DE19914756A1 - New benzothiophene derivatives useful as pesticides, especially fungicides, insecticides or acaricides for plant protection - Google Patents

Abstract

O-(Benzothienylmethyl)-oximes (I) and their E/Z isomers, E/Z isomer mixtures and/or tautomers, all in free or salt form, are new. O-(Benzothienylmethyl)-oximes of formula (I) and their E/Z isomers, E/Z isomer mixtures and/or tautomers, all in free or salt form, are new. X = CH or N; Y = OR1; and Z' = O; or X = N; Y = NHR2; and Z' = O, S or S(O); W = O or N(R6a); R1, R2 = H or alkyl; R3 = D, 3-8C alkenyl, 3-8C alkynyl or cycloalkyl (optionally substituted by 1-5 of halo, OD', 1-6C haloalkyl, NO2, CN, aryl and heteroaryl, where aryl and heteroaryl are themselves optionally substituted by 1-5 of halo, D', OD', SD', NO2 and CN); or phenyl, naphthyl or heteroaryl, all substituted by (R4)m; D = 1-6C alkyl; D' = D or 1-6C haloalkyl; m = 0-5; R4 = D', E', aryl-E-, cycloalkyl, halocycloalkyl, OD', S(O)pD', OSO2D', -D-OD', -D-S(O)pD', COD', COOD', CONHD, CON(D)2, CSNHD, CSN(D)2, alkoxyiminomethyl, NHD, N(D)2, halo, NO2, CN, CSNH2, SiMe3 or trialkylsilylmethyl; or -U-phenyl, phenyl, heteroaryl, heteroaryloxy or -O-V-phenyl, all ring substituted by (R5)n; or two adjacent R4 together = CH=CHCH=CH or 1-4C alkylenedioxy, both optionally substituted by 1-4 of alkyl and halo; E = 2-8C alkenyl or 2-8C alkynyl; E' = E, 2-8C haloalkenyl or 2-8C haloalkynyl; p = 0-2; R5 = D', E', aryl-E-, cycloalkyl, halocycloalkyl, OD', S(O)pD', OSO2D', -D-OD', -D-S(O)pD', COD', COOD', CONHD, CON(D)2, CSNHD, CSN(D)2, alkoxyiminomethyl, NHD, N(D)2, halo, NO2, CN, CSNH2, SiMe3 or trialkylsilylmethyl; or two adjacent R5 together = CH=CHCH=CH or 1-4C alkylenedioxy, both optionally substituted by 1-4 of alkyl and halo; n = 0-5; U = CH2, O or N(R6b); V = 1-8C alkylene; R6, R6a, R6b = H, alkyl, haloalkyl, alkoxymethyl, cycloalkyl, halocycloalkyl or CHO; A = direct bond, 1-10C alkylene, 1-10C haloalkylene, C(O) or C(S), provided that A can only be a direct bond if R7 = R8; R7 = R8, CN, OR8, N(R8)2, SR6, S(O)R8 or S(O)2R8; R8 = H, D', E', cycloalkyl, halocycloalkyl, trialkylsilyl or COOD; or aryl or heterocyclyl (both optionally substituted by one or more of halo, alkyl and haloalkyl); R9 = Me, CH2F or CHF2; unless specified otherwise alkyl moieties have 1-4C and cycloalkyl moieties 3-6C.

Description

Invention relates to a compound of the formula

wherein either
X is CH or N, Y OR ₁ and ZO, or
XN, Y is NHR ₂ and ZO, S or S (= O);
WO or NR _6a ;
R ₁ and R ₂ independently of one another are H or C ₁ -C ₄ alkyl;
R _{3 is} C ₁ -C ₆ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, which, if appropriate, are selected independently of one another with one to five substituents from the group consisting of Halogen, C ₁ -C ₆ halo-C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkoxy, NO ₂ , CN, aryl and heteroaryl; where the aryl and heteroaryl groups optionally, depending on the possibility of substitution on the ring system, with one to five substituents selected from the group consisting of halogen, halogen-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, halogen-C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, halo-C ₁ -C ₆ alkylthio, NO ₂ and CN are substituted; or wherein R ₃

is naphthyl substituted with (R ₄ ) _m or heteroaryl substituted with (R ₄ ) _m ;
m depending on the possibility of substitution on the ring system 0, 1, 2, 3, 4 or 5; where, when m is greater than 1, the radicals R _{4 are the} same or different;
R _{4 is} C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, halo C ₂ -C ₈ alkenyl, halo C ₂ -C ₈ -alkynyl, aryl-C ₂ -C ₈ -alkenyl, aryl-C ₂ -C ₈ -alkynyl, C ₃ -C ₆ -cycloalkyl, halo-C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -Alkoxy, halogen-C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio, halo gene-C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylsulfinyl, halogen-C ₁ -C ₆ - alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, halo-C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ alkylsulfonyloxy, halo-C ₁ -C ₆ alkylsulfonyloxy, C ₁ -C ₆ alkoxy-C ₁ -C ₆ -alkyl, halo-C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkylthio- C ₁ -C ₆ -alkyl, halo-C ₁ -C ₆ -alkylthio- C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylsulfinyl-C ₁ -C ₆ alkyl, halogen-C ₁ -C ₆ alkylsulfinyl-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkyl- sulfonyl-C ₁ -C ₆ -alkyl, halo-C ₁ -C ₆ -alkylsulfonyl-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkylcarbonyl, halogen-C ₁ -C ₆ -alkylcarbonyl, C ₁ - C ₆ alkoxycarbonyl, halo C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylaminocarbo nyl, C ₁ -C ₄ alkoxyiminomethyl, di (C ₁ -C ₆ alkyl) aminocarbonyl, where the alkyl groups may be the same or different; C ₁ -C ₆ alkylamino thiocarbonyl, di (C ₁ -C ₆ alkyl) aminothiocarbonyl, where the alkyl groups may be the same or different; C ₁ -C ₆ alkylamino, di (C ₁ -C ₆ alkyl) amino, where the alkyl groups may be the same or different; Halogen, NO ₂ , CN, thioamido, trimethylsilyl, -CH ₂ Si (C ₁ -C ₄ -al kyl) ₃ , where the alkyl groups are the same or different; two adjacent substituents R ₄ together form an unsubstituted or a one to four-fold substituted -CH = CH-CH = CH- or C ₁ -C ₄ -alkylenedioxy group, the substituents from the group consisting of C ₁ - C ₄ alkyl and halogen are selected;

a with (R _{5) n} substituted phenyl, _n substituted heteroaryl with (R _{5) n} substituted heteroaryloxy with (R ₅₎ or

R _{5 is} C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, halo-C ₂ -C ₈ alkenyl, halo-C ₂ -C ₈ -alkynyl, C ₃ -C ₆ -cycloalkyl, halogen-C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, halo gene-C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio , Halogen-C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylsulfinyl, Halo gen-C ₁ -C ₆ -alkylsulfinyl, C ₁ -C ₆ -alkylsulfonyl, halogen-C ₁ -C ₆ -alkyl- sulfonyl, C ₁ -C ₆ alkyl sulfonyloxy, halo C ₁ -C ₆ alkylsulfonyloxy, C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, halo C ₁ -C ₆ - alkoxy-C ₁ - C ₆ -alkyl, C ₁ -C ₆ -alkylthio-C ₁ -C ₆ -alkyl, halogen-C ₁ -C ₆ -alkylthio-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkylsulfinyl-C ₁ - C ₆ -alkyl, halo-C ₁ -C ₆ -alkylsulfinyl-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyl sulfonyl-C ₁ -C ₆ -alkyl, halo-C ₁ -C ₆ -alkylsulfonyl- C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylcarbonyl, halogen-C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, halogen-C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ - Alkylaminocarbonyl, C ₁ -C ₄ alkoxyiminomethyl, di (C ₁ -C ₆ -a alkyl) -aminocarbonyl, where the alkyl groups may be the same or different; C ₁ -C ₆ alkylamino thio carbonyl, di (C ₁ -C ₆ alkyl) aminothiocarbonyl, where the alkyl groups may be the same or different; C ₁ -C ₆ alkylamino, di (C ₁ -C ₆ alkyl) amino, where the alkyl groups may be the same or different; Halogen, NO ₂ , CN, thioamido, trimethylsilyl, -CH ₂ Si (C ₁ -C ₄ alkyl) ₃ , the alkyl groups being the same or different; an unsubstituted or two adjacent substituents R ₅ together a mono- to tetrasubstituted -CH = CH-CH = CH- or C ₁ -C ₄ -alkylenedioxy group, the substituents being selected from the group consisting of C ₁ -C ₄ -Alkyl and halogen are selected;
n 0, 1, 2, 3, 4 or 5; where, when n is greater than 1, the radicals R _{5 are the} same or different;
U -CH ₂ -, O or -NR _6b ;
VC ₁ -C ₈ alkylene;
R ₆ , R _6a and R _6b independently of one another are H, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxymethyl, C ₃ -C ₆ cycloalkyl, formyl or halogen C ₃ -C ₆ cycloalkyl;
R ₇ H, C ₁ -C ₄ alkyl, halo C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxymethyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, cyano, C ₃ -C ₆ cycloalkyl or halo C ₃ -C ₆ cycloalkyl;
A is a direct bond, C ₁ -C ₁₀ alkylene, -C (= O) -, -C (= S) - or halogen-C ₁ -C ₁₀ alkylene and
R _{7 is} a radical R ₈ ; or
AC ₁ -C ₁₀ alkylene, -C (= O) -, -C (= S) - or halogen-C ₁ -C ₁₀ alkylene and
R ₇ -CN, OR ₈ , N (R ₈ ) ₂ , where the radicals R _{8 are} identical or different, -SR ₈ , -S (= O) R ₈ , or -S (= O) ₂ R ₈ ;
R ₈ H, C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, halo-C ₁ -C ₆ alkyl, halo-C ₂ -C ₈ -alkenyl, halo-C ₂ -C ₈ -alkynyl or halo-C ₃ -C ₆ -cycloalkyl, -Si (C ₁ -C ₄ -al kyl) ₃ , where the alkyl groups may be the same or different;
C ₁ -C ₆ alkoxycarbonyl or an unsubstituted or one or more aryl or heterocyclyl substituted by substituents from the group consisting of halogen, C ₁ -C ₄ alkyl and halogen-C ₁ -C ₄ alkyl Group; and
R _{9 is} methyl, fluoromethyl or difluoromethyl;
and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, each in free form or in salt form, a process for the preparation and the use of these compounds, E / Z isomers and tautomers;
Pesticides, the active ingredient of which is selected from these compounds, E / Z isomers and tautomers; and a method of making and using these agents; Intermediates, and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in free form or in salt form, for the preparation of these compounds, optionally tautomers, in free form or in salt form, of these intermediates; and a process for making and using these intermediates and their tautomers.

In the literature, certain methoxyacrylic acid derivatives are harmful as active ingredients pesticide proposed. The biological properties of this known However, connections are not fully effective in the field of pest control satisfy why there is a need to establish further connections with pests controlling properties, especially for controlling insects and representatives of the order Acarina and in particular for combating phytopathogenic microorganisms to provide organisms, this task according to the invention by Providing the present compounds of formula (I) is dissolved.

Some compounds of the formula (I) and of the formulas (II) listed below bis (X) contain asymmetric carbon atoms, which makes the compounds optically active form can occur. Due to the existence of the C = X and Oximino double bonds can form the compounds in E and Z isomeric forms occur. Atropisomers of the compounds can also occur. The formulas (I) to (X) are all these possible isomeric forms and mixtures thereof, for example Racemates or E / Z isomer mixtures, and optionally their salts, even if this is not always mentioned specifically.

The general terms used above and below have, if not defined differently, the meanings listed below.

Carbon-containing groups and compounds contain, if not different defined, in each case 1 to and with 8, preferably 1 to and with 6, especially 1 to and with 4, especially 1 or 2, carbon atoms.

Alkyl - as a group per se and as a structural element of other groups and verbs such as haloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, Alkoxycarbonyl, alkylamino, alkoxyiminomethyl, alkylaminocarbonyl and alkylaminothiocar bonyl - is, taking due account of those included on a case by case basis Number of carbon atoms contained in the corresponding group or compound, either straight chain, d. H. Methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. B. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

Alkenyl - as a group per se and as a structural element of other groups and Compounds, such as from haloalkenyl -, in each case with due consideration the number of cases in the relevant group or connection, as the case may be  contained carbon atoms, either straight-chain, such as. B. vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, such as. B. iso-propenyl.

Alkynyl - as a group per se and as a structural element of other groups and Compounds, such as from haloalkynyl -, in each case with due regard to the on a case-by-case basis number of those in the corresponding group or connection contained carbon atoms, either straight-chain, such as. B. propargyl, 2-butynyl or 5-hexynyl, or branched, such as. B. 2-ethynylpropyl or 2-propargylisopropyl.

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

Alkylene - as a group per se and as a structural element of other groups and compounds, such as haloalkylene - is, in each case with due regard for the number of carbon atoms contained in the corresponding group or compound from case to case, either straight-chain, e.g. B. -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ CH ₂ -, or branched, e.g. B. -CH (CH ₃ ) -, -CH (C ₂ H ₅ ) -, -C (CH ₃ ) ₂ -, -CH (CH ₃ ) CH ₂ - or -CH (CH ₃ ) CH (CH ₃ ) -.

Aryl is phenyl or naphthyl, especially phenyl.

Heterocyclyl means a 5- to 7-membered aromatic or non-aromatic ring with one to three heteroatoms, which are selected from the group consisting of N, O and S. Preferred are aromatic 5- and 6-rings, which have a nitrogen atom as a heteroatom and optionally have a further heteroatom, preferably nitrogen or sulfur, especially nitrogen. Preferred heteroaryl radicals in the radical R ₁₀ are -pyrazinyl, -pyridyl (3 '), -pyridyl (2'), -pyridyl (4 '), -pyrimidinyl (2'), -pyrimidinyl (4 '), -pyrimidinyl (5' ), -Thiazolyl (2 '), -Oxazolyl (2'), -Furanyl (2 '), -Furanyl (3'), Tetrahydrofuranyl (3 '), -Thienyl (2'), -Thienyl (3 ') and -Thiazolyl (2 ').

Halogen - as a group per se and as a structural element of other groups and Compounds such as of haloalkyl, haloalkenyl and haloalkynyl - is fluorine, chlorine, Bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine, entirely especially fluorine.

Halogen-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkenyl or haloalkynyl, can be partially halogenated or perhalogenated, and in the case of multiple halogenation the halogen substituents can be the same or different. Examples of haloalkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkenyl, are methyl which is mono- to trisubstituted by fluorine, chlorine and / or bromine, such as CHF ₂ or CF ₃ ; the one to five times substituted by fluorine, chlorine and / or bromine ethyl, such as CH ₂ CF ₃ , CF ₂ CF ₃ , CF ₂ CCl ₃ , CF ₂ CHCl ₂ , CF ₂ CHF ₂ , CF ₂ CFCl ₂ , CF ₂ CHBr ₂ , CF ₂ CHClF, CF ₂ CHBrF or CClFCHClF; the propyl or isopropyl substituted one to seven times by 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 butyl or one of its isomers, substituted one to nine times by fluorine, chlorine and / or bromine, such as CF (CF ₃ ) CHFCF ₃ or CH ₂ (CF ₂ ) ₂ CF ₃ . Haloalkenyl is e.g. B. CH ₂ CH = CHCl, CH ₂ CH = CCl ₂ , CH ₂ CF = CF ₂ or CH ₂ CH = CHCH ₂ Br. Haloalkynyl is e.g. B. CH ₂ C∼CF, CH ₂ C∼CCH ₂ Cl or CF ₂ CF ₂ C∼CCH ₂ F.

Some compounds of the formula (I) and of the formulas (II) listed below bis (X) can, as is known to the person skilled in the art, be present as tautomers, for example when W is N in a compound of formula (I). It is therefore among the connections to understand these formulas above and below also corresponding tautomers, even if the latter are not specifically mentioned in every case.

Compounds of formula (I), and the formulas (II) to (X) listed below, which have at least one basic center, can, for. B. Form acid addition salts. These are, for example, with strong inorganic acids such as mineral acids, e.g. B. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as, for. B. by halogen, substituted C ₁ -C ₄ alkane carboxylic acids, for. B. acetic acid, such as unsaturated dicarboxylic acids, e.g. B. oxalic, malonic, Bern stone, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, for. B. ascorbic, lactic, malic, tartaric or citric acid, or like benzoic acid, or with organic sulfonic acids, such as, if necessary, for. B. by halogen, substituted C ₁ -C ₄ alkane or arylsulfonic acids, for. B. methane or p-toluenesulfonic acid. Furthermore, compounds of the formula (I) with at least one acidic group can form salts with bases. Suitable salts with bases are, for example, metal salts such as alkali or alkaline earth metal salts, e.g. B. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. B. ethyl, diethyl, triethyl or dimethyl propyl amine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. B. mono-, di- or triethanolamine. Corresponding internal salts can optionally also be formed. Preferred in the context of the invention are agrochemically advantageous salts; but also includes other salts which are used, for example, for the isolation or purification of free compounds of the formula (I) or their agrochemically usable salts. The compounds of the formulas (I) to (X) in free form are also to be understood above and below as the salts of the compounds of the formulas (I) to (X), and the salts, if appropriate and appropriately, also mean the corresponding free compounds .

The same applies to tautomers of these compounds. Is generally preferred the free form.

Preferred embodiments within the scope of the invention - in each case taking into account the above-mentioned requirements - are:

• (1) a compound of formula (I) wherein X is CH and Z is O;
• (2) a compound of formula (I) wherein X is N and Z is O;
• (3) a compound of formula (I) wherein YC ₁ -C ₂ alkoxy, especially methoxy;
• (4) a compound of formula (I) wherein R _{1 is} C ₁ -C ₂ alkyl, especially methyl;
• (5) a compound of formula (I) wherein R _{2 is} methyl;
• (6) a compound of formula (I) wherein
  R ₃ C ₁ -C ₆ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, which, if appropriate, independently of one another, depending on the possibility of substitution on the ring system, with one to five substituents selected from the group consisting of halogen, C ₁ -C ₆ alkoxy, halogen C ₁ -C ₆ alkyl, halogen C ₁ -C ₆ alkoxy, NO ₂ , CN, aryl and heteroaryl; the aryl and heteroaryl groups optionally, depending on the possibility of substitution on the ring system, with one to five substituents selected from the group consisting of halogen, halogen-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, halogen-C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, halo C ₁ -C ₆ alkylthio, NO ₂ and CN are substituted; or wherein R ₃
  with (R _{4) m} or naphthyl substituted with (R _{4) m} substituted heteroaryl and m is 1 or 2, especially 1;
• (7) a compound of formula (I) wherein
  R ₄ C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₃ -C ₆ cycloalkyl, halo C ₃ -C ₆ cycloalkyl, C ₁ - C ₆ alkoxy, halo-C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxycarbonyl, halo C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylamino, di (C ₁ -C ₆ alkyl) amino, where the alkyl groups can be the same or different; Halogen, NO ₂ , CN, thioamido, trimethylsilyl, -CH ₂ Si (C ₁ -C ₄ alkyl) ₃ , the alkyl groups being the same or different; two adjacent substituents R ₄ together form an unsubstituted or a mono- to tetrasubstituted -CH = CH-CH = CH- or -C ₁ -C ₄ -alkylenedioxy group, the substituents being selected from the group consisting of C ₁ -C ₄ alkyl and halogen are selected;
  a with (R _{5) n} substituted phenyl, _n substituted heteroaryl with (R _{5) n} substituted heteroaryloxy with (R ₅₎ or
  especially
  or a phenyl substituted with (R ₅ ) _n , and n is 1, 2 or 3, especially 1 or 2, especially 1;
• (8) a compound of formula (I) wherein
  R _{5 is} C ₁ -C ₆ alkyl, halogen-C ₁ -C ₆ alkyl, C ₁ -C ₂ alkoxy, halogen-C ₁ -C ₂ alkoxy, C ₃ -C ₆ cycloalkyl, halogen-C ₃ -C ₆ cycloalkyl, halogen, NO ₂ or CN;
  especially halogen-C ₁ -C ₂ -alkyl, halogen-C ₁ -C ₂ -alkoxy, halogen or NO ₂ ; in particular fluorine, chlorine, trifluoromethoxy or trifluoromethyl;
  is especially chlorine, trifluoromethoxy or trifluoromethyl;
• (9) a compound of formula (I) wherein
  R _{8 is} H or C ₁ -C ₂ alkyl, preferably C ₁ -C ₂ alkyl, especially methyl;
• (10) a compound of formula (I) wherein R _{9 is} methyl or fluoromethyl; is preferably methyl;
• (11) a compound of formula (I), wherein R _{6 is} H, C ₁ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl, especially methyl or ethyl, especially ethyl.
• (12) a compound of formula (I), wherein R _{6a is} H or C ₁ -C ₄ alkyl, especially H or methyl, especially H;
• (13) a compound of formula (I) wherein W is NH;
• (14) a compound of the formula (I) in which n is 0, 1 or 2, especially 1 or 2, especially 1 is;
• (15) a compound of formula (I) wherein
  A is a direct bond, C ₁ -C ₁₀ alkylene, or halo C ₁ -C ₁₀ alkylene;
  preferably a direct bond or C ₁ -C ₄ alkylene;
  especially a direct bond or methylene; and
  R _{7 is} a radical R ₁₀ ;
• (16) a compound of formula (I) wherein
  AR _{7 is} methyl or ethyl, especially ethyl;
• (17) a compound of the formula (I) in which U -NR _6b and R _{6b are} H, C ₁ -C ₄ -alkyl or formyl, especially H or methyl, in particular H.

Within the scope of the invention, those in Tables 1 to 9 are particularly preferred Compounds of formula (I) listed and optionally their E / Z isomers and E / Z isomer mixtures.

The invention further relates to a process for the preparation of the compounds of the formula (I) and, if appropriate, their E / Z isomers, E / Z isomers, mixtures and / or tautomers, in which A, W, X, Y, Z, R ₃ , R ₆ , R ₇ and R _{9 have} the same meaning as given above in formula (I), in each case in free form or in salt form, characterized in that

• a1) either a compound of the formula
  wherein X, Y, Z, R ₃ , R ₄ and R _{9 have} the meanings given for the formula (I) and X _{1 is} a leaving group, preferably in the presence of a base, with a compound of the formula
  wherein A, W, R ₃ , R ₆ and R _{7 have} the meanings given for the formula (I); or
• a2) a compound of the formula
  wherein A, W, R ₃ , R ₆ and R _{7 have} the meanings given for the formula (I), optionally in the presence of a base, with a compound of the formula
  wherein X, Y, Z and Rg have the meanings given for the formula (I); or
• a3) a compound of the formula
  in which W, X, Y, Z, R ₃ , R ₆ and R _{9 have} the same meaning as given above in formula (I) and in which the measures given above for the compounds of formula (I) apply, with a compound of formula
  X ₁ -AR ₇ (VII),
  which is known or can be prepared by methods known per se and in which A and R _{7 have} the same meaning as given above in formula (I) and X ₁ denotes a leaving group as in formula (II);
• b) for the preparation of a compound of the formula (I) in which Y is NHR ₈ and ZO, a compound of the formula (I) in which Y is OR ₁ , with a compound of the formula R ₈ NH ₂ which is known or according to known methods can be prepared and in which R _{8 has} the meanings given for the formula (I); or
• c) for the preparation of a compound of the formula (I) in which Y is NHR ₈ and ZS, a compound of the formula (I) in which YR _{8 is} NH ₂ and ZO, with P ₄ S ₁₀ or Lawesson's reagent [2.4 -Bis (methoxyphenyl -) - 1,3-dithia-2,4-diphosphetane-2,4-disulfide], or
• d) for the preparation of a compound of the formula (I) in which Z is SO, reacting a compound of the formula (I) in which ZS is an oxidizing agent;
  and in each case, if desired, a compound of the formula (I) or an E / Z isomer or tautomer thereof, either in free form or in salt form, according to the process or otherwise obtainable, in another compound of the formula (I) or an E. / Z isomer or tautomer thereof, in each case in free form or in salt form, a process-obtainable mixture of E / Z isomers is separated and the desired isomer is isolated and / or a process compound or otherwise obtainable free compound of the formula (I ) or an E / Z isomer or tautomer thereof in a salt or a salt of a compound of the formula (I) or an E / Z isomer or tautomer thereof obtainable according to the process or in another way in the free compound of the formula (I) or an E / Z isomer or tautomer thereof or converted to another salt.

Another object of the invention is a process for the preparation of the compounds of formula (VI), in each case in free form or in salt form, characterized in that

• e) a compound of the formula
  wherein X, Y, Z, R ₃ , R ₆ and R _{9 have} the same meaning as given above in formula (I), with a compound
  H ₂ NWAR ₇ (IX),
  which is known or can be prepared by processes known per se, and in which W, A and R _{7 have} the meanings given in formula (I).

Another object of the invention is a process for the preparation of the compounds of formula (VIII), in each case in free form or in salt form, characterized in that

• f) a compound of the formula
  which is known or can be prepared by processes known per se, and in which R ₃ and R _{6 have} the same meaning as indicated above in formula (I), with a compound of formula (II).

For starting materials listed above and below applies with regard to their E / Z isomers and tautomers that above for Verbin E / Z isomers and tautomers formulas (I) to what has been said in an analogous manner.

The reactions described above and below are known per se Way performed, e.g. B. in Ab or usually in the presence of a suitable Solvent or diluent or a mixture thereof, depending on Need under cooling, at room temperature or under heating, e.g. B. in one temperature range from about 0 ° C to the boiling point of the reaction medium, preferably from about 20 ° C to about + 120 ° C, especially 60 ° C to 80 ° C and, if necessary, in one closed vessel, under pressure, in an inert gas atmosphere and / or under water free conditions works. Particularly advantageous reaction conditions can Examples are taken.

The raw materials listed above and below are required for the manufacture of the compounds of formula (I) and optionally their E / Z isomers and tautomers can be used e.g. B. according to the information below.

Some of the compounds of the formulas (II) to (X) are known. As far as they are new, are they also form part of the invention.

The reactants can be as such, i.e. H. without adding a solution or Diluent, e.g. B. in the melt. Mostly is however, the addition of an inert solvent or diluent or a mixture the same advantageous.  

The reactions are preferably carried out at normal pressure and without Protective gas atmosphere; however, they are preferred under a protective gas atmosphere, e.g. B. nitrogen or argon, especially nitrogen.

The products are isolated using customary methods, e.g. B. by filtration, Crystallization, distillation or chromatography or any suitable combination of these Method.

Variants a1 / a2 / a3

Suitable leaving groups X ₁ in the compounds of formula (II) are e.g. B. hydroxy, C ₁ -C ₈ alkoxy, halo C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkanoyloxy, mercapto, C ₁ -C ₈ alkylthio, halo C ₁ -C ₈ alkylthio, C ₁ -C ₈ -alkanesulfonyloxy, halogen-C ₁ -C ₈ -alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy and halogen, especially halogen.

Suitable bases to facilitate the implementation are e.g. B. alkali metal or Alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or -alkylsilylamides, alkylamines, alkylenediamines, optionally N-alkylated, given if unsaturated, cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples include sodium hydroxide, hydride, amide, methoxide, acetate, carbonate, potassium tert-butoxide, hydroxide, carbonate, hydride, Lithium diisopropylamide, potassium bis (trimethylsilyl) amide, calcium hydride, triethylamine, Diisopropyl-ethyl-amine, triethylene diamine, cyclohexylamine, N-cyclohexyl-N, N-dimethyl-amine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, Benzyl trimethyl ammonium hydroxide and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU) called.

Examples of solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as Benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, Petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, Dichloroethane, trichlorethylene or tetrachlorethylene, esters, such as ethyl acetate, ether, 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, Dimethoxydiethylether, 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. Will the implementation in  Running in the presence of a base, bases used in excess, such as Triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline, as a solution or Diluents.

The reaction advantageously takes place in a temperature range from about 0 ° C. to about 180 ° C, preferably from about 10 ° C to about 80 ° C, in many cases in the range between Room temperature and the reflux temperature of the reaction mixture. Is preferred a reaction time from about 0.1 to about 24 hours, especially from about 0.5 to about 2 hours.

In a preferred embodiment of variant a1, a compound (II) is added 0 ° C to 80 ° C, preferably 10 ° C to 30 ° C, in an inert solvent, preferably an amide, especially N, N-dimethylformamide, in the presence of a metal hydride preferably sodium hydride, reacted with a compound (III). Particularly preferred Conditions for the reaction are described in the examples.

Variant b)

Examples of solvents or diluents are those in US Pat Variant a1 / a2 / a3 mentioned.

The reaction advantageously takes place in a temperature range from about 0 ° C. to about 180 ° C, preferably from about 10 ° C to about 80 ° C, in many cases in the range between Room temperature and the reflux temperature of the reaction mixture. Is preferred a reaction time from about 0.1 to about 24 hours, especially from about 0.5 to about 2 hours.

Particularly preferred conditions for the reaction are in the examples described.

Variant c)

Examples of solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons substances such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromine benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, Dichloroethane, trichlorethylene or tetrachlorethylene; Ethers, such as diethyl ether, dipropyl ether, Diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetra hydrofuran or dioxane; and sulfoxides such as dimethyl sulfoxide.

The reaction advantageously takes place in a temperature range from about 0 ° C. to about + 120 ° C, preferably from about 80 ° C to about + 120 ° C. A reaction time is preferred from about 0.1 to about 24 hours, especially from about 0.5 to about 2 hours.  

Variant d)

Suitable oxidizing agents are e.g. B. inorganic peroxides, such as Sodium perborate, or hydrogen peroxide, or organic peracids, such as Perbenzoic acid or peracetic acid, or mixtures of organic acids and Hydrogen peroxide, such as B. acetic acid / hydrogen peroxide.

The reactants can be used as such, ie without the addition of a solvent or diluent, e.g. B. in the melt. However, the addition of an inert solvent or diluent or a mixture thereof is usually advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, trichloromethane , Trichlorethylene or tetrachlorethylene; 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 or propanol; Amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, 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 an organic acid or peracid, excess acids, e.g. B. strong organic carboxylic acids, such as, e.g. B. by halogen, substituted C ₁ -C ₄ alkane carboxylic acids, for. B. formic acid, acetic acid or propionic acid, serve as a solvent or diluent.

The reaction advantageously takes place in a temperature range from about 0 ° C. to about + 120 ° C, preferably from about 0 ° C to about + 40 ° C. A reaction time of is preferred about 0.1 to about 24 hours, especially from about 05 to about 2 hours.

Variant e)

Suitable bases to facilitate the implementation are e.g. B. those which are mentioned in the variants a1 / a2 / a3.

Examples of solvents or diluents are those in the variants a1 / a2 / a3 mentioned.

The reaction advantageously takes place in a temperature range from about 0 ° C. to about 180 ° C, preferably from about 10 ° C to about 80 ° C, in many cases in the range between Room temperature and the reflux temperature of the reaction mixture. Is preferred  a reaction time from about 0.1 to about 24 hours, especially from about 0.5 to about 2 hours.

Variant f)

Suitable bases to facilitate the reaction and suitable leaving groups X ₁ in the compounds of the formula (II) are, for. B. those mentioned in the variant a1 / a2 / a3.

Examples of solvents or diluents are those in the variant a1 / a2 / a3 mentioned.

The reaction advantageously takes place in a temperature range from about 0 ° C. to about 180 ° C, preferably from about 10 ° C to about 80 ° C, in many cases in the range between Room temperature and the reflux temperature of the reaction mixture; is preferred a reaction time from about 0.1 to about 24 hours, especially from about 0.5 to about 2 hours.

The compounds of formulas (I) to (X) can be in the form of one of the possible Isomers or as a mixture thereof, e.g. B. depending on the number, absolute and relative Configuration of the asymmetric carbon atoms as pure isomers, such as antipodes and / or diastereomers, or as mixtures of isomers, such as mixtures of enantiomers, e.g. B. Racemates, mixtures of diastereomers or mixtures of racemates are present; The invention concerns both the pure isomers and all possible isomer mixtures and is pre- and to be understood accordingly below, even if stereochemical Details are not specifically mentioned in every case.

According to the process - depending on the choice of raw materials and working methods - or otherwise available diastereomer mixtures and racemate mixtures of compounds of the formula (I) to (X) due to the physico-chemical differences of the Components separated in a known manner into the pure diastereomers or racemates be, for example by fractional crystallization, distillation and / or Chromatography.

Correspondingly available mixtures of enantiomers, such as racemates, can be read off decompose known methods into the optical antipodes, for example by Recrystallization from an optically active solvent, by chromatography chiral adsorbents, e.g. B. High pressure liquid chromatography (HPLC) Acetyl cellulose, with the help of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, e.g. B. using chiral crown ethers, complexing only one enantiomer.  

In addition to the separation of the corresponding isomer mixtures, pure ones Diastereomers or enantiomers according to the invention also by generally known Methods of diastereoselective or enantioselective synthesis can be obtained, e.g. B. by the process according to the invention with starting materials with correspondingly suitable Stereochemistry.

The biologically more effective isomer is advantageously isolated or synthesized, e.g. B. enantiomers, or mixture of isomers, e.g. B. mixture of enantiomers, if the individual Components have different biological effectiveness.

The compounds of the formulas (I) to (X) can also be obtained in the form of their hydrates and / or others, for example optionally for the crystallization of solid Include solvents used in the present compounds.

The invention relates to all those embodiments of the method according to which one as a starting or intermediate at any stage of the process available connection and performs all or some of the missing steps, or a starting material in the form of a derivative or salt and / or its racemates or Antipodes used or in particular forms under the reaction conditions.

In the method of the present invention, those are preferably used Starting materials and intermediates are used, which are considered to be special at the beginning lead valuable compounds of formula (I).

The invention relates in particular to those described in Examples H1 to H5 Production method.

The compounds of formula (I) according to the invention are in the field of Pest control with favorable warm-blood, fish and plant tolerance Preventive and / or curative valuable even at low application concentrations Active ingredients with a very favorable biocidal spectrum. The inventive Active ingredients are sensitive to all or individual stages of development, however also from resistant, animal pests, such as insects and representatives of the order Acarina, and phytopathogenic mushrooms effective. The insecticidal, ovicidal and / or acaricidal The effect of the active compounds according to the invention can be direct, i. H. in a kill the pests, which immediately or after some time, for example in a Molting, entering, or their eggs, or indirectly, e.g. B. in a reduced egg laying and / or Hatching rate, showing the good effect of a mortality rate of corresponds to at least 50 to 60%.  

The animal pests mentioned include, for example, those which are in the European patent application EP-A-736'252 are mentioned. EP-A-736'252 is therefore per Reference included in the present subject matter.

The phytopathogenic fungi mentioned include, for example:
from the class of the fungi imperfecti, for example Botrytis spp., Pyricularia spp., Helminthosporium spp., Fusarium spp., Septoria spp., Cercospora spp. and Alternaria spp .;
from the class of the Basidiomycetes, for example Rhizoctonia spp., Hemileia spp. and Puccinia spp .;
from the class of the Ascomycetes, for example Venturia spp., Erysiphe spp., Podosphaera spp., Monilinia spp. and Uncinula spp .; and
from the class of the Oomycetes, for example Phytophthora spp., Pythium spp. and Plasmopara spp.

The active compounds according to the invention can be used in particular on plants especially on useful and ornamental plants in agriculture, horticulture and forestry, or on Parts such as fruits, flowers, foliage, stems, tubers or roots of such plants control pests of the type mentioned, d. H. contain or destroy, with parts of the plant that grow later still partly against these pests be protected.

Cereals such as wheat, barley, rye, oats, Rice, corn or sorghum; Beets such as sugar beet or fodder beet; Fruit, e.g. B. core, stone and Soft fruit such as apples, pears, plums, peaches, almonds, cherries or berries, e.g. B. strawberries, raspberries or blackberries; Legumes, such as beans, lentils, peas or soy; Oil fruits, such as rapeseed, mustard, poppy seeds, olives, sunflowers, coconut, castor oil, Cocoa or peanuts; Cucumber plants such as pumpkins, cucumbers or melons; Fiber plants such as cotton, flax, hemp or jute; Citrus, like oranges, Lemons, grapefruit or tangerines; Vegetables such as spinach, lettuce, asparagus, Cabbages, carrots, onions, tomatoes, potatoes or peppers; Laurels, like Avocado, cinnamon or camphor; as well as tobacco, nuts, coffee, egg fruits, Sugar cane, tea, pepper, grapevines, hops, banana plants, Natural rubber plants and ornamental plants.

The active compounds according to the invention are particularly suitable for combating Insects and representatives of the Acarina order, especially of plant-damaging ones eating insects such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens-Lar  ven, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., In cotton, fruit, corn, soybean, rapeseed and vegetable crops.

Further areas of application of the active compounds according to the invention are the protection of Inventories and warehouses and of material as well as protection in the hygiene sector of domestic and farm animals from pests of the type mentioned.

The invention therefore also relates to pesticides, such as, depending on desired targets and given conditions, emulsifiable concentrates to be selected, Suspension concentrates, directly sprayable or dilutable solutions, spreadable Pastes, diluted emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which - at least - contain one of the active substances according to the invention.

The active ingredient is in these agents in pure form, a solid active ingredient z. B. in one special grain size, or preferably together with - at least - one of the in the Formulation technology usual auxiliaries, such as extenders, for. B. solvents or solid carriers, or such as surface-active compounds (surfactants).

For example, solid excipients, solvents, Stabilizers, "slow release" auxiliaries, dyes and optionally surface-active Substances (surfactants). Carriers and auxiliaries all come from pesticides, especially for snail control agents, substances commonly used in Question. As auxiliaries, such as solvents, solid carriers, surface-active compounds solutions, nonionic surfactants, cationic surfactants, anionic surfactants and other auxiliaries substances in the agents used according to the invention, for example, come in the same Question as described in EP-A-736'252.

These pest control agents can, for example, be wettable Powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, Suspension concentrates or aerosols can be formulated. The means are, for example of the same type as described in EP-A-736'252.

The agents generally contain 0.1 to 99%, in particular 0.1 to 95%, of active ingredient and 1 to 99.9%, in particular 5 to 99.9%, - at least - of a solid or liquid Excipient, usually 0 to 25%, in particular 0.1 to 20%, of the surfactant can be (% means weight percent). While rather as a commodity concentrated means are preferred, the end user usually uses diluted agents that have significantly lower drug concentrations. Preferred Agents are composed in particular, as described in EP-A-736'252.  

The effect of the agents according to the invention can be increased by adding others Insecticidal, acaricidal and / or fungicidal active substances significantly broaden and adjust given circumstances. As active ingredient additives come z. B. Representative of following classes of active substance into consideration: organic phosphorus compounds, Nitrophenol derivatives, formamidines, ureas, benzoyl ureas, carbamates, pyrethroids, chlorinated hydrocarbons, neonicotinoids, macrolides and Bacillus thuringiensis- Preparations. The agents according to the invention can also include other solid or liquid Excipients, such as stabilizers, e.g. B. optionally epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, e.g. B. silicone oil, preserve agents, viscosity regulators, binders and / or adhesives, and fertilizers or other active ingredients to achieve special effects, e.g. B. bactericides, nematicides, Molluski zide or selective herbicides.

The agents according to the invention are produced in a known manner, at Absence of additives such. B. by grinding and / or sieving a solid active ingredient or mixture of active ingredients, e.g. B. to a certain grain size, and in the presence of at least one auxiliary z. B. by intimately mixing and / or grinding the Active substance or mixture of active substances with the excipient (s). These procedures for Production of the agents according to the invention and the use of the compounds of the Formula (I) for the preparation of these agents also form an object of the invention.

The procedures for using the funds, i.e. the procedures for combating Pests of the type mentioned, such as, depending on the intended goals and given Ratios to be selected, spraying, atomizing, dusting, brushing, pickling, Scattering or watering, and the use of pest control agents of the type mentioned are further objects of the invention. Typical application con concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, active ingredient. The application rates per hectare are generally 1 to 2000 g Active ingredient per hectare, in particular 10 to 1000 g / ha, preferably 20 to 600 g / ha.

A preferred application method in the field of crop protection is Apply to the foliage of the plants (leaf application), whereby application-free Align the frequency and application rate to the infestation pressure of the respective pest to let. The active ingredient can also get into the plants through the root system (systemic effect) by changing the location of the plants with a liquid soaks or the active ingredient in solid form in the location of the plants, e.g. B. in the ground,  brings z. B. in the form of granules (floor application). With water rice crops you can meter such granules into the flooded rice field.

The agents according to the invention are also suitable for the protection of plants Propagation material, e.g. B. seeds, such as fruits, tubers or grains, or Plant cuttings, against fungal infections and animal pests. The propagation material can be treated with the agent before spreading, seed z. B. before sowing to be stained. The active compounds according to the invention can also be applied to seeds can be applied (coating) by placing the grains in either a liquid medium soaks or coated them with a solid agent. The agent can also be applied of the propagation material to the place of application, e.g. B. when sowing in the furrow, be applied. These treatment methods for plant reproductive material and that Plant propagation material treated in this way are further objects of the invention.

The following examples serve to illustrate the invention. You restrict them Invention not one. Temperatures are given in degrees Celsius.

Manufacturing examples

Example H1

Preparation of (3- {2-ethoxyimino-1-methyl-2- [4- (3-trifluoromethylphenoxy) phenyl] ethylideneaminooxymethyl} benzo [.b.] Thiophen-2-yl) methoxyimino methyl acetate

3 g (3-bromomethyl-benzo - [. B.] Thiophen-2-yl) -methoxyimino acetic acid methyl ester of the formula

and 3.2 g of 1- [4- (3-trifluoromethylphenoxy) phenyl] -pro pane-1,2-dione 1 - (.O.-ethyl-oxime) -2-oxime of the formula

are added to 0.23 g of sodium hydride in 30 ml of dimethylformamide. The mix is made for Stirred for 30 minutes, acidified with acetic acid and with aqueous sodium bicarbonate solution neutral. The reaction mixture is extracted three times with ethyl acetate, which combined organic phases dried over magnesium sulfate and the solvent evaporated in vacuo. The residue is on silica gel with hexane / ethyl acetate (19: 1) as Eluent cleaned. The title compound is obtained as an oil.

Example H2

Preparation of 2- (3- {2-ethoxyimino-1-methyl-2- [4- (3-trifluoromethylphenoxy) phenyl] ethylideneaminooxymethyl} benzo [.b.] Thiophene-2-yl) -2-methoxyimino -.N.-methyl-acetamide of the formula

2.3 g (3- {2-ethoxyimino-1-methyl-2- [4- (3-trifluoromethylphenoxy) phe nyl] -ethylideneaminooxymethyl} -benzo [.b.] thiophen-2-yl) -methoxyimino methyl acetate, 2 ml of an 8 molar solution of methylamine in water and 10 ml of ethanol put together and left for one day at room temperature. Then it will The mixture was concentrated in vacuo and the residue on silica gel with hexane / ethyl acetate (9: 1) cleaned. The title compound is obtained as an oil.

Example H3

Preparation of (3- {2- (dimethylhydrazono) -1-methyl-2- [4- (3-trifluoro methylphenoxy) phenyl] ethylideneaminooxymethyl} benzo [.b.] Thiophen-2-yl) -methoxyimino acetic acid methyl ester of the formula

• a) 30 g of 1- [4- (3-trifluoromethylphenoxy) phenyl] propan-2-one oxime of the formula
  in 250 ml of toluene, 21 ml of 1,1-dimethylhydrazine and 1.5 g of zinc chloride are kept under reflux for 24 hours on a water separator. The reaction mixture is filtered and the filtrate is concentrated in vacuo. The residue is recrystallized from diethyl ether / hexane (1: 1). 1- (Dimethyl-hydrazono) -1- [4- (3-trifluoromethylphenoxy) phenyl] -pro pan-2-one oxime of the formula is obtained
  with a melting point of 171-174 ° C.
• b) 3 g of (3-bromomethyl-benzo [.b.] thiophen-2-yl) -methoxyimino methyl acetate and 3.2 g of 1- (dimethylhydrazono) -1- (4- (3-trifluoromethylphenoxy) phenyl] propane-2-one oxime are added to 0.23 g of sodium hydride in 30 ml of dimethylformamide. The mix is made for Stirred for 30 minutes, acidified with acetic acid and with aqueous sodium bicarbonate solution neutral. The reaction mixture is extracted three times with ethyl acetate combined organic phases dried over magnesium sulfate and the solvent evaporated in vacuo. The residue is treated on silica gel with hexane / ethyl acetate (19: 1) Eluent cleaned. The title compound is obtained as a resin.

Example H4

Preparation of (3- {2- (dimethylhydrazono) -1-methyl-2- [4- (3-trifluoromethylphenoxy) phenyl] ethylideneaminooxymethyl} benzo [.b.] Thiophene-2-yl) methoxyimino -.N.-methyl-acetamide of the formula

(3- {2- (Dimethylhydrazono) -1-methyl-2- [4- (3-trifluoromethylphenoxy) phenyl] ethylidenes aminooxymethyl} -benzo [.b.] thiophen-2-yl) -methoxyimino methyl acetate, 2 ml of a 8 molar solution of methylamine in water and 10 ml of ethanol are combined given and left for one day at room temperature. Then the mixture in the Concentrated in vacuo and the residue was purified on silica gel with hexane / ethyl acetate (9: 1). The title compound is obtained as an oil.

Example H5

In a manner analogous to that described in Examples H1 to H4 other compounds listed in Tables 1 to 9 are prepared. In the In the "Physical data" column of the tables, the specified temperatures each indicate the Melting point of the compound in question in ° C; c-Propyl means cyclopropyl.

Table A

Compounds of the general formula

Table 1

Compounds of the general formula (I.1) wherein X CH, Y OCH ₃ , WO and the substituents R ₄ , R ₆ and AR ₇ each correspond to one row of Table A. Compound 1A-25 resin.

Table 2

Compounds of the general formula (I.1), in which XN, Y OCH ₃ , WO and the combination of the substituents R ₄ , R ₆ and AR ₇ each correspond to one row of Table A.

Compounds of the formula

The information in the Phys. Data are melting points in ° C.  

Table 3

Compounds of the general formula (I.1), in which XN, Y NHCH ₃ , WO and the substituents R ₄ , R ₆ and AR ₇ each correspond to one row of Table A.

Compounds of the formula

The numbers in the Phys. Data are melting points in ° C.  

Table 4

Compounds of the general formula (I.1), in which X CH, Y OCH ₃ , W NH and the substituents R ₄ , R ₆ and AR ₇ each correspond to one row of Table A.

Table 5

Compounds of the general formula (I.1), in which XN, Y NHCH ₃ , W NH and the substituents R ₄ , R ₆ and AR ₇ each correspond to one row of Table A.

Table 6

Compounds of the general formula (I.1), in which XN, Y OCH ₃ , W NH and the substituents R ₄ , R ₆ and AR ₇ each correspond to one row of Table A.

Table 7

Compounds of the general formula (I.1) wherein X CH, Y OCH ₃ , W NCH ₃ and the substituents R ₄ , R ₆ and AR ₇ each correspond to one row of Table A.
Compound 7.A-2 resin.

Table 8

Compounds of the general formula (I.1), in which XN, Y OCH ₃ , W NCH ₃ and the substituents R ₄ , R ₆ and AR ₇ each correspond to one row of Table A.

Compound 8.A-2 resin
Compound 8.A-6 resin
Compound 8.A-22 122-125 ° C
Compound 8.A-27 95-97 ° C
Compound 8.A-30 oil
Compound 8.A-47 oil
Compound 8A-60 116-118 ° C
Compound 8.A-63 resin
Compound 8.A-65 resin
Compound 8.A-66 resin
Compound 8.A-80 resin.

Table 9

Compounds of the general formula (I.1), in which XN, Y NHCH ₃ , W NCH ₃ and the substituents R ₄ , R ₆ and AR ₇ each correspond to one row of Table A.

Compound 9.A-2 resin
Compound 9.A-6 foam
Compound 9.A-22 151-153 ° C
Compound 9.A-27 foam
Compound 9.A-47 resin
Compound 9.A-60 146-148 ° C
Compound 9.A-63 foam
9.A-65 compound foam
Compound 9.A-66 foam
Compound 9.A-80 89-94 ° C.

As examples of suitable formulations, such as emulsion concentrates, Solutions, dusts, wettable powders, extruder granules, coating granules or Suspension concentrates, especially those such as those described in EP-A-736'252, Examples F1 to F10 are listed, which are included here by reference.

Biological examples A) Microbicidal action Example B1 Effect against Phytophthora infestans on tomatoes a) Curative effect

Tomato plants of the "Red Gnome" variety are grown with a Zoospores suspension of the mushroom sprayed and sown in a cabin at 18 to 20 incubated humidity. Humidification interrupted after 24 hours. After this To dry off the plants, they are sprayed with a broth, which is used as a wettable powder contains formulated active substance in a concentration of 200 ppm. After the arrival the spray coating is dried, the plants are again in the wet room for 4 days set up. Number and size of the typical leaf that occurred after this time Stains are the yardstick for the effectiveness of the tested substances.  

b) Preventive-systemic effect

The active substance formulated as a wettable powder is used in a concentration of 60 ppm (based on on the soil volume) on the soil surface of a three-week-old potted Tomato plants of the "Red Gnome" variety. After waiting three days, the Leaf underside of the plants with a zoospore suspension of Phytophthora infestans sprayed. They were then in a spray booth at 18 to 20 C and more saturated for 5 days Humidity kept. After this time, typical leaf spots, their number, form and size serve to evaluate the effectiveness of the tested substances.

While untreated but infected control plants show 100% infection, the Active substances in Tables 1 to 9 infested in both tests to 20% or less pushed back.

Example B2 Effect against Plasmopara viticola (Bert. Et Curt.) (Beri. Et DeToni) on vines a) Residual preventive effect

"Chasselas" vine cuttings are grown in the greenhouse. in the At the 10-leaf stage, 3 plants are sprayed with a broth (200 ppm of active ingredient). After The plants on the underside of the leaf dry with the spray coating Spore suspension of the fungus infected evenly. The plants are then kept in a humid chamber for 8 days. After this time, there are clear signs Disease symptoms on the control plants. Number and size of the infection sites the treated plants serve as an evaluation benchmark for the effectiveness of the tested substances.

b) Curative effect

"Chasselas" vine cuttings are grown in the greenhouse and in the 10-leaf stage with a spore suspension of Plasmopara viticola on the underside of the leaf infected. After 24 hours in the wet room, the plants are covered with a Sprayed active ingredient broth (200 pm, 60 ppm, 20 ppm active ingredient). Then the Plants continue to be kept in the wet room for 7 days. After this time the show up Disease symptoms on the control plants. Number and size of the infection sites the treated plants serve as a benchmark for the effectiveness of tested substances.

Compared to the control plants, those with active ingredients in Tables 1 to 9 treated plants have an infestation of 20% or less. Especially with the  Connections 2.A-26, 2.A-28, 2.A-44, 2.A-50, 3.A-26, 3.A-44 and 4.A-52 will be one achieved a complete curative effect.

Example B3 Effect against Puccinia graminis on wheat a) Residual protective effect

Wheat plants are sprayed with an aqueous spray mixture (0.02% Active substance) dripping wet and 24 hours later with a Uredo spore suspension infected with the fungus. After an incubation period of 48 hours (conditions: 95 to 100 Percent relative humidity at 20 ° C) the plants in a greenhouse 22 ° C set up. The rust pustule development is assessed 12 days after Infection.

b) Systemic effect

5 days after sowing, an aqueous spray mixture (0.006% active substance, based on the soil volume) poured. Care is taken that the spray liquid does not come into contact with parts of the plant above ground. 48 hours later the plants are infected with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95 to 100 percent relative humidity activity at 20 ° C) the plants are placed in a greenhouse at 22 ° C. The Assessment of rust pustule development is made 12 days after infection.

The compounds in Tables 1 to 9 bring about a significant reduction in fungal attack, partly to 10-0%, especially for the compounds 2.A-31, 3.A-31, 3.A-52 and 3.A-53.

Example B4 Effect against Septoria nodomm on wheat

Wheat plants are in the 3-leaf stage with a spray powder of the active substances (2.8: 1) spray liquor (60 ppm AS) produced.

After 24 hours, the treated plants are treated with a conidia suspension of the Fungus infected. The plants then become 90-100% more relative for 2 days Incubated and incubated in a greenhouse for another 10 days Set up at 20-24 ° C. The fungal infection is assessed 13 days after the infection. When testing with the Connections 2.A-34, 2.A-50, 3.A-28, 3.A-33, 3.A-37, 3.A-50 and 3.A-53 had less than 1% of the wheat plants.  

B. Insecticidal effect Example B5 Effect against Aphis craccivora

Pea seedlings are infected with Aphis craccivora, then with a spray mixture, containing 100 ppm active ingredient, sprayed and then incubated at 20 ° C. From the comparison the number of dead aphids on the treated and untreated plants is 3 and 6 days later determined the percentage reduction in population (% effect). The Compounds in Tables 1 to 9 usually show good effects in this test.

Example B6 Effect against Diabrotica balteata

Corn seedlings are treated with an aqueous emulsion spray mixture containing 100 ppm of active ingredient fabric, sprayed, after the spray coating has dried on with 10 larvae of the second stage of Diabrotica balteata populated and then placed in a plastic container. From the ver is equal to the number of dead larvae between the treated and untreated plants 6 days later the percentage reduction in the population (% effect) was determined. The compounds of Tables 1 to 9 show good activity in this test. Especially connections 2.A-26, 2.A-28, 2.A-32, 3.A-1. 3.A-3, 3.A-9, 3.A-28 and 3.A-32 show over 80% effect in this test.

Example B7 Effect against Heliothis virescens

Young soybeans are mixed with an aqueous emulsion spray containing 100 ppm Active ingredient, sprayed, after the spray coating has dried on with 10 caterpillars of the first stage um populated by Heliothis virescens and then placed in a plastic container. From the Compare the number of dead caterpillars and the feeding damage between the treated and untreated plants 6 days later the percentage reduction in the popula tion and damage caused by feeding (% effect).

Most of the compounds in Tables 1 to 9 show good activity in this test. In particular, the compounds 2.A-1, 2.A-3, 2.A-28, 2.A-32 and 3.A-3 show over 80% Effect in this test.

Example B8 Action against Spodoptera littoralis

Young soybeans are mixed with an aqueous emulsion spray containing 100 ppm Active ingredient, sprayed, after the spray coating has dried on with 10 caterpillars of the third stage populated by Spodoptera littoralls and then placed in a plastic container. From the ver equal to the number of dead caterpillars and the feeding damage between the treated and Untreated plants will see the percentage reduction in population 3 days later and determined the percentage reduction in feeding damage (% effect).  

The compounds of Tables 1 to 9 show good activity in this test. Especially the compounds 2.A-1, 2.A-3, 2.A-28, 2.A-32 and 3.A-3 show over 80% activity in this test.

C. Acaricidal effects Example B9 Effect against Tetranychus urticae

Young bean plants are planted with a mixed population of Tetranychus urticae delt, 1 day later with an aqueous emulsion spray mixture containing 100 ppm of active ingredient, sprayed, incubated for 6 days at 25 ° C and then evaluated. From the comparisons of Number of dead eggs, larvae and adults on the treated and on the untreated Plants are determined the percentage reduction in the population (% effect).

The compounds of Tables 1 to 9 mostly show good effects in this test. In particular, compounds 2.A-1, 2.A-28, 2.A-29, 3.A-1, 3.A-28 and 3.A-32 show over 80% effect in this test.

Claims (11)

1. A compound of the formula
wherein either
X is CH or N, Y OR ₁ and ZO, or
XN, Y is NHR ₂ and ZO, S or S (= O);
WO or NR _6a ;
R ₁ and R ₂ independently of one another are H or C ₁ -C ₄ alkyl;
R _{3 is} C ₁ -C ₆ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, which are optionally selected independently of one another with one to five substituents selected from the group consisting of halogen , C ₁ -C ₆ alkoxy, halo-C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkoxy, NO ₂ , CN, aryl and heteroaryl; the aryl and heteroaryl groups optionally, depending on the possibility of substitution on the ring system, with one to five substituents selected from the group consisting of halogen, halogen-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, halogen-C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, halo-C ₁ -C ₆ alkyl thio, NO ₂ and CN are substituted; or wherein R ₃
is naphthyl substituted with (R ₄ ) _m or heteroaryl substituted with (R ₄ ) _m ;
m depending on the possibility of substitution on the ring system 0, 1, 2, 3, 4 or 5; where, when m is greater than 1, the radicals R _{4 are the} same or different;
R _{4 is} C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, halo C ₂ -C ₈ alkenyl, halo C ₂ -C ₈ -alkynyl, aryl-C ₂ -C ₈ -alkenyl, aryl-C ₂ -C ₈ -alkynyl, C ₃ -C ₆ -cycloalkyl, halo-C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ - Alkoxy, halogen-C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio, halogen-C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylsulfinyl, halogen-C ₁ -C ₆ -alkylsulfinyl, C ₁ -C ₆ -alkyl kylsulfonyl, halogen-C ₁ -C ₆ -alkyl-sulfonyl, C ₁ -C ₆ alkylsulfonyloxy, halo-C ₁ -C ₆ -al kylsulfonyloxy, C ₁ -C ₆ alkoxy-C ₁ -C ₆ -alkyl, halo-C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyl thio-C ₁ -C ₆ -alkyl, halo-C ₁ -C ₆ -alkylthio -C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylsulfinyl-C ₁ -C ₆ alkyl, halogen-C ₁ -C ₆ alkylsulfinyl-C ₁ -C ₆ alkyl, C ₁ -C ₆ - Alkyl-sulfonyl-C ₁ -C ₆ -alkyl, halogen-C ₁ -C ₆ -alkylsulfonyl-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkylcarbonyl, halogen-C ₁ -C ₆ -al kylcarbonyl, C ₁ -C ₆ -alkoxycarbonyl, halo-C ₁ -C ₆ -alkoxycarbonyl, C ₁ -C ₆ -Alkylaminocar bonyl, C ₁ -C ₄ alkoxyiminomethyl, di (C ₁ -C ₆ alkyl) aminocarbonyl, where the alkyl groups may be the same or different; C ₁ -C ₆ alkylamino thio carbonyl, di (C ₁ -C ₆ alkyl) aminothiocarbonyl, where the alkyl groups may be the same or different; C ₁ -C ₆ alkylamino, di (C ₁ -C ₆ alkyl) amino, where the alkyl groups may be the same or different; Halogen, NO ₂ , CN, thioamido, trimethylsilyl, -CH ₂ Si (C ₁ -C ₄ alkyl) ₃ , the alkyl groups being the same or different; two adjacent substituents R ₄ together form an unsubstituted or a mono- to tetrasubstituted -CH = CH-CH = CH- or C ₁ -C ₄ -alkylenedioxy group, the substituents being selected from the group consisting of C ₁ -C ₄ -Alkyl and halogen are selected;
a with (R _{5) n} substituted phenyl, _n substituted heteroaryl with (R _{5) n} substituted heteroaryloxy with (R ₅₎ or
R _{5 is} C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, halo-C ₂ -C ₈ alkenyl, halo-C ₂ -C ₈ -alkynyl, C ₃ -C ₆ -cycloalkyl, halogen-C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, halo gene-C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio , Halogen-C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylsulfinyl, Halo gen-C ₁ -C ₆ -alkylsulfinyl, C ₁ -C ₆ -alkylsulfonyl, halogen-C ₁ -C ₆ -alkyl- sulfonyl, C ₁ -C ₆ alkyl sulfonyloxy, halo C ₁ -C ₆ alkylsulfonyloxy, C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkoxy-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkylthio-C ₁ -C ₆ -alkyl, halo-C ₁ -C ₆ -alkylthio-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkylsulfinyl-C ₁ -C ₆ -alkyl, halo-C ₁ -C ₆ -alkylsulfinyl-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyl sulfonyl-C ₁ -C ₆ -alkyl, halo-C ₁ -C ₆ -alkylsulfonyl -C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylcarbonyl, haloC ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, haloC ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ -Alkylaminocarbonyl, C ₁ -C ₄ -alkoxyiminomethyl, di (C ₁ -C ₆ -a alkyl) -aminocarbonyl, where the alkyl groups may be the same or different; C ₁ -C ₆ alkylamino thio carbonyl, di (C ₁ -C ₆ alkyl) aminothiocarbonyl, where the alkyl groups may be the same or different; C ₁ -C ₆ alkylamino, di (C ₁ -C ₆ alkyl) amino, where the alkyl groups may be the same or different; Halogen, NO ₂ , CN, thioamido, trimethylsilyl, -CH ₂ Si (C ₁ -C ₄ alkyl) ₃ , the alkyl groups being the same or different; an unsubstituted or two adjacent substituents R ₅ together a mono- to tetrasubstituted -CH = CH-CH = CH- or C ₁ -C ₄ -alkylenedioxy group, the substituents being selected from the group consisting of C ₁ -C ₄ -Alkyl and halogen are selected;
n 0, 1, 2, 3, 4 or 5; where, when n is greater than 1, the radicals R _{5 are the} same or different;
U -CH ₂ -, O or -NR _6b ;
VC ₁ -C ₈ alkylene;
R ₆ , R _6a and R _6b independently of one another are H, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxymethyl, C ₃ -C ₆ cycloalkyl, formyl or halogen C ₃ -C ₆ cycloalkyl;
R ₇ H, C ₁ -C ₄ alkyl, halo C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxymethyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, cyano, C ₃ -C ₆ cycloalkyl or halo C ₃ -C ₆ cycloalkyl;
A is a direct bond, C ₁ -C ₁₀ alkylene, -C (= O) -, -C (= S) - or halogen-C ₁ -C ₁₀ alkylene and
R _{7 is} a radical R ₈ ; or
AC ₁ -C ₁₀ alkylene, -C (= O) -, -C (= S) - or halogen-C ₁ -C ₁₀ alkylene and
R ₇ -CN, OR ₈ , N (R ₈ ) ₂ , where the radicals R _{8 are} identical or different, -SR ₆ , -S (= O) R ₈ , or -S (= O) ₂ R ₈ ;
R ₈ H, C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, halo-C ₁ -C ₆ alkyl, halo-C ₂ -C ₈ -alkenyl, halo-C ₂ -C ₈ -alkynyl or halo-C ₃ -C ₆ -cycloalkyl, -Si (C ₁ -C ₄ -al kyl) ₃ , where the alkyl groups may be the same or different;
C ₁ -C ₆ alkoxycarbonyl or an unsubstituted or one or more aryl- or heterocyclyl- substituted by substituents from the group consisting of halogen, C ₁ -C ₄ -alkyl and halogen-C ₁ -C ₄ -alkyl Group; and
R _{9 is} methyl, fluoromethyl or difluoromethyl;
and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form. 2. A compound according to claim 1 of formula (I) in free form. 3. A compound according to any one of claims 1 or 2 of formula (I), wherein, wherein X is N and Z is O.   4. A compound according to any one of claims 1 or 2 of formula (I), wherein W is O. 5. A compound according to any one of claims 1 to 4 of formula (I), wherein AR _{7 is} methyl or ethyl. 6. pesticide, characterized in that there is at least one ver Binding according to claim 1 of formula (I) or optionally an E / Z isomer or Tautomeres thereof, in free form or in agrochemically usable salt form, as Active ingredient in an effective concentration and contains at least one auxiliary. 7. A method for producing an agent as described in claim 6, characterized indicates that the active ingredient is intimately mixed with the auxiliary (s) and / or married. 8. Use of a compound as described in claim 1, the formula (I), or optionally an E / Z isomer or tautomer thereof, in free form or in Agrochemically usable salt form for the preparation of an agent as in claim 6 described. 9. Use of a compound as described in claim 1, the formula (I), or one Means as described in claim 6 for controlling pests. 10. A method of combating pests, characterized in that one A compound as described in claim 1, of formula (I), or an agent as in claim 6 described, applied to the pests or their habitat. 11. The method according to claim 10 for the protection of plant propagation material, characterized in that the propagation material or the place of application of the propagation material treated.