EP0707582A1

EP0707582A1 - Pyrimidin-4-ylaminomethylquinoline derivatives as pesticides

Info

Publication number: EP0707582A1
Application number: EP94922239A
Authority: EP
Inventors: Harald Walter
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1993-07-09
Filing date: 1994-06-27
Publication date: 1996-04-24
Also published as: AU7344794A; IL110236A0; ZA944947B; MX9405202A; JPH09503746A; WO1995001975A1

Abstract

Compounds of formula (I) in which the substituent A is in the 6- or 7-position and in which: X is OR10, SR10 or N(R11)R12; and in which R1 to R12 have the meanings given herein, in free form or in salt form, can be used as agrochemical active ingredients for controlling pests.

Description

PYRIMIDIN-4-YLAMIN0METHYLQUIN0LINE DERIVATIVES AS PESTICIDES

The invention relates to novel pesticidally active compounds of the formula I

in which the substituent A is in the 6- or 7-position and in which:

RT is hydrogen, Cι-C₄alkyl, Cι-C₄alkoxy, halo-C₁-C alkyl having 1, 2 or 3 halogen atoms, or C₁-C₄alkylthio;

R₂ and R₃ independently of one another are hydrogen, C_rC al yl, halo-Cι-C₄alkyl having 1-5 halogen atoms, C₁-C₂alkoxy-C₁-C₄al yl, nitro-C_rC₄al yl, cyano-C₁-C₄alkyl, C₁-C₄alkanoyl-C₁-C₄alkyl, C₁-C₄a__ oxycarbonyl-C₁-C₄al yl, C₁-C₂alkylthio-C₁-C₄al yl, C₁-C₂al anesulfinyl-C₁-C₄alkyl, C₁-C₂al anesulfonyl-C₁-C₄al yl, C₂-C₄alkenyl, halo- C₂-C₄al enyl having 1, 2 or 3 halogen atoms, C₂-C₄al ynyl, C₃-CτCycloalkyl, C_rC₄alkoxy, halo-C₁-C₄alkoxy, Cι-C₄alkylthio, halo-Cι-C₄alkylthio, C₁-C₄alkylsulfinyl, C_rC₄alkylsulfonyl, amino, Ci- acylamino, nitro, cyano, hydroxyl or halogen; R₄ is hydrogen, C₁-C₄alkyl, halo-C₁-C₄alkyl having 1, 2 or 3 halogen atoms, C₁-C₂alkoxy-C₁-C₄al yl, nitro-C_rC₄alkyl, cyano-C_rC₄alkyl, C₃-C₅cycloalkyl, benzyl, C₁-C₄al anoyl, benzoyl, benzoyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen, Cι-C₂alkyl, nitro and cyano;

R₅ and R₆ independently of one another are hydrogen, C_rC₄alkyl, halo-C_rC₄alkyl having 1, 2 or 3 halogen atoms, C₁-C₂al oxy-C₁-C₄alkyl, nitro-C_rC₄alkyl, cyano-Cι-C₄alkyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkyl or C₃-C₆cycloalkyl which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C_rC₂al yl; R₇ is hydrogen, halogen, C,-C₄alkyl, cyclopropyl, C_rC₄alkoxy or C_rC₄alkylthio; X is OR₁₀, SR₁₀ or N(R_π)R₁₂; R₁₀ is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 12 carbon atoms and which is substituted or unsubstituted, a cyclic, saturated or unsaturated hydrocarbon radical which has not more than 10 carbon atoms and which is substituted or unsubstituted, substituted or unsubstituted benzyl; or a substituted or unsubstituted heterocyclyl radical;

R_π is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical which has not more than 8 carbon atoms and which is unsubstituted or substituted by 1-5 halogen atoms, -C^alkoxy. hydroxyl, nitro, cyano, C_rC₄alkanoyl, halo-C₁-C alkanoyl or

C_rC₄alkoxycarbonyl, a cyclic, saturated or unsaturated hydrocarbon radical which has not more than 10 carbon atoms or benzyl, in which the carbocycle is unsubstituted or mono- or disubstituted by halogen, Cι-C alkyl, halomethyl, nitro or cyano, or heterocyclyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, halomethyl, nitro or cyano;

R₁₂ is hydrogen or C₁-C alkyl; or

R and R₁₂ together with the nitrogen atom to which they are bonded are a heterocycle which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, -C^alkyl, halomethyl or nitro; or, if appropriate, a tautomer thereof, in each case in free form or in salt form.

The invention furthermore relates to the preparation of these compounds, to agrochemical compositions comprising at least one of these compounds as active ingredient, and to the use of the active ingredients or the pesticides, in particular as microbicides in agriculture and horticulture.

The compounds I and, if appropriate, their tautomers can exist in the form of salts. Since the compounds I have at least one basic centre, they can form, for example, acid addition salts. These are formed, for example, with mineral acids, for example sulfuric acid, a phosphoric acid or a hydrohalic acid, with organic carboxylic acids, for example acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, for example methane- or p-toluenesulfonic acid.

Furthermore, compounds of the formula I which have at least one acidic group can form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal salts or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or with an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. Furthermore, it may be possible for corresponding internal salts to be formed. Preferred within the scope of the invention are agrochemically advantageous salts.

The general terms used hereinbefore and hereinafter have the meanings given below, unless otherwise defined:

Alkyl groups, depending on the number of the carbon atoms, are straight-chain or branched and are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, sec-amyl, tert-amyl, 1-hexyl or 3-hexyl.

Alkenyl is to be understood as meaning straight-chain or branched alkenyl, for example allyl, methallyl, 1-methylvinyl or but-2-en-l-yl. Alkenyl radicals having a chain length of 3 to 4 carbon atoms are preferred.

Alkynyl too can be straight-chain or branched, depending on the number of the carbon atoms, for example it can be propargyl, but-1-yn-l-yl or but-l-yn-3-yl. Propargyl is preferred.

Unsaturated hydrocarbon radicals are alkenyl, alkynyl or alkenynyl groups having not more than 3 multiple bonds, for example butadienyl, hexatrienyl, 2-penten-4-ynyl.

Halogen or halo are fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

Haloalkyl can have identical or different halogen atoms, examples which may be mentioned being fluoromefhyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl.

Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy and tert-butyloxy; preferably methoxy and ethoxy.

Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy.

Cycloalkyl is, depending on the size of the ring, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

Cyclic unsaturated hydrocarbon radicals can be aromatic, for example phenyl and naphthyl, or not aromatic, for example cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctadienyl, or partially aromatic, for example tetrahydronaphthyl and indanyl.

Alkanoyl is either straight-chain or branched, in each case taking into consideration the number of carbon atoms involved. Possible examples are formyl, acetyl, propionyl, butyryl, pivaloyl or octanoyl.

In alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyl-, nitro- or cyano-substituted carbon-containing groups and compounds, such as alkoxyalkyl, alkylthioalkyl, alkanesulfinylalkyl, alkanesulfonylalkyl, nitroalkyl,cyanoalkyl and cyanoalkanesulfonyl, one of the hydrogen atoms in the unsubstituted base structure on which these groups and compounds are based is replaced by alkoxy, alkylthio, alkanesulfinyl, alkanesulfonyl, nitro or cyano.

A heterocyclyl radical is to be understood as meaning 5- or 6-membered, aromatic and nonaromatic rings having hetero atoms N, O and/or S. Moreover, an unsubstituted or substituted benzo group may be fused to such a heterocyclyl radical bonded to the remaining moiety. Examples of heterocyclyl groups are pyridyl, pyrimidinyl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, triazolyl, thienyl, furanyl, pyrrolyl, morpholinyl, oxazolyl and the corresponding partially or fully hydrogenated rings. Examples of heterocyclyl groups having a fused benzo group are quinolyl, isoquinolyl, benzoxazolyl, quinoxalinyl, benzothiazolyl, benzimidazolyl, indolyl, indolinyl.

All the abovementioned enumerations are by way of example and not by way of limitation.

Preferred compounds within the scope of the invention are

(1) compounds of the formula I in which:

R₁₀ is an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 8 carbon atoms and which is unsubstituted or substituted by 1-5 halogen atoms, C_rC₂alkoxy, hydroxyl, nitro, cyano, halo-Cι-C alkanoyl or C_rC₄alkoxycarbonyl, a cyclic, saturated or unsaturated hydrocarbon radical which has not more than 10 carbon atoms, or benzyl in which the carbocycle is unsubstituted or mono- or disubstituted by halogen, C-i-C^alkyl, halomethyl, nitro or cyano, or heterocyclyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, Cj-C₂alkyl, halomethyl, nitro or cyano, or a 5- to 7-membered lactone ring.

(2) Compounds of the formula I in which:

Rio is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 12 carbon atoms and which is unsubstituted or substituted by tri(C₁-C₄alkyl)silyl or by an epoxy group; or the group

-CH(U)(CH₂)_mCO-W, in which:

U is hydrogen, C_j- alkyl, cyano or Cj-Cgalkoxycarbonyl;

W is - alkoxy, C₃-C₆cycloalkoxy or the group -N(T₁)T₂ m is 0, 1 or 2 and

Tι and T₂ independently of one another are hydrogen, Cj-Cgalkyl, which is unsubstituted or substituted by 1-3 halogen atoms, hydroxyl, nitro, cyano, C₁-C alkanoyl, halo-Cj-C₄alkanoyl or C₁-C alkoxycarbonyl, or C C₆alkenyl which is unsubstituted or substituted by 1-3 halogen atoms, C_rC₆alkynyl which is unsubstituted or substituted by

1-3 halogen atoms, a cyclic, saturated or unsaturated hydrocarbon radical having not more than 10 carbon atoms or benzyl in which the carbocycle is unsubstituted or mono- or disubstituted by halogen, C₁-C₂alkyl, halomethyl, nitro or cyano, or heterocyclyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of C₁-C₂alkyl, halogen, halomethyl, nitro or cyano; or

Tj and T₂ together with the nitrogen atom to which they are bonded form a 5-7-membered heterocycle which can additionally have O, S and/or N as ring atoms, in which the additional nitrogen is unsubstituted or substituted by C₁-C₄alkyl, phenyl, C_rC₄alkanoyl, benzoyl or benzyl and in which the carbon atoms of the heterocycle are unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, Cj-C₂alkyl, halomethyl or nitro.

(3) Compounds of the formula I in which:

R₁₀ is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 6 carbon atoms and which is unsubstituted or substituted by tri(C₁-C₄alkyl)silyl or an epoxy group; or the group

-CH₂-CO-W, in which:

W is C_rC₆alkoxy, C₃-C₆cycloalkoxy or the group

Ti and T₂ independently of one another are hydrogen, - alkyl, halo-Ci- alkyl having

1-3 halogen atoms, C₃-C₆cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl, naphthyl, or

T_x and T₂ together with the nitrogen atom to which they are bonded are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.

(4) Compounds of the formula I in which:

R_j is hydrogen or C₁-C₄alkyl;

R₂ is hydrogen, C₁-C alkyl, halo-C₁-C₄alkyl having 1, 2 or 3 halogen atoms,

C₁-C₂alkoxy-C₁-C alkyl, cyclopropyl, ethynyl or halogen;

R₃ is fluorine or chlorine;

R is hydrogen or Ci-C^alkyl;

R₅ is C₁-C₄alkyl;

R₆ is hydrogen;

R₇ is hydrogen or halogen;

X is OR₁o. SR₁₀ σr N(R₁₁)R₁₂;

R₁₀ is C₁-C alkyl, halo-C₁-C₄alkyl having 1, 2 or 3 halogen atoms, C C^alkoxy-

C_rC₄alkyl, hydroxy-C_rC₄alkyl, nitro-C_rC₄alkyl, cyano-C_rC₄alkyl, C₁-C₄alkanoyl-

C C₄alkyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkyl, C₂-C₄alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C₂-C₄alkynyl, C₃-Cτcycloalkyl, C₄-C₈cycloalkenyl, benzyl, phenyl which is unsubstituted or mono- or disubstituted by halogen, C_j-C^alkyl, nitro or cyano, or pyridine, pyrimidine or triazine, these heterocycles in each case being unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, Ci-C^alkyl, trifluoromethyl or cyano, or a 5-membered lactone ring;

R_π is hydrogen, C₁-C₄alkyl, halo-C_rC alkyl having 1, 2 or 3 halogen atoms,

C₁-C₂alkoxy-C₁-C₄alkyl, hydroxy-C₁-C₄alkyl, nitro-C₁-C₄alkyl, cyano-C₁-C₄alkyl,

C₁-C alkanoyl-C₁-C alkyl, C₁-C alkoxycarbonyl-C₁-C₄alkyl, C₂-C₄alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C₂-C₄alkynyl, C₃-C₇cycloalkyl,

C₄-C₈cycloalkenyl, benzyl, phenyl, which is unsubstituted or mono- or disubstituted by halogen, C_rC₂alkyl, nitro or cyano, R₁₂ is hydrogen or Cι-C₄alkyl; or

Rjj and R₁₂ together with the nitrogen atom to which they are bonded are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.

Preferred groups amongst the compounds mentioned under (4) are furthermore the following:

(4.1) Compounds in which X is SRJ_Q.

(4.2) Compounds in which X is OR₁₀.

(5) Compounds of the formula I in which: R_ is hydrogen or C₁-C alkyl;

R₂ is hydrogen, C_rC₄alkyl, halo-C_rC alkyl having 1, 2 or 3 halogen atoms,

C₁-C₂alkoxy-C₁-C₄alkyl, cyclopropyl, ethynyl or halogen;

R₃ is chlorine;

R₄ is hydrogen or C₁-C alkyl;

R₅ is C_rC₄alkyl;

R₆ is hydrogen;

R is hydrogen;

X is OR₁₀ or SR₁₀;

R₁₀ is the group -CH₂-CO-W,

W is C₁-C₆alkoxy, C₃-C₆cycloalkoxy or the group

T and T₂ independently of one another are hydrogen, - alkyl, halo-Cj-Cgalkyl having

Tj and T₂ together with the nitrogen atom to which they are bonded are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.

(6) Compounds of the formula LI

in which:

R₂ is hydrogen, methyl or ethyl;

R₃ is fluorine or chlorine;

R₅ is methyl or ethyl;

R₇ is hydrogen or fluorine;

X is ORιo, SRι₀ or N(Rιι)R₁₂;

Rio is C_rC₄alkyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, vinyl, allyl, 2-propynyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyanomethyl or

Cι-C₄alkoxycarbonylmethyl;

Rn is hydrogen, Ci- alkyl, cyclohexyl, cyclopropyl or phenyl;

R₁₂ is hydrogen; or

R_πand R_l2 together with the nitrogen atom to which they are bonded are piperidine, morpholine or 2,6-dimethylmorpholine.

(7) Compounds of the formula 1.2

in which:

R₂ is hydrogen, methyl or ethyl;

R₃ is fluorine or chlorine;

R₅ is methyl or ethyl;

R is hydrogen or fluorine;

C C₄alkoxycarbonylmethyl;

Rn is hydrogen, Cι-C₄alkyl, cyclohexyl, cyclopropyl or phenyl;

R₁₂ is hydrogen; or

Rnand R₁₂ together with the nitrogen atom to which they are bonded are piperidine, morpholine or 2,6-dimethylmorpholine.

(8) Compounds of the formula I a

in which

R₁₀ is Ci-Csalkyl which is unsubstituted or mono- to trisubstituted by halogen, or

C₂-C₅alkenyl which is unsubstituted or mono- to trisubstituted by halogen.

The compounds of the formula I and, if appropriate, the tautomers thereof, in each case in free form or in salt form, can be prepared as follows: (A) a) to prepare a compound of the formula I , in which X is SRι₀: a compound of the formula II

in which the substituent A is in the 6- or 7-position and in which Ri to R₇ are as defined for formula I is reacted with a compound of the formula IH

in which Rι₀ is as defined in formula 1 and Z is an easily detachable nucleofugic radical; preferably in the presence of a base, particularly preferably by first reacting a compound of the formula II with a base and subsequently with a compound of the formula El; or

b) to prepare a compound of the formula I in which X is OR₁₀ or N(Rn)R₁₂: a compound of the formula I in which X is SRio is reacted with a compound of the formula IN

M-X (IV)

in which:

M is hydrogen, Li⁺, Νa⁺, K⁺, l/2Mg²⁺ or a quaternary ammonium ion;

X is ORio or N(Rn)R₁₂ and in which RIQ, R_Π and R₁₂ are as defined for formula I; if appropriate in the presence of a base; or

c) to prepare a compound of the formula I in which R₄ is as defined for formula I but is other than hydrogen: a compound of the formula I in which R₄ is hydrogen is reacted with a compound of the formula V

R₄'-Z' (V)

in which R₄' is as defined for R₄ in formula I but is other than hydrogen, and Z' is an easily detachable nucleofugic radical; preferably in the presence of a base.

(B) A compound of the formula VII

in which the substituent A is in the 6- or 7-position and in which R-_^ to R₇ are as defined for formula I is reacted with phosphorus oxychloride, thionyl chloride or sulfuryl chloride to give a compound of the formula Niπ

and this compound is subsequently reacted with a compound of the formula IN'

M-X' (IN')

in which:

M is hydrogen, Li⁺, Νa⁺, K⁺, l/2Mg²⁺ or a quaternary ammonium ion;

X' is OR₁₀, SR₁₀ or N(Rn)R₁₂ and in which R₁₀, Rn and R_i2 are as defined for formula I; if appropriate in the presence of a base.

(C) A compound of the formula IX

(DC)

in which the substituent A is in the 6- or 7-position and in which Rj to R₇ and X are as defined for formula I is reacted with an oxidant. Examples of suitable oxidants are an iron(III) salt, SeO₂, MnO₂, H₂O₂, Br_2j Cl₂, 1₂, SO₃, H SO₄, HNO₃, N-bromosuccinimide, benzoquinones, for example 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ) or O₂ in the presence of a dehydrogenation catalyst.

(D) HZ is eliminated, in the presence of base or acid, from a compound of the formula DC

in which the substituent A is in the 6- or 7-position and in which Ri to R₇ and X are as defined for formula I and in which Z is an easily detachable nucleofugic radical.

The reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, conventionally, in the presence of a suitable solvent or diluent or a mixture of these, the process being carried out, as appropriate, with cooling, at room temperature or with heating, for example in a temperature range from approximately -80°C to the boiling point of the reaction medium, preferably from approximately -20°C to approximately +150°C and, if required, in a sealed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Typical reaction conditions can be found in the examples.

Examples of nucleofugic radicals Z or Z' are: fluorine, chlorine, bromine, iodine, C_j-Cgalkylthio, such as methylthio, ethylthio or propylthio, C_rC₈alkanoyloxy, such as acetoxy, (halo-)C₁-Cgalkanesulfonyloxy, such as methanesulfonyloxy, ethanesulfonyloxy or trifluoromethanesulfonyloxy, or substituted or unsubstituted phenylsulfonyloxy, such as benzenesulfonyloxy or p-toluenesulfonyloxy, and furthermore also hydroxyl.

Suitable bases are the hydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides or alkylsilylamides of alkali metals or alkaline earth metals, or alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium carbonate, potassium tert-butanolate, potassium carbonate, lithium - diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, benzyltrimethylammonium hydroxide and l,8-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reactants can be reacted with each other as such, i.e. without an addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert diluent or solvent or a mixture of these is advantageous. The following may be mentioned as examples of such solvents or diluents: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons, such as benzene, toluene, xylene, chlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane or trichloroethane; ethers, such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran or dioxane; ketones, such as acetone or methyl ethyl ketone; alcohols, such methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; esters, such as ethyl acetate or butyl acetate; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile; and sulfoxides, such as dimethyl sulfoxide. Bases employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +180°C, preferably from approximately +20°C to approximately +130°C, in many cases at the reflux temperature of the solvent used.

Alternatively, the reaction can be carried out with phase-transfer catalysis in an organic solvent, for example methylene chloride or toluene, in the presence of an aqueous alkaline solution, for example sodium hydroxide solution, and of a phase transfer catalyst, for example tetrabutylammonium hydrogen sulfate.

A compound I which can be obtained according to the invention or by another route or, if appropriate, a tautomer of this compound, can be converted into another compound I in a manner known per se by replacing one or more substituents of the starting compound I in the customary manner by another substituent.

For example,

- substituents which do not contain halogen, or unhalogenated aromatic or heteroaromatic part-structures of rings can be halogenated to give halogen-containing substituents or halogenated aromatic or heteroaromatic part-structures of rings;

- halogen substituents can be exchanged for other substituents, such as cyano, alkylthio or alkoxy substituents;

- alkanoyl, benzoyl or sulfonyl substituents can be exchanged for easily exchangeable hydrogen or

- N-hydrogen can be exchanged for N-alkyl, N-benzyl, N-aryl, N-heteroaryl, N-alkanoyl, N-benzoyl or N-sulfonyl;

- sulfides can be oxidized to give sulfoxides and sulfones; or

- carbonyl groups can be sulfated to give thiocarbonyl groups.

The invention relates to the pure isomers and to all isomer mixtures which are possible.

The invention also relates to novel starting materials and intermediates used for the preparation of the compounds of the formula I, to their use and to processes for their preparation.

The compounds of the formulae II, Nπ and IX can be prepared by known methods as shown in the equation.

In this equation, A, Rι₀, Z, M and X are as defined above.

The following are suitable as oxidants: an iron(III) salt, SeO₂, MnO₂, H₂O₂, Br₂ Cl₂, 1₂, SO₃, H₂SO₄, HΝO₃, N-bromosuccinimide, benzoquinones, for example 2,3-dichloro-5,6- dicyano-l,4-benzoquinone (DDQ) or O₂ in the presence of a dehydrogenation catalyst Examples of thionating agents are phosphorus pentasulfide or 2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide ("Lawesson's reagent").

The preparation of the compounds of the formula IX, DC, XI and XII is described, for example, in Swiss Patent Application Nos. 509/93-0 (date of application: February 18th, 1993), 617/93-3 (date of application: March 2nd, 1993) and 1788/93-2 (date of

Equation

oxidation

thionation thionation

oxidation

R10-Z

IX application: June 16th, 1993).

The compounds of the formulae III, IV, V and VI are known or can be prepared by known methods.

Pyrimidines which are amino-substituted in the 4-position have already been disclosed, for example in Patent Application No. WO 92/08704. The compounds I of the present invention differ structurally from these known compounds in a characteristic manner; moreover, the compounds of the formula I of the present invention have an unexpectedly powerful microbicidal, insecticidal, nematicidal and acaricidal activity. Protection of the plants may take place by direct action on the pests and also by activating and stimulating the plant's defence system (immunization).

The compounds of the formula I can be used in the agricultural sector and in related fields as active ingredients for the control of plant pests. The active ingredients according to the invention are distinguished by a powerful activity at low rates of concentration and by the fact that they are well tolerated by plants and environmentally friendly. They have highly advantageous curative, preventive and systemic properties and can be used for protecting a large number of crop plants. Using the active ingredients of the formula I, the pests which are found on plants or parts of plants (fruits, flowers, foliage, stalks, tubers, roots) of a range of crops of useful plants can be contained or destroyed, and parts of plants which are formed at a later point in time are also left unharmed, for example by phytopathogenic microorganisms.

Compounds of the formula I can also be used as seed-dressing agents for the treatment of plant propagation material, in particular seed (fruits, tubers, kernels) and nursery plants (for example rice) for protecting them against fungal infection and against soil-borne phytopathogenic fungi.

The compounds I are active for example against phytopathogenic fungi from the following classes: Fungi imperfecti (for example Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (for example Rhizoctonia, Hemileia, Puccinia). Moreover, they are active against the classes of the Ascomycetes (for example Venturia and Eiysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes (for example Phytophthora, Pythium, Plasmopara). Moreover, the compounds I according to the invention are valuable active ingredients for controlling pests of the order of the Acarina and the classes of the Insecta and Nematoda in agricultural crop plants and ornamentals, in particular in cotton, vegetable and fruit crops, in forests, in the protection of stored products and materials and in the hygiene sector, and of animal pests, in particular in domestic animals and productive livestock. They are active against a range of development stages. Their activity becomes apparent from immediate destruction of the pests or only after some time has elapsed, for example during molting, or from markedly reduced oviposition and/or hatching rates. The Acarina include, for example, Boophilus spp. and Tetranychus spp., the Nematoda include, for example, Heterodera glycines, and the Insecta include, for example, Nilaparvata lugens, Plutella xylostella and Musca domestica.

Examples of target crops for the use in crop protection within the scope of the invention are the following types of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar and fodder beet); pome fruit, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soya beans); oil crops (oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa, groundnuts); cucurbits (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, red pepper); the laurel family (avocado, cinnamon, camphor), and plants such as tobacco, nuts, coffee, egg plants, sugar cane, tea, pepper, vines, hops, the banana family, latex plants and ornamentals.

Active ingredients I are conventionally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients. These other active ingredients can be, for example, fertilizers, trace element mediators or other preparations which have an effect on the growth of plants. Other substances which can be used are selective herbicides and also insecticides, fungicides, bactericides, nematicides, moUuscicides or mixtures of a plurality of these preparations, if appropriate together with other carriers, surfactants or other application-enhancing additives conventionally used in the art of formulation.

Suitable carriers and additives can be solid or liquid and are those substances which are expedient in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. A preferred method for applying an active ingredient of the formula I or an agrochemical composition which comprises at least one of these active ingredients, is applying it to the foliage (foliar application). The frequency and rate of application will depend on the risk of infestation with the pathogen in question. Alternatively, the active ingredients I can also reach the plant via the soil through the root system (systemic action), by drenching the locus of the plant with a liquid preparation or by incorporating the substances in solid form into the soil, for example in the form of granules (soil application). In the case of paddy rice, such granules can be metered into the flooded rice field. However, the compounds I can also be applied to the seed kernels for seed treatment (coating) by soaking the kernels or tubers in a liquid preparation of the active ingredient or by coating them with a solid preparation.

The compounds I are employed as pure active ingredients or, preferably, together with auxiliaries conventionally used in the art of formulation. To this end, they are expediently processed in a known manner, for example to give emulsion concentrates, spreadable pastes, ready-to-spray or ready-to-dilute solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, for example by encapsulation in, for example, polymeric substances. The methods of application, such as spraying, atomizing, dusting, scattering, brushing on or pouring, as well as the nature of the compositions are selected to suit the intended aims and the prevailing circumstances.

Advantageous rates of application are, in general, 5 g to 2 kg of active ingredient (A.I.) per hectare (ha), preferably 10 g to 1 kg of A.L/ha, in particular 20 g to 600 g of A.L/ha. When used as seed-dressing agents, it is advantageous to use dosage rates from 10 mg to 1 g of active ingredient per kg of seed.

The formulations, i.e. the compositions, preparations or combinations which comprise the active ingredient of the formula I and, if desired, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and or grinding the active ingredient with extenders, such as solvents, solid carriers and, if appropriate, surface-active compounds (surfactants).

The following are possible as solvents: aromatic hydrocarbons, preferably the fractions C₈ to Cι₂, for example xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and epoxidized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, and water.

Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly-disperse silica or highly-disperse absorptive polymers. Possible paniculate, adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, or non-sorptive carrier materials, for example calcite or sand. Moreover, a large number of pregranulated materials of inorganic or organic nature can be used, such as dolomite or comminuted plant residues.

Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants which have good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be formulated. Surfactants are also to be understood as meaning mixtures of surfactants.

Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.

Examples of non-ionic surfactants which may be mentioned are nonylphenol polyethoxyethanols, castor oil polyglycol ether, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethylene ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.

The cationic surfactants are, especially, quaternary ammonium salts which have at least one alkyl radical having 8 to 22 carbon atoms as N substituent and lower, free or halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents.

Other surfactants conventionally used in the art of formulation are known to the expert or can be found in the relevant specialist literature. As a rule, the agrochemical preparations comprise 0.1 to 99 percent by weight, in particular 0.1 to 95 percent by weight, of active ingredient of the formula 1, 99.9 to 1 percent by weight, in particular 99.8 to 5 percent by weight, of a solid or liquid additive, and 0 to 25 percent by weight, in particular 0.1 to 25 percent by weight, of a surfactant.

While concentrated compositions are more preferred as commercially available goods, the end user will, as a rule, use dilute compositions.

The compositions can also comprise other additives, such as stabilizers, defoamers, viscosity regulators, binders or adhesives, and also fertilizers or other active ingredients for achieving specific effects.

The examples which follow illustrate the invention described above without limiting its scope. Temperatures are given in degrees centigrade. The following abbreviations are used: Ac = acetyl; Et = ethyl; i-Pr = isopropyl; Me = methyl; Ph = phenyl; Pr = n-propyl; Bu = n-butyl; m.p. = melting point; ds = diastereomer, reg = regioisomer. "NMR" means "nuclear magnetic resonance spectrum"; MS = mass spectrum. " " means "percent by weight", unless a different unit is used for indicating the relevant concentrations.

Examples for the preparation of the compounds according to the invention

Example H- la: 0.9 g of 7-[l-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-3,4-dihydro-2 -methylthioquinoline and 0.86 g of 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ) are introduced into 20 ml of absolute dioxane in a sulfonation flask at room temperature and the mixture is stirred for approximately 6 hours at 85-90°C. After cooling, the mixture is diluted with 100 ml of ethyl acetate and 30 ml of water, the organic phase is separated off, and the aqueous phase is then extracted twice using ethyl acetate. The organic phase is dried over sodium sulfate, the solvent is removed by distillation under a waterpump vacuum and the residue is purified by column chromatography on silica gel (eluent: n-hexane/tetrahydrofuran 3:1). 0.6 g of 7-[l-(5-chloro-6- ethylpyrimidin-4-ylamino)ethyl]-2-methylthioquinoline is obtained in the form of a white powder (m.p. 82-84°C).

Other compounds which can be prepared analogously to the procedure described in Example H-la or using one of the abovementioned procedures are those listed in the tables below.

Table 1 Compounds of the general formula I.l

Ex. ^R2 ^R3 ^R5 ^R7 ^X Physical data

1.1 Me Cl Me

1.2 Et Cl Me

1.3 Me Cl Me

1.4 Et Cl Me

1.5 Et Cl Et

1.6 Me Cl Me

1.7 Et Cl Me oil; 1H NMR

1.8 Et Cl Et

1.9 Me Cl Et

1.10 Et Cl Me oil; 1H NMR

1.11 Et Cl ^' Et

1.12 Me Cl Me

1.13 Et Cl Me oil; 1H NMR

1.14 Et Cl Et

1.15 Me Cl Me

1.16 Et Cl Me oil; 1H NMR

1.17 Et Cl Et

1.18 Me Cl Me

1.19 Et Cl Me oil; ^lU NMR

1.20 Et Cl Et

1.21 Me Cl Me

1.22 Et Cl Me oil; 1H NMR

1.23 Me Cl Me Ex. R₂ R₃ R₅ R₇ X Physical data

oil; ^l NMR

oil; ^lH NMR

oil; Η NMR

1.38 Et Cl Me H S oil; *H NMR

oil

oil, ^lH NMR

oil Ex. ^R2 ^R3 ^R5 ^R7 ^X Physical data

oil, *H NMR

oil, ^XH NMR

1.91 Et Cl Me H

1.92 Et Cl Me H SCH₂CONHphenyl oil, ^lH NMR

1.93 Et Cl Me H SCH₂CONH — Y-CI m.p. 73-77°C Ex. R R₃ Rg R₇ X Physical data

1.94 Et Cl Me H SCH₂CONH m.p. 65-70°C

1.95 Et Cl Me H

1.96 Et Cl Me H OCH₂CH₃ m.p. 63-70°C

1.98 Et Cl Me H SCHCON ^H-O

Me

1.99 Et Cl Me H SCH₂CON(Me)₂

1.100 Et Cl Me H SCH₂CON(CH₂CH₃)₂ oil, ^lH NMR

1.102 Et Cl Me H SCH₂CON oil, ^JH NMR

Me

1.104 Et Cl Me H SCH₂CO (cis)

1.105 Et Cl Me H SCH₂CO N -Me Ex. R₂ R₃ R₅ R₇ X Physical data

1.106 Et Cl Me H

1.107 Et Cl Me H SCH₂COMe

1.108 Et Cl Me H SCH₂COCH₂CH₃

1.109 Et Cl Me H ^SCH2 ~~<^\

1.110 Et Cl Me H SCHCON(Me)₂

CN

1.111 Et Cl Me H SCH₂CH=C(Me)₂

1.112 Et Cl Me H SCH₂CH=CH-G≡C-Si(Me)₃ (E/Z) mixture

Table 2 Compounds of the general formula 1.2

Physical data

oil, 1H NMR

oH, *H NMR

oil, ^lH NMR

oil, 1H NMR

oil, ^l NMR Bsp. R₂ R₃ R₅ R₇ X Physical data

oil, ^l NMR

oil, 1H NMR

oil, ^JH NMR

2.37 Me Cl Me H S X

2.38 Et Cl Me H S oil, *H NMR

2.39 Et Cl Me F SMe

2.40 Et Cl Me F SEt

2.41 Et Cl Me F SCH₂CF₃ oil

2.42 Me Cl Me H OMe

2.43 Et Cl Me H OMe oil, 1H NMR

2.44 Et Cl Et H OMe

2.45 Me Cl Me H OEt

2.46 Et Cl Me H OEt

2.47 Me Cl Me H OCH₂CF₃ oil Bsp. R₂ R₃ R₅ R₇ X Physical data

2.48 Et Cl Me H OCH₂CF₃ oil

2.49 Et Cl Et H OCH₂CF₃

2.50 Et Cl Me H OCH₂CH=CH₂

2.51 Et Cl Me H OCH₂C≡CH

2.52 Et Cl Me H HN-Bu

2.54 Et Cl Me H N O

Bsp. R₂ R₃ R₅ R₇ X Physical data

resin; ^LH-NMR resin; ^LH-NMR

Bsp. R₂ R₃ R₅ R₇ X Physical data

2.93 Et Cl Me H SCH₂CONH Cl

2.95 Et Cl Me H SCH₂CONH — ff

2.98 Et Cl Me H SCHCONH I-HQ

Me

2.99 Et Cl Me H SCH₂CON(Me)₂

2.100 Et Cl Me H SCH₂CON(CH₂CH₃)₂ resin; Η-NMR

Bsp. R₂ R₃ R₅ R₇ X Physical data

2.105 Et Cl Me H SCH₂CON N -Me

2.106 Et Cl Me H

2.107 Et Cl Me H SCH₂COMe

2.108 Et Cl Me H SCH₂COCH₂CH₃

2.109 Et Cl Me H ^SCH2 ~^\

^O

2.110 Et Cl Me H SCHCON(Me)₂

CN

2.111 Et Cl Me H SCH₂CH=C(Me)₂ resin; ^XH-NMR

2.112 Et Cl Me H SCH₂CH=CH-OC-Si(Me)₃ resin; Η-NMR (E/Z) mixture

Table 3: NMR data (Spectra recorded in CDC1₃)

Example 1H NMR data (ppm/multiplicity/proton number)

H-1.8 1.26/t/3H; 1.43/t/3H; 1.67/d/3H; 2.79/q/2H; 3.33/q/2H; 5.50/m/lH;

5.66/d/lH; 7.19/d/lH; 7.62-7.67/m/2H; 7.81-7.93/m/2H; 8.39/s lH

H-1.10 1.26/1 3H; 1.68/d/3H; 2.79/q/2H; 3.61-3.72/m/2H; 4.63/t/lH; 4.79/t/lH;

5.50/m/lH; 5.68/d/lH; 7.21/d/lH; 7.64-7.68/m/2H; 7.87-7.92/m/2H; 8.38/s/lH

H-1.13 1.26/t/3H; 1.68/d/3H; 2.79/q/2H; 4.22/q/2H; 5.51/m/lH; 5.67/d/lH;

7.24/d/lH; 7.67-7.7 l/m/2H; 7.93/s/lH; 7.96/s/lH; 8.38/s/lH

H-1.16 1.07/t/3H; 1.26/t/3H; 1.67/d/3H; 1.79/m/2H; 2.79/m 2H; 3.30/t/2H;

5.50/m/lH; 5.66/d/lH; 7.20/d/lH; 7.63-7.66/m/2H; 7.83-7.92/m/2H; 8.38/s/lH

H-1.19 1.26/t/3H; 1.68/d/3H; 2.79/q/2H; 4.06/s/3H; 5.08/m/lH; 5.65/d/lH;

6.89/d/lH; 7.63/dd/lH; 7.67/s/lH; 7.83/d/lH; 7.95/d/lH; 8.40/s lH;

H-1.22 l,26/t/3H; l,68/d/3H; 2,46/m 2H; 2,79/m 2H; 3,47/m/2H; 5,50/m/lH;

5,67/d/lH; 7,19/d/lH; 7,66-7,69/m/2H; 7,88-7,94/m/2H; 8,38/s lH;

H-1.24 0.97Λ/3H; 1.26/t 3H; 1.49/m/2H; 1.61-1.80/m 5H; 2.79/m/2H;

3.33Λ/2H; 5.50/m/lH; 5.66/d/lH; 7.19/d/lH; 7.64/dd/lH; 7.66/s/lH; 7.85/d/lH; 7.91/d/lH; 8.39/s/lH

H-1.28 1.26Λ/3H; 1.68/d 3H; 2.79/q/2H; 4.01/d/2H; 5.12/m/lH; 5.34/m/lH;

6.01/m/lH; 7.21/d/lH; 7.64-7.67/m/2H; 7.85-7.94/m/2H; 8.39/s/lH

H-1.34 1.26/t/3H; 1.67/d/3H; 1.60-1.85/m/6H; 2.27/m/2H; 2.79/q/2H;

5.50/m/lH; 5.66/d/lH; 7.19/d/lH; 7.62-7.66/m 2H; 7.84/d/lH; 7.91/d/lH; 8.39/s/lH H-1.38 1.26Λ/3H; 1.68/d 3H; 1.77-1.90/m/6H; 2.80/q/2H; 3.33/t 2H; 3.56/t/2H;

5.50/m/lH; 5.66/d/lH; 7.19/d/lH; 7.63-7.67/m/2H; 7.83-7.92/m/2H; 8.39/s/lH

H-1.43 1.23/t/3H; 1.46/d/6H; 1.68/d 3H; 2.79/q/2H; 4.23/m/lH; 5.50/m/lH;

5.66/d/lH; 7.17/d/lH; 7.64/dd/lH; 7.66/s/lH; 7.85/d/lH; 7.91/d/lH; 8.39/s/lH

H-1.60 1.05/1/3H; 1.26/t/3H; 1.44/d/3H; 1.67/d/3H; 1.66-1.81/m/2H; 2.79/q/2H;

4.13/m/lH; 5.50/m/lH; 5.66/d/lH;

H-1.68 1.26/t/3H; 1.68/d/3H; 1.65-2.20/m/6H; 2.79/q/2H; 4.87/m/lH;

5.50/m/lH; 5.69/d/lH; 5.88/m/2H; 7.17/d/lH; 7.63-7.66/m/2H; 7.85/d/lH; 7.91/d/lH; 8.39/s/lH

H-1.76 1.26/1/3H; 1.68/d/3H; 2.53/q/2H; 2.79/q/2H; 3.39/1 2H; 5.05-5.17/m/2H;

5.50/m/lH; 5.66/d/lH; 5.87-5.94/m/lH; 7.20/d/lH; 7.63-7.67/m/2H; 7.85/d/lH; 7.91/d/lH; 8.39/s/lH

H-1.81 1.26/t/3H; 1.67/t 3H; 1.81/t/3H; 2.79/q/2H; 4.12/m/2H; 5.50/m/lH;

5.66/d/lH; 7.22/d/lH; 7.64-7.68/m/2H; 7.88-7.95/m/2H; 8.39/s/lH

H-1.90 0.39/m/2H; 0.70/m/2H; 1.26/t/3H; 1.69/d/3H; 2.70/m/lH; 2.79/q/2H;

3.87/S/2H; 5.51/m/lH; 5.68/d/lH; 7.26/d/lH; 7.70-7.96/m/4H; 8.38/s/lH

H-1.92 1.24/t 3H; 1.71/d/3H; 2.80/q/2H; 4.03/s/2H; 5.54/m/lH; 5.69/d/lH;

7.06/t/lH; 7.21-7.34/m/3H; 7.44/d 2H; 7.78/d/2H; 8.00/t/2H; 8.39/s/lH; 10.1/s/lH

H-1.100 1.13Λ/3H; 1.23-l,35/m/6H; 1.68/d/3H; 2.79/q/2H; 3.42/q/2H; 3.55/q/2H;

4.29/S/2H; 5.49/m/lH; 5.65/d/lH; 7.24-7.28/m/lH; 7.62-7.67/m/2H; 7.82-7.89/m/2H; 8.39/s/lH

H-1.102 1.26Λ/3H; 1.57-1.65/m/6H; 1.68/d/3H; 2.79/q/2H; 4.33/s/2H;

5.50/m/lH; 5.65/d/lH; 7.26/d/lH; 7.63-7.68/m/2H; 7.86-7.90/m/2H; 8.39/s/lH H-2.7 1.26Λ 3H; 1.44/t/3H; 1.69/d/3H; 2.80/q/2H; 3.33/m/2H; 5.53/m/lH;

5.71/d/lH; 7.18/d/lH; 7.43/dd/lH; 7.69/d/lH; 7.83-7.90/m/2H; 8.39/s/lH

H-2.10 1.26/t 3H; 1.70/d/3H; 2.80/q/2H; 3.64-3.73/m/2H; 4.64/t/lH; 4.82/t/lH;

7.19/d/lH; 7.45/dd/lH; 7.71/d/lH; 7.86-7.90/m/2H; 8.39/s/lH

H-2.13 1.19Λ/3H; 1.63/d/3H; 2.73/q/2H; 4.07-4.24/m/2H; 5.46/m/lH;

5.64/d/lH; 7.16/d/lH; 7.41/dd/lH; 7.66/d/lH; 7.85-7.89/m/2H; 8.31/s/lH

H-2.16 1.09/1/3H; 1.26/1/3H; 1.69/d/2H; 1.81/m 2H; 2.79/q/2H; 3.32/m/2H;

5.53/m/lH; 5.70/d/lH; 7.18/d/lH; 7.43/dd/lH; 7.69/d/lH; 7.82-7.89/m/2H; 8.38/s/lH

H-2.19 1.26/t/3H; 1.47/d/6H; 1.69/d/3H; 2.80/q/2H; 4.24/m/lH; 5.53/m/lH;

5.70/d/lH; 7.16/d/lH; 7.43/dd/lH; 7.69/d lH; 7.83-7.89/m/2H; 8.38/s/lH

H-2.22 1.25/t/3H; 1.69/d/3H; 2.63/m/2H; 2.80/q/2H; 3.49/m/2H; 5.53/m/lH;

5.60/d/lH; 7.10/d/lH; 7.45/dd/lH; 7.70/d lH; 7.85-7.90/m/2H; 8.38/s/lH

H-2.24 1.06/t 3H; 1.26/t 3H; 1.46/d/3H; 1.70/d/3H; 1.68-1.76/m/2H; 2.80/q/2H;

4.12/m/lH; 5.53/m/lH; 5.71/d/lH; 7.17/d/lH; 7.43/d/lH; 7.69/d/lH; 7.82-7.88/m/2H; 8.39/s/lH

H-2.28 1.26/1/3H; 1.69/d 3H; 2.79/q/2H; 4.02/m/2H; 5.13/m/lH; 5.36/m/lH;

5.53/m lH; 5.70/d/lH; 5.96-6.10/m/lH; 7.19/d/lH; 7.44/dd/lH; 7.70/d/lH; 7.84-7.90/m/2H; 8.38/s/lH

H-2.31 1.26/1/3H; 1.70/d/3H; 2.20/t/lH; 2.80/q/2H; 4.17/m/2H; 5.53/m/lH;

5.70/d/lH; 7.21/d/lH; 7.46/dd/lH; 7.71/d/lH; 7.89-7.93/m/2H; 8.38/s/lH H-2.38 1.26Λ/3H; 1.69/d/3H; 1.70-2.10/m/6H; 2.80/q/2H; 4.90/m/lH;

5.54/m/lH; 5.72/d/lH; 5.89/m/2H; 7.16/d/lH; 7.44/dd/lH; 7.69/d/lH; 7.83-7.87/m/2H; 8.39/s/lH

H-2.83 0.01/S/9H; 1.12Λ/3H; 1.55/d/3H; 2.66/q/2H; 4.06/s/2H; 5.39/m/lH;

5.57/d/lH; 7.06/d/lH; 7.31/dd lH; 7.57/d/lH; 7.74-7.78/m/2H; 8.24/s/lH

H-2.84 1.21/S/9H (E or Z isomer); 1.26/m/6H (E and Z isomer); 1.29/s/9H (E or

Z isomer); 1.48/d/3H (E or Z isomer); 1.70/d/3H (E or Z isomer); 2.80/q/4H (E and Z isomer); 4.08/m/2H (E or Z isomer); 4.21/m/2H (E or Z isomer); 5.52/m/2H (E and Z isomer); 5.72/dd/2H (E and Z isomer); 6.20/m/2H (E and Z isomer); 7.19/d/lH (E or Z isomer); 7.20/d/lH (E or Z isomer); 7.46/m/2H (E and Z isomer); 7.70/m/2H (E and Z isomer); 7.83-7.93/m/4H (E and Z isomer); 8.39/s 2H (E and Z isomer)

H-2.100 1.20/t/3H; 1.23-1.35/m 6H; 1.69/d/3H; 2.80/q/2H; 3.42/m/2H;

3.55/m 2H; 4.28/d/2H; 5.52/m/lH; 5.70/d/lH; 7.25/d/lH; 7.44/dd/lH; 7.71/d/lH; 7.81-7.89/m/2H; 8.38/s/lH

H-2. Ill 1.26Λ/3H; 1.70/d/3H; 1.74/s 3H; 1.79/s/3H; 2.79/q/2H; 3.99/d/2H;

5.40/m/lH; 5.52/m/lH; 5.71/d/lH; 7.18/d/lH; 7.45/dd/lH; 7.70/d/lH; 7.83-7.90/m/2H; 8.38/s/lH

Formulation examples of active ingredients of the formula I

Examples F-1.1 to F-1.3: Emulsion concentrates

Components F-1.1 F-1.2 F-1.3

Active ingredient of Table 1 or 2 25% 40% 50%

Calcium dodecylbenzenesulfonate 5% 8% 6%

Castor oil polyethylene glycol ether

(36 mol of ethyleneoxy units) 5%

Tributylphenol polyethylene glycol ether

(30 mol of ethyleneoxy units) - 12% 4%

Cyclohexanone - 15% 20%

Xylene mixture 65% 25% 20%

Emulsions of any desired dilution can be prepared from these emulsion concentrates using water.

Exam le F-2: Emulsion concentrate

Emulsions of any desired dilution can be prepared from this emulsion concentrate using water.

Examples F-3.1 to F-3.4: Solutions

Components F-3.1 F-3.2 F-3.3 F-3.4

The solutions are suitable for use in the form of microdrops.

Examples F-4.1 to F-4.4: Granules

Components F-4.1 F-4.2 F-4.3 F-4.4

Active ingredient of Table 1 or 2

Kaolin

Highly disperse silica

Attapulgite

The active ingredient according to the invention is dissolved in dichloromethane, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo. Examples F-5.1 and F-5.2: Dusts

Components F-5.1 F-5.2

Active ingredient Table 1 or 2 2% 5%

Highly disperse silica 1% 5%

Talc 97%

Kaolin - 90%

Ready-to-use dusts are obtained by intimately mixing all components.

Examples F-6.1 to F-6.3: Wettable powders

Components F-6.1 F-6.2 F-6.3

Active ingredient of Table 1 or 2 25% 50% 75%

Sodium ligninsulfonate 5% 5%

Sodium lauryl sulfate 3% - 5%

Sodium diisobutylnaphthalene sulfonate - 6% 10%

Octylphenol polyethylene glycol ether

(7 to 8 mol of ethyleneoxy units) - 2% -

Highly disperse silica 5% 10% 10%

Kaolin 62% 27%

All components are mixed, and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration. Biological examples: A. Microbicidal activities

B-l: Activity against Puccinia graminis in wheat a) Residual-protective activity

6 days after sowing, wheat plants are sprayed to drip point with an aqueous spray mixture (0.2 % of active ingredient) prepared with a wettable powder of the active ingredient, and, 24 hours later, infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (environment: 95 to 100 percent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. 12 days after infection, the fungus infestation is assessed.

b) Systemic activity

An aqueous spray mixture (0.006 % of active ingredient relative to the soil volume) prepared with a wettable powder of the active ingredient is poured next to wheat plants 5 days after sowing. Care is taken that the spray mixture does not come into contact with aerial parts of the plants.48 hours later, the plants are infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (environment: 95 to 100 percent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°C. 12 days after infection, the fungus infestation is assessed. Compounds of Tables 1 and 2 exhibit good activity.

Example B-2: Activity against Phytophthora infestans in tomatoes a) Residual-protective activity

Tomato plants are grown for three weeks and then sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 24 hours later, infected with a sporangia suspension of the fungus. The fungus infestation is assessed 5 days after the infection, during which period a relative atmospheric humidity of 90 to 100 % and a temperature of 20° are maintained.

b) Systemic activity

Tomato plants are grown for three weeks and then an aqueous spray mixture (0.006 % of active ingredient based on the soil volume) prepared with a wettable powder of the active ingredient is poured next to them. Care is taken that the spray mixture does not come into contact with the aerial parts of the plants. After 48 hours, the plants are infected with a sporangia suspension of the fungus. The fungus infestation is assessed 5 days after the infection, during which period a relative atmospheric humidity of 90 to 100 % and a temperature of 20° are maintained.

Compounds of Tables 1 and 2 exhibit good activity.

Example B-3: Residual-protective activity against Cercospora arachidicola in groundnuts Groundnut plants with a height of 10 to 15 cm are sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 48 hours later, infected with a conidia suspension of the fungus. The plants are incubated for 72 hours at 21° and at high atmospheric humidity and then placed in a greenhouse until the typical lesions appear. The activity of the active ingredients is assessed 12 days after infection on the basis of number and size of the lesions. Compounds of Tables 1 and 2 exhibit good activity.

Example B-4: Activity against Plasmopara viticola on vines

Vine seedlings in the 4- to 5-leaf stage are sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 24 hours later, infected with a sporangia suspension of the fungus. The fungus infestation is assessed 6 days after infection, during which period a relative atmospheric humidity of 95 to 100 % and a temperature of 20° are maintained. Compounds of Tables 1 and 2 exhibit good activity.

Example B-5: Activity against Colletotrichum lagenarium in cucumbers Cucumber plants are grown for 2 weeks and then sprayed with a spray mixture (concentration 0.002 %) prepared with a wettable powder of the active ingredient. After 2 days, the plants are infected with a spore suspension (1.5x10^s spores/ml) of the fungus and incubated for 36 hours at 23°C and high atmospheric humidity. The incubation is then continued at normal atmospheric humidity and at approximately 22°C. The incidence of fungus infestation is assessed 8 days after infection. Compounds of Tables 1 and 2 exhibit good activity.

Example B-6: Residual-protective activity against Venturia inaequalis in apples Apple cuttings having fresh shoots of a length of 10 to 20 cm are sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 24 hours later, infected with a conidia suspension of the fungus. The plants are incubated for 5 days at a relative atmospheric humidity of 90 to 100 % and then placed for a further 10 days in a greenhouse at 20 to 24°. The fungus infestation is assessed 12 days after infection. Compounds of Tables 1 and 2 exhibit good activity.

Example B-7: Activity against Erysiphe graminis in barley a) Residual-protective activity

Barley plants approximately 8 cm high are sprayed to drip point with an aqueous spray mixture (0.02 % of active ingredient) prepared with a wettable powder of the active ingredient and, 3 to 4 hours later, dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. 12 days after infection, the fungus infestation is assessed.

Compounds of Tables 1 and 2 exhibit good activity.

b) Systemic activity

An aqueous spray mixture (0.002 % of active ingredient based on the soil volume) prepared with a wettable powder of the active ingredient is poured next to barley plants approximately 8 cm in height. Care is taken that the spray mixture does not come into contact with the aerial parts of the plants. 48 hours later, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. 12 days after infection, the fungus infestation is assessed. Compounds of Tables 1 and 2 exhibit good activity.

Example B-8: Activity against Podosphaera leucotricha in apple shoots

Apple cuttings having fresh shoots approximately 15 cm in length are sprayed with a spray mixture (0.06 % of active ingredient). After 24 hours, the treated plants are infected with a conidia suspension of the fungus and placed in a controlled environment cabinet at 20°C and a relative atmospheric humidity of 70 %.12 days after infection, the fungus infestation is assessed.

Compounds of Tables 1 and 2 exhibit good activity.

Biological Examples: B. Acaricidal, insecticidal and nematicidal activities

B-9: Activity against Tetranychus urticae (Acarina)

Young bean plants are populated with a mixed population of Tetranychus urticae and, one day later, sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. The plants are subsequently incubated for 6 days at 25°C and then evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with those on the untreated plants.

Compounds of Tables 1 and 2 exhibit good activity.

B-10: Activity against a mixed population of Tetranychus cinnabarinus (Acarina).

Dilution series.

Dwarf beans in the 2-leaf stage are populated with a mixed population (eggs, larvae/nymphs, adults) of an OP-tolerant Tetranychus cinnabarinus strain. 24 hours after infection, the products are applied to the plants in an automatic spray cabin at dosage rates of 200, 100 and 50 mg of A.I./1. The substances are formulated and are diluted with water to give the dosage rates in question.

2 and 7 days after application, the test is evaluated for percentage mortality of

- eggs,

- larvae/nymphs and

- adults.

Compounds of Tables 1 and 2 in dilutions of as little as 50 mg of AJJlitre show a mortality of over 70 %.

B-ll: Activity against Nilparvata lugens (Insecta)

Rice plants are treated with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. After the spray coating has dried on, the rice plants are populated with plant hopper larvae of the 2nd and 3rd stage. The test is evaluated 21 days later. The percentage reduction in population (% activity) is determined by comparing the number of surviving plant hoppers on the treated plants with those on the untreated plants. Compounds of Tables 1 and 2 exhibit an activity of over 90 %.

B-12: Activity against Plutella xylostella caterpillars (Insecta)

Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. After the spray coating has dried on, the cabbage plants are populated with 10 Plutella xylostella caterpillars of the third stage and placed in a plastic container. The test is evaluated 3 days later. The percentage reduction in population and the percentage reduction of the feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on the untreated plants. Compounds of Tables 1 and 2 exhibit good activity. Example B-13: Activity against Musca domestica (Insecta) A lump of sugar is treated with a solution of the test substance in such a way that the concentration of test substance in the sugar is 250 ppm after drying overnight. This treated lump together with a wet cottonwool ball and 10 adult Musca domestica of an OP-resistant strain is placed onto an aluminium dish, and this is covered with a glass beaker and incubated at 25°C. After 24 hours, the mortality rate is determined. Compounds of Tables 1 and 2 exhibit good activity.

- B-14: Activity against Heterodera glycines (Nematoda) in soya beans Sandy soil is infested with eggs of the soybean cyst nematode H. glycines, approximately 6000 eggs per pot. The test substances are subsequently mixed in, at the relevant concentrations, lc pots (180 ccm) are then filled with the treated and infested soil, and three soybeans (cv. Maple Arrow) are sown per pot. Each treatment is replicated three times. The pots are incubated in the greenhouse for four to five weeks at approximately 27°C. The plants are then carefully removed from the pots, the roots are washed, and the number of cysts is determined.

The compounds of Tables 1 and 2 exhibit good activity against Heterodera glycines, as can be seen from the virtually complete reduction in cyst formation.

Claims

What is claimed is:

1. A compound of the formula I

in which the substituent A is in the 6- or 7-position and in which:

R₁ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, halo-C₁-C₄alkyl having 1, 2 or 3 halogen atoms, or C₁-C₄alkylthio;

R₂ and R₃ independently of one another are hydrogen, C₁-C₄alkyl, halo-C₁-C₄alkyl having 1-5 halogen atoms, C₁-C₂alkoxy-C₁-C₄alkyl, nitro-C₁-C₄alkyl, cyano-C₁-C₄alkyl,

C₁-C₄alkanoyl-C₁-C₄alkyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkyl, C₁-C₂alkylthio-C₁-C₄alkyl, C₁-C₂alkanesulfinyl-C₁-C₄alkyl, C₁-C₂alkanesulfonyl-C₁-C₄alkyl, C₂-C₄alkenyl, halo- C₂-C₄alkenyl having 1, 2 or 3 halogen atoms, C₂-C₄alkynyl, C₃-C₇cycloalkyl,

C₁-C₄alkoxy, halo-C₁-C₄alkoxy, C₁-C₄alkylthio, halo-C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, amino, C₁-C₄ cylamino, nitro, cyano, hydroxyl or halogen;

R₄ is hydrogen, C₁-C₄aIkyl, halo-C₁-C₄alkyl having 1, 2 or 3 halogen atoms,

C₁-C₂alkoxy-C₁-C₄alkyl, nitro-C₁-C₄alkyl, cyano-C₁-C₄alkyl, C₃-C₅cycloalkyl, benzyl, C₁-C₄alkanoyl, benzoyl, benzoyl whose phenyl group is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen, C₁-C₂alkyl, nitro and cyano;

R₅ and R₆ independently of one another are hydrogen, C₁-C₄alkyl, halo-C₁-C₄alkyl having 1, 2 or 3 halogen atoms, C₁-C₂alkoxy-C₁-C₄alkyl, nitro-C₁-C₄alkyl, cyano-C₁-C₄alkyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkyl or C₃-C₆cycloalkyl which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C₁-C₂alkyl; R₇ is hydrogen, halogen, C₁-C₄alkyl, cyclopropyl, C₁-C₄alkoxy or C₁-C₄alkylthio;

X is OR₁₀, SR₁₀ or N(R_{1 1})R₁₂;

R₁₀ is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 12 carbon atoms and which is substituted or unsubstituted, a cyclic, saturated or unsaturated hydrocarbon radical which has not more than 10 carbon atoms and which is substituted or unsubstituted, substituted or unsubstituted benzyl; or a substituted or unsubstituted heterocyclyl radical;

R_{1 1} is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical which has not more than 8 carbon atoms and which is unsubstituted or substituted by 1-5 halogen atoms, C₁-C₂alkoxy, hydroxyl, nitro, cyano, C₁-C₄alkanoyl, halo-C₁-C₄alkanoyl or

C₁-C₄alkoxycarbonyl, a cyclic, saturated or unsaturated hydrocarbon radical which has not more than 10 carbon atoms or benzyl, in which the carbocycle is unsubstituted or mono- or disubstituted by halogen, C₁-C₂alkyl, halomethyl, nitro or cyano, or heterocyclyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of C₁-C₂alkyl, halogen, halomethyl, nitro or cyano;

R₁₂ is hydrogen or C₁-C₄alkyl; or

R₁₁ and R₁₂ together with the nitrogen atom to which they are bonded are a heterocycle which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, C₁-C₂alkyl, halomethyl or nitro;

or, if appropriate, a tautomer thereof, in each case in free form or in salt form.

2. A compound of the formula I according to claim 1, in which

R₁₀ is an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 8 carbon atoms and which is unsubstituted or substituted by 1-5 halogen atoms,C₁-C₂alkoxy, hydroxyl, nitro, cyano, C₁-C₄alkanoyl, halo-C₁-C₄alkanoyl or

C₁-C₄alkoxycarbonyl, a cyclic, saturated or unsaturated hydrocarbon radical which has not more than 10 carbon atoms, or benzyl in which the carbocycle is unsubstituted or mono- or disubstituted by halogen, C₁-C₂alkyl, halomethyl, nitro or cyano, or heterocyclyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, C₁-C₂alkyl, halomethyl, nitro or cyano, or a 5- to

7-membered lactone ring.

3. A compound of the formula I according to claim 1, in which

R₁₀ is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 12 carbon atoms and which is unsubstituted or substituted by

tri(C₁-C₄alkyl)silyl or by an epoxy group; or the group

-CH(U)(CH₂)_mCO-W,

in which:

U is hydrogen, C₁-C₄alkyl, cyano or C₁-C₆alkoxycarbonyl;

W is C₁-C₆alkoxy, C₃-C₆cycloalkoxy or the group -N(T₁)T₂

m is 0, 1 or 2 and

T₁ and T₂ independently of one another are hydrogen, C₁-C₆alkyl, which is unsubstituted or substituted by 1-3 halogen atoms, C₁-C₂alkoxy, hydroxyl, nitro, cyano, C₁-C₄alkanoyl, halo-Q^alkanoyl or C₁-C₄alkoxycarbonyl, or C₁-C₆alkenyl which is unsubstituted or substituted by 1-3 halogen atoms, C₁-C₆alkynyl which is unsubstituted or substituted by 1-3 halogen atoms, a cyclic, saturated or unsaturated hydrocarbon radical having not more than 10 carbon atoms or benzyl in which the carbocycle is unsubstituted or mono- or disubstituted by halogen, C₁-C₂alkyl, halomethyl, nitro or cyano, or heterocyclyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of C₁-C₂alkyl, halogen, halomethyl, nitro or cyano; or

Ti and T₂ together with the nitrogen atom to which they are bonded form a 5-7-membered heterocycle which can additionally have O, S and/or N as ring atoms, in which the additional nitrogen is unsubstituted or substituted by C₁-C₄alkyl, phenyl, C₁-C₄alkanoyl, benzoyl or benzyl and in which the carbon atoms of the heterocycle are unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, C₁-C₂alkyl, halomethyl or nitro.

4. A compound of the formula I according to claim 3, in which

R₁₀ is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical which has not more than 6 carbon atoms and which is unsubstituted or substituted by

tri(C₁-C₄alkyl)silyl or an epoxy group; or the group

-CH₂-CO-W,

in which:

W is C₁-C₆alkoxy, C₃-C₆cycloalkόxy or the group -N(T₁)T₂;

T₁ and T₂ independently of one another are hydrogen, C₁-C₆alkyl, halo-C₁-C₆alkyl having

T₁ and T₂ together with the nitrogen atom to which they are bonded are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.

5. A compound of the formula I according to claim 1, in which

R₁ is hydrogen or C₁-C₄alkyl;

R₂ is hydrogen, C₁-C₄alkyl, halo-C₁-C₄alkyl having 1, 2 or 3 halogen atoms,

C₁-C₂alkoxy-C₁-C₄alkyl, cyclopropyl, ethynyl or halogen;

R₃ is fluorine or chlorine;

R₄ is hydrogen or C₁-C₄alkyl;

R₅ is C₁-C₄alkyl;

R₆ is hydrogen; R₇ is hydrogen or halogen;

X is OR₁₀. SR₁₀ σr N(R₁₁)R₁₂;

R₁₀ is C₁-C₄alkyl, halo-C₁-C₄alkyl having 1, 2 or 3 halogen atoms, C₁-C₂alkoxy- C₁-C₄alkyl, hydroxy-C₁-C₄alkyl, nitro-C₁-C₄alkyl, cyano-C₁-C₄alkyl, Cι-C₄alkanoyl- C₁-C₄alkyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkyl, C₂-C₄alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C₂-C₄alkynyl, C₃-C₇cycloalkyl, C₄-C₈cycloalkenyl, benzyl, phenyl which is unsubstituted or mono- or disubstituted by halogen, C₁-C₂alkyl, nitro or cyano, or pyridine, pyrimidine or triazine, these heterocycles in each case being unsubstituted or mono- to trisubstituted by identical or different substituents from the series consisting of halogen, C₁-C₂alkyl, trifluoromethyl or cyano, or a 5-membered lactone ring;

R₁₁ is hydrogen, C₁-C₄alkyl, halo-C₁-C₄alkyl having 1, 2 or 3 halogen atoms,

C₁-C₂alkoxy-C₁-C₄alkyl, hydroxy-C₁-C₄alkyl, nitro-C₁-C₄alkyl, cyano-C₁-C₄alkyl, C₁-C₄alkanoyl-C₁-C₄alkyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkyl, C₂-C₄alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C₂-C₄alkynyl, C₃-C₇cycloalkyl, C₄-C₅cycloalkenyl, benzyl, phenyl, which is unsubstituted or mono- or disubstituted by halogen, C₁-C₂alkyl, nitro or cyano,

R₁₂ is hydrogen or C₁-C₆alkyl; or

Rn and R₁₂ together with the nitrogen atom to which they are bonded are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.

6. A compound of the formula I according to claim 5, in which

X is SR₁₀.

7. A compound of the formula I according to claim 5, in which

X is OR₁₀.

8. A compound of the formula I according to claim 1, in which

R₁ is hydrogen or C₁-C₄alkyl;

C₁-C₂alkoxy-C₁-C₄alkyl, cyclopropyl, ethynyl or halogen;

R₃ is chlorine;

R₄ is hydrogen or C₁-C₄alkyl;

R₅ is C1-C₄alkyl;

R₆ is hydrogen;

R₇ is hydrogen; X is OR₁₀ or SR₁₀;

R₁₀ is the group -CH₂-CO-W,

W is C₁-C₆alkoxy, C₃-C₆cycloalkoxy or the group -N(T₁)T₂;

T₁ and T₂ independendy of one another are hydrogen, C₁-C₆alkyl, halo-C₁-C₆alkyl having

9. A compound according to claim 1, of the formula 1.1

in which:

R₂ is hydrogen, methyl or ethyl;

R₃ is fluorine or chlorine;

R₅ is methyl or ethyl;

R₇ is hydrogen or fluorine;

X is OR₁₀, SR₁₀ orN(R₁₁)R₁₂;

R₁₀ is C₁-C₄alkyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, vinyl, allyl, 2-propynyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyanomethyl or

C₁-C₄alkoxycarbonylmethyl;

R₁₁ is hydrogen, C₁-C₄alkyl, cyclohexyl, cyclopropyl or phenyl;

R₁₂ is hydrogen; or

R₁₁and R₁₂ together with the nitrogen atom to which they are bonded are piperidine, morpholine or 2,6-dimethylmorpholine.

10. A compound according to claim 1, of the formula 1.2

in which:

R₂ is hydrogen, methyl or ethyl;

R₃ is fluorine or chlorine;

R₅ is methyl or ethyl;

R₇ is hydrogen or fluorine;

X is OR₁₀, SR₁₀ or N(R₁₁)R₁₂;

C₁-C₄alkoxycarbonylmethyl;

R₁₁ is hydrogen, C₁-C₄alkyl, cyclohexyl, cyclopropyl or phenyl;

R₁₂ is hydrogen; or

R₁₁ and R₁₂ together with the nitrogen atom to which they are bonded are piperidine, morpholine or 2,6-dimethylmorpholine.

11. A compound according to claim 1 of the formula I.1a

in which

R₁₀ is C₁-C₅alkyl which is unsubstituted or mono- to trisubstituted by halogen, or

C₂-C₅alkenyl which is unsubstituted or mono- to trisubstituted by halogen.

12. A process for the preparation of the compound of the formula I according to claim 1, which comprises reacting:

a) to prepare a compound of the formula I , in which X is SR₁₀: a compound of the formula II

in which the substituent A is in the 6- or 7-position and in which R₁ to R₇ are as defined for formula I with a compound of the formula III R₁₀-Z (III) in which R₁₀ is as defined in formula 1 and Z is an easily detachable nucleofugic radical; preferably in the presence of a base, particularly preferably by first reacting a compound of the formula π with a base and subsequently with a compound of the formula III; or b) to prepare a compound of the formula I in which X is OR₁₀ or N(R₁₁)R₁₂:

a compound of the formula I in which X is SR₁₀ with a compound of the formula IV

M-X (IV) in which:

M is hydrogen, Li⁺, Na⁺, K⁺, 1/2Mg²⁺ or a quaternary ammonium ion;

X is OR₁₀ or N(R₁₁)R₁₂ and in which R₁₀, R₁₁ and R₁₂ are as defined for formula I; if appropriate in the presence of a base; or c) to prepare a compound of the formula I in which R₄ is as defined for formula I but is other than hydrogen: .

a compound of the formula I in which R₄ is hydrogen with a compound of the formula V

R₄'-Z' (V) in which R₄' is as defined for R₄ in formula I but is other than hydrogen, and Z' is an easily detachable nucleofugic radical; preferably in the presence of a base.

13. A process for the preparation of a compound of the formula I according to claim 1, which comprises reacting: a compound of the formula VII

in which the substituent A is in the 6- or 7-position and in which R₁ to R₇ arc as defined for formula I with phosphorus oxychloride, thionyl chloride or sulfuryl chloride to give a compound of the formula VIII

and this compound with a compound of the formula IV' M-X' (IV') in which:

M is hydrogen, Li⁺, Νa⁺, K⁺, 1/2Mg²⁺ or a quaternary ammonium ion;

X' is OR₁₀, SR₁₀ or N(R₁₁)R₁₂ and in which R₁₀, Rn and R₁₂

are as defined for formula I; if appropriate in the presence of a base.

14. A process for the preparation of a compound of the formula I according to claim 1, which comprises reacting a compound of the formula IX

in which the substituent A is in the 6- or 7-position and in which R₁ to R₇ and X are as defined for formula I with an oxidant

15. A process according to claim 14, wherein the oxidant is an iron(m) salt, SeO₂, MnO₂, H₂O₂, Br₂ Cl₂, I₂, SO₃, H₂SO₄, HNO₃, N-bromosuccinimide, 2,3-dichloro-5,6-dicyano- 1,4-benzoquinone or O₂ in the presence of a dehydrogenation catalyst.

16. A process for the preparation of a compound of the formula I according to claim 1, which comprises reacting a compound of the formula IX'

in which the substituent A is in the 6- or 7-position and in which R₁ to R₇ and X are as defined for formula I and in which Z is an easily detachable nucleofugic radical in the presence of a base or an acid, with the elimination of HZ.

17. A composition for protecting plants against attack by pests, which comprises, as active ingredient, at least one compound according to claim 1 in free form or in agrochemically utilizable salt form together with a suitable carrier material.

18. A composition according to claim 17, the pests being phytopathogenic

microorganisms.

19. A composition according to claim 17, the pests being insects, Acarina or nematodes.

20. A composition for protecting plants against attack by pests, which comprises, as active ingredient, at least one compound according to claim 2 in free form or in agrochemically utilizable salt form together with a suitable carrier material.

21. A composition according to claim 20, the pests being phytopathogenic

microorganisms.

22. A composition according to claim 20, the pests being insects, Acarina or nematodes.

23. A process for the preparation of a composition according to claim 17, which comprises intimately mixing the active ingredient with the adjuvants and/or carrier material.

24. The use of a compound of the formula I according to claim 1 for protecting plants against attack by pests.

25. The use according to claim 24, the pests being phytopathogenic microorganisms.

26. The use according to claim 24, the pests being insects, Acarina or nematodes.

27. A method of protecting plants against attack by pests, which comprises applying, as active ingredient, a compound according to claim 1 to the plants, to parts of the plants and/or the locus of the plants.

28. A method according to claim 27, the pests being phytopathogenic microorganisms.

29. A method according to claim 27, the pests being insects, Acarina or nematodes.

30. A method of protecting plants against attack by pests, which comprises applying, as active ingredient, a compound according to claim 2 to the plants, to parts of the plants and/or the locus of the plants.

31. A method according to claim 30, the pests being phytopathogenic microorganisms.

32. A method according to claim 30, the pests being insects, Acarina or nematodes.

33. Method according to claim 27, wherein the seed is treated.

34. Seed which has been treated according to claim 33.