JP2002501038A - Organic nitrile derivatives and their use as pesticides - Google Patents

Abstract

  (57) [Summary]   Formula (I) Embedded image A compound of the above formula wherein A₁And A_TwoRepresents, independently of one another, an aryl radical or a heteroaryl radical, and where appropriate A₁Is a substituent (R_3a)_n1And, where appropriate, A _TwoIs a substituent (R_3b)_n2And n1 and n2 independently of one another are 0, 1, 2, 3 or 4;_3aAnd R_3bAre independently of one another, for example halogen, C₁~ C₆Alkyl, C_Two~ C_FourAlkynyl, halogen-C₁~ C₆Alkyl, halogen-C_Two~ C_FourAlkynyl, C₁~ C₆Alkoxy, halogen-C₁~ C₆Alkoxy, C_Two~ C₆Alkenyloxy, C_Two~ C₆Alkynyloxy or halogen-C_Two~ C₆Alkenyloxy, R_TwoIs R_2aAnd R_2aIs -C₁~ C₆Alkyl-NR₁₁R₁₂, -COC₉~ C₂₀Alkyl, -C₁~ C₆Alkyl-OC₁~ C₆Alkyl-OC₁~ C₆Alkyl or -CH_TwoO (C = O) C₁~ C₆Is alkyl,OrR_3aOr R_3bAt least one is -CR_Five= CR_FiveR₁₄, -NR₁₁R₁₂, -C (= O) CN, -C (= O) C (= O) OC₁~ C₆Alkyl, -CR₇= NOR_TenOr a 5- or 6-membered heteroaryl ring linked by a carbon atom,_TwoIs R_2aOr R_2bWhere R_2aIs as defined above, and R_2bIs, for example, hydrogen, -OH, C₁~ C₆Alkyl or C₁~ C₆Alkoxy oreitherAnd R₁₄Is, for example, hydrogen, halogen, C₁~ C₆Alkyl or halogen-C₁~ C ₆Alkyl, X is O or S, p is 0, 1 or 2;_FiveIs independently H or C₁~ C₈Alkyl, R₆Is, for example, independently H, C₁~ C₈Alkyl or C_Three~ C₆Cycloalkyl, R₇Is, for example, H, C₁~ C₈Alkyl, C_Two~ C₈Alkenyl or halogen-C₁~ C₈Alkyl, R₈Is C₁~ C₈Alkyl, C_Two~ C₈Alkenyl or halogen-C₁~ C₈Alkyl, R₉Is C₁~ C₆Alkyl, halogen-C₁~ C_FourAlkyl or aryl;_TenIs H, C₁~ C₆Alkyl, C_Three~ C₆Cycloalkyl, phenyl or benzyl;₁₁And R₁₂Are, for example, independently of one another, H, C₁~ C₆Compounds which are alkyl or phenyl and, where appropriate, possible E / Z isomers, mixtures of E / Z isomers, and / or tautomers of the compounds are in free form or in pesticide form. It can be used as a pesticidal active ingredient in a form acceptable as and can be prepared by known methods.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the formula

[0002]

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A compound of the formula: wherein A is₁And A_TwoAre independently of one another in each case a monocyclic or bicyclic
Represents an aryl radical or a heteroaryl radical.
The reel radical is, independently of the other, a hetero radical selected from the group consisting of N, O and S.
It has from 1 to 4 (including 4) atoms, and if appropriate A₁Is a substituent (R_3a)_n1And, where appropriate, A _Two Is a substituent (R_3b)_n2And n1 and n2 have a ring structure A₁And A_TwoDue to the possibility of substitution in
Is independently 1, 2, 3 or 4; and

(A) R_3aAnd R_3bAre independently hydrogen, halogen, C₁~ C₆Alkyl,
Halogen-C₁~ C₆Alkyl, C_Two~ C_FourAlkenyl, C_Two~ C_FourAlkynyl
, Halogen-C_Two~ C_FourAlkenyl, halogen-C_Two~ C_FourAlkynyl, C₁~
C₆Alkoxy, halogen-C₁~ C₆Alkoxy, C_Two~ C₆Alkenyloxy
Si, C_Two~ C₆Alkynyloxy, halogen-C_Two~ C₆Alkenyloxy, ha
Logen-C_Two~ C₆Alkynyloxy, -OH, -SF_Five, -CHO, -C (=
O) -C₁~ C₆Alkyl, -C (= O) -halogen-C₁~ C₆Alkyl,-
C (= O) -OC₁~ C₆Alkyl, -C (= O) -O-halogen-C₁~ C₆ Alkyl, -OC (= O) N (R₆)_Two(Where both substituents R₆Are each other
Independent)), -CN, -NO_Two, -S (= O)_TwoN (R₆)_Two(Where both
Substituent R₆Are independent of each other), -S (= O)_p-C₁~ C₆Alkyl,-
S (= O)_p-Halogen-C₁~ C₆Alkyl, -OS (= O)_p-C₁~ C ₆ Alkyl, -OS (= O)_p-Halogen-C₁~ C₆Alkyl, phenyl,
Benzyl, phenoxy or benzyloxy (where the phenyl,
Each of the benzyl, phenoxy, or benzyloxy radicals is unsubstituted
Or the aromatic ring is halogen, cyano, NO_Two, C₁~ C₆Alkyl, halo
Gen-C₁~ C₆Alkyl, C₁~ C₆Alkoxy and halogen-C₁~ C₆ Mono- to penta-substituted independently of each other by a substituent selected from the group consisting of alkoxy
) And R_TwoIs R_2aOrOr

(B) R _3a and R _3b are independent of each other as defined in (A), wherein at least one of R _3a or R _3b is —CR ₅ ＣＲCR ₅ R ₁₄ , —NR ₁₁ R ₁₂ ,
—C (＝ O) CN, —C (＝ O) C (＝ O) O—C ₁ -C ₆ alkyl, —CR ₁₅ ＮＯNOR ₁₀ , or a 5- or 6-membered heteroaryl ring, wherein Where appropriate, said heteroaryl ring is selected from the group consisting of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, NO ₂ and CN, depending on the possibility of substitution in said ring. And R ₂ is R _2a or R _2b , or

(C) R_3aHas one of the meanings defined above in (A) or (B)
Has, R_3bIs hydrogen, halogen, C₁~ C₆Alkyl, halogen-C₁~ C₆Alkyl
, C_Two~ C_FourAlkenyl, C_Two~ C_FourAlkynyl, halogen-C_Two~ C_FourArche
Nil, halogen-C_Two~ C_FourAlkynyl, C₁~ C₆Alkoxy, halogen-C ₁ ~ C₆Alkoxy, C_Two~ C₆Alkenyloxy, C_Two~ C₆Alkynyloxy
Si, halogen-C_Two~ C₆Alkenyloxy, halogen-C_Two~ C₆Alkynyl
Oxy, -OH, -SF_Five, -CHO, -C (= O) -C₁~ C₆Alkyl,-
C (= O) -halogen-C₁~ C₆Alkyl, -C (= O) -OC₁~ C₆Al
Kill, -C (= O) -O-halogen-C₁~ C₆Alkyl, -OC (= O) N
(R₆)_Two(Where the two substituents R₆Are independent of each other), -CN,-
NO_Two, Phenyl, benzyl, phenoxy or benzyloxy (where
Each of the phenyl, benzyl, phenoxy, or benzyloxy radicals
Is unsubstituted or the aromatic ring is halogen, cyano, NO_Two, C₁~
C₆Alkyl, halogen-C₁~ C₆Alkyl, C₁~ C₆Alkoxy and ha
Logen-C₁~ C₆A substituent independently selected from the group consisting of alkoxy
-S at the 4-position (= O)_p-C₁~ C₆Alkyl
Is -S (= O) at the 4-position_p-Halogen-C₁~ C₆Alkyl (however,
Substituent R_3bIs -S (= O)_p-C₁~ C₆Alkyl or -S (= O)_p−
Halogen-C₁~ C₆Alkyl) and R_TwoIs R_2aOr R_2bOreitherAnd

In groups (A), (B) and (C) above, where appropriate, R _2a is —C ₁ -C ₆ alkyl-NR ₁₁ R ₁₂ , —C (＝ X) —R _7a , -COC ₉ -C _{20 alkyl, -CH 2 O (C = O} ) C 1 ~C 6 alkyl, -C ₁ -C ₆ alkyl -O-C _{1 ~C 6} alkyl -O-C _{1 ~C 6} alkyl, -CH ₂ O (C = O
) C ₂ -C _{6 alkenyl, -CH 2 O (C = O} ) C 2 ~C 6 alkynyl, -C (
= S) OC ₂ ~C ₆ alkenyl, -C (= S) OC ₂ ~C ₆ alkynyl, -C (
= S) SC ₁ ~C _{6 alkyl, -C (= S) SC 2} ~C 6 alkenyl, -C (=
S) SC ₂ ~C _{6 alkynyl, -C (= O) SC 1} ~C 6 alkyl, -C (= O
) SC ₂ -C _{6 alkenyl, -C (= O) SC 2} ~C 6 alkynyl, -C (= S
) NR ₁₁ R ₁₂ , —C (＝ O) NR ₁₀ OR ₁₃ , —CH ₂ OC ₂ -C ₆ alkenyl,
-CH ₂ OC ₂ ~C ₆ alkynyl, -CH ₂ OC ₂ ~C ₆ haloalkenyl or -CH ₂ OC ₂ ~C ₆ haloalkynyl,

[0008] R_2bIs hydrogen, -OH, C₁~ C₆Alkyl, C₁~ C₆Alkoxy, C_Three~ C ₆ Cycloalkyl, C_Three~ C₆Alkenyl, C_Three~ C₆Alkynyl, halogen-
C₁~ C₆Alkyl, halogen-C_Three~ C₆Alkenyl, C_Three~ C₆Alkynyl
, Benzyl or benzoyl (wherein the benzyl or benzoyl radical
Is a group in which the aromatic ring is halogen, -CN, NO_Two, C₁~ C₆Alkyl, C₁~ C₆A
Lucoxy, halogen-C₁~ C₆Alkyl and halogen-C₁~ C₆Alkoki
Are independently mono- to tri-substituted by a substituent selected from the group consisting of
, C₁~ C₆Alkoxy-C₁~ C₆Alkyl, cyano-C₁~ C₆Alkyl,
-C (= X) -R_7a, -C (= X) -R_7b, -OC (= O) -R_7a, -C (= O
) -C (= O) -R_7a, -OC (= O) -R_7b, -C (= O) -C (= O) -R _7b , -S (= O)_pN (R₆)_Two(Where the two substituents R₆Are independent of each other
), Cyano, -C₁~ C₆Alkyl-N (R_Five) -C (= O) -R₈, −
C₁~ C₆Alkyl-SC (= S) -R₈, -C₁~ C₆Alkyl-S (= O
)_p-R₉, -S (= O)_p-R₉Or -CH_Two−N (R_Ten) -SO_Two-R ₉ And

X is O or S; p is 0, 1 or 2; R ₅ is independently H or C ₁ -C ₈ alkyl; R ₆ is independently H, C ₁ -C ₈ alkyl , C ₃ -C ₆ cycloalkyl, phenyl or benzyl, wherein said phenyl or benzyl group is, where appropriate, an aromatic ring is halogen, —CN, NO ₂ , C ₁ -C ₆ alkyl, C ₁ -C ₆ alkyl; C ₄ alkoxy, halogen-C ₁ -C ₆ alkyl and halogen-C ₁ -C ₆ alkoxy, which are independently mono-trisubstituted with a substituent selected from the group consisting of two) or two alkyl radicals R ₆ together with the nitrogen atom to which they are attached form a 5- to 7-membered ring wherein, where appropriate, the CH ₂ group
And 5- or 7-membered rings are mono- or di-substituted by C ₁ -C ₄ alkyl, if appropriate, substituted by a heteroatom selected from the group consisting of and S. Is)

[0010] R_7aIs C₁~ C₆Alkoxy-C₁~ C₆Alkyl, CH_TwoCH_TwoCF_TwoCl
, C₁~ C₆Alkylthio-C₁~ C₆Alkyl, acyloxy-C₁~ C₆A
Lucyl, halogen-C_Three~ C₆Cycloalkyl, C_Three~ C₆Cycloalkyl-C ₁ ~ C₆Alkyl, halogen-C_Three~ C₆Cycloalkyl-C₁~ C₆Alkyl
, Aryloxy-C₁~ C₆Alkyl, or phenyl, benzyl, phenoxy
Or aryloxy-C₁~ C₆Alkyl (halogen, nitro, cyano,
C₁~ C_FourAlkyl, halogen-C₁~ C_FourAlkyl and halogen-C₁~ C _Four Substituted with one to three substituents selected from the group consisting of alkoxy)
Yes, R_7bIs H, C₁~ C₈Alkyl, C_Two~ C₈Alkenyl or halo-C₁~ C ₈ Alkyl, halo-C_Two~ C₈Alkenyl, C₁~ C₈Alkoxy, halo-C₁ ~ C₈Alkoxy, C_Three~ C₆Cycloalkyl, phenyl, benzyl, phenoxy
Benzyloxy or -N (R₆)_Two(Where the two R₆Is German
Standing)

R ₈ is C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen-C ₁ -C ₈ alkyl, halogen -C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, phenyl, benzyl or- N (R ₆ ) ₂ (where the two radicals R ₆ are independent of each other), and R ₉ is C ₁ -C ₆ alkyl, halogen-C ₁ -C ₄ alkyl or aryl (
Unsubstituted or substituted, or C ₁ -C ₆ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₁ -C ₄ alkoxy, halogen, cyano, halogen -C ₁ -C ₄ alkyl, halogen - C ₂ -C ₄ alkenyl, halogen -C ₂ -C ₄ alkynyl, are one to three substituents each independently halogen -C ₁ -C ₄ alkoxy and substituents chosen from the group consisting of nitro),

R ₁₀ is H, C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, phenyl or benzyl (where the phenyl and benzyl radicals are unsubstituted or the aromatic ring is C ₁ -C ₆ C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, halogen -C ₁ -C ₄ alkyl, halogen -C ₁ -C ₄ alkoxy and one to three times independently of one another with a substituent chosen from the group consisting of nitro Has been replaced)
And

[0013] R₁₁And R₁₂Are independently H, C₁~ C₆Alkyl, phenyl, -COC ₁ ~ C₆Alkyl, -COC₁~ C₆A haloalkyl, -COphenyl or
Or together with a 5- or 6-membered saturated or unsaturated ring (where
If appropriate, one or more, in particular one CH-group or CH_TwoThe group is O,
Substituted by a heteroatom selected from the group consisting of N and S,
In such a case, the 5- or 6-membered ring may be halogen, C₁~ C_FourAlkyl, C₁~ C _Four Haloalkyl, C₁~ C_FourHaloalkoxy, NO_TwoAnd the group consisting of CN
Selected from 1 to 3 substituents independently of each other) or
Or the two substituents R₁₁And R₁₂Together

[0014]

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Wherein q is 2 or 3 and R₁₃Is H, C₁~ C₆Alkyl, C_Two~ C₆Alkenyl, C_Two~ C₆Alkini
And R₁₄Is hydrogen, C₁~ C₆Alkyl, halogen-C_Three~ C₆Alkyl, C₁~ C ₆ Alkoxy, halogen-C₁~ C₆Alkoxy, C_Two~ C₆Alkenyloxy
, -CHO, -C (= O) -C₁~ C₆Alkyl, -C (= O) -halogen-C ₁ ~ C₆Alkyl, -C (= O) -OC₁~ C₆Alkyl, -C (= O) -O-
Halogen-C₁~ C₆Alkyl, -CN, -NO_Two, -S (= O)_TwoN (R₆) _Two (Where the two substituents R₆Are independent of each other), -S (= O)_p-C ₁ ~ C₆Alkyl, -S (= O)_p-Halogen-C₁~ C₆Alkyl, -OS
(= O)_pC₁~ C₆Alkyl, -OS (= O)_pHalogen-C₁~ C₆Al
Kill, phenyl, benzyl, or benzyloxy (where the phenyl, benzyl,
Each of the benzyl or benzyloxy substituents is unsubstituted or aromatic.
The aromatic ring is halogen, cyano, NO_Two, C₁~ C₆Alkyl, halogen-C₁~ C ₆ Alkyl, C₁~ C₆Alkoxy and halogen-C₁~ C₆From alkoxy
Which are independently mono- to penta-substituted by a substituent selected from the group consisting of
R₁₅Is hydrogen, C₁~ C₆Alkyl or halogen-C₁~ C₆Is alkyl
Regarding the compound,

If appropriate, the E / Z isomers, the mixture of E / Z isomers and / or the tautomers (in each case in free or salt form) of the compounds in question ) With respect to the preparation method and use of these compounds, E / Z isomers and tautomers, pesticides wherein the active ingredient is selected from these compounds, E / Z isomers and tautomers, and These compositions, the intermediates in free or salt form for preparing these compounds and, where appropriate, their tautomers in free or salt form And methods for preparing and using these intermediates and their tautomers.

In the literature, certain phenylhydrazine derivatives have been proposed as active ingredients in pesticides. However, the biological properties of these known compounds are:
It is not entirely satisfactory in the field of pest control, for which it is necessary to supply further compounds with pesticidal properties, especially for the control of insects and members of the order Acarina. Correspondingly, the problem is solved by developing the compounds of the formula (I) according to the invention.

Some of the compounds of formula (I) contain an asymmetric carbon atom, which can result in the compounds in optically active form. Due to the presence of the C = N double bond, the compounds may occur in E and Z isomers. In addition, atropisomers of the compound may occur. Formula (I) encompasses all these possible isomeric forms and mixtures thereof (eg, racemic or E / Z isomer mixtures).

Unless otherwise specified, the generic names used above and below have the following meanings. Unless otherwise specified, in each case there are 1 to 8 (including 8), preferably 1 to 6 (including 6), especially 1 to 6, carbon-containing groups and compounds.
It contains four (including four), especially one or two, carbon atoms.

Alkyl (as the group itself and as a structural element of other groups and compounds (eg alkyl halides, alkoxy or alkylthio)) is in each case the number of carbon atoms in the group or compound concerned. With due consideration of the linear (ie methyl, ethyl, propyl, butyl, pentyl or hexyl),
Or a branched chain (eg, isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, neopentyl or isohexyl).

[0021] (As the group itself and other groups and compounds, such as alkenoxy (alk
alkenyl), as a structural element of alkenyl), alkenyl halides or alkenoxy halides) is in each case straight-chain (for example vinyl, 1 -Methylvinyl, allyl, 1-butenyl or 2-hexyl), or branched (eg isopropenyl).

Alkynyl (as the group itself and as a structural element of other groups and compounds, such as alkynyl halides), in each case, takes into account the number of carbon atoms in the group or compound concerned. To a linear chain (eg, propargyl, 2-
Either butynyl or 5-hexynyl), or branched (eg, 2-ethynylpropyl or 2-propargylisopropyl). C ₃ -C ₆ cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Aryl is phenyl or naphthyl, especially phenyl.

Bicyclic heteroaryl is a radical that may contain one or more heteroatoms independently in only one ring (eg quinolinyl, quinoxalinyl, indolinyl,
Benzothiophenyl or benzofuranyl) and radicals contained in both rings (such as pteridinyl or prenyl).

(As groups themselves and as structural elements of other groups and compounds, such as alkyl, alkenyl and alkynyl halides)
Halogen is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine,
Especially fluorine or chlorine, very particularly chlorine.

Groups and compounds substituted with halogen and containing carbon (eg alkyl halides, alkenyl halides or alkynyl halides) may be partially halogenated or perhalogenated, When repeatedly halogenated, those halogen substituents may be the same or different. Examples of alkyl halides (as groups themselves and as a structural element of other groups and compounds (eg alkenyl halides)) are fluorine, chlorine and / or
Or methyl mono- to tri-substituted by bromine (eg CHF ₂ or CF ₃ ), ethyl mono- to penta-substituted by fluorine, chlorine and / or bromine (eg 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 C
HBrF or CClFCHClF), fluorine, chlorine and / or one to seven substituted by are propyl or isopropyl with bromine (e.g. CH ₂ CHBrC
_{H 2 Br, CF 2 CHFCF 3} , CH 2 CF 2 CF 3 or CH (CF _{3) 2)}
And fluorine, chlorine and / or one of one to nine butyl are substituted or its isomers by bromine (e.g. CF (CF ₃₎ CHFCF ₃ or CH ₂ (C
F ₂ ) ₂ CF ₃ ). The alkenyl halide is, for example, CH ₂ CH ＝ CHC
1, CH ₂ CH ＝ CCl ₂ , CH ₂ CF ＝ CF ₂ or CH ₂ CH ＝ CHCH ₂ Br. Alkynyl halides include, for example, CH ₂ C≡CF, CH ₂ C≡CC
H ₂ Cl or CF ₂ CF ₂ C≡CCH ₂ F.

Some of the compounds of formula (I), as is well known to those skilled in the art, occur as tautomers, especially when R ₂ is H. Accordingly, it is understood that the compounds of formula (I) above and below also include the corresponding tautomers, even if not otherwise stated in each case.

Compounds of the formula (I) which show at least one basic center can form, for example, acid addition salts. These may be employed, for example, with the aid of inorganic strong acids (for example mineral acids (for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrogen halides)) and organic strong carboxylic acids (for example halogens where appropriate). Substituted C ₁ -C ₄ alkane carboxylic acids (eg acetic acid), where appropriate unsaturated dicarboxylic acids (eg oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid), hydroxy Using carboxylic acids (eg, ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid), or benzoic acid) or using organic sulfonic acids (
In general, they are formed using, for example, C ₁ -C ₄ alkanesulfonic acids or arylsulfonic acids, where appropriate, for example by halogen, such as methanesulfonic acid or p-toluenesulfonic acid. In a broader sense, compounds of formula (I) having at least one acid radical are capable of forming salts with bases. Suitable salts with bases are, for example, metal salts (generally alkali or alkaline earth metal salts, such as sodium, potassium or magnesium salts), or ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, monohydrate. -, Di- or tri-lower alkylamines (e.g. ethyl-, diethyl-, triethyl- or dimethylpropylamine), or mono-, di- or tri-hydroxy lower alkylamines (e.g. mono-, di- or triethanolamine) )) And salt. If appropriate, the corresponding internal salts may be formed. Above and below, the compound of formula (I) in free form is
It is understood that their corresponding salts are also included and, where appropriate, their salts are also meant to mean the free compounds of the formula (I). The same applies to the tautomers of the derivatives of the compounds of the formula (I) and their salts. In each case, the free form is generally preferred.

The following forms are preferred within the scope of the present invention. (1) A ₁ and A ₂ are independent of each other

[0029]

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[0030]

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A substituent selected from the group consisting of phenyl, naphthyl, pyridyl or thiadiazolyl, especially phenyl or pyridyl, especially phenyl,

[0032] R ₃ corresponds to R _3a and R _3b of the formula (I), R _3a and R _3b halogen is independently, -CN, NO _2, halogen -C ₁ ~
C ₂ alkyl, C ₁ -C ₂ alkoxy or halogen -C ₁ -C ₂ alkoxy,
Halogen -C ₂ -C ₅ alkenoxy or halogen -C ₂ -C ₅ alkynoxy,
R ₄ is H, C ₁ -C ₄ alkyl, especially chlorine, —CN, CF ₃ or OCF ₃ (where m + n is greater than 1 the radicals R _3a and R _3b are independent of each other) , Phenyl or benzyl, especially H and methyl,

N is 0-5, especially 1-3, depending on the possibility of substitution in the ring structure, the value of n in A ₁ is independent of the value of n in A ₂ , and m is a ring the possibility of substitution in the structure, a 0 to 4, m in a ₁
Is independent of the value of m in A ₂ , wherein the sum of m + n is from 0 to 5, especially 1, 2 or 3.

(2) A ₂ is furanyl, thienyl,

[0035]

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A compound of formula (I), wherein R ₂ is R _2a or R _2b , corresponding to a substituent selected from the group consisting of: (3) The compound of the formula (I), wherein A ₁ and A ₂ are phenyl.

(4) R _2a is —C ₁ -C ₆ alkyl-NR ₁₁ R ₁₂ , —C (＝ X) —R _7a , —C
OC ₉ -C ₂₀ alkyl, -C ₁ -C ₆ alkyl-OC ₁ -C ₆ alkyl-O-
C ₁ -C _{6 alkyl, -CH 2 O (C = O} ) C 1 ~C 6 alkyl, -CH ₂ O (
C ＝ O) C ₂ -C ₆ alkenyl, —CH ₂ O (C ＝ O) C ₂ -C ₆ alkynyl,
_{-C (= S) OC 2 ~C} 6 alkenyl, _{-C (= S) OC 2 ~C} 6 alkynyl,
_{-C (= S) SC 1 ~C} 6 _{alkyl, -C (= S) SC 2} ~C 6 alkenyl, -
_{C (= S) SC 2 ~C} 6 _{alkynyl, -C (= O) SC 1} ~C 6 alkyl, -C
(= O) SC ₂ ~C ₆ alkenyl, -C (= O) SC ₂ ~C ₆ alkynyl, -C
_{(= S) NR 11 R 12} , -C (= O) NR 10 OR 13, -CH 2 OC 2 ~C 6 alkenyl, -CH ₂ OC ₂ ~C ₆ alkynyl, -CH ₂ OC ₂ ~C ₆ haloalkenyl or a -CH ₂ OC ₂ ~C ₆ haloalkynyl,

In particular, R_2aIs -CH_TwoAlkyl-NR₁₁R₁₂, -COC₉~ C₂₀Alkyl
, -C₁~ C_TwoAlkyl-OC₁~ C_TwoAlkyl-OC₁~ C_TwoAlkyl,
-CH_TwoO (C = O) C₁~ C_TwoAlkyl, -CH_TwoO (C = O) C_Two~ C_FourA
Lucenyl, -CH_TwoO (C = O) C_Two~ C_FourAlkynyl, -C (= S) OC_Two~
C_FourAlkenyl, -C (= S) OC_Two~ C_FourAlkynyl, -C (= S) SC₁~
C_TwoAlkyl, -C (= S) SC_Two~ C_FourAlkenyl, -C (= S) SC_Two~ C _Four Alkynyl, -C (= O) SC₁~ C_TwoAlkyl, -C (= O) SC_Two~ C_Four Alkenyl, -C (= O) SC_Two~ C_FourAlkynyl, C₁~ C_FourAlkylthio-
C₁~ C_TwoAlkyl, -C (= S) NR₁₁R₁₂, -C (= O) NR_TenOR₁₃, −
CH_TwoOC_Two~ C_FourAlkenyl, -CH_TwoOC_Two~ C_FourAlkynyl, -CH_TwoO
C_Two~ C_FourHaloalkenyl or -CH_TwoOC_Two~ C_FourHaloalkynyl,

In particular, when R _2a is —CH ₂ alkyl—NR ₁₁ R ₁₂ , —COC ₉ -C ₂₀ alkyl,
C ₁ -C ₂ alkyl-OC ₁ -C ₂ alkyl-OC ₁ -C ₂ alkyl, -C
_{H 2 O (C = O)} C 1 ~C 2 _{alkyl, -C (= O) SC 1} ~C 2 alkyl, -
CH ₂ OC ₂ -C ₄ alkenyl or —CH ₂ OC ₂ -C ₄ alkynyl, wherein R _2a is —CON (OCH ₃ ) CH ₃ , —C (O) NHCOCH ₃ , —C
_{OSC 2 H 5, -COSCH 3,} -CH 2 OC (O) C (CH 3) 3, -CH 2 OC 2 H 4 OCH 3, -CH 2 OCH 2 CH = CH 2, -CH 2 OCH 2 C≡ C
H, a -COC ₁₀ H _21, compounds of formula (I).

(5) R _2b is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, —C (＝ X) —R _7a , —C (＝ O) —C ₁ -C ₄ alkyl, -C (=
O) - halogen -C ₃ -C _{6 alkenyl, -C (= O) -C 3} ~C 6 cycloalkyl, -C (= O) -O- C 1 ~C 2 alkyl, -C (= O) - C (= O) -O
—C ₁ -C ₂ alkyl, —C (＝ O) —C (＝ O) —N (R ₆ ) ₂ , cyano, benzoyl or benzyl wherein the benzoyl or benzyl radical is aromatic if necessary ring, halogen, -CN, NO _2, and is one to three substituents independently with substituents selected from the group consisting trifluoromethoxy and trifluoromethyl), or -C (= O) -N (R ₆ ) ₂ and

The two substituents R₆Are, independently of one another, H, C₁~ C_FourAlkyl, C_Three~ C ₆ Cycloalkyl, phenyl or benzyl (where the phenyl or benzyl is
A jyl group may have an aromatic ring, if necessary, halogen, -CN, C₁~ C_FourAlkyl,
C₁~ C_FourAlkoxy, halogen-C₁~ C_TwoAlkyl and halogen-C₁~
C_TwoMono- or tri-substituted independently from each other by a substituent selected from the group consisting of alkoxy
Or two alkyl radicals R₆But they combine
Together with the nitrogen atom to form a 5- or 6-membered ring.
Here, if necessary, CH_TwoThe group is substituted by an O atom or NH;
Where necessary, the 5- or 6-membered ring is substituted with methyl).

R _2b is hydrogen, C ₁ -C ₃ alkyl, C ₁ -C ₂ alkoxy-C ₁ -C ₂ alkyl, —C (＝ O) —C ₁ -C ₂ alkyl, —C (＝ O) — fluoro -C ₄ -C ₆ alkenyl, -C (= O) - cyclopropyl, -C (= O) -O- C 1 ~C 2 alkyl, -C (= O) -C ( = O) -O- C ₁ -C ₂ alkyl, -C (= O) -
C (= O) -N (R 6) 2, cyano, benzyl or o- nitrobenzyl, -C
(＝ O) —N (R ₆ ) ₂ or —C (＝ O) —C ₆ H ₅ (where the phenyl ring is selected from the group consisting of halogen, NO ₂ , trifluoromethoxy and trifluoromethyl) Which are likewise mono- to tri-substituted by

The two radicals R ₆ are, independently of one another, H, C ₁ -C ₄ alkyl, cyclopropyl, phenyl or benzyl (wherein the phenyl or benzyl group is an aromatic ring, if necessary, Are independently mono- or di-substituted by a substituent selected from the group consisting of chlorine, -CN and OCF ₃ ), or two alkyl radicals R ₆ are substituted with the nitrogen atom to which they are attached. (where the ₂ group CH, where appropriate, O are replaced by atoms or NCH ₃₎ forms a 6-membered ring together is, compounds of formula (I). (6) The compound of the formula (I), wherein A ₁ is a pyridyl radical.

(7) (R_3a)_n1Is Cl, C1_Two, C1_Three,-(CF_Three)_Two, Cl-CF_Three , NO_Two, -CN, C1_Two-NO_Two, -OCF_Three, -CF_Three, Cl-CF_Three, C
1_Two-CF_Three, C1_Two-OCF_Three, -Cl_Two-F, C1_Two-Br, Cl-CF_Three -F, Cl-Br-CH_Three,-(CH_Three)_Two-Br, C1_Three-CF_Three, C1_Two−
F-CF_Three, F_Two-CF_Three-Cl, C1_Two-CN, C1_Two-CF_Three, C1_Two-S
CF_Three, C1_Two-OCF_Three, C1_Two-O_TwoCF_Three, C1_Two-SO_TwoCH_Three, C1 _Two -OCF_TwoBr, C1_Two-OCF_TwoH, C1_Two-C_TwoF_Five, (NO_Two)_Two-C
F_Three, (NO_Two)_Two-Cl, C1_Two-SO_TwoCH_ThreeOr C1_Two-OSO_TwoCF _Three And

In particular, 2-Cl, 2,3-Cl_Two, 2,4-Cl_Two, 2,6-Cl_Two, 2,4,6-Cl_Three, 3,5- (
CF_Three)_Two, 2-Cl-4-CF_Three, 2-NO_Two, 2-CN, 3-CN, 4-CN, 2,6-Cl _Two -4- NO_Two, 4-OCF_Three, 4-CF_Three, 3-CF_Three, 2-Cl-4-CF_Three, 2-Cl-
4-NO_Two, 2,6-Cl_Two-4- CF_Three, 2,6-Cl_Two-4-OCF_Three, 2,6-Cl_Two-4-F, 2,6-Cl_Two-4-Br, 2-Cl-4-CF_Three -6-F, 2-Cl -4-Br -6-CH_Three,
2,6- (CH_Three)_Two-4-Br, 2,3,6-Cl_Three-4- CF_Three, 2,6-Cl_Two-3-F-4-C
F_Three, 2,3-F_Two-4- CF_Three-6-Cl, 2,6-Cl_Two-4- CN, 2,4-Cl_Two-6- CF _Three , 2,6-Cl_Two-4- SCF_Three, 2,6-Cl_Two-4- SOCF_Three, 2,6-Cl_Two-4- SO _Two CF_Three, 2,6-Cl_Two-4- SO_TwoCH_Three, 2,6-Cl_Two-4- OCF_TwoBr, 2,6-C
l_Two-4- OCF_TwoH, 2,6-Cl_Two-4- C_TwoF_Five, 2,6- (NO_Two)_Two-4- CF_Three,
2,6- (NO_Two)_Two-4-Cl, 2,6-Cl_Two-4- OSO_TwoCH_ThreeOr 2,6-Cl_Two -4- OSO_TwoCF_ThreeAnd

In particular, 2,3-Cl_Two, 2,4-Cl_Two, 2,6-Cl_Two, 2,4,6-Cl_Three, 3,5- (CF _Three )_Two, 2-Cl-4-CF_Three, 2-CN, 3-CN, 4-CN, 2,6-Cl_Two-4- NO_Two,
4-OCF_Three, 4-CF_Three, 3-CF_Three, 2-Cl-4-CF_Three, 2-Cl-4-NO_Two, 2,6-
Cl_Two-4- CF_Three, 2,6-Cl_Two-4- OCF_Three, 2,6-Cl_Two-4-F, 2,6-Cl_Two-3
-F-4-CF_Three, 2,3-F_Two-4- CF_Three-6-Cl, 2,6-Cl_Two-4- CN, 2,4-Cl _Two -6- CF_Three, 2,6-Cl_Two-4- SCF_Three, 2,6-Cl_Two-4- SOCF_Three, 2,6-Cl _Two -4- SO_TwoCF_Three, 2,6-Cl_Two-4- C_TwoF_Five, 2,6- (NO_Two)_Two-4- CF_Three,
2,6- (NO_Two)_Two-4-Cl, 2,6-Cl_Two-4- OSO_TwoCH_ThreeOr 2,6-Cl_Two -4- OSO_TwoCF_ThreeA compound of formula (I), wherein

(8) One (R_3b)_n2Is -S (= O) at position 4._p-C_l~ C₆Archi
-Or (-O) at the 4-position_p-Halogen-C_l~ C₆Alkyl, especially-
S (= O)_p-C_l~ C_ThreeAlkyl or -S (= O)_p-Halogen-C_l~ C _Three Alkyl, more specifically, -S (= O)_p-Halogen-C_l~ C_ThreeAlkyl,
In particular, n2 is 1 and R_3bIs SOCF_Three, SOC_TwoF_Five, SOCHF_Two,
SOCF_TwoBr, SOCF_TwoCl, SOCF_TwoCF_TwoBr, SOCF_TwoCF_TwoC
1, SCF_Three, SC_TwoF_Five, SCHF_Two, SCF_TwoBr, SCF_TwoCl, SCF _Two CF_TwoBr, SCF_TwoCF_TwoCl, SO_TwoCF_Three, SO_TwoC_TwoF_Five, SO_TwoC
HF_Two, SO_TwoCF_TwoBr, SO_TwoCF_TwoCl, SO_TwoCF_TwoCF_TwoBr, SO _Two CF_TwoCF_TwoA compound of formula (I), wherein the compound is Cl.

(9) (R_3b)_n2Is -CN, Cl, C1_Two, F, F_Two, Br, -NO_Two,-(
NO_Two)_Two, -NO_Two-CF_Three, CF_Three,-(CF_Three)_Two, -CN-CF_Three, C
l-CF_Three, F-CN, -Cl-CN, -OCF_Three, -Cl-NO_Two, -CH_Three -NO_Two, -OCH_Three-NO_Two, -C₆H_Five, -C₆H_Four-F, -C₆H_Four-C
1, -C₆H_Four-CF_Three, -C₆H_Four-CF_Three, -C₆H_Four-NO_Two, -C₆H _Three − (CF_Three)_Two, -C₆H_Three-Cl_Two, -C₆H_Three-(Cl-F), -FC
N, F-NO_Two, Cl-NO_Two, Cl-NO_Two, -CHO, SCF_Three, SOCF _Three , SO_TwoCF_ThreeOr -C (= O) CF_ThreeAnd

In particular, 4-CN, 3-CN, 4-Cl, 3,4-Cl_Two, 2,3-Cl_Two, 3,5-Cl_Two, 2,5-
Cl_Two, 3,5-F_Two, 2,6-F_Two, 4-Br, 2-F, 4-NO_Two, 2-NO_Two-4- CF_Three,
3-CF_Three, 4-CF_Three, 3,5- (CF_Three)_Two, 2-CN-4-CF_Three, 2-Cl-4-CF_Three , 2-F-4-CN, 3-Cl-4-CN, 4-OCF_Three, 3-OCF_Three, 4-Cl-3-NO_Two , 2-Cl-4-NO_Two, 3-CH_Three-4- NO_Two, 3-OCH_Three-4- NO_Two, 4-C₆H_Five , 4-C₆H_Four-4- F, 4-C₆H_Four-4-Cl, 4-C₆H_Four-4- CF_Three, 4-C₆H_Four -3- CF_Three, 4-C₆H_Four-3- NO_Two, 4-C₆H_Three-(3,5-CF_Three)_Two, 4-C₆H _Three -2,4-Cl_Two, 4-C₆H_Three-3,4-Cl_Two, 4-C₆H_Three-3,5-Cl_Two, 4-C₆H _Three -(3-Cl-4-F), 2-F-4-CN, 2-F-4-NO_Two, 2-Cl-4-NO_Two,Four-
Cl-3-NO_Two, 4-CHO, 4-SCF_Three, 4-SOCF_Three, 4-SO_TwoCF_ThreeOr
4-C (= O) CF_ThreeAnd

In particular, 4-CN, 3-CN, 4-Cl, 3,4-Cl ₂ , 2,3-Cl ₂ , 3,5-Cl ₂ ,
2,5-Cl ₂ , 3,5-F ₂ , 2,6-F ₂ , 2-F, 2-NO ₂ -4-CF ₃ , 4-NO ₂ , 3-C
_{F 3, 4-CF 3,} 3,5- (CF 3) 2, 2-CN -4-CF 3, 2-Cl -4-CF 3, 2-
F -4-CN, 3-Cl -4-CN, 4-OCF 3, 3-OCF 3, 4-Cl -3-NO 2, 2-
_{Cl -4-NO 2, 3-} CH 3 -4- NO 2, 3-OCH 3 -4- NO 2, 4-C 6 H 5, 2-
F -4-CN, 2-F -4-NO 2, 2-Cl -4-NO 2, 4-Cl -3-NO 2, 4-CHO
A compound of formula (I), which is 4-SCF ₃ , 4-SOCF ₃ , 4-SO ₂ CF ₃ or 4-C (＝ O) CF ₃ .

(10) The compound of the formula (I), wherein R _2b is hydrogen. (11) Formula (I) wherein n1 is 1, 2, 3 or 4, preferably 2 or 3.
Compound. (12) The compound of the formula (I), wherein n2 is 1 or 2, preferably 1. (13) The formula (I) wherein n1 is 2, 3, or 4, and n2 is 1 or 2.
Compound.

(14) R ₁₁ and R ₁₂ independently of one another are H, C ₁ -C ₂ alkyl, phenyl,
—COC ₁ -C ₂ alkyl, —CO phenyl, or together with a 5- or 6-membered saturated or unsaturated ring, where, where appropriate, one CH— group or CH ₂ - group, O, it is replaced by a heteroatom selected from the group consisting of N and S, the 5-membered ring or 6-membered ring where appropriate, C ₁ ~
C ₂ alkyl, C ₁ -C ₂ haloalkyl, NO ₂ , and CN, which are substituted with one or two substituents selected from the group consisting of CN), or the two substituents R ₁₁ and R ₁₂ is a ring together

[0053]

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And q is 2, in particular where R ₁₁ and R ₁₂ independently of one another are H, C ₁ -C ₂ alkyl, phenyl,-
COC ₁ -C ₂ alkyl, -CO-phenyl, especially H, methyl or ethyl, the compounds of formula (I).

(15) at least one of R _3a and / or R _3b is —CR ₅ ＣＲCR ₅ R ₁₄ , and R ₁₄ is hydrogen, C ₁ -C ₆ alkyl, halogen —C ₁ -C ₆ alkyl, — CHO
_{, -C (= O) -C 1} ~C 6 alkyl, -C (= O) - halogen -C ₁ -C _{6 alkyl, -C (= O) -OC 1} ~C 6 alkyl, -C (= O ) -O-halogen-
C ₁ -C _{6 alkyl, -CN, -NO 2, -S (} = O) 2 N (R 6) 2 ( where the two substituents R ₆ are independent of one another), - S (= O ) _p -C ₁ ~C ₆ alkyl, phenyl, benzyl or benzyloxy, and R ₅ is hydrogen or C ₁ -C ₂ alkyl, in particular, R _3a or R _3b is -CR ₅ = CR ₅ R ₁₄ And R ₁₄ is hydrogen, C ₁ -C ₂ alkyl, halogen-C ₁ -C ₂ alkyl, phenyl or benzyl, and R ₁₅ is methyl or CF ₃ .

(16) The compound of the formula (I), wherein R ₅ is independently H or C ₁ -C ₂ alkyl. (17) n2 is 1 and (R _3b ) _n2 is SCH ₃ , SCF ₃ , SC ₂ H ₅ , SC ₂ F ₅ , SOCH ₃ , S
OC ₂ H ₅ , SOC ₂ F ₅ , SO ₂ N (CH ₃ ) ₂ , SO ₂ N (C ₂ H ₅ ) ₂ ,
SO ₂ CH ₃ , SO ₂ CF ₃ , SO ₂ C ₂ H ₅ , SO ₂ C ₂ F ₅ , SOCF ₃ ,
SOCHF ₂ , SOCF ₂ Br, SOCF ₂ Cl, SOCF ₂ CF ₂ Br, SO
_{CF 2 CF 2 Cl, SCHF 2} , SCF 2 Br, SCF 2 Cl, SCF 2 CF 2 Br, SCF 2 CF 2 Cl, SO 2 CHF 2, SO 2 CF 2 Br, SO 2 CF 2 Cl, SO 2 CF 2 CF ₂ Br or SO ₂ CF ₂ CF ₂ Cl, especially SCF ₃ ,
_{SC 2 H 5, SOCF 3,} SOC 2 H 5, SO 2 CF ₃ or SO ₂ C ₂ F _5, and R ₂ is R _2a or R _2b, especially _{H, -CH 2 OC 2 H 5} , -COCH ₃ ,-
_{CH 3, -CN, -CH 2 C≡CH} , -C 2 H 5, -COOCH 3 or -CO
A compound of formula (I), wherein N (CH ₃ ) OCH ₃ .

Particularly preferred within the scope of the present invention are the compounds of formula (I) listed in Tables III to XXVII, and where appropriate the E / Z isomers and E / Z isomers of said compounds.
It is a mixture of Z isomers.

A further object of the invention is: a) for the preparation of compounds of formula (I), wherein the substituents A ₁ and A ₂ are as defined above and R ₂ is hydrogen, aa Diazotization of a compound of the formula A ₁ -NH ₂ (III), wherein A ₁ is as defined above for formula (I), and ab) the diazonium salt and a compound of the formula

[0059]

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Wherein A ₂ is as defined above for formula (I), and W is hydrogen or a cleavable group.

B) Equation

[0062]

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Wherein A ₁ , A ₂ and R ₂ are as defined above for R _2a and R _2b in the compound of formula (I).

[0064]

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Wherein A ₁ , A ₂ and R ₂ are as defined above for R _2a and R _2b in the compound of formula (I), and Hal is a halogen atom, preferably chlorine or bromine. With a metal cyanide, preferably an alkali metal cyanide, especially sodium cyanide, or

[0066] c) R ₂ is for the preparation of different compounds of formula (I) is a H, a compound of formula (I) preferably in the presence of a base, R ₂ is hydrogen, the formula R ₂ -Q (V) wherein R ₂ is as defined above for R _2a and R _2b in formula (I) and is a Q leaving group. Including

Then, if desired, in each case the compound of formula (I) in free form or in the form of a salt, or the E / Conversion of the Z isomer or tautomer to another compound of formula (I) in free or salt form or the E / Z isomer or tautomer of the compound, the above method or other Separation of the mixture of E / Z isomers obtainable by means of and isolation of the desired isomer, and / or free form of the formula ( Conversion of the compound of I) or the E / Z isomer or tautomer of said compound to a salt form, or a compound of formula (I) in the form of a salt, obtainable by the methods described above or by other means Or Conversion of the E / Z isomer or tautomer of the compound into a compound of formula (I) in free form or the E / Z isomer or tautomer of the compound or another salt; And their E / Z isomers, where appropriate, E / Z
A process for the preparation of mixtures of isomers and / or their tautomers, which in each case are in free or salt form.

A further object of the present invention is that d) the free or salt form of the formula

[0069]

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Wherein A ₁ , A ₂ and R ₂ are as defined above for R _2a and R _2b in the compound of formula (I), and Hal is a halogen atom. And, where appropriate, for the preparation of E / Z isomers and tautomers of the compound,

[0071]

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Wherein A ₁ and A ₂ and R ₂ have the same meaning as defined above for R _2a and R _2b in formula (IIa) Reaction, or

E) Formula

[0074]

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Wherein R ₂ and the two radicals A ₁ and A ₂ have the same meaning as defined above for A ₁ , A ₂ , R _2a and R _2b in formula (I) ,
Hal is a halogen atom, preferably chlorine. ) For the preparation of a compound of the formula

[0076]

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Wherein R ₂ and the two radicals A ₁ and A ₂ have the same meaning as defined above in formula (IIb), and N-bromosuccinimide or N-chloro Reaction with succinimide in the presence of a thioether,

Then, if desired, in each case the compound of formula (II) in free form or in the form of a salt or the E / Conversion of the Z isomer or tautomer into another compound of formula (II) in free or salt form or the E / Z isomer or tautomer of the compound, the above method or other Separation of the mixture of E / Z isomers obtainable by means of and isolation of the desired isomer, and / or free form of the formula ( Conversion of the compound of II) or the E / Z isomer or tautomer of said compound to a salt form, or a compound of formula (II) in the form of a salt, obtainable by the above method or other means Or this Converting the E / Z isomer or tautomer of the compound to the compound of formula (II) in free form or the E / Z isomer or tautomer of the compound or another salt. Preparation method.

The reactions described above and below are carried out in a known manner, the work being carried out, depending on the requirements, with cooling, at room temperature or with heating, for example at about 0 ° C.
C. to the boiling point of the reaction medium, preferably at a temperature ranging from about 20.degree. C. to about + 120.degree. C., in particular 60.degree. C. to 80.degree. For example in nitrogen or argon and / or under anhydrous conditions. The reaction is preferably carried out under nitrogen at standard pressure. The reactants can be reacted with each other as such, ie, without the addition of solvents or diluents, for example in the melt. However, in most cases it is advantageous to add an inert solvent or diluent, or a mixture thereof. Particularly advantageous reaction conditions are described in the examples.

The isolation of the products is carried out according to customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these methods.

Variant a): aa) The diazotization is carried out under conditions well known to those skilled in the art, ie, strong inorganic acids such as mineral acids such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or halogenated acids In the presence of hydrogen)), usually in the presence of water, but also in pure sulfuric acid.

Depending on the basicity of the aromatic amine, the reaction is carried out at a temperature ranging from about −10 ° C. to about + 20 ° C. or, if necessary, at a higher temperature, for example 60 ° C. to 80 ° C. .

[0083] The reaction time is preferably from about 1 to about 2 hours. The product is not usually isolated, but is further processed in the next reaction step. Particularly preferred conditions for the above reaction are described in Example H6 / a.

Ab) The reaction is usually carried out in the presence of water, preferably with an organic carboxylic acid (eg,
It is carried out in the presence of formic acid, chloroacetic acid, trifluoroacetic acid, cyanoacetic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, the addition of acetic acid being particularly preferred.

The eliminable group W is understood to mean an electrophilic group which can easily be eliminated under widely performed reaction conditions. This inter alia suitable are, -C (= O) with R or -OC (= O) R (where, R is H, C ₁ -C ₄ alkyl, halogen -C ₁ ~
C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen -C ₁ -C ₄ alkoxy, -C
N, or organic sulfonate (e.g. if necessary C ₁ -C ₄ alkane sulfonates or aryl sulfonate is substituted by halogen, for example methanesulfonate, trifluoromethanesulfonate or p- toluenesulfonate) a).

The reaction is conveniently carried out in a temperature range from about -10 ° C to about + 30 ° C, preferably from about 0 ° C to about + 25 ° C. The reaction time is preferably about 0.5 to about 8 hours, especially about 2 to about 4 hours.

Variant b): Suitable for the reaction are transition metal cyanides such as CuCN or Ni (
CN) ₂ , and alkaline earth metal cyanides and alkali metal cyanides,
Among them are KCN and NaCN.

Examples of solvents or diluents are aromatic, aliphatic and cycloaliphatic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether , Hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane,
Dichloroethane, trichloroethane or tetrachloroethene), esters (eg, ethyl acetate), ethers (eg, diethyl ether, dipropyl ether,
Diisopropyl ether, dibutyl ether, t-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetrahydrofuran or dioxane), ketone (for example, acetone, methyl ethyl ketone or methyl isobutyl ketone), alcohol ( For example, methanol, ethanol,
Propanol, isopropanol, butanol, ethylene glycol or glycerol), amide (eg, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide), nitrile ( For example acetonitrile or propionitrile),
And sulfoxide (eg, dimethyl sulfoxide), or water. Preferred are alcohol and water or mixtures of alcohol / water.

The reaction is conveniently carried out in a temperature range from about 0 ° C. to about 80 ° C., preferably from about 20 ° C. to about 30 ° C., often from room temperature to the reflux temperature of the reaction mixture. The reaction time is preferably from about 0.1 to about 24 hours, especially from about 3 to about 5 hours.

In a preferred embodiment of variant b), the compound of formula (II) is reacted with sodium cyanide in a mixture of ethanol / water at room temperature.

Variant c): Suitable leaving groups Q in the compounds of the formula (V) are, for example, hydroxy, C ₁ -C ₈ alkoxy, halogen-C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkanoyloxy, mercapto , C ₁ -C ₈ alkylthio, halogen -C ₁ -C ₈ alkylthio,
C ₁ -C ₈ alkanesulfonyloxy, halogen-C ₁ -C ₈ alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy or halogen, especially halogen, especially It is bromine or chlorine.

Bases suitable for promoting the reaction include, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, Alkylamines, alkylenediamines, cycloalkylamines (where appropriate N-alkylated and where appropriate unsaturated), basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples are sodium hydroxide, hydride,
Amides, methanolates, acetates, and carbonates, potassium t-butanolate, hydroxide, carbonate, hydride, lithium diisopropylamide, potassium bis (trimethylsilyl) amide, calcium hydride, triethylamine, diisopropyl Ethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, Benzyltrimethylammonium hydroxide and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU). Preferred are alkali metal and alkaline earth metal carbonates, alkylamines and alkali metal or alkaline earth metal alkanolates.

Examples of solvents or diluents are aromatic, aliphatic and cycloaliphatic hydrocarbons (generally benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane) ,
Ethers (eg, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetrahydrofuran or dioxane), esters (ethyl acetate And methyl acetate), and sulfoxides (eg, dimethyl sulfoxide). Preferred are ethers (eg, t-butyl methyl ether, tetrahydrofuran or dioxane), and esters (eg, ethyl acetate).

The reaction is conveniently carried out in a temperature range from about 0 ° C. to about + 120 ° C., preferably from about 0 ° C. to about + 80 ° C. The reaction time is preferably from about 0.1 to about 24 hours, especially from about 0.5 to about 2 hours.

Variant d): The reaction is carried out in the presence of an acid catalyst, for example by displacing a carboxylic acid (for example, formic acid, acetic acid, malonic acid or oxalic acid) or a sulfonic acid (for example, if necessary, for example by halogen). It is preferably carried out in the presence of certain C ₁ -C ₄ alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid, trifluoromethanesulfonic acid or p-toluenesulfonic acid.

Particularly suitable are solvents suitable for azeotropically removing water. Examples of such solvents or diluents are aromatic, aliphatic and cycloaliphatic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether. ,
Hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane or tetrachloroethene), ester (eg, ethyl acetate), ether (eg, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, dimethoxy diethyl ether) ), Ketones (eg, methyl isobutyl ketone), alcohols (eg, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol).

The reaction is conveniently effected in a temperature range from about 60 ° C. to about 180 ° C., preferably from about 80 ° C. to about 130 ° C., often at the reflux temperature of the reaction medium. Preferred reaction times are preferably about 6 to about 72 hours, especially about 12 to about 48 hours.

In a preferred embodiment of variant d), the reaction is carried out at 80 ° C. to 140 ° C. in an alcohol or an aromatic hydrocarbon in the presence of a C ₁ -C ₄ carboxylic acid.

Variant e): Preferred halogenating agents are Cl ₂ , Br ₂ , SOCl ₂ , SO ₂ Cl ₂ , POC
l _3, is PCl _3, PCl ₅ and COCl _2. Examples of solvents or diluents are aromatic, aliphatic and cycloaliphatic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, Cyclohexane, dichloromethane, chloroform, tetrachloromethane,
Dichloroethane, trichloroethane or tetrachloroethene), esters (eg, ethyl acetate), ethers (eg, diethyl ether, dipropyl ether,
Diisopropyl ether, dibutyl ether, t-butyl methyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetrahydrofuran or dioxane), ketone (eg, acetone, methyl ethyl ketone or methyl isobutyl ketone), amide (eg, N, N-dimethylformamide, N, N -Diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide), nitriles (eg acetonitrile or propionitrile).

The reaction is conveniently carried out in a temperature range from about 0 ° C. to about 180 ° C., preferably from about 50 ° C. to about 100 ° C., often from room temperature to the reflux temperature of the reaction mixture. It is. The reaction time is not critical, and a reaction time of about 0.1 to about 24 hours, especially about 3 to about 6 hours, is preferred.

The compounds of the formulas (I), (IIa), (IIb) and (VIII) can be, for example, pure isomers (eg enantiomers and / or diastereomers) or mixtures of isomers (eg enantiomers) Depending on the number and the absolute and relative configuration of the asymmetric carbon atoms as a mixture of the compounds (e.g., racemates), even if they exist in one of the possible isomeric forms or as a mixture thereof. Well, the present invention relates both to the pure isomers and to mixtures of all possible isomers, even if the stereochemical details are not specifically stated in every case, It is understood as follows.

The compounds of the formulas (I), (IIa), (IIb) which can be obtained as described in the above process or by other means (depending on the starting materials and the chosen operating procedure)
Mixtures of the diastereomers and racemates of the compounds of the formulas) and (VIII) can be prepared by known techniques, for example by fractional crystallization, distillation and / or chromatography, due to the physicochemical differences in the constituents. It can be separated into pure diastereomers or racemates.

The separation of the correspondingly obtainable mixtures of enantiomers (for example racemates) can be carried out by known methods, for example by recrystallization from optically active solvents, chromatography on chiral sorbents (for example acetylcellulose) High pressure liquid chromatography (HPLC)), the use of suitable microorganisms, cleavage by specific immobilized enzymes, for example by the formation of clathrates using chiral crown ethers which complex only one enantiomer , Can be achieved.

According to the present invention, except for the isolation of the corresponding isomer mixtures, generally known diastereomeric or enantioselective synthetic methods are applied, for example the corresponding suitable By practicing the method of the invention using an extract having a steric configuration, pure diastereomers or enantiomers can be obtained.

In each case, the individual components of the more biologically active isomers (eg enantiomers) or mixtures of isomers (eg mixtures of enantiomers) show differences in biological potency In some cases, it is advantageous to isolate or synthesize these isomers or mixtures of isomers.

The compounds of the formulas (I), (IIa), (IIb) and (VIII) can also be obtained in the form of their hydrates and / or for example for the crystallization of compounds existing in solid form It may also contain other solvents used if necessary.

The present invention starts from a compound which can be obtained as the main material or an intermediate in any stage of the above-mentioned process, carries out all or some of the missing steps, or obtains a derivative or salt and It relates to all embodiments of the process of using or producing (especially under the reaction conditions described above) the starting materials in the form of / or their racemates or enantiomers.

In the process of the invention, the starting materials and intermediates used are preferably those which lead to the compounds of the formula (I) which were initially described as being particularly useful. The invention particularly relates to the production methods described in Examples H1, H2, H4 and H5.

The starting materials used according to the invention for preparing the compounds of the formula (I) and of the compounds of the formulas (II), (III), (IV) and (VIII), which are novel, and Intermediates, as well as their use and their method of preparation, likewise form an object of the present invention.

The compounds of the formulas (IIa), (IIb) and (VIII) and their use for preparing the compounds of the formula (I) represent a further object of the invention. The compounds of formulas (III) to (VI) and (IX) are known and can be prepared according to known methods.

A further object of the present invention uses compounds of formula (I), wherein A ₁ and A ₂ and R ₂ have the same meanings as defined above for formula (I). It is a method of controlling pests by using the method.

The compounds of the formula (I) according to the invention are prophylactic and / or
Or a reactive substance that has therapeutic benefits, even at low concentrations in warm-blooded animals,
It offers a very favorable range of biocide activity, with favorable resistance in fish and plants. The compositions according to the invention are active against all or individual stages of development of normally susceptible and also resistant pests, such as those belonging to the order of the insects and mites. The insecticidal, ovicidal, and / or acaricidal activity of the compositions of the present invention, as such, kills pests directly (ie, immediately or after some time has elapsed, such as when molting occurs). ) Or indirectly (eg, reducing egg production and / or hatchability), good efficacy corresponding to a control rate (mortality) of at least 50-60%.

Pests include, for example, Lepidoptera, Coleoptera, Orthoptera, Isoptera, Chaptera,
Nitaceae, furoptera, hymenoptera, stink bugs, homoptera, hymenoptera, diptera, flea orders,
Included are those belonging to the order Coleoptera and Acarina, especially preferred are the control of pests of the genus and species described in EP-A-736,252, which is incorporated herein by reference. .

Plants, especially crops and ornamental plants in agriculture, horticulture and forestry, or pests of the type mentioned above, which occur on parts of such plants, such as fruits, flowers, leaves, stems, tubers or roots, of the present invention The active ingredient can be used to control, ie suppress or eradicate, this protection remaining for any subsequently growing plant parts.

The crops of interest include, inter alia, cereals (eg, wheat, barley, rye, oats, rice, corn or sorghum), beets (eg, sugar beet or corn beet), fruits (eg, pear fruits, stones) Fruits and small fruits (eg apples, pears, plums, peaches, almonds, cherries or berries (eg strawberries, raspberries or blackberries)), legumes (eg kidney beans, lentils, peas or soybeans), oily fruits (Eg, oilseed rape, mustard, poppy, olive, sunflower, coconut, castor, cacao or peanut), cucumber plants (eg, pumpkin, cucumber or melon), fiber plants (eg, cotton, flax, hemp or jute), citrus fruits ( For example, orange, lemon, grapefruit or mandarin), vegetables (e.g. Spinach, lettuce, asparagus, various cabbages, carrots, leeks, tomatoes, potatoes or paprika), camphor trees (eg avocado,
Cinnamon or camphor), and tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamental plants.

The active ingredients according to the invention may be those belonging to the order of the insects and mites, especially the crops in the cultivated plants of cotton, fruits, maize, soybeans, oilseed rape and vegetables,
Insects that hurt (eg Anthonomus grandis, Diabrotica balteata, Heliot
his virescens larvae, Plutella xylostella and Spodoptera littoralis la
rvae) and spider mites (eg Tetranychus spp.).

Another area of application of the active ingredients according to the invention is the protection of stored products and storage and materials from pests of the above-mentioned type and, in hygiene areas, in particular, the protection of livestock.

Thus, the present invention provides compounds of formula (I) wherein A ₁ , A ₂ and R ₂ are
It has the same meaning as defined above for I). However, pesticides comprising 1-phenylhydrazono-2-nitriloethylbenzene), such as emulsifiable concentrates, suspension concentrates, directly sprayable or diluents comprising at least one active ingredient according to the invention Encapsulation in possible solutions, spreadable pastes, dilute emulsions, sprayable powders, soluble powders, dispersible powders, wettable powders, fine powders, granules or polymeric substances (intended purpose and dominance Selected according to the environment).

The active compounds can be in pure form (solid active compound of a specific particle size) or, preferably, (at least) one of the auxiliaries conventionally used in the compounding art (eg bulking agents ( (E.g. solvents or solid carriers) or surface-active compounds (surfactants)) in these compositions.

Suitable auxiliaries (eg solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants and anionic surfactants) used according to the invention in the abovementioned compositions ) Is European Patent Publication No. 736,252 (CASE 20400)
(Included in the purpose of the invention by reference).

In general, the composition comprises 0.1-99%, especially 0.1-95%, of the active ingredient and 1
Comprise from 9 to 99.9%, especially from 5 to 99.9% of (at least) one solid or liquid adjuvant, wherein from 0 to 25%, in particular from 0.1 to 20%, of the composition are generally surfactants Good (% in each case means% by weight). Although commercial compositions tend to favor concentrated compositions, end consumers generally use dilute compositions with significantly lower concentrations of active ingredients. Preferred compositions are constituted in particular as described in EP-A-736,252.

The activity of the compositions according to the invention is fully extended or adapted to the prevailing environment by adding other pesticidal, acaricide and / or fungicidal substances. be able to. Further active ingredients are, for example, the following classes of substances: Organic phosphorus compounds, nitrophenols and derivatives, formamidine, urea,
Carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis
It is a compound. The compositions of the present invention may also include stabilizers (eg, epoxidized vegetable oils where appropriate, such as epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (eg, silicone oils), preservatives, Other solid or liquid auxiliaries, such as viscosity modifiers, binders and / or tackifiers, and also fertilizers or specific agents such as acaricides, fungicides, nematicides, molluscicides or selection Active herbicides) can also be included.

The compositions according to the invention can be prepared in a known manner, for example by grinding and / or sieving the solid active ingredient or a mixture of active ingredients in the presence of auxiliaries, for example to a specific particle size, In the presence of at least one adjuvant, for example, the active ingredient or a mixture of active ingredients is intimately mixed with the adjuvant (s) and / or
Or prepared by grinding. These methods for preparing the compositions of the invention and the use of the compounds of formula (I) for preparing these compositions likewise form an object of the invention.

The method of application of the composition, ie the method of controlling pests of the type mentioned, for example by spraying, atomizing, dusting, coating, dressing, scattering or pouring (selected according to the intended purpose and the prevailing environment) ), And the use of the above compositions for controlling pests of said type are further objects of the present invention. Typical concentrations of the active ingredient are 0.1-1000 ppm, preferably 0.1-5
00 ppm. The application rates are generally from 1 to 2000 g of active ingredient (ai) per hectare (ha equals approximately 2.471 acres), in particular from 10 to 1000 g.a.i./ha, preferably from 20 to 600 g.a.i./ha.

A preferred method of application for crop protection is to apply the active ingredient to the foliage of plants (leaf application). The number of applications and the amount of application depend on the intensity of infestation by the pests in question. Dependent. However, the active ingredient can be passed through the soil, through the roots, by soaking the location of the plant with the liquid composition, or by applying the compound in solid form (eg, in the form of granules) to the soil (soil application). It can also penetrate plants (systemic effects). In the case of paddy rice cultivation, the granules may be metered and supplied to a paddy field filled with water.

The compositions of the present invention are also suitable for protecting plant propagation material (eg, seeds (eg, fruits, tubers or berries) or plant seedlings) from fungal infection and pests. . The propagation material can be treated with the composition before the start of cultivation, for example, the seeds can be dressed before sowing. Soaking the seeds in the liquid composition,
Alternatively, the active ingredients of the present invention can also be applied to seeds by coating them with a solid composition (coating). When introducing a propagation material to a cultivation place, for example, when sowing seeds in a seed furrow, the composition can also be applied. Procedures for treating plant propagation material and propagation material thus treated are further objects of the present invention.

The present invention is illustrated by the following examples. They do not limit the invention. Temperatures are given in degrees Celsius.

[0128] Preparation Example H1: the formula of 4-nitrobenzoic acid -N '- (2,6-dichloro-4-trifluoromethylphenyl) - Preparation of hydrazine

[0129]

Embedded image

A solution of 35.85 g of 4-nitrobenzoyl chloride in 150 mL of dichloromethane was added to 10 mL
To 45.1 g of 2,6-dichloro-4-trifluoromethylphenylhydrazine in 00 mL of dichloromethane is added dropwise with stirring at 0-5 ° C. over a period of about 60 minutes, then stirring is further carried out at room temperature. Continue for 60 minutes. While stirring the mixture vigorously for 20 minutes, 20.4 g of triethylamine are fed. Then stirring is continued for 3 hours at room temperature. The organic phase is washed three times with 500 ml of water each time, dried over sodium sulphate and freed of the solvent in a rotary evaporator. Recrystallization of the residue from toluene gives the title product, mp 188-190 ° C.

Example H2: Preparation of 4- {1-[(2,6-dichloro-4-trifluoromethylphenyl) hydrazono] -chloromethyl} -nitrobenzene of the formula

[0132]

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To a solution of 69.3 g of 4-nitrobenzoic acid-N '-(2,6-dichloro-4-trifluoromethylphenyl) -hydrazine in 600 mL of toluene was stirred 33.9 g of thionyl chloride at room temperature. Add dropwise while adding. Next, the mixture is heated to 105 ° C. and stirred for 6 hours. After cooling, the mixture is concentrated to dryness by evaporation on a rotary evaporator and the residue is crystallized from toluene. The title compound having a melting point of 117-118 ° C. is obtained (compound 1.20).

Example H3: Other compounds listed in Table I can be prepared by procedures analogous to those described in Example H2.

Table I: Compounds of the formula

[0136]

Embedded image

[0137]

[Table 1]

[0138]

[Table 2]

Example H4 Preparation of 4- {1-[(2,6-dichloro-4-trifluoromethylphenyl) hydrazono] -2-nitriloethyl} nitrobenzene of the formula

[0140]

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To a solution of 10.7 g of sodium cyanide in 240 mL of water and 160 mL of ethanol was added 51.5 g of solid 4- {1-[(2,6-dichloro-4-trifluoromethylphenyl) hydrazono] chloro Methyl-nitrobenzene is added in several portions over a period of about one hour. The reaction mixture is stirred at room temperature for 18 hours, then poured into 6 L of ice water. The precipitate is filtered, washed three times with water, dissolved in ethyl acetate and washed with a 15% NaCl solution. The organic phase is dried over sodium sulfate, filtered and concentrated to dryness by evaporation on a rotary evaporator. The residue is crystallized from toluene. This gives the title compound with a melting point of 160-161 ° C.

Example H5 Preparation of 4- {1-[(2,6-dichloro-4-trifluoromethylphenyl) -N-methyl-N-methoxycarbamoylhydrazono] -2-nitriloethyl} nitrobenzene of the following formula

[0143]

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To 1.2 g of 4- {1-[(2,6-dichloro-4-trifluoromethylphenyl) hydrazono] -2-nitriloethyl} nitrobenzene in 50 mL of tetrahydrofuran was added 0.44 g.
Of finely ground potassium t-butyrate is added at room temperature. 10 of the mixture
After stirring for a minute, a deep red solution results. 0.48 g of methylmethoxycarbamoyl chloride is added and the mixture is stirred for 3 hours. The solvent is removed in a rotary evaporator and the residue is dissolved in ethyl acetate. The ethyl acetate phase was washed with water and NaCl
Wash with solution, dry over sodium sulfate and concentrate to dryness by evaporation under reduced pressure. The residue is chromatographed on a column of silica gel using a 5: 1 ratio of hexane: tetrahydrofuran. Concentration of the 6th to 14th fractions by evaporation gives the title compound with a melting point of 96-97 ° C (compound 2.1).

Example 6: Other compounds listed in Tables II and III can also be prepared by procedures analogous to those described in Example H5.

Table II: Compounds of the formula

[0147]

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C ₃ H ₃ F ₂ cyc is 2,2-difluoro-cycloprop-1-yl, and 4-C (NOMe) CF ₃ represents the substituent 4-C (＝ NOCH ₃ ) CF ₃ .

[0149]

[Table 3]

[0150]

[Table 4]

[0151]

[Table 5]

[0152]

[Table 6]

[0153]

[Table 7]

[0154]

[Table 8]

[0155]

[Table 9]

[0156]

[Table 10]

[0157]

[Table 11]

Table III: Compounds of the formula

[0159]

Embedded image

[0160]

[Table 12]

[0161]

[Table 13]

[0162]

[Table 14]

[0163]

[Table 15]

[0164]

[Table 16]

[0165]

[Table 17]

[0166]

[Table 18]

[0167]

[Table 19]

[0168]

[Table 20]

[0169]

[Table 21]

[0170]

[Table 22]

[0171]

[Table 23]

[0172]

[Table 24]

[0173]

[Table 25]

[0174]

[Table 26]

[0175]

[Table 27]

[0176]

[Table 28]

Table IV: Compounds of the formula

[0178]

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In the above formula, (R _3a ) _n1 is 2,6-Cl ₂ -4-CF ₃ , and R ₂ and (R _3b ) _n2 each correspond to a row in Table A.

Table V: Compounds of general formula (Ib) wherein (R _3a ) _n1 is 2,4,6-Cl ₃ and R ₂ and (R _3b ) _n2 are each one row of Table A Corresponding to).

Table VI: Compounds of general formula (Ib) wherein (R _3a ) _n1 is 2-Cl -4-CF ₃ and R ₂ and (R _3b ) _n2 are each one row of Table A Corresponding to).

Table VII: Compounds of general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -4-NO ₂ ,
R ₂ and (R _3b ) _n2 each correspond to one row of Table A).

Table VIII: Compounds of general formula (Ib) wherein (R _3a ) _n1 is 2,6-Cl ₂ -4-OCF ₃ and R ₂ and (R _3b ) _n2 are Corresponding to one row).

Table IX: Compounds of general formula (Ib), wherein (R _3a ) _n1 is 2,6-Cl ₂ -4-F and R ₂ and (R _3b ) _n2 are each 1 One row).

[0185]Table X: A compound of the general formula (Ib) wherein (R_3a)_n1Is 2,6-Cl_Two-4-Br and R _Two And (R_3b)_n2Each correspond to one row of Table A).

Table XI: Compound of general formula (Ib) (where (R _3a ) _n1 is 2-Cl -4-CF ₃ -6-F and R ₂ and (R _3b ) _n2 are Corresponding to one row).

Table XII: Compounds of the general formula (Ib) (where (R _3a ) _n1 is 2,3,6-Cl ₃ -4-CF ₃ and R ₂ and (R _3b ) _n2 are A corresponding to one row).

Table XIII: Compounds of general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -3-F -4-CF ₃ , and R ₂ and (R _3b ) _n2 are Each corresponding to one row of Table A).

Table XIV: Compounds of general formula (Ib) (where (R _3a ) _n1 is 2,3-F ₂ -4-CF ₃ -6-Cl and R ₂ and (R _3b ) _n2 are Each corresponding to one row of Table A).

Table XV: Compounds of general formula (Ib), wherein (R _3a ) _n1 is 2,6-Cl -4-CN and R ₂ and (R _3b ) _n2 are each one of Table A Row).

Table XVI: Compounds of general formula (Ib) (where (R _3a ) _n1 is 2,4-Cl ₂ -6 CF ₃ ,
R ₂ and (R _3b ) _n2 each correspond to one row of Table A).

Table XVII: Compounds of general formula (Ib), wherein (R _3a ) _n1 is 2,6-Cl ₂ -4-SCF ₃ , and R ₂ and (R _3b ) _n2 are Corresponding to one row).

Table XVIII: Compounds of general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -4-SOCF ₃ and R ₂ and (R _3b ) _n2 are Corresponding to one row).

Table XIX: Compounds of general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -4-SO ₂ CF ₃ and R ₂ and (R _3b ) _n2 are A corresponding to one row).

Table XX: Compounds of general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -4-SO ₂ CH ₃ and R ₂ and (R _3b ) _n2 are A corresponding to one row).

Table XXI: Compound of the general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -4-OCF ₂ Br and R ₂ and (R _3b ) _n2 are Corresponding to one row).

Table XXII: Compound of general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -4-OCF ₂ H and R ₂ and (R _3b ) _n2 are Corresponding to one row).

Table XXIII: Compounds of general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -4-C ₂ F ₅ and R ₂ and (R _3b ) _n2 are A corresponding to one row).

Table XXIV: Compounds of general formula (Ib) wherein (R _3a ) _n1 is 2,6- (NO ₂ ) ₂ -4-CF ₃ and R ₂ and (R _3b ) _n2 are (Corresponds to one row of Table A).

Table XXV: Compounds of the general formula (Ib) (where (R _3a ) _n1 is 2,6- (NO ₂ ) ₂ -4-Cl and R ₂ and (R _3b ) _n2 are A corresponding to one row).

Table XXVI: Compounds of the general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -4-OSO ₂ CH ₃ and R ₂ and (R _3b ) _n2 are A corresponding to one row).

Table XXVII: Compounds of the general formula (Ib) (where (R _3a ) _n1 is 2,6-Cl ₂ -4-OSO ₂ CF ₃ and R ₂ and (R _3b ) _n2 are A corresponding to one row).

Table XXVIII: Compounds of general formula (Ib) wherein (R _3a ) _n1 is 2,6-Cl ₂ -4-SF ₅
R ₂ and (R _3b ) _n2 each correspond to one row of Table A).

Examples of formulations of the compounds of the present invention, ie, solutions, granules, fines, wettable powders, emulsifiable concentrates, coated granules, and suspension concentrates, are eg EP-A-580
, 553 (Case 19164), examples F1 to F10.

[0205] Biological Examples Example B1: Heliothis eggs Heliothis virescens attached to egg resistance effect filter paper killing against virescens, briefly test solution comprising a mixture of the active ingredient to be tested in acetone / water 400 ppm Soak. After the test solution has dried, the eggs are cultured in petri dishes. After 6 days, the hatch rate (%) of the egg is compared to that of the untreated control (decrease hatch rate (%)).

The compounds listed in Tables III-V show good activity against Heliothis virescens. In particular, compounds 2.1-2.5, 2.8-2.13 and 3.7 show a response of more than 80%.

Example B2: Action on caterpillars of Spodoptera littoralis Young soybean plants are sprayed with an aqueous emulsion containing 400 ppm of active ingredient. After the spray deposit has dried, the soybean plant is inoculated with 10 third instar larvae of Spodoptera littoralis and placed in a plastic container. After 3 days, they are evaluated. Population reduction (%) and feeding damage (% response) by comparing the number of dead larvae and the degree of feeding damage in treated plants to that of untreated plants Is measured.

The compounds of Table I show good potency against Spodoptera littoralis in this test. In particular, compounds 2.1-2.5, 2.7-2.18 and 3.7-3.9 show a response of more than 80%.

Example B3: Action on Diabrotica balteara larvae Corn seedlings are sprayed with an aqueous emulsion containing 400 ppm of active ingredient. After drying of the spray deposits, Diabrotica bal
Inoculate 10 teara second instar larvae into plastic containers. Six days later,
Evaluate them. The population reduction (response (%)) is determined by comparing the number of dead larvae in the treated plants to that of the untreated plants.

The compounds of Tables III-V show good efficacy against Diabrotica balteara in this test. In particular, compounds 2.1-2.4, 2.6, 2.7, 2.11, 2.25-2.28 and 3.9 show a response of over 80%.

Example B4: Action on Plutella xylostella caterpillars Young cabbage plants are sprayed with an aqueous emulsion containing 400 ppm of active ingredient. After the spray deposits dry, the cabbage plants are treated with Plutella xylostell
Inhabit 10 third-instar larvae of a and put them in a plastic container. After 3 days, they are evaluated. Population reduction (%) and feeding damage (% response) by comparing the number of dead larvae and the degree of feeding damage in treated plants to that of untreated plants Is measured.

The compounds of Tables III-V show good efficacy against Plutella xylostella in this test.

Example B5: Action on Tetranychus urticae Young kidney plants were inoculated with a mixed population of Tetranychus urticae and one day later
Spray an aqueous emulsion containing 400 ppm of active ingredient. 25 ℃ of the plant
For 6 days and then evaluated. Population reduction (% response) is determined by comparing the number of dead eggs, larvae, and adults in treated plants to that of untreated plants.

The compounds of Tables III-V show good potency against Tetranychus urticae in this test.

Example B6: Action on Aphis craccivora Pea seedlings are infected with Aphis craccivora and then sprayed with an emulsion containing 400 ppm of active ingredient and cultured at 20 ° C. They are evaluated after 3 and 6 days. Population reduction (response (%)) is measured by comparing the number of dead aphids in the treated plants to that of the untreated plants.

The compounds of Tables III-V show good potency against Aphis craccivora in this test. In particular, compounds 2.7, 2.22 and 3.8 show a response greater than 80%.

Example B7: Action on Myzus persicae Pea seedlings are infected with Myzus persicae and then sprayed with an emulsion containing 400 ppm of active ingredient and cultured at 20 ° C. They are evaluated after 3 and 6 days. Population reduction (response (%)) is measured by comparing the number of dead aphids in the treated plants to that of the untreated plants.

The compounds of Tables III-V show good potency against Myzus persicae in this test. In particular, compounds 3.7 and 3.13 show a response greater than 80%.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 43/40 101 A01N 43/40 101C 43/80 102 43/80 102 43/832 47/02 47/02 47/12 A 47/12 47/28 Z 47/28 C07C 317/32 C07C 317/32 323/48 323/48 C07D 213/57 C07D 213/57 271/12 271/12 275/02 275/02 307 / 66 307/66 333/42 333/42 A01N 43/82 103 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU , MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K) E, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ , DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM , TR, TT, UA, UG, US, UZ, VN, YU, ZW (72) Inventor Hüter, Otmer Franz Germany, Day 79539 Lehrach, Black Forest Strasse 57 (72) Inventor Pasqual, Alphonse Tseha, Switzerland --4056 Basel, Kannenfeld Platz 3 (72) Inventor Kriz, Miroslav Slovakia, 851 01 Bratislava, Fedinova 6 (72) Inventor Toller, Stephans, Germany Day 79111 Fleibrg, Andreas-Hoffer-Strasse 150A F-term (reference) 4C033 AA05 AA17 4C055 AA01 BA01 BA02 BA30 BB17 CA01 CA02 CA30 CB17 DA01 4C056 AA01 AB02 AC04 AD03 AE03 FA01 FB01 FC07 4H006 AA01 AA03 AB02 TA03 TA05 TB02 TB03 TB40 4H01 BB BB AC04 BC05 DA02 DA13 DA15 DA16 DB05 DD03 DD04 DE15 sUMMARY continued] kill, halogen -C ₁ -C ₄ alkyl or aryl, R ₁₀ is H, C ₁ -C ₆ alkyl, C ₃ -C ₆ a cycloalkyl, phenyl or benzyl, reduction R ₁₁ and R ₁₂ were H, C ₁ -C ₆ alkyl or independently for example one another is phenyl And / or, where appropriate, the E / Z isomers, mixtures of E / Z isomers and / or tautomers of the compounds in which they may be present, in free or pesticidal form. It can be used as a pesticidal active ingredient in an acceptable form as well as can be prepared by a known method.

Claims (14)

[Claims] 1. A compound of the formula (I)A compound of the above formula wherein A₁And A_TwoAre independently of one another in each case a monocyclic or bicyclic
Represents an aryl radical or a heteroaryl radical.
The reel radical is, independently of the other, a hetero radical selected from the group consisting of N, O and S.
It has from 1 to 4 (including 4) atoms, and if appropriate A₁Is a substituent (R_3a)_n1And, where appropriate, A _Two Is a substituent (R_3b)_n2And n1 and n2 have a ring structure A₁And A_TwoDue to the possibility of substitution in
Is independently 1, 2, 3 or 4; and (A) R_3aAnd R_3bAre independently hydrogen, halogen, C₁~ C₆Alkyl,
Halogen-C₁~ C₆Alkyl, C_Two~ C_FourAlkenyl, C_Two~ C_FourAlkynyl
, Halogen-C_Two~ C_FourAlkenyl, halogen-C_Two~ C_FourAlkynyl, C₁~
C₆Alkoxy, halogen-C₁~ C₆Alkoxy, C_Two~ C₆Alkenyloxy
Si, C_Two~ C₆Alkynyloxy, halogen-C_Two~ C₆Alkenyloxy, ha
Logen-C_Two~ C₆Alkynyloxy, -OH, -SF_Five, -CHO, -C (=
O) -C₁~ C₆Alkyl, -C (= O) -halogen-C₁~ C₆Alkyl,-
C (= O) -OC₁~ C₆Alkyl, -C (= O) -O-halogen-C₁~ C₆ Alkyl, -OC (= O) N (R₆)_Two(Where both substituents R₆Are each other
Independent)), -CN, -NO_Two, -S (= O)_TwoN (R₆)_Two(Where both
Substituent R₆Are independent of each other), -S (= O)_p-C₁~ C₆Alkyl,-
S (= O)_p-Halogen-C₁~ C₆Alkyl, -OS (= O)_p-C₁~ C ₆ Alkyl, -OS (= O)_p-Halogen-C₁~ C₆Alkyl, phenyl,
Benzyl, phenoxy or benzyloxy (where the phenyl,
Each of the benzyl, phenoxy, or benzyloxy radicals is unsubstituted
Or the aromatic ring is halogen, cyano, NO_Two, C₁~ C₆Alkyl, halo
Gen-C₁~ C₆Alkyl, C₁~ C₆Alkoxy and halogen-C₁~ C₆ Mono- to penta-substituted independently of each other by a substituent selected from the group consisting of alkoxy
) And R_TwoIs R_2aOrOr (B) R_3aAnd R_3bAre independent of each other as defined in (A)
R_3aOr R_3bAt least one is -CR_Five= CR_FiveR₁₄, -NR₁₁R₁₂,
-C (= O) CN, -C (= O) C (= O) OC₁~ C₆Alkyl, -CR₁₅ = NOR_TenOr a 5- or 6-membered heteroaryl ring (wherein
In some cases, the heteroaryl ring may be a halo,
Gen, C₁~ C_FourAlkyl, C₁~ C_FourHaloalkyl, NO_TwoAnd from CN
R 1-3 is substituted with 1 to 3 substituents selected from the group_TwoIs R_2aOr R_2bOrOr (C) R_3aHas one of the meanings defined above in (A) or (B)
Has, R_3bIs hydrogen, halogen, C₁~ C₆Alkyl, halogen-C₁~ C₆Alkyl
, C_Two~ C_FourAlkenyl, C_Two~ C_FourAlkynyl, halogen-C_Two~ C_FourArche
Nil, halogen-C_Two~ C_FourAlkynyl, C₁~ C₆Alkoxy, halogen-C ₁ ~ C₆Alkoxy, C_Two~ C₆Alkenyloxy, C_Two~ C₆Alkynyloxy
Si, halogen-C_Two~ C₆Alkenyloxy, halogen-C_Two~ C₆Alkynyl
Oxy, -OH, -SF_Five, -CHO, -C (= O) -C₁~ C₆Alkyl,-
C (= O) -halogen-C₁~ C₆Alkyl, -C (= O) -OC₁~ C₆Al
Kill, -C (= O) -O-halogen-C₁~ C₆Alkyl, -OC (= O) N
(R₆)_Two(Where the two substituents R₆Are independent of each other), -CN,-
NO_Two, Phenyl, benzyl, phenoxy or benzyloxy (where
Each of the phenyl, benzyl, phenoxy, or benzyloxy radicals
Is unsubstituted or the aromatic ring is halogen, cyano, NO_Two, C₁~
C₆Alkyl, halogen-C₁~ C₆Alkyl, C₁~ C₆Alkoxy and ha
Logen-C₁~ C₆A substituent independently selected from the group consisting of alkoxy
-S at the 4-position (= O)_p-C₁~ C₆Alkyl
Is -S (= O) at the 4-position_p-Halogen-C₁~ C₆Alkyl (however,
Substituent R_3bIs -S (= O)_p-C₁~ C₆Alkyl or -S (= O)_p−
Halogen-C₁~ C₆Alkyl) and R_TwoIs R_2aOr R_2bOreitherIn the above groups (A), (B) and (C), if appropriate, R_2aIs -C₁~ C₆Alkyl-NR₁₁R₁₂, -C (= X) -R_7a, -COC₉ ~ C₂₀Alkyl, -CH_TwoO (C = O) C₁~ C₆Alkyl, -C₁~ C₆Al
Kill-OC₁~ C₆Alkyl-OC₁~ C₆Alkyl, -CH_TwoO (C = O
) C_Two~ C₆Alkenyl, -CH_TwoO (C = O) C_Two~ C₆Alkynyl, -C (
= S) OC_Two~ C₆Alkenyl, -C (= S) OC_Two~ C₆Alkynyl, -C (
= S) SC₁~ C₆Alkyl, -C (= S) SC_Two~ C₆Alkenyl, -C (=
S) SC_Two~ C₆Alkynyl, -C (= O) SC₁~ C₆Alkyl, -C (= O
) SC_Two~ C₆Alkenyl, -C (= O) SC_Two~ C₆Alkynyl, -C (= S
) NR₁₁R₁₂, -C (= O) NR_TenOR₁₃, -CH_TwoOC_Two~ C₆Alkenyl,
-CH_TwoOC_Two~ C₆Alkynyl, -CH_TwoOC_Two~ C₆Haloalkenyl or
-CH_TwoOC_Two~ C₆Haloalkynyl, R_2bIs hydrogen, -OH, C₁~ C₆Alkyl, C₁~ C₆Alkoxy, C_Three~ C ₆ Cycloalkyl, C_Three~ C₆Alkenyl, C_Three~ C₆Alkynyl, halogen-
C₁~ C₆Alkyl, halogen-C_Three~ C₆Alkenyl, C_Three~ C₆Alkynyl
, Benzyl or benzoyl (wherein the benzyl or benzoyl radical
Is a group in which the aromatic ring is halogen, -CN, NO_Two, C₁~ C₆Alkyl, C₁~ C₆A
Lucoxy, halogen-C₁~ C₆Alkyl and halogen-C₁~ C₆Alkoki
Are independently mono- to tri-substituted by a substituent selected from the group consisting of
, C₁~ C₆Alkoxy-C₁~ C₆Alkyl, cyano-C₁~ C₆Alkyl,
-C (= X) -R_7a, -C (= X) -R_7b, -OC (= O) -R_7a, -C (= O
) -C (= O) -R_7a, -OC (= O) -R_7b, -C (= O) -C (= O) -R _7b , -S (= O)_pN (R₆)_Two(Where the two substituents R₆Are independent of each other
), Cyano, -C₁~ C₆Alkyl-N (R_Five) -C (= O) -R₈, −
C₁~ C₆Alkyl-SC (= S) -R₈, -C₁~ C₆Alkyl-S (= O
)_p-R₉, -S (= O)_p-R₉Or -CH_Two−N (R_Ten) -SO_Two-R ₉ X is O or S; p is 0, 1 or 2;_FiveIs independently H or C₁~ C₈Alkyl, R₆Are independently H and C₁~ C₈Alkyl, C_Three~ C₆Cycloalkyl, phenyl
Or benzyl (where the phenyl or benzyl group is, where appropriate,
The aromatic ring is halogen, -CN, NO_Two, C₁~ C₆Alkyl, C₁~ C_FourAlkoki
Si, halogen-C₁~ C₆Alkyl and halogen-C₁~ C₆From alkoxy
Are independently mono- to tri-substituted by a substituent selected from the group consisting of
Or two alkyl radicals R₆Together with the nitrogen atom to which they are attached
To form a 5- to 7-membered ring (where CH_TwoThe group is O
Is substituted by a heteroatom selected from the group consisting of and S, or
NH, and where appropriate the 5- to 7-membered ring is C₁~ C_FourAl
Mono- or di-substituted with a kill)_7aIs C₁~ C₆Alkoxy-C₁~ C₆Alkyl, CH_TwoCH_TwoCF_TwoCl
, C₁~ C₆Alkylthio-C₁~ C₆Alkyl, acyloxy-C₁~ C₆A
Lucyl, halogen-C_Three~ C₆Cycloalkyl, C_Three~ C₆Cycloalkyl-C ₁ ~ C₆Alkyl, halogen-C_Three~ C₆Cycloalkyl-C₁~ C₆Alkyl
, Aryloxy-C₁~ C₆Alkyl, or phenyl, benzyl, phenoxy
Or aryloxy-C₁~ C₆Alkyl (halogen, nitro, cyano,
C₁~ C_FourAlkyl, halogen-C₁~ C_FourAlkyl and halogen-C₁~ C _Four Substituted with one to three substituents selected from the group consisting of alkoxy)
Yes, R_7bIs H, C₁~ C₈Alkyl, C_Two~ C₈Alkenyl or halo-C₁~ C ₈ Alkyl, halo-C_Two~ C₈Alkenyl, C₁~ C₈Alkoxy, halo-C₁ ~ C₈Alkoxy, C_Three~ C₆Cycloalkyl, phenyl, benzyl, phenoxy
Benzyloxy or -N (R₆)_Two(Where the two R₆Is German
R)₈Is C₁~ C₈Alkyl, C₁~ C₈Alkoxy, halogen-C₁~ C₈A
Lucyl, halogen-C₁~ C₈Alkoxy, C₁~ C₈Alkylthio, phenyl
, Benzyl or -N (R₆)_Two(Where the two radicals R₆Is German
R)₉Is C₁~ C₆Alkyl, halogen-C₁~ C_FourAlkyl or aryl (
Unsubstituted or C₁~ C₆Alkyl, C_Two~ C_FourAlkenyl, C_Two ~ C_FourAlkynyl, C₁~ C_FourAlkoxy, halogen, cyano, halogen-C₁ ~ C_FourAlkyl, halogen-C_Two~ C_FourAlkenyl, halogen-C_Two~ C_FourAl
Quinyl, halogen-C₁~ C_FourSelected from the group consisting of alkoxy and nitro
Are independently mono- to tri-substituted by substituents);_TenIs H, C₁~ C₆Alkyl, C_Three~ C₆Cycloalkyl, phenyl or
Benzyl (where the phenyl and benzyl radicals are unsubstituted
Or the aromatic ring is C₁~ C_FourAlkyl, C₁~ C_FourAlkoxy, halogen, silicon
Ano, halogen-C₁~ C_FourAlkyl, halogen-C₁~ C_FourAlkoxy and
Nitro independently substituted with one to three substituents selected from the group consisting of nitro)
Yes, R₁₁And R₁₂Are independently H, C₁~ C₆Alkyl, phenyl, -COC ₁ ~ C₆Alkyl, -COC₁~ C₆A haloalkyl, -COphenyl or
Or together with a 5- or 6-membered saturated or unsaturated ring (where
If appropriate, one or more, in particular one CH-group or CH_TwoThe group is O,
Substituted by a heteroatom selected from the group consisting of N and S,
In such a case, the 5- or 6-membered ring may be halogen, C₁~ C_FourAlkyl, C₁~ C _Four Haloalkyl, C₁~ C_FourHaloalkoxy, NO_TwoAnd the group consisting of CN
Selected from 1 to 3 substituents independently of each other) or
Or the two substituents R₁₁And R₁₂Is a ring togetherQ is 2 or 3 and R₁₃Is H, C₁~ C₆Alkyl, C_Two~ C₆Alkenyl, C_Two~ C₆Alkini
And R₁₄Is hydrogen, C₁~ C₆Alkyl, halogen-C_Three~ C₆Alkyl, C₁~ C ₆ Alkoxy, halogen-C₁~ C₆Alkoxy, C_Two~ C₆Alkenyloxy
, -CHO, -C (= O) -C₁~ C₆Alkyl, -C (= O) -halogen-C ₁ ~ C₆Alkyl, -C (= O) -OC₁~ C₆Alkyl, -C (= O) -O-
Halogen-C₁~ C₆Alkyl, -CN, -NO_Two, -S (= O)_TwoN (R₆) _Two (Where the two substituents R₆Are independent of each other), -S (= O)_p-C ₁ ~ C₆Alkyl, -S (= O)_p-Halogen-C₁~ C₆Alkyl, -OS
(= O)_pC₁~ C₆Alkyl, -OS (= O)_pHalogen-C₁~ C₆Al
Kill, phenyl, benzyl, or benzyloxy (where the phenyl, benzyl,
Each of the benzyl or benzyloxy substituents is unsubstituted or aromatic.
The aromatic ring is halogen, cyano, NO_Two, C₁~ C₆Alkyl, halogen-C₁~ C ₆ Alkyl, C₁~ C₆Alkoxy and halogen-C₁~ C₆From alkoxy
Which are independently mono- to penta-substituted by a substituent selected from the group consisting of
R₁₅Is hydrogen, C₁~ C₆Alkyl or halogen-C₁~ C₆Is alkyl
Compounds and, where appropriate, E / Z isomers of the compounds, and mixtures of E / Z isomers
And / or tautomers (in each case in free form or
In the form of salts), the active ingredients from these compounds, E / Z isomers and tautomers
Pesticides are chosen. 2. The compound of formula (I) according to claim 1, which is in free form. 3. A compound of formula (I) according to claim 1, wherein A ₁ and A ₂ are phenyl.
). 4. R_2aIs -C₁~ C₆Alkyl-NR₁₁R₁₂, -COC₉~ C ₂₀ Alkyl, -C₁~ C₆Alkyl-OC₁~ C₆Alkyl-OC₁~ C₆ Alkyl, -CH_TwoO (C = O) C₁~ C₆Alkyl, -CH_TwoO (C = O) C _Two ~ C₆Alkenyl, -CH_TwoO (C = O) C_Two~ C₆Alkynyl, -C (= S
) OC_Two~ C₆Alkenyl, -C (= S) OC_Two~ C₆Alkynyl, -C (= S
) SC₁~ C₆Alkyl, -C (= S) SC_Two~ C₆Alkenyl, -C (= S)
SC_Two~ C₆Alkynyl, -C (= O) SC₁~ C₆Alkyl, -C (= O) S
C_Two~ C₆Alkenyl, -C (= O) SC_Two~ C₆Alkynyl, -C (= S) N
R₁₁R₁₂, -C (= O) NR_TenOR₁₃, -CH_TwoOC_Two~ C₆Alkenyl, -C
H_TwoOC_Two~ C₆Alkynyl, -CH_TwoOC_Two~ C₆Haloalkenyl or -C
H_TwoOC_Two~ C₆4. A compound of formula (I) according to claims 1 to 3, which is a haloalkynyl.
object. 5. n1 is 2, 3 or 4, and n2 is 1 or 2.
5. A compound of formula (I) according to claims 1-4. 6. At least one compound of formula (I) according to claim 1 as active ingredient, either in free or pesticidally acceptable form, and at least one compound of formula (I). A pesticidal composition comprising an adjuvant. 7. A method for controlling pests, comprising applying the composition according to claim 6 to pests or habitats thereof. 8. A method for controlling insects and members belonging to the order Acarina according to claim 7.
The method described in. 9. A method for preparing a composition according to claim 6, comprising at least one adjuvant and comprising homogeneously mixing and / or grinding the adjuvant and the active ingredient. 10. Use of a compound of formula (I) according to claim 1, in free or pesticidally acceptable form, for preparing a composition according to claim 6. . 11. Use of the composition according to claim 6, for controlling pests. 12. Use according to claim 11, for protecting plant propagation material. 13. The method according to claim 7, for protecting a plant propagation material, comprising treating a plant propagation material or a cultivation area of the plant propagation material. 14. A plant propagation material treated according to the method of claim 13.