include at least one C 8 -C 22 alkyl group and further substituents are lower, halogenated or halogenated alkyl, benzyl or lower hydroxyalkyl. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, such as stearyltrimethylammonium chloride and benzyldi (2-chloroethyl) ethylammonium bromide.

Suitable anionic surfactants include both water-soluble soaps and synthetic surfactants. Suitable soaps are the higher carbon fatty acids (C ₃ 0 ^-C 22> alkali metal salts, alkaline earth metal salts, unsubstituted or substituted ammonium salts such as «··· ···· natural acid or stearic acid or natural oils derived from coconut oil or tall oil). Sodium or potassium salts of mixtures of fatty acids, and other surfactants which may be mentioned are fatty acid methyl esters. sulfates are usually in the form of alkali metal salts, alkaline earth metal salts, unsubstituted or substituted ammonium salts and the alkyl groups usually contain from 8 to 22 carbon atoms, the alkyl groups also include the alkyl part of the acyl groups; sodium or potassium salts of sulphonic acid esters or mixtures of fatty alcohol sulphates of natural fatty acids. Salts of ethyl alcohol oxide adducts of fatty alcohol sulfates and sulfonates also belong to this group. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and the fatty acid group contains about 8 to 22 carbon atoms. Alkylarylsulfonates include, for example, the sodium, potassium or triethanolamine salts of the dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid / formaldehyde condensation product. Suitable phosphates are, for example, salts of the adduct of pnonylphenol (4-14) with an ethylene oxide unit or phospholipids.

The compositions will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the active ingredient and from 1 to 99.9% by weight, preferably from 5 to 99.9% by weight, of at least one solid or liquid excipient. % by weight, preferably 0.1-20% by weight

- 50 surfactants. Because concentrated formulations are preferred as a commercial product, diluted, low active ingredient formulations are usually used by the end user.

Some particularly preferred compositions are described below (percentages by weight).

Emulsifiable concentrates

agent

Surfactant

Solvent

powders

agent

Solid support

Suspension concentrates

agent

Water

Surfactant

Wettable powders

agent

Surfactant

Solid support

granules

agent

1-90% preferably 5-20% 1-30% preferably 10-20% 5-98% preferably 70-85%

0.1-10%, preferably 0.1-1%

99.9-90%, preferably 99.9-99%

5-75%, preferably 10-50%

94-24%, preferably 88-30%

1-40%, preferably 2-30%

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

0.5-30%, preferably 3-15%

Solid support

99.5-70%, preferably 97-85% ···· ····

By adding other insecticidal agents, the compositions of the present invention may be broadened in their spectrum of action and adapted to the appropriate conditions. Suitable active ingredients which may be incorporated into the composition include, for example, organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, acylureas, carbamates, pyrethroids, nitroenamines and derivatives, chlorinated hydrocarbons and Bacillus thuringiensis preparations.

The compositions of the invention also include solid or liquid carriers such as stabilizers such as epoxidized or epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soybean oil), antifoam agents such as silicone oil, preservatives, viscosity regulators or binders, and binders. fertilizers and, for example, acaricidal, bactericidal, fungicidal, nematocidal, molluscicidal or selective herbicides for specific effects.

The compositions of the invention may be prepared in a known manner, for example by grinding, sieving and / or pressing the active ingredient or mixtures of active ingredients without excipients, for example to produce a specific particle size, and in the presence of at least one excipient, for example, thoroughly mixing and / or grinding . The invention further provides a process for the preparation of the compositions of the invention and the use of the compounds of formula I for the preparation of these compositions.

* ♦

Another aspect of the present invention are methods of applying the composition, including methods for controlling pests of the aforementioned types, such as spraying, spraying, dusting, application, dressing, spraying or molding, which are selected for the desired purposes and conditions. and the use of preparations for controlling the aforementioned pests. Typical application concentrations are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm. Usually the application range is 1-2000 g active ingredient / ha, in particular 101000 g / ha, preferably 20-600 g / ha.

A preferred application in the field of crop protection is application on the foliage of plants, the frequency and extent of which are determined by the risk of attack by the pest in question. Alternatively, the active ingredient may reach the plant via its root (systemic action), by flooding the plant site with a liquid formulation, or by delivering a solid active ingredient, e.g., to the soil, in the form of granules. In the case of natural rice, such granules may be added to the flooded rice fields.

The compositions of the invention are useful for protecting plant propagating material such as seeds, fruits, tubers or seeds, or seedlings against animal pests. Propagating material may be treated with the composition prior to planting, for example, seeds prior to sowing. Alternatively, the active compounds of the present invention may be used for seed dressing (coating) or soaking in a liquid formulation or coating with a solid formulation. Alternatively, · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

The compositions of the invention can be applied at the planting site when the propagation material is planted, for example, during sowing in the seedbed. The invention also relates to methods of treating propagating material and to propagating material treated by such method. The following examples are intended to illustrate the invention but are not intended to limit it. Temperatures are given in degrees Celsius.

Production examples:

The compounds are obtained as a mixture of isomers, in most cases in the form of a viscous oil. They can be purified by column chromatography. NMR spectra and elemental analyzes correspond to the structure required.

Example H1: 4-Chloro-4-trifluoromethoxybenzophenone

To a solution of 4-trifluoromethoxybenzonitrile (10.8 g) in 4-chlorophenylmagnesium bromide in ether (22.9 g of 1-bromo-4-chlorobenzene and 2.88 g of magnesium turnings in 80 ml of ether) was added dropwise and Keep at reflux for 24 hours.

After cooling, 50 ml of 50% sulfuric acid are added at 20-30 ° C; after the exotherm has subsided, the mixture is stirred at room temperature for one hour. The phases are separated and the aqueous phase is extracted again with ether. The combined organic layer was treated with saturated NaHCO ₃ solution and saturated NaCl solution. The solid product was purified by flash chromatography (ethyl acetate / hexane 1:20) to give 14.3 g of the title compound in crystalline form. Mp 74-75 ° C.

«··· ···· * ·

Example Η2: 4-Chloro-4-trifluoromethoxybenzophenone hydrazone g 4-Chloro-4'-trifluoromethoxybenzophenone, 9.70 g hydrazine hydrate and 2 ml acetic acid in 270 ml absolute alcohol are carefully maintained at reflux for 10 hours. The solvent was evaporated and the residue was taken up in dichloromethane and the mixture was washed with water. Evaporation of the dry organic phase gave 9.34 g of the title compound as white fat crystals.

Example H3: 4-Chloro-4'-trifluoromethoxybenzophenone-N-acetylhydrazone (Compound 1.1 of 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 MgSO ₄ and evaporated. The residue was stirred in cold hexane and filtered.

The title compound is obtained as a mixture of isomers as white crystals. M.p .: 129-131 ° C.

Example H4: 4-Chloro-4'-trifluoromethoxybenzophenone-N-methylhydrazone 1.50 g of 4-chloro-4'-trifluoromethoxybenzophenone, 1.25 g of methylhydrazine and 0.4 ml of acetic acid in 45 ml of ethanol warm gently to reflux and keep at this temperature for 24 hours. The mixture was evaporated, the residue was taken up in dichloromethane and the mixture was washed with water. Dried over _MgSO4 and concentrated to obtain 1.48 g of the title compound as a yellow oil.

···· · »· * ·,. * ·.

, *. «···,

-> «·· ·· · .. ·; ·· · *

Example 5: 4-Chloro-4'-trifluoromethoxybenzophenone-N-formyl-N-methylhydrazone (Compound 1.6 of Table 1) g of sodium formate was introduced into 12.5 ml of ether with stirring and exclusion of moisture, and 14.7 of acetyl- chloride is added dropwise at 0 ° C. Stirring is continued at room temperature for several hours, the sodium chloride is filtered off and the mixture is washed with dry ether. 14.22 g of an ethereal solution of formyl acetate are obtained.

An amount of this solution containing about 0.28 g of formyl acetate was added dropwise to a solution of 1.48 g of 4-chloro-4'-trifluoromethylbenzophenone-N-methylhydrazone in 20 ml of ether. After a few hours, the reaction is complete and the mixture is treated with ice water, the organic phase is collected, washed again with water and dried over magnesium sulfate. After evaporation of the solvent, the residue was purified by flash chromatography (ethyl acetate / hexane 1: 3). The product is obtained as a mixture of isomers in the form of a yellow oily wax.

Example H6 1- (4-Chlorophenyl) -4-dimethylamino-1- (4-trifluoromethoxyphenyl) -2,3-diaza-1,3-pentadiene (Table 2, Compound 2.1)

A solution of 0.85 g of 4-chloro-4'-trifluoromethoxybenzophenone hydrazone in 15 ml of toluene was treated with 0.66 g of N, N-dimethylacetamide dimethylacetal. The mixture was then heated at reflux for 18 hours. The mixture was cooled and the solvent was completely evaporated and the brown residue was purified by flash chromatography (ethyl acetate / hexane 1: 5). The title

Φ ··· ····

Compound 56 is obtained as yellow crystals as a mixture of isomers. Mp: 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 (Table 3, Table 3).

compound)

0.75 g of 1-ethanesulfonyl-1-aza-3-oxa-1-pentene and 0.85 g of N-ethyldiisopropylamine are added to a solution of 0.85 g of 4-chloro-4'-trifluoromethoxybenzophenone hydrazone in 15 ml of toluene. The mixture was stirred at reflux for 20 hours. After cooling, the solvent was completely evaporated and the residue was purified by flash chromatography (ethyl acetate / hexane 1: 2). The title compound is obtained as a mixture of isomers in the form of yellow crystals.

Example H8: 4-Bromo-difluoromethoxy-4'-chlorobenzophenone

Oil (2.58 g, 80% sodium hydride) was added in three equal portions at 25-30 ° C to a stirred solution of 25 g of 4-chloro-4'-hydroxybenzophenone in 150 ml of dimethylformamide and the mixture was stirred at room temperature for 16 hours. stirred. The reaction mixture was then poured into 800 ml of water and extracted three times, each time using 300 ml of ethyl acetate. The organic phase is evaporated and the residue is purified by column chromatography (silica gel, hexane / ethyl acetate 20.1). White crystals are obtained, m.p. 52-55 ° C.

• · • · · · .. - · · · · · · · · · · ·

Example Η9: 4-Bromo-difluoromethoxy-4'-chlorobenzophenone hydrazone

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

Example H10: 4-Bromo-difluoromethoxy-4-chloro-benzophenone-N-acetylhydrazone (Table 1, Compound 1.27)

Triethylamine (0.30 g) was added dropwise at 20-25 ° C to a solution of 1.0 g of 4-bromo-difluoromethoxy-4'-chlorobenzophenone hydrazone and 0.23 g of acetyl chloride in 20 ml of tetrahydrofuran and the mixture was stirred for 90 min. Stir at room temperature for 1 minute. The organic phase was evaporated and the residue was purified by column chromatography (silica gel, hexane: ethyl acetate = 3: 1). 118120 ° C.

Hll example

Other compounds listed in Tables 1, 2, 3 and 5 are H3,

They can be prepared analogously to the procedures described in Examples H6, H7 and H10. The compounds listed in Table 4 can be prepared in analogy to the procedures described in Examples H2 and H9.

In these tables, the numbers in the Physical Data column represent the melting point.

• · ·

- 58 Table 1

Woman. ^R i (R ₂ ) n ^r 3 ^r 6 ^r 7 physical data 1.1 ocf ₃ 4-C1 H H ch ₃ 129-31 ° 1.2 OCF ₂ CF ₂ Br 4-C1 H H ch ₃ 128-43 ° 1.3 ocf ₃ 4-C1 H H I-C3H7 121-3 ° 1.4 ocf ₃ 4-C1 H H ^C 6 ^H 5 wax 1.5 ocf ₃ 4-C1 H H cC ₃ H ₅ 155-6 ° 1.6 ocf ₃ 4-C1 H ch ₃ H oil / wax 1.7 ocf ₃ 4-C1 H H ^cc 6 ^_h 11 158-64 ° 1.8 ocf ₃ 4-C1 H H ^nc 3 ^H 7 136-8 ° 1.9 ocf ₃ 4-C1 H ch ₃ ch ₃ amorphous material 1:10 ocf ₃ 4-C1 H ch ₃ I-C3 H7 amorphous material 1:11 ocf ₃ 4-C1 H ch ₃ ^C 6 ^R 5 resin 1:12 ocf ₃ 4-C1 H ch ₃ cC ₃ H ₅ resin 1:13 QCF2 ^ 'F'2Br 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-C1 H H 3-thienyl 118-33 ° 1:16 OCF 3 4-C1 H H 2-thienyl 160-2 ° 1:17 ocf ₃ 4-C1 H H 5-Cl-2-thienyl 159-61 ° 1:18 ocf ₃ 4-C1 H 5-C1-2- chlorobenzoyl 5-Cl-2-thienyl amorphous material 1:19 ocf ₃ 4-C1 H H 3-Cl-2-thienyl 187-9 ° 1:20 ocf ₃ 4-C1 H H benzo [b] -thiene 2-yl 178-80 ° 1:21 ocf ₃ 4-C1 H H 3-Cl-benzo [b] - 213-5 °

thien-2-yl

1:22 ocf ₃ 4-Cl H ch ₃ 2-thienyl amorphous material 1:23 OCF ₂ CF ₂ Br 4-Cl H ch ₃ H resin 1:24 OCF ₂ Br 4-Cl H ch ₃ ch ₃ resin 1:25 OCF ₂ Br 4-Cl H ch ₃ H resin 1:26 OCF ₂ Br 4-Cl H H ^c 2 ^h 5 119-30 ° 1:27 OCF ₂ Br 4-Cl H H ch ₃ 118-20 ° 1:28 OCF ₂ Br 4-Cl H ch ₃ <= - c ₃ h ₅ resin 1:29 OCF ₂ Br 4-Cl H ch ₃ ^c 2 ^h 5 resin 1:30 ocf ₃ 4-Cl H ch ₃ 3-thienyl amorphous material 1:31 OCF ₂ CF ₂ Br 4-F H ch ₃ H resin 1:32 OCF ₂ Br 4-F H H ^c 2 ^h 5 110-21 ° 1:33 OCF ₂ Br 4-F H H ch ₃ 118-28 ° 1:34 ocf ₃ 4-Cl H ch ₃ 5 Cj_-2-thienyl amorphous material 1:35 ocf ₃ 4-Cl H ch ₃ 3-Cj-benzo [b] - thien-2-yl amorphous material 1:36 ocf ₃ 4-Cl H CH3 3-C-2-thienyl amorphous material 1:37 ocf ₃ 4-Cl H ch ₃ benzo [b] -thiene 2-yl amorphous material 1:38 ocf ₂ ci 4-Br H ^c 2 ^h 5 ch ₃ 1:39 ocf ₂ ci 4-Br H ^c 2 ^h 5 ^c 2 ^h 5 1:40 ocf ₂ ci 4-Br H ch ₃ cC ₃ H ₅ 1:41 OCFR ₂ Br 4-Br H ch ₃ H 1:42 ocf ₃ 4-F H H ch ₃ 1:43 ocf ₃ 4-tC ₄ H ₉ H H ch ₃ 1:44 ocf ₃ 4-OCF ₃ H H ch ₃ 1:45 ocf ₃ 4-OCF ₃ H ch ₃ H 1:46 ocf ₃ 3,4- _C12 H H H 1:47 ocf ₃ 2,4- _C12 H ch ₃ ch ₃ 1:48 ocf ₃ 3-C1 H ^c 2 ^H 5 ch ₃ 1:49 ocf ₃ 2.5- _C12 H ch ₃ ch ₃ 1:50 ocf ₃ 3,5-Cl2 H cC ₃ H ₅ H 1:51 ocf ₃ 2-F, 4-Cl H ch ₃ H 1:52 ocf ₃ 2-Br H H ch ₃ 1:53 ocf ₃ 3-CH ₃ , 4-Cl H ch ₃ ^c 2 ^H 5 1:54 ocf ₃ 3-CH ₃ , 4-Cl H ^c 2 ^h 5 ch ₃ 1:55 ocf ₃ 3,5- (CF ₃ ) ₂ H H í-c ₃ h ₇ 1:56 ocf ₃ 2-Cl, 5-CF ₃ H nC ₃ H ₇ H 1:57 ocf ₃ 4-Br H H H

• · • ·

1:58 ocf ₃ 4-Br H H ch ₃ 136-40 ° 1:59 ocf ₃ 4-Br H H ^c 2 ^h 5 1.60 ocf ₃ 4-Br H H cC ₃ H ₅ 164-7 ° 1.61 ocf ₃ 4-Br H H í-c ₃ h ₇ 136-8 ° 1.62 ocf ₃ 4-Br H H n- ^c 3 ^H 7 1.63 ocf ₃ 4-Br H H ^c 6 ^h 5 130-1 ° 1.64 ocf ₃ 4-Br H H 2-thienyl 1.65 ocf ₃ 4-Br H H 3-thienyl 1.66 ocf ₃ 4-Br H ch ₃ H oil 1.67 ocf ₃ 4-Br H ch ₃ ch ₃ 85-93 ° 1.68 ocf ₃ 4-Br H ch ₃ ^c 2 ^h 5 1.69 ocf ₃ 4-Br H ch ₃ cC ₃ H ₅ oil 1.70 ocf ₃ 4-Br H ch ₃ í-c ₃ h ₇ amorphous material 1.71 ocf ₃ 4-Br H ch ₃ nC ₃ H ₇ 1.72 ocf ₃ 4-Br H ch ₃ ^C 6 ^H 5 1.73 ocf ₃ 4-Br H ch ₃ 2-thienyl 1.74 ocf ₃ 4-Br H ch ₃ 3-thienyl 1.75 OCF ₂ Br 4-Br H H H 1.76 OCF ₂ Br 4-Br H H ch ₃ 116-8 ° 1.77 OCF ₂ Br 4-Br H H cc ₃ h ₅ 140-6 ° 1.78 OCF ₂ Br 4-Br H H í-c ₃ h ₇ 110-3 ° 1.79 OCF ₂ Br 4-Br H H nC ₃ H ₇ 99-108 ° 1.80 OCF ₂ Br 4-Br H H ^c 6 ^h 5 1.81 OCF ₂ Br 4-Br H ch ₃ H amorphous material 1.82 OCF ₂ Br 4-Br H ch ₃ ch ₃ amorphous material 1.83 OCF ₂ Br 4-Br H ch ₃ ^g_c 3 ^h 5 oil 1.84 OCF ₂ Br 4-Br H ch ₃ í-c ₃ h ₇ oil 1.85 OCF ₂ Br 4-Br H ch ₃ nC ₃ H ₇ oil 1.86 OCF ₂ Br 4-Br H ch ₃ ^c 6 ^h 5 1.87 OCF ₂ CF ₂ Br 4-Br H H H 1.88 OCF ₂ CF ₂ Br 4-Br H H ch ₃ 1.89 OCF ₂ CF ₂ Br 4-Br H H í-c ₃ h ₇ 1.90 OCF ₂ CF ₂ Br 4-Br H H ^c 6 ^h 5 1.91 OCF ₂ CF ₂ Br 4-Br H ch ₃ H 1.92 OCF ₂ CF ₂ Br 4-Br H ch ₃ ch ₃ 1.93 OCF ₂ CF ₂ Br 4-Br H ch ₃ í-c ₃ h ₇ 1.94 OCF ₂ CF ₂ Br 4-Br H ch ₃ ^C 6 ^H 5 1.95 ocf ₃ 4-F H H H

• ·

- 61 ···· ····

1.96 ocf ₃ 4-F H H ch ₃ 1.97 ocf ₃ 4-F H H í-c ₃ h ₇ 1.98 ocf ₃ 4-F H ch ₃ H 1.99 ocf ₃ 4-F H ch ₃ ch ₃ 1100 ocf ₃ 4-F H CH3 I-C3H7 1101 ocf ₃ 4-Cl H ^c 2 ^h 5 H 1102 ocf ₃ 4-Cl H ^c 2 ^h 5 ch ₃ 1103 ocf ₃ 4-Cl H ^c 2 ^h 5 í-c ₃ h ₇ 1104 ocf ₃ 4-Br H ^c 2 ^h 5 H 1105 ocf ₃ 4-Br H ^c 2 ^h 5 ch ₃ 1106 ocf ₃ 4-Br H ^c 2 ^h 5 í-c ₃ h ₇ 1107 OCF ₂ Br 4-F 3-C1 H ch ₃ 115-25 ° 1108 OCF ₂ Br 4-F 3-C1 H ^C 2 ^H 5 87-95 ° 1109 OCF ₂ Br 4-F 3-C1 H cC ₃ H ₅ 133-44 ° 1110 OCF ₂ Br 4-F 3-C1 H í-c ₃ h ₇ 97-107 ° 1111 ocf ₃ 4-Cl H H (ch ₂ ) ₃ ch = cf ₂ 89-93 ° 1112 ocf ₃ 4-Br H H (ch ₂ ) ₃ ch = cf ₂ 143-7 ° 1113 ocf ₃ 4-Cl H ch ₃ (ch ₂ ) ₃ ch = cf ₂ 1114 OCF ₂ Br 4-Cl 3-C1 H ch ₃ 101-6 ° 1115 OCF ₂ Br 4-Cl 3-C1 H í-c ₃ h ₇ 114-43 ° 1116 OCF ₂ Br 4-Cl 3-C1 H ^c 2 ^h 5 105-11 ° 1117 ocf ₃ 4-Br H ch ₃ 6-chloropyrid-3- yl amorphous material 1118 ocf ₃ 4-Br H ch ₃ 5-chloro-thien-2- yl 109-12 ° 1119 OCF ₂ Br 4-Cl 3-C1 H ch ₂ ci amorphous material 1120 OCF ₂ Br 4-Cl 3-C1 H ^c - ^c 3 ^h 5 129-34 ° 1121 OCF ₂ Br 4-Cl 3-C1 ch ₃ ^c 2 ^h 5 resin 1122 OCF ₂ Br 4-Cl 3-C1 ch ₃ ch ₃ resin 1123 OCF ₂ Br 4-Cl 3-C1 ch ₃ H resin 1124 OCF ₂ Br 4-Cl 3-C1 ch ₃ ch ₂ ci resin 1125 OCF ₂ Br 4-Cl 3-C1 H cooc ₂ h ₅ 165-9 ° 1126 OCF ₂ Br 4-Cl 3-C1 H COOCH 3 149-60 ° 1127 OCF ₂ Br 4-Cl 3, 5 — Cl ₂ H ch ₃ 129-34 ° 1128 OCF ₂ Br 4-Cl 3,5-Cl ₂ H ^c - ^c 3 ^H 5 192-3 ° 1129 OCF ₂ Br 4-Cl 2,5-Cl ₂ H í-c ₃ h ₇ 170-3 ° 1130 OCF ₂ Br 4-Cl 3,5-Cl ₂ H ^C 2 ^H 5 143-5 ° 1131 OCF ₂ Br 4-Cl 3-C1 H I-C ^ Hg 88-96 °

1132 1133 OCF ₂ Br ocf ₃ 4-Cl 4-Br 3-C1 H H ch ₃ nC ₃ H _? (ch ₂ ) ₃ ch = cf ₂ 87-99 ° 1134 OCF ₂ Br 4-Cl H H ^c_c 3 ^h 5 127-31 ° 1135 OCF ₂ Br 4-Cl H H ⁿ -C ₃ H ₇ 88-107 ° 1136 OCF ₂ Br 4-Cl H H í-c ₃ h ₇ 106-12 ° 1137 OCF ₂ Br 4-Br H H -C ₄ H ₉ 119-21 ° 1138 OCF ₂ Br 4-Br H H ^c 2 ^h 5 108-14 ° 1139 OCF ₂ Br 4-Br H ch ₃ -C ₄ H ₉ resin 1140 OCF ₂ Br 4-Br H ch ₃ ^c 2 ^h 5 amorphous material 1141 OCF ₂ Br 4-Cl 3-F H ch ₃ 116-20 ° 1142 OCF ₂ Br 4-Cl 3-Br H ch ₃ 90-6 ° 1143 OCF ₂ Br 4-Cl 3-Br H ^C 2 ^H 5 97-104 ° 1144 OCF ₂ Br 4-Cl 3-F H ^c 2 ^h 5 122-5 ° 1145 OCF ₂ Br 4-Cl 3-F ch ₃ H resin 1146 OCF ₂ Br 4-Cl 3-Br ch ₃ H resin 1147 OCF ₂ Br 4-Cl 3-Br ch ₃ ch ₃ resin 1148 OCF ₂ Br 4-Cl 3-F ch ₃ ch ₃ resin 1149 OCF ₂ Br 4-Cl 3-C1 CHO H 1150 OCF ₂ Br 4-Cl 3-C1 CHO ch ₃ 1151 OCF ₂ Br 4-Cl 3-C1 CHO ^c 2 ^h 5 1152 OCF ₂ Br 4-Cl 3-C1 CHO ch ₂ ci 1153 OCF ₂ Br 4-Cl 3-C1 CHO í-c ₃ h ₇ 1154 OCF ₂ Br 4-Cl 3-C1 CHO cf ₃ 1155 OCF ₂ Br 4-Cl 3-C1 CHO ^c 6 ^h 5 1156 OCF ₂ Br 4-Cl 3-C1 ch ₃ co H 1157 OCF ₂ Br 4-Cl 3-C1 ch ₃ co ch ₃ 1158 OCF ₂ Br 4-Cl 3-C1 ch ₃ co ^c 2 ^h 5 1159 OCF ₂ Br 4-Cl 3-C1 ch ₃ co ch ₂ ci 1160 OCF ₂ Br 4-Cl 3-C1 ch ₃ co ^CC 3 ^H 7 1161 OCF ₂ Br 4-Cl 3-C1 ch ₃ co cf ₃ 1162 OCF ₂ Br 4-Cl 3-C1 ch ₃ co ^c 6 ^h 5 1163 OCF ₂ Br 4-Cl H H and ₃ 1164 ocf ₃ 4-CF ₃ H H n (ch ₃ ) ₂ 1165 ocf ₃ 4-CF ₃ H H ch ₃ 1166 OCF ₂ Br 4-Cl H í-c ₃ h ₇ H oil 1167 OCF ₂ Br 4-Cl H í-c ₃ h ₇ ch ₃ resin 1168 OCF ₂ Br 4-Cl H í-c ₃ h ₇ ^C 2 ^H 5 resin 1169 OCF ₂ Br 4-Cl H í-c ₃ h ₇ n-C3H7 resin

- 63 ···· ···· · · · · · · · · · · · · ·

1.170 OCF ₂ Br 4-C1

1.171 OCF ₂ Br 4-C1

H ^ic 3 ^H 7 í-C ₃ H ₇

H-C3H-7 NHCH3 resin resin. spreadsheet

rl ^R 2 ^r 3 r ₄ ^R 5 physical data 1 OCF 3 cl H ch ₃ N (CH ₃ ) ₂ 52-4 ° 2 OCF ₃ cl H ch ₃ N (OCH ₃ ) CH ₃ oil 3 OCF ₂ Br cl H ch ₃ N (CH ₃ ) ₂ 46-74 ° 4 OCF ₃ Br H ch ₃ sch ₃ 5 OCF 3 cl H H sch ₃ 6 OCF ₃ F H ch ₃ N (CH ₃ ) 2 7 OCF ₃ Br H H N (CH ₃ ) ₂ 8 OCF ₂ CF ₂ Br cl H c ₂ h ₅ and ₃ 9 OCF ₃ cl H c ₂ h ₅ ° c ₂ h ₅ 10 OCF 3 cl H ^c 2 ^H 5 and ₃ 11 OCF ₃ cl H nC ₃ H ₇ N (CH ₃ ) 2 12 OCF ₃ cl H I-C3H 7 nh ₂ 13 OCF 3 cl H C ₂ «5 NHCH3 14 OCF ₃ 0CF3 H ch ₃ oc ₂ h ₅ 15 ocf ₃ OCF 3 H H SO3CH3 16 Br 4-C1 H ch ₃ CH3 amorphous material 17 OCF ₂ Br cl 3-C1 ch ₃ N (CH ₃ ) ₂ resin 18 OCF ₂ Br cl 3,5-Cl ₂ ch ₃ N (CH ₃ ) 2 resin 19 OCF ₂ Br Br H ch ₃ N (CH ₃ ) ₂ resin 20 OCF ₂ CF ₂ Br cl H ch ₃ N (C ₂ H ₅ ) ₂

- 64 ···

2:21 OCF ₂ Br cl H ch ₃ n (ch ₃ ) ₂ 2:22 OCF ₂ Br F H ch ₃ N (CH ₃ ) ₂ 2:23 OCF ₂ Br cl 3-F ch ₃ N (CH ₃ ) ₂ resin 2:24 OCF ₂ Br cl 3-F ch ₃ n (ch ₃ ) ₂ resin

Table 3

1. ^R 1 ^R 2 ^R 3 ^R 6 r ₇ ^R 18 physical data 1 ocf ₃ cl H H H so ₂ c ₂ h ₅ wax 2 ocf ₃ cl H H H so ₂ ch ₂ c ₆ h wax 3 ocf ₃ cl H H H 5 so ₂ c ₆ h ₅ wax 4 ocf ₃ cl H ch ₃ H so ₂ c ₂ h ₅ 5 ocf ₃ Br H ch ₃ ch ₃ so ₂ c ₂ h ₅ 6 ocf ₃ cl cl ch ₃ H so ₂ c ₂ h ₅ 7 OCF ₂ Br cl H H H so ₂ c ₂ h ₅ 8 OCF ₂ Br Br H H H so ₂ c ₆ h ₅ 9 OCF ₂ Br cl cl H H so ₂ c ₂ h ₅ 10 OCF ₂ Br cl H ch ₃ H so ₂ c ₂ h ₅ 11 OCF ₂ Br cl H ch ₃ ch ₃ so ₂ c ₂ h ₅ 12 OCF ₃ Br cl cl ch ₃ ch ₃ so ₂ c ₂ h ₅

Table 4

Woman. ^R 1 ^R 2 ^R 3 Physical data 4.1 OCF ₂ CF ₂ Br cl H amorphous material 4.2 ocf ₃ cl H oil 4.3 OCF ₂ Br cl H 45-9 ° 4.4 ocf ₃ Br H 74-8 ° 4.5 OCF ₂ Br cl cl oil 4.6 OCF ₂ Br cl F oil 4.7 OCF ₂ Br cl Br oil

Table 5

Woman. ^R 1 ^R 2 ^R 3 ^R 6 r ₇ ^R 21 physical data 5.1 OCF ₂ Br cl cl H cf ₃ resin 5.2 OCF ₂ Br cl F H ^cr 3 cf ₃ 80-96 ° 5.3 OCF ₂ Br cl Br H cf ₃ cf ₃ resin 5.4 OCF ₂ Br cl cl H ch ₃ ch ₃ resin 5.5 OCF ₂ Br cl F H ch ₃ ch ₃ oil 5.6 OCF ₂ Br cl Br H ch ₃ ch ₃ resin 5.7 OCF ₂ Br cl H H ch ₃ ch ₃ 5.8 OCF ₂ Br cl H H cf ₃ cf ₃

- 66 - • · · · • • • · • · ···· ·· • · · · • ·· · • · · · • · · 5.9 OCF ₂ Br cl H ch ₃ ch ₃ ch ₃ 5:10 OCF ₂ Br cl H ch ₃ cf ₃ cf ₃ 5:11 OCF ₂ Br cl F ch ₃ ch ₃ ch ₃ 5:12 OCF ₂ Br cl F ch ₃ cf ₃ cf ₃ 5:13 OCF ₂ Br cl Br ch ₃ ch ₃ ch ₃ 5:14 OCF ₂ Br cl Br ch ₃ cf ₃ cf ₃ 5:15 OCF ₂ Br cl cl ch ₃ ch ₃ ch ₃ 5:16 OCF ₂ Br cl. CL ch ₃ cf ₃ cf ₃ 5:17 OCF ₂ Br Br H H ch ₃ and ₃ 5:18 OCF ₂ Br Br H H ch ₃ oc ₂ h ₅ 5:19 ocf ₃ Br H H ch ₃ ch ₃ 5:20 ocf ₃ cl H H ch ₃ ch ₃

Formulation examples (% by weight . means) a) b) c) Example FI: emulsion concentrate agent 25% 40% 50% Calcium dodecylbenzene sulfonate 5% 8% 6% Castor oil is a polyethylene glycol ether (36 mol EO) 5% - - Tributyl phenol polyethylene glycol ether (30 mol EO) - 12% 4% cyclohexanone - 15% 20% Xylene mixture 65% 25% 20%

The finely divided active ingredient and excipients are obtained in the form of an emulsion concentrate to give an emulsion of the desired concentration in water.

diluted by mixing and mixing any · ··· ··· *

Example F2: the) b) c) d) agent 80% 105 5% 95% Ethylene glycol monomethyl ether 20% - - - Polyethylene glycol (molecular weight 400) 70% - - N-methyl-pyrrolidin-2-one - 20% - - Epoxidized coconut oil - - 1% 5% Light petroleum (Boiling point 160-190 °) - - 94% - Finely ground active ingredient and your assistant mixing materials to obtain a solution which for use. suitable for microdroplets form Example F3: Granules the) b) c) d) agent 5% 10% 8% 21% Kaolin 94% - 79% 54% Highly dispersed silica gel 1% - 13% 7% Attapulgit - 90% - 18% The active ingredient is in dichloromethane Dissolve the solution support

spray and evaporate the solvent in vacuo.

Example F4: Powders the) b) agent 2% 5% Highly dispersed silica gel 1% 5% talc 97%

Kaolin

90% ····. ··· ··

X «

- 68 Ready-to-use powders are obtained by mixing the active ingredient with.

the carriers

Example F5: Wettable Powders the b) c) agent 25% 50% 75% Sodium lignosulfonate 5% 5% - Sodium lauryl sulfa 3% - 5% Sodium diisobutyl naphthalene sulfonate 6% 10% Octylphenol polietilénglikoléter (7-8 mol EO) 2% Highly dispersed silica gel 5% 10% 10% Kaolin 62% 27%

The active ingredient and the excipients are ground together in a mill. Thus, a wettable powder is obtained by diluting any suspension of the desired concentration which is suitable with water.

Example F6: Emulsion concentrate

Active ingredient 10%

Octyl phenol polyethylene glycol ether (4-5 moles EO) 3%

Calcium dodecylbenzene sulphonate 3%

Ricinus oil-polyethylene glycol ether (36 mol EO) 4%

Cyclohexanone 30%

Xylene mixture

50% · · · · ·

The finely divided active ingredient and excipients are combined to form an emulsion concentrate which can be diluted with water to form any desired emulsion.

Example F7: Powders

agent

talc

Kaolin

a) b)

5% 8%

95%

92%

Ready-to-use powders by mixing carriers by grinding

Example F8: Extruded Granules Active ingredient

Sodium lignosulfonate

carboxymethylcellulose

Kaolin is obtained from the active ingredient and is in a suitable mill

10%

2%

1%

87%

The active ingredient and excipients are mixed, milled, moistened with water, extruded and granulated and the granules are air-dried.

Example F9: Coated Granules

Active ingredient 3%

Polyethylene glycol (MW 200) 3%

Kaolin

94%

The active ingredient is added to the kaolin moistened with polyethylene glycol in a blender to give a powder-free coated granulate.

Example F10: Suspension concentrate

agent 40% ethylene glycol 10% Nonylphenol polietilénglikoléter (15 moles EO) 6% Sodium lignin sulphonate 10% Carboxymethylcellulose 1% Aqueous formaldehyde 0.2% solution (37% Aqueous silicone oil emulsion 0.8% solution (75% Water 32%

The finely divided active ingredient and the excipients are mixed to form a suspension concentrate which can be diluted with water to give a suspension of the desired concentration.

Biological examples

Example B1: Activity against Spodoptera littoral caterpillar

Young soybean plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. After the spray coating has dried, the soybean plants are planted in 10 third-stage Spodoptera littoralis caterpillars and placed in a plastic container. After 3 days, the assay is evaluated. Percentage decrease in population or percentage reduction in damage (% effect) on number of dead larvae and damage to treated and untreated plants * 4

- 71 · · · ·. In this study,

The compounds of Tables 1, 2, 3, 4 and 5 show good activity in a

Against Spittoptera littoral. Show an effect of over 80% on 1.1,

1.3-1.14, 1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.761.79, 1.81-1.85, 1.107-1.111, 1.114, 1.117, 1.121-1.123, 1.1311.133, 1.135-1.138, 1.140, Compounds 2.3, 2.17 and 2.19.

Example B2 Activity against Heliothis virescens larvae

Young soybean plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. After the spray coating had dried, the soybean plants were planted with 10 first-stage Heliotis virescens caterpillars and placed in a plastic container. The study was evaluated 6 days later. Percentage reduction in population or percentage reduction in damage (% effect) was determined by comparing the number of larvae killed and the damage to treated and untreated plants. In this assay, the compounds of Tables 1, 2, 3, 4 and 5 show good activity in a

Against Spittoptera littoral. Show an effect of over 80% on 1.1,

1.3-1.14, 1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.761.79, 1.81-1.85, 1.107-1.112, 1.114, 1.116.1.117, 1.120-1.123,

1.125, 1.131-1.133, 1.135-1.138, 1.140, 2.1-2.3, 2.16, 2.17,

2.19, 4.1-4.4. compounds.

Example B3: Ovicidal activity against Heliotis virescens

Heliothis virescens eggs, placed on filter paper, were briefly immersed in an aqueous solution of acetone containing 400 ppm of test substance. After drying the test solution, the eggs are incubated in a Petri dish. 6 days after hatching eggs • · · · · · ·

percent rate is evaluated by untreated control of compared to (% of emergence decrease) in this the study 1, 2, 3, 4 and 5. spreadsheet compounds good

show activity against Heliothis virescens. They show an effect above 80%, especially 1.1-1.14, 1.58, 1.60, 1.61, 1.63, 1.66,

1.67, 1.70, 1.76-1.79, 1.81-1.85, 1.107-1.112, 1.114-1.117,

1.120-1.123, 1.125, 1.126, 1.131-1.133, 1.135-1.138, 1.140, 2.12.3, 2.16, 2.17, 2.19, 3.2, 3.3, 4.1, 4.2, 4.4 and 4.5.

compounds.

Example B4: Activity against Diabrotica balteata larvae

Corn seedlings were sprayed with an aqueous emulsion mixture containing 400 ppm of active ingredient. After the spray had dried, the corn plants were planted with 10 larvae of Diabrotica balteata in their second stage of development and placed in a plastic container. The study was evaluated after 6 days. Percentage of population decline (% effect) was determined by comparing the number of dead larvae on treated and untreated plants. In this study,

The compounds of Tables 2, 3, 4 and 5 show good activity in a

Diabrotica against balteata. They show an effect above 80% in particular for 1.1, 1.2, 1.4, 1.6, 1.58, 1.61, 1.66, 1.67, 1.76-1.79, 1.811.84, 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. compounds.

• · • · • · · · · · · · · · · · · · · · · · ·

- Example 73-5: Action against Plutella xylostella caterpillars

Young cabbage plants are sprayed with an aqueous emulsion mixture containing 400 ppm of active ingredient. After the coating has dried, 10 Plutella xylostella caterpillars are placed on cabbage plants in a third stage of development and placed in a plastic container. After 3 days, the assay is evaluated. Percentage reduction in population or percentage reduction in damage (% effect) was determined by comparing the number of larvae killed and the damage to treated and untreated plants. In this study,

The compounds of Tables 1, 2, 3, 4 and 5 show good activity

Plutella against xylostella. They show an effect above 80%, especially 1.1, 1.3-1.14,1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70,

1.76-1.79, 1.81-1.85, 1.107-1.111, 1.114, 1.117, 1.121-1.123,

1.132, 1.133, 1.135-1.138, 1.140, 2.2, 2.3, 2.17 and 2.19.

Claims (22)

Claims A compound of formula (I) wherein: X is a group of formula (a) or (b), (a) 'N' Ν '.R _e (b) r; r < ^y n is 0, 1, 2, 3, 4 or 5, if n is greater than 1 then R ^{2 is the} same or different; o is 0, 1, 3, 3 or 4; if o is greater than 1 then R ^{3 is the} same or different; R ⁴ is perhalogen (C 1-4) alkoxy; R ² is halogen, C 1 -C 8 alkyl, halo-C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halo-C 1 -C 8 alkoxy, C 1 -C 8 alkylthio -, halo (C 1 -C 8) alkylthio, (C 1 -C 8) alkylsulfinyl, halo (C 1 -C 8) alkylsulfinyl, (C 1 -C 8) alkylsulfonyl, halo (C 1 -C 8) alkylsulfonyl, CN, or phenyl; • · · · • · - 75 R ² is halogen, C 1-8 alkyl, halo (C 1-8 alkyl) or halo (C 1-8 alkoxy); R ⁴ is H, halo, C 1-8 alkyl, C3-C6 cycloalkyl, halo (C1-C8 alkyl), (C 1 -C 8) alkoxy, (C 1 -C 8) alkoxy (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy (C 1 -C 8) alkoxy, (C 1 -C 8) alkylthio - or NR 4; R ⁵ is C 1 -C 8 alkyl, NR 1 - R ¹¹ , OR ²⁰ , SR ²⁰ or SO ₂ R ²⁰ ; R ⁶ is hydrogen, C 1 -C 8 alkyl, C 3 -C 6 cycloalkyl, halo-C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 1 -C 8 alkynyl, C 1 -C 8 acyl- or phenyl; R ⁷ is hydrogen, unsubstituted or substituted C 1 -C 8 alkyl, C 3 -C 6 cycloalkyl, (C 3 -C 6 cycloalkyl) -C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 1 -C 8 alkynyl, C3-C6 cycloalkenyl, (C3-C6 cycloalkenyl) -C1-C8 alkyl, or (C3-C6 cycloalkyl) -C1-C8 alkenyl, which may have from 1 to 8 halogen atoms. C 1 -C 4 alkyl, halo-C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halo-C 1 -C 8 alkoxy, -C 1 -C 8 alkyl-S (O) p where p is They may be substituted with 0, 1 or 2, (C 1 -C 8) alkoxy-carbonyl, di- (C 1 -C 8) -alkylamino, and (C 1 -C 8) -alkanoyloxy; phenyl or heteroaryl, unsubstituted or substituted with C 1-6 alkyl or halogen; • · · • · · · - (C 1 -C 8) alkoxy, NR ⁴⁶ R ⁴⁷ , COOR ⁶ , or SR ⁶ ; R ⁸ and R ⁹ are each independently hydrogen, C 1-8 alkyl, or OH; R ⁴⁹ is hydrogen, C 1-8 alkyl, C 3-6 cycloalkyl, halo (C 1-8 alkyl), halo (C 1-8 alkoxy) (C 1-8 alkyl), phenyl -, OR ⁴² , S (O) _m R ⁴³ , (m is 0, 1 or 2) or NR ⁴⁴ R ⁴³ ; R ⁴⁴ is hydrogen, (C 1 -C 8) alkyl, (C 3 -C 6) cycloalkyl, halo (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy (C 1 -C 8) alkyl, allyl, C 1-8 -alkyl-allyl, haloallyl or propargyl; R ⁴² is hydrogen, C 1-8 alkyl, halo (C 1-8 alkyl), (C 1-8 alkoxy) (C 1-8 alkyl), C 3-6 cycloalkyl, 2-8. C 1 -C 5 alkenyl, halo (C 2 -C 8) alkenyl or propargyl; R ⁴³ is hydrogen, C 1 -C 8 alkyl, halo-C 1 -C 8 alkyl, phenyl, or NR ⁴⁴ R ⁴³ ; R ⁴⁴ and R ⁴³ are each independently hydrogen, C 1-8 alkyl, halo (C 1-8) alkyl, phenyl, C 1-8 alkylamido, di- (C 1-8 alkyl) amido or NH ₂ ; R ⁴⁶ and R ⁴⁷ are each independently hydrogen, C 1 -C 8 alkyl, halo-C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 1 -C 8 alkoxy NH ₂ ; R ⁴⁸ is S (O) m R ¹⁹ -, - m is 0, 1 or 2 - NO 2 - or CN; R ^ ¹ is C1-8 alkyl, halo (C1-8 alkyl) -, C 3-6 cycloalkyl, phenyl, benzyl or NR ^ rI 5_ group; R ^21-1 represents C1-8 alkyl, halo (C1-8 alkyl) - or C 3-6 cycloalkyl; Y is oxygen, sulfur, NR ^1-8 - or CHC (O) ² - * - group; and R ²¹ is H, (C 1 -C 8) alkyl, halo (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy or phenyl, with the proviso that compounds of formula (I) wherein X is -N = C (R ⁴ ) R 4, R 1 is OCF ₃ , o is 0, n is 1, R ⁴ is CH ₃ and r 5 is -Ν (ΟΗ ₃ ) ΟΟΗ ₃ , R ^{2 is} other than fluorine and chlorine - their E / Z isomers and tautomers, in each case free or in salt form; A compound of formula (I) according to claim 1, wherein n is 1 or 2, if n is greater than 1, the radical R ^{2 is the} same or different or, where appropriate, an E / Z isomer or tautomeric form. A compound of formula (I) according to claim 1, wherein o is 0 or 1 or, where appropriate, an E / Z isomer or tautomer thereof. A compound of formula (I) according to claim 1, wherein R ⁴ is a perhalogen (C 1 -C 2) alkoxy or, optionally, an E / Z isomer or tautomer thereof. A compound of formula (I) according to claim 1 wherein R ² is halogen or, if appropriate, an E / Z isomer or tautomer thereof. The compound of formula I according to claim 1, wherein n is 1 or 2, wherein when n is greater than 1, R ² is the same or different and o is 0 or 1, R ² is perhalogen (C 1 -C 2 alkoxy), R ² is halogen, C 1-4 alkyl, halo (C 1-4 alkyl) or halo (C 1-4 alkoxy), R ² is hydrogen, halogen or methyl, R 4 is hydrogen or C 1-4 alkyl, R ⁵ is C 1 -C 4 alkyl, NR ^{2 (} R ²² , OR ²⁰ , SR ²⁰ or SO ₂ R ²⁰⁾ ; R ⁶ is hydrogen, C 1-4 alkyl, C 3-6 cycloalkyl, or C 1-6 acyl, R ⁷ is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, phenyl or heteroaryl, unsubstituted or substituted with halo, C 1 -C 2 alkyl and C 1 -C 2 alkoxy, or C 1 -C 2 alkoxy or NR ² ®R ²⁷ alkyl, 0 ^R2 is hydrogen, C1-2 alkyl, phenyl, or OR ²² group, R ²² is hydrogen, C 1 -C 2 alkyl, C 3 -C 6 cycloalkyl, allyl or (C 1 -C 4 alkyl) allyl R 2 is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl -, (C 2 -C 4) alkenyl or propargyl, (R 6) and (R 1) 4 - independently of one another hydrogen or (C 1 -C 4) -alkyl, (R 18) is SC ^ R ¹⁵⁵ , NO ₂ or CN, R ¹⁹ is C 1 -C 2 alkyl or benzyl, R ²⁹ is C 1-2 alkyl or C 3-6 cycloalkyl and Y is O, S, or NR ¹⁸ or, where appropriate, an E / Z isomer or tautomer thereof. The compound of formula I according to claim 1, wherein n is 1, o is 0 or 1, R 1 is perhalogen methoxy, R ² is halogen, C 1-2 alkyl, halo (C 1-2 alkyl) or halo (C 1-2 alkoxy) R ² is hydrogen, chloro or fluoro, R 4 is hydrogen or C 1-4 alkyl, R ⁵ is NR ^ R b or OR ^88, R ⁶ is hydrogen or C 1-4 alkyl, R ⁷ is hydrogen, C 1-4 alkyl, C 3-6 cycloalkyl, phenyl, unsubstituted or halo-substituted heteroaryl, C 1-2 alkoxy or NR ¹⁶ R ¹⁷ ; R ¹⁰ and R ¹¹ are each independently hydrogen, C 1 -C ² alkyl, or OR ^{2 '} , R ¹² is hydrogen, C 1 -C 2 alkyl or C 3 -C 6 cycloalkyl; - 80 R ¹⁶ and R ¹⁷ are each independently C 1 -C 2 alkyl, R ¹⁰ represents SO ₂ R ^ly , R ¹⁹ is C 1 -C 2 alkyl or benzyl, R ²⁸ is C 1-2 alkyl and Y is oxygen or NR ^1-8 group or where appropriate, an E / Z isomer or tautomer thereof. The compound of formula I according to claim 1, wherein n is 1, o is 0 or 1, R ⁴ is perhalogen methoxy, ^R2 is halogen, methyl, halomethyl or halogénmetoxi group, R ³ is hydrogen, chlorine or fluorine, R ⁴ is hydrogen or C 1-4 alkyl, R- ¹ is NR- ¹ - R ¹ - ⁴ or OR ² -, R ⁶ is hydrogen or C 1-4 alkyl, 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 1 -C ³ R ³⁷ , and R ³³ is each independently hydrogen, C 1-2 alkyl or OR ³² , R ³² is hydrogen, C 1 -C 2 alkyl or C 3 -C 6 cycloalkyl, and R ³⁷ is independently C 1 -C 2 alkyl, R ³⁸ is SC ^ R ⁴ ^, R ³⁹ is C 1 -C 2 alkyl or benzyl, ············· · · R ²⁰ is C 1-2 alkyl and Y is O or NR ¹⁸ or, where appropriate, an E / Z isomer or tautomer thereof. 9th 4-chloro-4'-trifluoromethoxybenzophenone-N-cyclopropylcarbonylhydrazone or an E / Z isomer according to claim 1. Process for the preparation of the compounds of formula (I) according to claim 1 and their corresponding isomers and tautomers, in each case in the form of the free compound or a salt thereof, subject to the foregoing limitations, a) for the preparation of compounds of formula I wherein Y is oxygen, ^R 6 is a compound of formula II known or may be prepared in an analogous manner to known compounds, wherein n, o, R ¹ , R ² , R ³ and are as defined or possible in formula (I), E / Z isomer or a tautomeric form, as a free compound or in salt form with an R ⁷ COX compound ³ - wherein X ¹ is a leaving group, preferably halogen, in particular chlorine, and ^R7 is ( The compound of formula I is preferably reacted in the presence of a base, or (b) for the preparation of compounds of formula (I) which are sulfur, Y is oxygen or (III), a compound of general formula (III) which is known in the formula n, o, R ¹ , known or analogously and R ² and R ^{3 are} represented by the general formula R ₆ N H ₂ N (IV), a compound of formula IV, known or analogous to known compounds, wherein Y is oxygen or sulfur and R ⁷ is as defined in formula (I) and is a free compound or salt is preferably reacted in the presence of an acid, or c) for the preparation of compounds of formula I wherein Y is sulfur, a compound of formula I wherein Y is oxygen and R ⁶ is preferably C 1-8 alkyl is reacted with phosphorus pentasulfide; or ·· · · · · (D) for the preparation of compounds of formula (I):. wherein Y is sulfur and R ⁶ is hydrogen, (V), a compound (V) of the formula - which can be prepared analogously known or known compounds and in which n, p, R ^4, R ^2, R ³ and R ⁷ is an E / Z isomer of formula (I) or a possible isomer thereof which is reacted with H ₂ S as the free compound or in the form of a salt, preferably in the presence of a base, or e) a compound of formula (I) wherein R ⁶ is hydrogen, with R 1 X ² wherein X ² is a leaving group such as halogen, trifluoromethylsulfonyl, toluenesulfonyl or benzenesulfonyl, preferably halogen; optionally in the presence of a base, or f) for the preparation of compounds of formula I wherein Y is NR ^{48 of} a compound of formula II X ₃ (VI), ···· ····· · · · 84 with a compound of Formula VI, which may be prepared in an analogous manner to known or known compounds wherein R ⁷ and R ¹⁸ are as defined for Formula I, X ² is a leaving group such as halogen or 1- With a C4 alkoxy, preferably ethoxy, or its possible E / Z isomer, preferably in the form of a free compound or a salt, in the presence of a base or an acid, or g) for the preparation of compounds of formula I wherein R ⁵ is NR ¹⁰ R ¹⁴ , a compound of formula II wherein R ^{6 is} hydrogen RO11 a compound of formula (VII): - which has been obtained and wherein R ⁴ is known or from corresponding known compounds by analogous methods, is reacted with R ¹⁰ and R ¹¹ are as defined in formula (I), R is C1-4 alkyl, or h) for the preparation of compounds of formula I wherein R ⁵ is NR ¹⁰ R ¹ · ⁴ , Cl '(VIII), a compound of formula VIII, which is known and may be prepared in an analogous manner to the corresponding known compounds by reaction of, for example, Y with oxygen and R ⁶ with hydrogen with phosphorus pentachloride, wherein n, p, R ^4, R ^3, R ³ and R ⁴ are as defined in formula (I) - or a possible E / Z isomers, as a free compound or a salt is preferably reacted with a compound of formula NHrIOrH presence of a base, and in any case required for the procedure or the compounds of formula (I) or their tautomeric form obtained in different ways, in each case in the free form or in the form of a salt, can be converted to another compound of formula (I), E / Z or isomer by resolution of the isomeric mixture obtained / or (I) by converting the compound of formula (I) to a compound of formula (I) or a tautomer of E / Z or a free compound or tautomer of formula (I) by converting a salt of a compound of formula (I) By converting it to the E / Z isomer or various salts thereof. 11. A pesticidal composition comprising as active ingredient at least one compound of formula (I) according to claim 1 in free form or in the form of an agriculturally useful salt and optionally at least one excipient. 12. The composition of claim 11, wherein the composition is used to control insects and acarina. ···· «··· • · A process for preparing a composition comprising at least one excipient according to claim 11, characterized in that the active ingredient is thoroughly mixed with the excipient (s) and / or ground. Use of a compound of formula (I) according to claim 1 as a free compound or as an agriculturally useful salt for the preparation of a composition according to claim 11. Use of a composition according to claim 11 for controlling pests. Use of a composition according to claim 15 for the protection of plant propagation material. 17. A method of controlling pests, wherein the composition of claim 11 is applied to the pests and their surroundings. 18. The method of protecting a plant propagation material according to claim 17, wherein the propagation material or the site of propagation material is treated. 19. The plant propagation material treated by the method of claim 18. 20. A compound of the formula: R _c ···· ···· in which η, o, R ¹ , R ² and R ® are as defined in formula (I) or, where appropriate, in the form of the E / Z isomer or tautomer thereof, in free form or as a salt thereof. provided that for formula (II) compounds of formula I, wherein R6 is hydrogen, p is 0, n is 0 or 1 and R ² is 4-n-butyl, R ¹ is other than OCF ₃ group. 21. A process for the preparation of a compound of formula (II) according to claim 20 in free form or in salt, characterized in that i) a compound of formula (IX) cox _A (IX) which is known or may be prepared in an analogous manner to the corresponding known compounds wherein R ¹ is as defined for formula (I), X ⁴ is halogen, preferably chlorine - With a benzene derivative mono- or polysubstituted with R ² as defined in formula (I) under conventional conditions of the Friedel-Crafts reaction, or j) a compound of the formula X Rí r \ CN (X), ···· ········· · · Or a compound of formula 88 or a multiple thereof which is known or may be prepared in an analogous manner to the corresponding known compounds and wherein R ⁴ is as defined for formula (I); with a phenyl-magnesium halide monosubstituted with a specified R ² group, preferably phenylmagnesium bromide, under the usual conditions of the Grignard reaction, or k) a compound of the formula XI, which is known or may be prepared in an analogous manner to the corresponding known compounds wherein n, o, R ² and R ³ are as defined in formula I - Br (CF ₂ ) pBr with a compound of formula wherein p is 1, 2, 3 or 4, preferably in the presence of a strong base such as sodium hydride, potassium hydride or potassium tert-butoxide, or to form compounds of formula II wherein R ⁴ is OCF _{3 for} reacting a compound of formula (XI) with CCl ₃ in the presence of hydrogen fluoride or for the preparation of a compound of formula (II) wherein R ⁴ is OCF ₂ Cl for a compound of formula (XI) in the presence of fluoride with C ^CO COCO CO and if desired, the product is hydrogen • · ······ 9 9 «· Further reacting with 89 fluorides to form a compound of formula II wherein R ⁴ is OCF 3, or To produce 1) (II) compounds wherein R ⁴ is OCF 3, one (formula XII) which is known or may be prepared in an analogous manner to the corresponding known compounds and wherein η, o, R ² and R ³ are as defined for formula (I), with hydrogen fluoride, preferably an oxidizing agent, preferably 1,3-dibromo-5,5- -dimethylhydantoin and a base, preferably pyridine, or m) for the preparation of compounds of formula II wherein R ⁴ is OCF 3, a compound of formula XIII (XHD, - which is known or may be prepared in an analogous manner to the corresponding known compounds and wherein η, o, R ² and R ³ are as defined for formula (I) and R is C 1 -C 4 alkyl - with PClg and C and reacting the resulting ···· ······· product with SbF ₃ and SbCl ₅ and subsequently hydrolyzing the resulting benzophenone derivative with R ⁶ NHNH 2 and / or optionally converting the compound of formula (II) obtained by the process or by different means into other compound of formula (II) and / or resolving the isomeric mixture obtained by the process and isolating the desired isomer. Use of a compound of formula (II) according to claim 20 in the free compound or salt form for the preparation of a compound according to claim 1.