KR20010012997A - O-Benzyl oxime ether derivatives and their use as pesticides - Google Patents

Abstract

Applicable herein are compounds of Formula I; Methods of preparation thereof and uses thereof; Pesticides in which the active ingredient is selected from the above compounds; Methods of making such compositions and uses thereof; Intermediates for preparing such compounds; And methods of making such intermediates and uses thereof.

Formula I

In the above formula,

X is CH or N, Y is OR ₁ , Z is O,

X is N, Y is NHR ₈ and Z is O, S or S (= 0);

R ₁ is C ₁ -C ₄ alkyl;

R ₂ is C ₂ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl;

R ₃ and R ₄ are each independently of one another, for example H, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy;

R ₈ is H or C ₁ -C ₄ alkyl;

R ₉ is methyl, fluoromethyl or difluoromethyl;

A is a direct bond, C ₁ -C ₁₀ alkylene, -C (= O)-, -C (= S)-or halo-C ₁ -C ₁₀ alkylene, R ₇ is a radical R _10, or

A is C ₁ -C ₁₀ alkylene, -C (= O)-, -C (= S)-or halo-C ₁ -C ₁₀ alkylene, R ₇ is -CN, OR ₁₀ , N (R ₁₀ ) ₂ or -S (= 0) _p R ₁₀ ;

p is 0, 1 or 2;

G is O, S or -O-CH _2- ;

R ₅ and R ₆ are each in particular unsubstituted or substituted C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulphi Nil, C ₁ -C ₆ alkylsulfonyl or C ₁ -C ₆ alkylsulfonyloxy;

R ₁₀ is H or, for example, unsubstituted or substituted C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl or C ₃ -C ₆ cycloalkyl.

Description

O-benzyl oxime ether derivatives and their use as pesticides

The present invention provides in each case the compounds of the general formula (I) in free or salt form, and optionally possible E / Z isomers, mixtures of E / Z isomers and / or tautomers; Methods for their preparation and the use of these compounds, E / Z isomers and tautomers; Insecticides wherein the active ingredient is selected from the above compounds, E / Z isomers and tautomers; Methods of making these compositions and uses thereof; Intermediates, and optionally, its possible E / Z isomers, mixtures of E / Z isomers and / or tautomers, optionally in the free form or salts thereof, for the preparation of these compounds Tautomers in the form; And methods of preparing these intermediates and their tautomers and uses thereof.

In the above formula,

X is CH or N, Y is OR ₁ , Z is O,

X is N, Y is NHR ₈ and Z is O, S or S (= 0);

R ₁ is C ₁ -C ₄ alkyl;

R ₂ is C ₂ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl;

R ₃ and R ₄ are each independently of each other H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, OH, CN, NO ₂ , (C ₁ -C ₄ alkyl) ₃ -Si group, wherein the alkyl group Is the same or different), halogen, (C ₁ -C ₄ alkyl) S (═O) _m , (halo-C ₁ -C ₄ alkyl) S (═O) _m , halo-C ₁ -C ₄ alkyl or Halo-C ₁ -C ₄ alkoxy;

R ₈ is H or C ₁ -C ₄ alkyl;

R ₉ is methyl, fluoromethyl or difluoromethyl;

m is 0, 1 or 2;

A is a direct bond, C ₁ -C ₁₀ alkylene, -C (= O)-, -C (= S)-or halo-C ₁ -C ₁₀ alkylene, R ₇ is a radical R _10, or

A is C ₁ -C ₁₀ alkylene, -C (= O)-, -C (= S)-or halo-C ₁ -C ₁₀ alkylene, R ₇ is -CN, OR ₁₀ , N (R ₁₀ ) ₂ (wherein radicals R ₁₀ are the same or different), or —S (═O) _p R ₁₀ ;

p is 0, 1 or 2;

G is O, S or —O—CH ₂ —, where the —CH ₂ group is bonded to a ring designated by K;

R ₅ and R ₆ are C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, 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, halo-C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, halo-C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkyl Sulfonyl, 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, halo-C ₁ -C ₆ alkylsulfinyl-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylsulfonyl-C ₁ -C ₆ alkyl, halo- C ₁ -C ₆ alkylsulfonyl-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylcarbonyl, halo-C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, halo-C _1- C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylaminocarbonyl, C ₁ -C ₆ alkoxyiminomethyl, di (C ₁ -C ₆ alkyl) aminocarbonyl, wherein Alkyl groups are the same or different), C ₁ -C ₆ alkylaminothiocarbonyl, di (C ₁ -C ₆ alkyl) aminothiocarbonyl, wherein the alkyl groups are the same or different, C ₁ -C ₆ Alkylamino, di (C ₁ -C ₆ alkyl) amino (where alkyl groups are the same or different), halogen, NO ₂ , CN, thioamido, trimethylsilyl, CH ₂ Si (C ₁ -C ₄ alkyl) ₃ wherein the alkyl group is the same or different, an unsubstituted or mono- to tetrasubstituted C ₁ -C ₄ alkylenedioxy group wherein the substituent is selected from the group consisting of C ₁ -C ₄ alkyl and halogen ) Wherein when q is greater than 1 the radicals R ₅ are the same or different and when n is greater than 1 the radicals R ₆ are the same or different and the radicals R ₅ and R ₆ are independent of each other;

n is 0, 1, 2, 3, 4 or 5;

q is 0, 1, 2, 3 or 4;

R ₁₀ is mono-substituted each by a substituent selected from the group consisting of H, C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, or halogen Polysubstituted C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl or C ₃ -C ₆ cycloalkyl, or -Si (C ₁ -C ₄ alkyl) ₃ , wherein alkyl Groups are the same or different), C ₁ -C ₆ alkoxycarbonyl, mono-substituted or substituted by a substituent selected from the group consisting of unsubstituted or halogen, C ₁ -C ₄ alkyl and halo-C ₁ -C ₄ alkyl Substituted aryl or heterocyclyl group;

Provided that when R ₂ is ethyl, R ₁ , R ₈ and R ₉ are methyl, R ₃ and R ₄ are hydrogen, q is 0, Z is oxygen and AR ₇ is methyl, group -G -Phenyl is not 3-trifluoromethylbenzyloxy, 4-fluorobenzyloxy or 4-fluorophenoxy at the 4-position, respectively.

In the literature of the art, numerous methoxyacrylic acid derivatives have been proposed as active ingredients of pesticides. However, the biological properties of these known compounds are not sufficiently satisfactory in the field of pest eradication, and therefore, additional compounds having pesticidal properties for eradicating representative insects of the species Aarina, in particular for the eradication of phytopathogenic microorganisms, Need to provide This problem is solved by the present invention by providing a compound of formula (I) of the present invention.

Many of the compounds of formula (I), and the compounds of formulas (III), (IV), (VI), (VII) and (VII) described below contain asymmetric carbon atoms, and as a result, such compounds can be produced in optically active form. Because C = X and oximino double bonds are present, the compounds can be produced in E and Z isomeric forms. Atropisomers of the compounds may also be produced. Although they are not specifically mentioned each time in the compounds of the formulas (I), (III), (IV), (VI) and (X) to XIII, all possible isomeric forms thereof and also mixtures thereof, for example racemates or E / Z isomers Mixtures, and optionally salts thereof. In the compounds of the formulas I, III, IV, VI, XII and XIII, the E-isomers indicate that E in each formula is preferred.

Unless otherwise stated, general terms used herein have the following meanings.

The carbon containing groups and compounds each contain 1 to 8, in particular 1 to 6, more particularly 1 to 4, very particularly 1 or 2 carbon atoms.

Alkyl as its own group and also other groups and compounds, such as haloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkylamino, alkoxyiminomethyl, alkylaminocarbo Alkyl and alkylaminothiocarbonyl as alkyl units in each case are linear, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, in each case, taking into account the number of carbon atoms contained in these groups or compounds. For example, isopropyl, isobutyl, secondary-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

Alkenyl as its own group and also other groups and compounds, such as alkenyl as structural units of haloalkenyl, in each case, taking into account the number of carbon atoms contained in these groups or compounds, For example, vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or side chains such as isopropenyl.

Alkynyl as its own group and also other groups and compounds, for example alkynyl as the structural unit of haloalkynyl, in each case taking into account the number of carbon atoms contained in these groups or compounds, For example, propargyl, 2-butynyl or 5-hexynyl, or side chains such as 2-ethynylpropyl or 2-propargylisopropyl.

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

Alkylene as its own group and also other groups and compounds, for example alkylene as structural units of haloalkylene, in each case taking into account the number of carbon atoms contained in these groups or compounds, is a straight chain, eg For example, —CH ₂ CH ₂ —, CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ CH ₂ —, or a side chain such as —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, in particular phenyl.

Heterocyclyl is a 5-7 membered aromatic or non-aromatic ring having 1-3 heteroatoms selected from the group consisting of N, O and S. Preference is given to aromatic five- and six-membered rings having one nitrogen atom as the hetero atom and optionally further hetero atoms, preferably nitrogen or sulfur, in particular nitrogen. Preferred heteroaryl radicals are pyrazinyl, 3'-pyridyl, 2'-pyridyl, 4'-pyridyl, 2'-pyrimidinyl, 4'-pyrimidinyl, 5'-pyrimidinyl, 2'- Thiazolyl, 2'-oxazolyl, 2'-furanyl, 3'-furanyl, 3'-tetrahydrofuranyl, 2'-thienyl, 3'-thienyl and 2'-thiazolyl.

Halogen as its own group and also as the structural unit of other groups and compounds, for example haloalkyl, haloalkenyl and haloalkynyl, is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, more particularly fluorine Or chlorine, very particularly fluorine.

Halo-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkenyl or haloalkynyl, may be partially halogenated or overhalogenated, and in the case of multi-halogenation, the halogen substituents may be the same or different. Examples of haloalkyl as its own group and also haloalkyl as structural units of other groups and compounds, for example haloalkenyl, are mono- or tri-substituted methyl, for example, fluorine, chlorine and / or bromine CHF ₂ or CF ₃ ; Ethyl monosubstituted or substituted by fluorine, chlorine and / or bromine, for example, 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; Propyl or isopropyl mono-substituted or substituted by fluorine, chlorine and / or bromine, respectively, for example CH ₂ CHBrCH ₂ Br, CF ₂ CHFCF ₃ , CH ₂ CF ₂ CF ₃ or CH (CF ₃ ) ₂ ; And butyl or isomers thereof, such as mono (substituted or substituted), for example, CF (CF ₃ ) CHFCF ₃ or CH ₂ (CF ₂ ) ₂ CF ₃ , respectively, substituted by fluorine, chlorine and / or bromine. Haloalkenyl is, for example, CH ₂ CH = CHCl, CH ₂ CH = CCl ₂ , CH ₂ CF = CF ₂ or CH ₂ CH = CHCH ₂ Br. Haloalkynyl is, for example, CH ₂ C≡CF, CH ₂ C≡CCH ₂ Cl or CF ₂ CF ₂ C≡CCH ₂ F.

Many of the compounds of formula (I), and the compounds of formulas (III), (IV), (VI), (X) and (XIII) to be described below, are known to those skilled in the art, for example, tautomers when AR ₇ is H. May exist in the form of It is to be appreciated that the compounds of the formulas (I), (III), (IV), (VI), (X) and (XIII) mentioned herein include the corresponding tautomers, although not specifically mentioned in each case.

Compounds of formula (I) having one or more basic centers, and the compounds of formulas (III), (IV), (VI), (X) and (XIII) to (X) described below, may form acid addition salts, for example. Such salts include, for example, strong inorganic acids such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acid; Unsubstituted or substituted, for example, halo-substituted C ₁ -C ₄ alkanecarboxylic acids (eg acetic acid), saturated or unsaturated dicarboxylic acids (eg oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid) Strong organic carboxylic acids such as hydroxycarboxylic acid (eg, ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid) or benzoic acid; Or organic sulfonic acids such as unsubstituted or substituted, for example, halo-substituted C ₁ -C ₄ alkane- or aryl-sulfonic acids (eg methane or p-toluene-sulfonic acid). Moreover, compounds of formula (I) having one or more acid groups can form salts with bases. Suitable salts with bases include, for example, metal salts such as alkali metal or alkaline earth metal salts such as sodium, potassium or magnesium salts; Or ammonia or organic amines such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines such as ethyl-, diethyl-, triethyl- or dimethyl-propyl- Amines) or salts with mono-, di- or tri-hydroxy-lower alkylamines such as mono-, di- or tri-ethanolamines. It is also possible to form the corresponding internal salts. Within the present invention, agrochemically advantageous salts are preferred, but salts which are used for the separation and / or purification of the free compounds of formula (I) or agrochemically acceptable salts thereof are undesirable for agrochemical applications. It should be recognized herein that the free compound of formula (I) also includes the corresponding salt of formula (I), and that the salts of the compound of formula (I) also include the corresponding free compound of formula (I). The same applies to the tautomers of the compounds of the formulas (I), (III), (IV), (VI), and (VII) to (XIII) and salts thereof. In each case, the glass form is generally preferred.

In each case, taking into account the above-mentioned clues, preferred embodiments within the present invention are as follows:

(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 Y is C 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 ethyl, propyl, butyl, isopropyl, isobutyl, secondary-butyl or tert-butyl, in particular ethyl or propyl, more particularly ethyl;

(6) R ₃ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, OH, CN, NO ₂ , halogen, halo-C ₁ -C ₄ alkyl or halo-C ₁ -C ₄ alkoxy, preferably Preferably a compound of formula (I) which is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen, in particular H, methyl, methoxy, chlorine or fluorine, more particularly H;

(7) R ₄ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, OH, CN, NO ₂ , halogen, halo-C ₁ -C ₄ alkyl or halo-C ₁ -C ₄ alkoxy, preferably Preferably a compound of formula (I) which is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen, in particular H, methyl, methoxy, chlorine or fluorine, more particularly H;

(8) a compound of formula I wherein R ₈ is H or C ₁ -C ₂ alkyl, preferably C ₁ -C ₂ alkyl, especially methyl;

(9) a compound of formula I wherein R ₉ is methyl or fluoromethyl, preferably methyl;

(10) R ₆ is halogen, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, halo-C ₃ -C ₆ cycloalkyl Or CH ₂ Si (CH ₃ ) ₃ , in particular halogen, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkoxy and halo-C ₁ -C ₄ alkyl, in particular halogen, C ₁ -C ₄ alkyl, halomethyl Or halomethoxy, more particularly chlorine, trifluoromethyl, trifluoromethoxy or tert-butyl;

(11) a compound of formula I wherein n is 1 or 2, preferably 1;

(12) a compound of Formula I wherein G is O or -O-CH _2- , in particular O;

(13) R ₅ is halogen, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, halo-C ₃ -C ₆ cycloalkyl Or CH ₂ Si (CH ₃ ) ₃ and q is 0, 1, 2 or 3, preferably 0, 1 or 2, in particular 0 or 1, more particularly 0;

(14) 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, in particular a direct bond or methylene ;

(15) a compound of formula I wherein A is a direct bond and R ₇ is C ₁ -C ₄ alkyl, CH ₂ -CH═CH ₂ or CH ₂ -C≡CH, in particular methyl or ethyl, more particularly ethyl;

(16) X is N, Y is OCH ₃ , Z is O, R ₂ is ethyl, R ₃ and R ₄ are H, AR ₇ is ethyl, G is O, q is 0 and n Is 1 and R ₆ is CF ₃ .

Particularly preferred within the present invention are the compounds of formula (I) shown in Tables 1 to 4, and optionally mixtures of E / Z and E / Z isomers thereof.

The present invention

a1) reacting a compound of formula (II), which may be known or prepared according to a method known per se, with a compound of formula (III), preferably in the presence of a base;

a2) reacting a compound of formula IV with a compound of formula V, optionally in the presence of a base, which may be prepared according to known or per se known methods;

a3) reacting a compound of formula VI with a compound of formula VII;

b) A compound of formula R ₈ NH ₂ , wherein a compound of formula I wherein Y is OR ₁ , can be prepared according to known or self-known methods to prepare a compound of formula I wherein Y is NHR ₈ and Z is O Or wherein R ₈ is as defined for Formula I;

c) To prepare a compound of formula I wherein Y is NHR ₈ and Z is S, a compound of formula I wherein Y is R ₈ NH ₂ and Z is O is selected from P ₄ S ₁₀ or a lotion reagent [2,4-bis; -(Methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide];

d) reacting a compound of formula I, wherein Z is S, with an oxidizing agent to prepare a compound of formula I, wherein Z is SO,

In each case, if necessary, in each case in the form of free or salt, a compound of formula (I) or an E / Z isomer or tautomer thereof, which can be obtained according to said process or by a different method, in each case To a different compound of formula (I) or an E / Z isomer or tautomer thereof in free or salt form; A free compound of formula (I) or an E / Z isomer thereof which separates a mixture of E / Z isomers which can be obtained according to the above process and isolating the desired isomer and / or which can be obtained according to the above process or by different methods Or converting the tautomer to a salt; The salts of the compounds of formula (I) or E / Z isomers or tautomers thereof, which may be obtained according to the above processes or by different methods, are converted into the free compounds of formula (I) or E / Z isomers or tautomers thereof, or different salts. Including n, q, A, G, X, Y, Z, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₉ , including conversion, are as defined for Formula I above and The proviso provisions mentioned for compounds of formula (I) apply, in each case in free or salt form, the compounds of formula (I), and optionally the E / Z isomers, mixtures of E / Z isomers and / or earth It relates to a method for producing an automer.

X ₁ -AR ₇

In the above formula,

n, q, A, G, X, Y, Z, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₉ are as defined for Formula I above and mentioned for Formula I above Clues provisions apply,

X ₁ is a leaving group.

In addition, the present invention

e) n, q, A, G, R ₂ , R ₅ , R ₆ and R ₇ react a compound of formula IV as defined in formula I with H ₂ NOH or a salt thereof, optionally in the presence of a base;

f) reacting a compound of formula (VII) with a compound of formula (VII), optionally in the presence of a base, which may be prepared according to known or per se known methods,

In each case, if desired, in each case a compound of formula III or an E / Z isomer or tautomer thereof, which can be obtained according to the process or by a different method, in free or salt form, in each case To a different compound of Formula III or an E / Z isomer or tautomer thereof in free or salt form; A free compound of formula (III) or an E / Z isomer thereof which separates a mixture of E / Z isomers obtainable according to the above process and isolating the desired isomer and / or which can be obtained according to the above process or by a different method. Or converting the tautomer to a salt; A salt of a compound of formula III or an E / Z isomer or tautomer thereof, which may be obtained according to the above process or by a different method, may be converted into a free compound of formula III or an E / Z isomer or tautomer thereof, or a different salt To a process for the preparation of the compound of formula III in each case in free or salt form, including the conversion.

R ₇ AONH ₂

In the above formula,

n, q, G, A, R ₂ , R ₅ , R ₆ and R ₇ are as defined in formula (I).

In addition, the present invention

g) a process for preparing a compound of formula (VI) in each case in free or salt form, including reacting a compound of formula (X) with hydroxylamine.

In the above formula,

n, q, G, X, Y, Z, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₉ are as defined in formula (I).

In addition, the present invention

h) a process for preparing a compound of formula (VII) in each case in free or salt form, including reacting a compound of formula (VII) with a compound of formula (II).

In addition, the present invention

i) a process for preparing a compound of formula (VII) in each case in free or salt form, including reacting a compound of formula (XI) with nitrite, which may be known or prepared according to a method known per se:

In the above formula,

n, q, G, R ₂ , R ₅ and R ₆ are as defined in formula (I).

The invention also relates to novel intermediates of the following formulas (XII) and (XIII) and to processes for the preparation of compounds of the formulas (III), (II) and (XIII) known per se.

k) (XII) + alkylnitrite

―― ＞ (XIII)

l) (XIII) + (VII)-> (IV)

m) (IV) + hydroxylamine-> (III)

In the compounds of the formulas XII and XIII,

R ₂ , R ₅ , R ₆ , R ₇ , A, G, q and n are as defined in formula (I).

The above discussion of the E / Z isomers and tautomers of the compounds of formulas (I) and (III) similarly applies to the E / Z isomers and tautomers of the starting materials mentioned herein.

The reactions described herein are carried out in the manner known per se, for example in the absence or conventional presence of suitable solvents or diluents, or mixtures thereof, wherein the reaction is carried out at room temperature or, for example, with cooling, if necessary, The heating is carried out at a temperature of from about 0 ° C. to the boiling point of the reaction medium, preferably from about 20 to about + 120 ° C., in particular from 60 to 80 ° C. Particularly advantageous reaction conditions are given in this example.

The reactants can react with each other by themselves, ie without addition of solvents or diluents, for example in molten form. In general, however, it is advantageous to add inert solvents or diluents or mixtures thereof.

The reaction is carried out, if necessary, in a closed vessel under pressure and a protective gas atmosphere, for example under nitrogen or argon, in particular under nitrogen and / or anhydrous conditions, in particular under an inert gas atmosphere and atmospheric pressure.

The product is usually separated by conventional methods such as filtration, crystallization, distillation or chromatography, or by appropriate combination of these methods.

The starting materials described herein used to prepare the compounds of formula (I), and optionally their E / Z isomers and tautomers, may be prepared according to known or self-known methods, for example the methods described below in detail below. Can be.

Processes a1) / a2) / a3) and h):

Suitable leaving groups X ₁ in compounds II and VII are, for example, 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, halo-C ₁ -C ₈ alkanesulfonyloxy, benzenesulfonyloxy, toluene-sulfonyloxy and halogen , Preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy and halogen, in particular halogen.

Suitable bases for promoting the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, unsubstituted or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples thereof include sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium acetate and sodium carbonate, potassium tert-butanolate, potassium hydroxide, potassium carbonate and potassium hydride, lithium diisopropylamide, potassium bis (trimethylsilyl ) Amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N , N-dimethylamino) pyridine, quinuclidin, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diaza-bicyclo [5.4.0] undec-5-ene (DBU) may be mentioned Can be.

Examples of solvents useful for carrying out the reaction are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, for example benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene Petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; Esters such as ethyl acetate; Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydi Ethyl ether, tetrahydrofuran and dioxane; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol; Amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and hexamethylphosphate triamide; Nitriles such as acetonitrile and propionitrile; And sulfoxides such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, the base used in excess, for example triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline may act as a solvent or diluent.

It is advantageous to carry out the reaction in a temperature range of about 0 to about 180 ° C., in particular about 10 to about 80 ° C., in many cases at room temperature to the reflux temperature of the reaction mixture. It is preferred that the reaction time is from about 0.1 to about 24 hours, in particular from about 0.5 to about 2 hours.

In a preferred embodiment of step a1), compound II is metal hydride, preferably hydrogenated, in an inert solvent, preferably amide, especially N, N-dimethylformamide, at 0-80 ° C, preferably 10-30 ° C. React with compound III in the presence of sodium.

Particularly preferred conditions for the reaction are described in Examples P1e) and P1f).

Process b):

Examples of solvents or diluents useful for carrying out the reaction include those mentioned in processes a1) / a2) / a3) and h).

It is advantageous to carry out the reaction in a temperature range of about 0 to about 180 ° C., in particular about 10 to about 80 ° C., in many cases at room temperature to the reflux temperature of the reaction mixture. It is preferred that the reaction time is from about 0.1 to about 24 hours, in particular from about 0.5 to about 2 hours.

Particularly preferred conditions for the reaction are described in Example P1g).

Process c):

Examples of solvents or diluents useful for carrying out the reaction are: aromatic, aliphatic and cycloaliphatic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bro Parent benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydi Ethyl ether, tetrahydrofuran and dioxane; And sulfoxides such as dimethyl sulfoxide.

It is advantageous to carry out the reaction in a temperature range of about 0 to about + 120 ° C, in particular about 80 to about + 120 ° C. It is preferred that the reaction time is from about 0.1 to about 24 hours, in particular from about 0.5 to about 2 hours.

Process d):

Suitable oxidizing agents include, for example, inorganic peroxides such as sodium perborate or hydrogen peroxide; Organic peracids such as perbenzoic acid or peracetic acid; Or mixtures of organic acids and hydrogen peroxide, for example acetic acid / hydrogen peroxide.

Examples of solvents or diluents useful for carrying out the reaction are: aromatic, aliphatic and cycloaliphatic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bro Parent benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; Esters such as ethyl acetate; Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydi Ethyl ether, tetrahydrofuran and dioxane; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Alcohols such as methanol, ethanol and propanol; Amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and hexamethylphosphate triamide; Nitriles such as acetonitrile and propionitrile; And sulfoxides such as dimethyl sulfoxide. If the reaction is carried out in the presence of an organic acid or peracid, the acid used in excess, for example a strong organic carboxylic acid, for example an unsubstituted or substituted (eg halo-substituted) C ₁ -C ₄ alkane carboxylic acid For example, formic acid, acetic acid or propionic acid may act as a solvent or diluent.

It is advantageous to carry out the reaction in a temperature range of about 0 to about +120 ° C, in particular about 0 to about +40 ° C. It is preferred that the reaction time is from about 0.1 to about 24 hours, in particular from about 0.5 to about 2 hours.

Process e) / g):

Suitable bases for catalyzing the reaction are, for example, those mentioned in the processes a1) / a2) / a3) / h). Examples of solvents or diluents useful for carrying out the reaction include those mentioned in processes a1) / a2) / a3) / h).

It is advantageous to carry out the reaction in a temperature range of about 0 to about 180 ° C., in particular about 10 to about 80 ° C., in many cases at room temperature to the reflux temperature of the reaction mixture. It is preferred that the reaction time is from about 0.1 to about 24 hours, in particular from about 0.5 to about 2 hours.

Process f):

Suitable bases for catalyzing the reaction are, for example, those mentioned in the processes a1) / a2) / a3) / h). Examples of solvents or diluents useful for carrying out the reaction include those mentioned in processes a1) / a2).

It is advantageous to carry out the reaction in a temperature range of about 0 to about 180 ° C., in particular about 10 to about 80 ° C., in many cases at room temperature to the reflux temperature of the reaction mixture. It is preferred that the reaction time is from about 0.1 to about 24 hours, in particular from about 0.5 to about 2 hours.

In a preferred embodiment of step f), the compound of formula (VII) is reacted with the compound of formula (VII) in an inert solvent, preferably an amine, in particular pyridine, at 0 to 120 ° C, preferably 60 to 120 ° C. Particularly preferred conditions for the reaction are described in Example P1d).

Process i):

Suitable reactants are especially alkyl nitrites, preferably isopentyl nitrite.

Acids suitable for catalyzing the reaction are, for example, hydrochloric acid and nitric acid, in particular gaseous hydrogen chloride.

Suitable solvents are those mentioned in process d), in particular ethers such as diethyl ether, di-n-butyl ether and methyl isobutyl ether; Or alcohols such as ethanol and methanol.

It is advantageous to carry out the reaction at a temperature range of about 0 to about 180 ° C., preferably about 0 to 80 ° C., in particular at room temperature. It is preferred that the reaction time is from about 0.1 to about 24 hours, in particular from about 0.5 to about 2 hours.

Particularly preferred conditions for the reaction are described in Example P1c).

The compounds of the formulas (I) to (XIII) are purely in isomeric form (eg, colon and / or depending on the form of one of the possible isomers or mixtures thereof, for example the number of asymmetric carbon atoms and their absolute and relative coordination thereof). Diastereoisomers) or mixtures of isomers, for example, mixtures of enantiomers (such as racemates), mixtures of diastereomers or mixtures of racemates; The present invention therefore relates to both pure isomers and mixtures of all possible isomers, so it should be recognized that all of these are referred to herein, although the stereochemical description is not specifically mentioned in each case.

Mixtures of diastereoisomers of the compounds of formulas (I), (III), (IV), (VI), (VIII) and (XIII) to (XIII) and (C) of racemates which can be obtained according to the selected starting materials and processes On the basis of chemical differences it can be partitioned into pure diastereomers or racemates by known methods, for example fractional crystallization, distillation and / or chromatography.

Mixtures of enantiomers, such as racemates, which can be obtained thereby are recrystallized from known methods, such as optically active solvents, or chromatographed on chiral adsorbents, for example, with the aid of a suitable microorganism, acetyl cellulose. By means of high pressure liquid chromatography on the phase or by cleavage with a specific immobilizing enzyme (for example, only one enantiomer is complexed), for example, via the formation of inclusion compounds using chiral crown ethers. Can be split

Apart from the partitioning of the mixture of the corresponding isomers, according to the invention, generally known diastereoselective or enantioselective synthesis methods are employed, for example the processes according to the invention using starting materials with suitable stereochemistry. By doing this, pure diastereomers or enantiomers can be obtained.

As long as the individual components have different biological activities, it is advantageous to isolate or synthesize biologically more active isomers such as enantiomers or mixtures of isomers such as enantiomers.

Compounds of Formulas (I), (III), (IV), (VI), (VII) and (XIII) to (XIII) also include those which can be obtained in the form of their hydrates and / or can be used to crystallize the compound in solid form. can do.

The present invention utilizes compounds which can be obtained as starting materials or intermediates at any stage of the process as starting materials and performs all or part of the remaining steps, or the starting materials are derived from derivatives or salts and / or racemates or colones thereof. It relates to all embodiments of the process used in the form or formed especially under the reaction conditions.

In the process of the invention, preference is given to using starting materials and intermediates which give rise to the compounds of general formula (I) described earlier as particularly preferred.

The invention particularly relates to the production process described in Examples P1a) to g).

The invention also relates to the starting materials and intermediates used according to the invention in the preparation of the compounds of the formula (I), in particular the compounds of the formulas (III), (IV), (VI) and (VII) to (XIII), their use and methods for their preparation. It is about. Preferred meanings of R ₂ , R ₅ , R ₆ , R ₇ , A, G, q and n in these compounds of Formulas III, IV, VI, VIII and XIII are as defined in the compounds of Formula I. In particular, the compounds of the formulas (III) and (VII) can be prepared analogously to Examples P1d) and P1c), respectively.

In the field of pest control, warm-blooded animals, fish and plants are useful protective and / or therapeutically active ingredients, although the compounds of formula (I) according to the invention have a very favorable bactericidal spectrum even at low concentrations. The compounds of the invention are effective against normally sensitive animal pests as well as resistant animal pests such as insects and representative pests of Acarina throat, and all or individual developmental stages of phytopathogenic fungi. Insecticidal, scattering and / or mite parasitic action of the compounds of the invention may be, for example, indirectly, either immediately or after a short time during stripping, ie killing pests or their eggs, or lowering egg laying or hatching rates. It can be shown in a phosphorous manner, and excellent activity corresponds to a mortality rate of 50 to 60% or more.

The animal pests mentioned are, for example, those described in EP-A-736 252. Pests mentioned in EP-A-736 252 are incorporated herein by reference.

Phytopathogenic fungi mentioned are, for example:

Fungi imperfecti rivers such as Botrytis species, Pyricularia species, Helminthosporium species, Fusarium species, Septoria ), Cercospora and Alternaria species; Basidiomycetes river, such as, for example, Rhizoctonia species, Hemileia species, and Puccinia species; Ascomycetes rivers such as the Venturia species, the Erysiphe species, the Podosphaera species, the Monilinia species, and the Uncinula species ; And Oomycetes rivers such as Phytophthora species, Pythium species and Plasmopara species.

Using the compounds according to the invention, they are produced on plants, more particularly on plants and ornamental plants useful for agriculture, horticulture and forestry, or on parts of such plants, for example fruits, flowers, leaves, stems, tubers or roots. Pests of the above-mentioned types can be controlled, ie inhibited or eliminated, and parts of plants which are grown later are also protected against these pests.

Target crops are in particular cereals such as wheat, barley, rye, oats, rice, corn and sorghum; Beet, for example beet and forage beet; Fruits such as pomes, nucleus and nectars such as apples, pears, plums, peaches, almonds, cherries or berry, such as strawberries, raspberries and blackberries; Leguminous plants, such as beans, migraine, peas and soybeans; Oil plants such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and peanuts; Gourds, zucchini, cucumbers and melons; Fiber plants such as cotton, flax, hemp and jute; Citrus plants such as oranges, lemons, grapes and mandarins; Vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes and peppers; Camphor plants such as avocados, cinnamon and camphor, and tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants as well as ornamental plants.

The compounds according to the invention are representative of insects in cotton, fruit, corn, soybean, rapeseed and vegetable crops and representative pests of Acarina neck, in particular plant-feeding insects such as Antonomomus grandis ( Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae and spiders, eg For example, it is particularly suitable for controlling Tetranychus species.

A further field of use of the compounds according to the invention is in the protection of stored goods and stocks and materials, and in the field of hygiene, especially in the protection of pets and livestock against pests of the above mentioned types.

Accordingly, the present invention relates to pesticides, such as emulsifiable thickeners, suspension thickeners, directly sprayable or dilutable solvents, coatable pastes, dilute emulsions, wettable powders, solubles comprising at least one compound of the present invention. It relates to powders, dispersible powders, wettable powders, dusts, granules or encapsulating agents in polymeric materials, and formulations of this type are selected according to the purpose and environment.

The active ingredients are used in these compositions in solid form, i.e. as solid active ingredients of a particular particle size, or are preferably auxiliaries customary in the formulation art, for example thickeners (such as solvents or solid carriers) or surfactant compounds ( Surfactants).

They act as formulation aids such as solid carriers, solvents, stabilizers, "sustained release" adjuvants, colorants and any surfactants (surfactants). All materials commonly used in plant protection compositions, in particular slug and snail control compositions, are considered carriers and auxiliaries. Suitable auxiliaries for the compositions used according to the invention, for example solvents, solid carriers, surfactant compounds, nonionic surfactants, cationic surfactants, anionic surfactants and other auxiliaries, for example EP-A The same material as described in -736 252. Said adjuvant mentioned in EP-A-736 252 is incorporated herein by reference.

The pest control composition may be formulated, for example, in the form of wettable powders, dusts, granules, solvents, emulsifiable concentrates, emulsions, suspension concentrates or aerosols. Such compositions are of the same type as described, for example, in EP-A-736 252.

The composition typically comprises 0.1 to 99% of the active ingredient, preferably 0.1 to 95% and 1 to 99.9%, preferably 5 to 99.9% of one or more solid or liquid auxiliaries, generally 0 to 9 of such compositions. 25%, preferably 0.1 to 20% may be a surfactant (in each case% is by weight). Commercially available products are preferably formulated as thickeners, while end users will usually use dilute formulations having substantially lower active ingredient concentrations. Preferred formulations are in particular the compositions described in EP-A-736 252, Examples F1 to F8.

The activity of the compositions according to the invention can be substantially expanded and adapted to the dominant environment by the addition of other pesticidal, mite parasitic and / or fungicidal active ingredients. Examples of suitable additional active ingredients include representatives of the following class of compounds: organophosphorus compounds, nitrophenol derivatives, formamidine, urea, benzoylurea, carbamate, pyrethroid, chlorinated hydrocarbons, neonicotinoids, macrolides And Bacillus thuringiensis preparations. The compositions according to the invention also contain further solid or liquid auxiliaries, for example stabilizers such as vegetable oils or epoxidized vegetable oils (eg epoxidized coconut oil, rapeseed oil or soybean oil), antifoaming agents. Silicone oils, preservatives, viscosity modifiers, binders and / or thickeners, as well as other active ingredients for obtaining fertilizers or special effects, such as fungicides, nematicides, molluscicides or Optional herbicides.

The compositions according to the invention are known, in the absence of an adjuvant, for example, by grinding and / or sieving a solid active ingredient or mixture of active ingredients, for example to a specific particle size, in the presence of one or more adjuvant, For example, the active ingredient or mixture of active ingredients is prepared by mixing and / or polishing well with the adjuvant (s). The invention also relates to a process for the preparation of the compositions according to the invention and to the use of the compounds of formula (I) in the preparation of these compositions.

The invention also provides a method of applying the composition, i.e. a method for controlling pests of the type mentioned, such as spraying, spraying, dusting, coating, dressing, spraying or injecting, selected according to the purpose and governing environment; And the use of such compositions for controlling pests of the type mentioned. Typical concentrations of the active ingredient are 0.1 to 1000 ppm, preferably 0.1 to 500 ppm. Application rates per hectare are generally 1 to 2000 g, in particular 10 to 1000 g / ha, preferably 20 to 600 g / ha, per hectare.

The preferred method of application in the field of plant protection is to apply to the leaves of the plant (leaf applications), the number of applications and the rate of application being determined according to the risk of transmission by the pest in question. However, if the site where the plant is located is impregnated in a liquid formulation or if the active ingredient is incorporated in the form of the plant where the plant is located in solid form, e. Can be penetrated into (full penetration action). In rice crops, such granules can be applied in metered quantities to paddy fields.

The compositions according to the invention are also suitable for protecting elements for plant growth, for example seeds or plant cuttings, such as fruits, tubers or grains, from fungal infections and animal pests. Such propagating urea can be treated with the formulation prior to drinking water, for example dressing before seeding. The compounds of the invention can also be applied to the kernels by coating them with liquid formulations or by coating them with solid formulations (coatings). The formulation can also be applied to the site of planting when the propagating element is planted, for example seed sulcus at sowing. The invention also relates to a method for treating urea for plant growth and to a plant growth component treated thereby.

The following examples are intended to illustrate the invention. These do not limit the invention. The temperature is ° C.

Manufacturing Example

Example P1:

(2- {2- [4- (3-trifluoromethylphenoxy) -phenyl] -2-ethoxyimino-1-ethyl-ethylidene-aminooxymethyl} -phenyl) -3-methoxy-acrylic acid Methyl Ester (Compound 1.1)

a) 1- (4-fluorophenyl) -butan-1-one

106.5 g of butyric acid chloride are added dropwise to a mixture of 180 g of 4-fluorobenzene and 147 g of aluminum chloride at 70 ° C. over 1 hour. The mixture is stirred at 80 ° C. for 45 minutes, cooled to room temperature and poured into a mixture of 1 liter of ice and 150 ml of concentrated HCl. Extract twice with 300 ml of diethyl ether and the combined organic extracts are washed with water and sodium chloride solution, dried over sodium sulphate and the solvent is removed by evaporation in vacuo. The resulting crude product is distilled off and purified to give the title product having a boiling point of 103 to 105 ° C. (15 mbar).

b) 1- [4- (3-trifluoromethylphenoxy) -phenyl] -butan-1-one

158.8 g of 1- (4-fluorophenyl) -butan-1-one are slowly added to a mixture of 154.2 g of 3-hydroxytrifluoromethylbenzene, 197 g of potassium carbonate and 1200 ml of N, N-dimethylacetamide at room temperature, The mixture is heated and then stirred at 180 ° C. for 10 hours. The mixture is then cooled to room temperature, filtered and the filtrate is concentrated by evaporation in vacuo. The residue is dissolved in diethyl ether and the organic phase is washed once with water, once with 10% potassium hydroxide solution and once with saturated sodium chloride solution, dried over sodium sulfate and concentrated by evaporation. The solid product is filtered off and dried under vacuum to afford the title compound having a melting point of 35 to 36 ° C.

c) 1- [4- (3-trifluoromethylphenoxy) -phenyl] -butane-1,2-dione-2-oxime

HCl gas was introduced in 1 liter of diethyl ether for 1 minute, followed by 277 g of 1- [4- (3-trifluoromethylphenoxy) -phenyl] -butan-1-one. 126.2 g of isopentyl nitrite is added dropwise to this mixture, the reaction mixture is stirred at room temperature for 5 hours, then HCl gas is introduced again for 1 minute, and the reaction mixture is left at room temperature for 14 hours. The reaction mixture is filtered and the filtrate is concentrated by evaporation in vacuo. The residue is slurried with hexane and filtered, and the filter residue is dried under vacuum to give the title compound having a melting point of 74 to 75 ° C.

d) 1- [4- (3-trifluoromethylphenoxy) -phenyl] -butane-1,2-dione-1- [ethyloxime] -2-oxime

A mixture of 70 g of 1- [4- (3-trifluoromethylphenoxy) -phenyl] -butane-1,2-dione-2-oxime and 21.3 g of O-ethylhydroxylamine hydrochloride in 250 ml of pyridine was refluxed. Boil for 1 hour. Once cooled, the reaction mixture is dissolved in 500 ml of ethyl acetate and the organic phase is washed once with water, once with 10% HCl solution and once with saturated sodium chloride solution, dried over sodium sulphate and then evaporated to concentrate. The crude product is recrystallized from n-hexane. The title compound is obtained which has a melting point of 122 to 124 ° C.

e) (2- {2- [4- (3-trifluoromethylphenoxy) -phenyl] -2-ethoxyimino-1-ethyl-ethylidene-aminooxymethyl} -phenyl) -3-methoxy Acrylic acid methyl ester (compound 1.1)

7.0 g of 1- [4- (3-trifluoromethylphenoxy) -phenyl] -butane-1,2-dione-1- [ethyloxime] -2-oxime dissolved in 30 ml of N, N-dimethylformamide Is added dropwise to a suspension of 0.83 g of sodium hydride (55% in oil) in 50 ml of N, N-dimethylformamide, and the reaction mixture is stirred at room temperature for 15 minutes. Subsequently, 5.25 g of 2- (bromomethyl) -α- (methoxy-methylene) -phenylacetic acid methyl ester in 20 ml of N, N-dimethylformamide are added dropwise and the reaction mixture is further stirred at room temperature for 1 hour. The mixture is then acidified with acetic acid and concentrated by evaporation in vacuo. The residue is dissolved in ethyl acetate and the solution is washed three times with water and once with saturated sodium chloride solution, dried over sodium sulfate and then concentrated by evaporation in vacuo. Purification by flash chromatography (silica gel, ethyl acetate / hexane 1: 3) affords the title compound having a melting point of 71 to 73 ° C.

f) (2- {2- [4- (3-trifluoromethylphenoxy) -phenyl] -2-ethoxyimino-1-ethyl-ethylidene-aminooxymethyl} -phenyl) -3-methyl Mino-Acrylic Acid Methyl Ester (Compound 2.1)

10.0 g of 1- [4- (3-trifluoromethylphenoxy) -phenyl] -butane-1,2-dione-1- [ethyloxime] -2-oxime dissolved in 25 ml of N, N-dimethylformamide Was added dropwise to a suspension of 1.2 g of sodium hydride (55% in oil) in 50 ml of N, N-dimethylformamide, and then the reaction mixture was stirred at room temperature for 15 minutes. Subsequently, 7.5 g of 2- (bromomethyl) -α- (methoxy-imino) -phenylacetic acid methyl ester in 20 ml of N, N-dimethylformamide are added dropwise and the reaction mixture is further stirred at room temperature for 1 hour. The mixture is then acidified with acetic acid and concentrated by evaporation in vacuo. The residue is dissolved in ethyl acetate and the solution is washed three times with water and once with saturated sodium chloride solution, dried over sodium sulfate and then concentrated by evaporation in vacuo. Purification by flash chromatography (silica gel, ethyl acetate / hexane 1: 3) affords the title compound having a melting point of 73 to 75 ° C.

g) (2- {2- [4- (3-trifluoromethylphenoxy) -phenyl] -2-ethoxyimino-1-ethyl-ethylidene-aminooxymethyl} -phenyl) -3-methyl Mino-Acrylic Methyl Amide (Compound 3.1)

(2- {2- [4- (3-trifluoromethylphenoxy) -phenyl] -2-ethoxyimino-1-ethyl-ethylidene-aminooxymethyl} -phenyl) -3-methylimino- A mixture of 4 g of acrylic acid methyl ester and 5.2 ml of an 8 M solution of methylamine in ethanol is allowed to stand for 16 hours at room temperature. The solvent is then evaporated to dryness in vacuo. The residue was stirred with hexane and filtered, then the filter residue was dried under vacuum to afford the title compound having a melting point of 113 to 115 ° C.

Example P2:

Other compounds listed in Tables 1-4 can also be prepared in a manner similar to that described in Example P1. In the column "physical data" of the table, the temperatures presented in each case represent the melting point of the compound in question.

Biological Example

A) bactericidal action

Example B1: Action on Phytophthora infestans on Tomato

a) therapeutic action

After 3 weeks of incubation, the tomato plants of the "Red Gnome" variety are sprayed with a fungal suspension of fungi and incubated in a humidity chamber of 18-20 ° C. and saturated humidity. Humidity treatment is stopped after 24 hours. When the plants are dry, they are sprayed with a mixture prepared at a concentration of 200 ppm from the wet powder formulation of the test compound. After this spray-coating has dried, the plant is again placed in a humidity room for 4 days. The number and size of typical leaf spots seen after this time serve as an measure to assess the efficacy of the test compound.

b) prophylactic-total penetration action

The wet powder formulation of the test compound is poured at a concentration of 60 ppm (based on the volume of the soil) along the soil surface planted with the three-weekly tomato plants of the "Red Gnome" variety. After waiting for 3 days, spray a drift suspension of phytophthora infestans on the back of the leaves of the plant. The plants thus treated are then placed in a spray cabinet for 5 days at 18-20 ° C. and saturated humidity. After this period, typical leaf spots appeared, their number and size being used to assess the efficacy of the test compound.

The invasion rate in the untreated and infected control plants was 100% while the invasion rate was lowered to 20% or less in both tests when the compounds from Tables 1-4 were used. In particular, in the case of using the compounds 1-1 to 1-6, 2-1 to 2-6 and 3-1 to 3-6, even when the test compound is used at a concentration of 20 ppm, invasion is continuously and completely inhibited.

Example B2: Action on Plasmopara viticola (Bert. Et Curt.) (Berl. Et DeToni) on vines

a) residual-preventive action;

Vine cuttings of the "Chasselas" strain are grown in a greenhouse. In the 10-leaf step, three plants are sprayed with a mixture containing 200 ppm of active ingredient. After the spray-coated has dried, the plant is uniformly infected on the back of the leaves with a fungal spore suspension. The plant is then left in the humidity room for 8 days. After this time, distinct disease symptoms appeared in control plants. The number and size of infection sites on the treated plants serves as an measure to assess the efficacy of the test compound.

b) therapeutic action

The vine cuttings of the "Kazellas" variety are incubated in a greenhouse and, at the 10-leaf stage, infected on the backside of the leaves using a spore suspension of Plasmopara viticola. After 24 hours in the humidity room, the plants are sprayed with a mixture comprising 200 ppm, 60 ppm and 20 ppm of active ingredient. This plant is then held for 7 more days in a humidity chamber. After this time, disease symptoms appeared in control plants. The number and size of infection sites on the treated plants serves as an measure to assess the efficacy of the test compound.

Compared to the control plants, plants treated with the compounds from Tables 1-4 were found to have less than 20% invasion rate. In particular, when compounds 1-1 to 1-6, 2-1 to 2-6 and 3-1 to 3-6 are used, complete therapeutic action is continuously obtained even when the test compound is used at a concentration of 20 ppm. .

Example B3: Action on Puccinia graminis on wheat

a) residual-preventive action;

Six days after sowing, the wheat plants are sprayed with an aqueous spray mixture (0.02% active ingredient) dropwise and infected with a fungal summer seed suspension 24 hours later. After 48 hours of incubation (condition: 95-100% relative humidity at 20 ° C.), the plants are placed in a greenhouse at 22 ° C. An assessment of myococcal pustules is performed 12 days after infection.

b) full penetration

For 5 days after sowing, the wheat plants are fed with an aqueous spray mixture (0.006% active ingredient based on soil volume). Care should be taken to ensure that such spray mixtures do not come into contact with some of the plants on the soil. After 48 hours the plants treated as above are infected with a fungus summer seed suspension. After 48 hours of incubation (condition: 95-100% relative humidity at 20 ° C.), the plants are placed in a greenhouse at 22 ° C. An assessment of myococcal pustules is performed 12 days after infection.

Compounds from Tables 1-4 significantly reduced fungal invasion, in some cases down to 10-0%. In particular, when using compounds 1-1 to 1-6, 2-1 to 2-6 and 3-1 to 3-6, the disease was completely inhibited (0-5% invasion).

Example B4: Action on Erysiphe graminis on barley

a) residual-protective action

Aqueous spray mixture (0.02% active ingredient) is added dropwise to barley plants about 8 cm in height and sprinkled with fungi conidia 3-4 hours later. The infected plants are placed in a greenhouse at 22 ° C. Fungal invasion is assessed 10 days after infection.

b) full penetration

Barley plants about 8 cm in height are watered with an aqueous spray mixture (0.002% active ingredient based on soil volume). Care should be taken to ensure that such spray mixtures do not come into contact with some of the plants on the soil. After 48 hours the fungi conidia are sprinkled on the plants treated as above. The infected plants are placed in a greenhouse at 22 ° C. Ten days after infection, fungal invasion is assessed.

Compounds from Tables 1-4 can generally inhibit disease invasion by less than 20% and in some cases completely inhibit it.

Example B5: Action on Septoria nodorum on wheat

The wheat plants are sprayed in a 3-leaf stage with a spray mixture (60 ppm a.i.) prepared from the wet powder formulation of the test compound.

After 24 hours, the plants thus treated are infected with the fungal conidia. The plants are then incubated for 2 days at 90-100% relative humidity and left for another 10 days in a greenhouse at 20-24 ° C. Fungal invasion is assessed 13 days after infection. Less than 1% of wheat plants have been invaded.

B. Insecticidal Actions

Example B6: Action on Apis craccivora

The pea seed is infiltrated with Apis Krasivora and subsequently sprayed with a spray mixture containing 100 ppm of test compound, followed by incubation at 20 ° C. The population reduction rate (% activity) is determined by comparing the number of killed aphids on the treated plants after 3 and 6 days with the number of killed aphids on the untreated plants.

Compounds from Tables 1-4 generally show good activity in this test. In particular, compounds 1-1 to 1-6, 2-1 to 2-6 and 3-1 to 3-6 exhibit at least 80% activity in this test.

Example B7: Action on Diabrotica balteata

Corn seed is sprayed with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. After this spray-coated was dried, the corn seedlings were allowed to live in the second stage of 10 Diabrotica valteata larvae, and then placed in a plastic container, after 6 days of dead larvae on the treated plants. The population reduction rate (% activity) is determined by comparing the number to the number of killed larvae on untreated plants.

Compounds from Tables 1-4 generally show good activity in this test. In particular, compounds 1-1 to 1-6, 2-1 to 2-6 and 3-1 to 3-6 exhibit at least 80% activity in this test.

Example B8 Actions on Heliothis virescens

Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of test compound. After this spray-coating is dried, the plants are allowed to live in the first stage of the ten heliotis nonresense caterpillars and then placed in a plastic container. After 6 days, the population reduction rate and the percentage of nutritional damage reduction (% activity) are determined by comparing the number of killed caterpillars on the treated plants and the nutritional damage with the number of killed caterpillars on the untreated plants and nutritional damage.

Most of the compounds from Tables 1-4 show good activity in this test. In particular, compounds 1-1 to 1-6, 2-1 to 2-6 and 3-1 to 3-6 exhibit at least 80% activity in this test.

Example B9: Action against Spodoptera littoralis

Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. After this spray-coating is dried, the plants are allowed to live in the third stage of the 10 Spododotera litoralis caterpillars and then placed in a plastic container. After 3 days, the population reduction rate and the percentage of nutrient damage reduction (% activity) are determined by comparing the number of killed caterpillars on the treated plants and the nutritional damage with the number of killed caterpillars on the untreated plants and nutritional damage.

Compounds from Tables 1-4 show good activity in this test. In particular, compounds 1-1 to 1-6, 2-1 to 2-6 and 3-1 to 3-6 exhibit at least 80% activity in this test.

C. mite parasitic action

Example B10: Action on Tetranychus urticae

The young soybean plants are allowed to live with a mixed population of tetranicus urticae, and after 1 day they are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. The plants are then incubated at 25 ° C. for 6 days and then evaluated. The population reduction rate (% activity) is determined by comparing the number of killed eggs, larvae and adults on the treated plants with the number of killed eggs, larvae and adults on the untreated plants.

Compounds from Tables 1-4 generally show good activity in this test. In particular, compounds 1-1 to 1-6, 2-1 to 2-6 and 3-1 to 3-6 exhibit at least 80% activity in this test.

Claims (29)

In each case in free or salt form, a compound of formula (I), or possibly a mixture of E / Z isomers, and / or tautomers thereof, if appropriate. Formula I In the above formula, X is CH or N, Y is OR ₁ , Z is O, X is N, Y is NHR ₈ and Z is O, S or S (= 0); R ₁ is C ₁ -C ₄ alkyl; R ₂ is C ₂ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl; R ₃ and R ₄ are each independently of each other H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, OH, CN, NO ₂ , (C ₁ -C ₄ alkyl) ₃ -Si group, wherein the alkyl group Is the same or different), halogen, (C ₁ -C ₄ alkyl) S (═O) _m , (halo-C ₁ -C ₄ alkyl) S (═O) _m , halo-C ₁ -C ₄ alkyl or Halo-C ₁ -C ₄ alkoxy; R ₈ is H or C ₁ -C ₄ alkyl; R ₉ is methyl, fluoromethyl or difluoromethyl; m is 0, 1 or 2; A is a direct bond, C ₁ -C ₁₀ alkylene, -C (= O)-, -C (= S)-or halo-C ₁ -C ₁₀ alkylene, R ₇ is a radical R _10, or A is C ₁ -C ₁₀ alkylene, -C (= O)-, -C (= S)-or halo-C ₁ -C ₁₀ alkylene, R ₇ is -CN, OR ₁₀ , N (R ₁₀ ) ₂ (wherein radicals R ₁₀ are the same or different), or —S (═O) _p R ₁₀ ; p is 0, 1 or 2; G is O, S or —O—CH ₂ —, where the —CH ₂ group is bonded to a ring designated by K; R ₅ and R ₆ are C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, 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, halo-C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, halo-C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkyl Sulfonyl, 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, halo-C ₁ -C ₆ alkylsulfinyl-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylsulfonyl-C ₁ -C ₆ alkyl, halo- C ₁ -C ₆ alkylsulfonyl-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylcarbonyl, halo-C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, halo-C _1- C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylaminocarbonyl, C ₁ -C ₆ alkoxyiminomethyl, di (C ₁ -C ₆ alkyl) aminocarbonyl, wherein Alkyl groups are the same or different), C ₁ -C ₆ alkylaminothiocarbonyl, di (C ₁ -C ₆ alkyl) aminothiocarbonyl, wherein the alkyl groups are the same or different, C ₁ -C ₆ Alkylamino, di (C ₁ -C ₆ alkyl) amino (where alkyl groups are the same or different), halogen, NO ₂ , CN, thioamido, trimethylsilyl, CH ₂ Si (C ₁ -C ₄ alkyl) ₃ wherein the alkyl group is the same or different, an unsubstituted or mono- to tetrasubstituted C ₁ -C ₄ alkylenedioxy group wherein the substituent is selected from the group consisting of C ₁ -C ₄ alkyl and halogen Where q is greater than 1, the radicals R ₅ are the same or different, and when n is 2 the radicals R ₆ are the same or different and the radicals R ₅ and R ₆ are independent of each other; n is 0, 1, 2, 3, 4 or 5; q is 0, 1, 2, 3 or 4; R ₁₀ is mono-substituted each by a substituent selected from the group consisting of H, C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, or halogen Polysubstituted C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl or C ₃ -C ₆ cycloalkyl, or -Si (C ₁ -C ₄ alkyl) ₃ , wherein alkyl Groups are the same or different), C ₁ -C ₆ alkoxycarbonyl, mono-substituted or substituted by a substituent selected from the group consisting of unsubstituted or halogen, C ₁ -C ₄ alkyl and halo-C ₁ -C ₄ alkyl Substituted aryl or heterocyclyl group; Provided that when R ₂ is ethyl, R ₁ , R ₈ and R ₉ are methyl, R ₃ and R ₄ are hydrogen, q is 0, Z is oxygen and AR ₇ is methyl, group -G -Phenyl is not 3-trifluoromethylbenzyloxy, 4-fluorobenzyloxy or 4-fluorophenoxy at the 4-position, respectively. The compound of formula I according to claim 1 in free form. 3. Compounds of formula I according to claim 1 or 2, wherein X is CH and Z is O. 3. Compounds of formula I according to claim 1 or 2, wherein X is N and Z is O. The compound of formula I according to any one of claims 1 to 4, wherein Y is C ₁ -C ₂ alkoxy. The compound of formula I according to any one of claims 1 to 5, wherein R ₂ is ethyl, propyl or cyclopropyl. _3. The compound of claim 1, wherein R ₃ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, OH, CN, NO ₂ , halogen, halo-C ₁ -C ₄ alkyl or halo-C _1- C ₄ alkoxy. 3. The compound of claim 1, wherein R ₄ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, OH, CN, NO ₂ , halogen, halo-C ₁ -C ₄ alkyl or halo-C _1- C ₄ alkoxy. 3. Compounds of formula I according to claim 1, wherein R ₈ is H or C ₁ -C ₂ alkyl. 4. 10. Compounds of formula I according to any one of claims 1 to ₉ , wherein R ₉ is methyl or fluoromethyl. 11. The compound of claim 1, wherein R ₆ is halogen, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkoxy, C ₃ -C ₆ cyclo A compound of formula I wherein alkyl, halo-C ₃ -C ₆ cycloalkyl or CH ₂ Si (CH ₃ ) ₃ . 12. Compounds of formula I according to claim 11, wherein n is 1 or 2. The compound of formula I according to claim 1 or 2, wherein G is oxygen. The compound of claim 1, wherein R ₅ is halogen, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkoxy, C ₃ -C ₆ cyclo A compound of formula I wherein alkyl, halo-C ₃ -C ₆ cycloalkyl or CH ₂ Si (CH ₃ ) ₃ . 15. A compound of formula I according to claim 14, wherein q is 0, 1, 2 or 3. The compound of formula I according to any one of claims 1 to 15, wherein AR ₇ is methyl or ethyl. a1) reacting a compound of Formula II with a compound of Formula III; a2) reacting a compound of Formula IV with a compound of Formula V; a3) reacting a compound of formula VI with a compound of formula VII; b) To prepare a compound of formula I wherein Y is NHR ₈ and Z is O, the compound of formula I wherein Y is OR ₁ is a compound of formula R ₈ NH ₂ , wherein R ₈ is As defined); c) reacting a compound of formula (I) wherein Y is R ₈ NH ₂ and Z is O with P ₄ S ₁₀ or a lotion reagent to prepare a compound of formula (I) wherein Y is NHR ₈ and Z is S; d) n, q, A, G, X, Y, Z, R ₂ , R, including reacting a compound of formula I, wherein Z is S, with an oxidant, to prepare a compound of formula I, wherein Z is SO _{Free form in each case where 3} , R ₄ , R ₅ , R ₆ , R ₇ and R ₉ are as defined for Formula I of claim 1 and the proviso provisions mentioned in paragraph 1 for compounds of Formula I apply Or a process of preparing a compound of formula (I), or, optionally, E / Z isomers, mixtures of E / Z isomers and / or tautomers thereof in salt form. Formula II Formula III Formula IV Formula V Formula VI Formula Ⅶ X ₁ -AR ₇ In the above formula, n, q, A, G, X, Y, Z, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₉ are as defined for Formula I of claim 1 and for Formula I The aforementioned clue provisions apply, X ₁ is a leaving group. e) a compound of formula (IV) according to claim 17, wherein n, q, A, G, R ₂ , R ₅ , R ₆ and R ₇ are defined for formula (I) of claim ₁ with H ₂ NOH or a salt thereof; React; f) A process for preparing a compound of formula (III) as defined in claim 17, in each case in free or salt form, including reacting a compound of formula (VII) with a compound of formula (VII). Formula Ⅷ Formula Ⅸ R ₇ AONH ₂ In the above formula, n, q, G, A, R ₂ , R ₅ , R ₆ and R ₇ are as defined for Formula I of claim 1. g) A process for preparing a compound of formula (VI) as defined in claim 17, in each case in free or salt form, including reacting a compound of formula (V) with hydroxylamine. Formula Ⅹ In the above formula, n, q, G, X, Y, Z, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₉ are as defined for Formula I of claim 1. h) A process for preparing a compound of formula (X) in each case in free or salt form, comprising reacting a compound of formula (X) as defined in claim 18 with a compound of formula (II) as defined in claim 17. i) A process for preparing a compound of formula (VII) as defined in claim 18, in each case in free or salt form, including reacting a compound of formula (XI) with nitrite. Formula XI In the above formula, n, q, G, R ₂ , R ₅ and R ₆ are as defined for Formula I of claim 1. As the active ingredient in an effective active concentration, at least one compound of formula I according to claim 1 in free form or in agrochemically acceptable salt form, or, optionally, an E / Z isomer or tautomer thereof; And pesticides comprising one or more adjuvants. A method for preparing a composition as described in claim 22 by intimately mixing and / or polishing the active ingredient with the adjuvant (s). A compound of formula (I) as described in claim 1, or optionally an E / Z isomer or toto, in the preparation of a composition as described in claim 22, in free or agrochemically acceptable salt form. Uses of the hair. Use of a compound of formula (I) as described in claim 1 or a composition as described in claim 22 in controlling pests. A method of controlling pests, comprising applying a compound of formula (I) as described in claim 1 or a composition as described in claim 22 to a pest or a habitat thereof. 27. The method of claim 26, comprising treating the growth factor or cultivation site of the growth factor. An element for plant propagation treated according to the method of claim 27. In each case in free or salt form a compound of formula (III), or, if appropriate, possible E / Z isomers, mixtures of E / Z isomers and / or tautomers. Formula III In the above formula, n, q, A, G, R ₂ , R ₅ , R ₆ and R ₇ are as defined for Formula I of claim 1.