EP0966467A1

EP0966467A1 - Annulated azole derivatives useful as microbicidal agents

Info

Publication number: EP0966467A1
Application number: EP98906961A
Authority: EP
Inventors: Lutz Assmann; Hans-Ludwig Elbe; Ralf Tiemann; Klaus Stenzel
Original assignee: Bayer AG
Current assignee: Bayer CropScience AG
Priority date: 1997-03-04
Filing date: 1998-02-19
Publication date: 1999-12-29
Also published as: DE19708688A1; US6387922B2; AU6297298A; US6214840B1; US6569869B2; WO1998039331A1; PL335462A1; US20010029237A1; KR20000071079A; CZ312699A3; JP2001513783A; CN1249752A; BR9808142A; US20020143184A1

Abstract

New annulated azole derivatives of formula (I) are disclosed, in which R<1>, R<2>, A and G have the meanings given in the description, as well as their acid addition salts and metal salt complexes, several processes for preparing these substances and their use as plant-protecting and material-protecting microbicidal agents.

Description

FURNISHED AZOLE DERIVATIVES AS MICROBICIDES

The present invention relates to new fused azole derivatives, several processes for their preparation and their use as microbicides in crop protection and in

Material protection.

It has already become known that certain fused azole derivatives have fungicidal properties (cf. DE-A 195 23 446). So z. B. Use l- (3,5-dimethyl-isoxazole-4-sulfonyl) -lH-benzotriazole to combat fungi. The

Efficacy of this substance is good, but leaves something to be desired in some cases at low application rates.

There have now been new fused azole derivatives of the formula

A in which

Rl and R ^ together with the carbon atoms to which they are attached represent an optionally substituted heterocyclic ring or an optionally substituted benzo-fused heterocyclic ring,

G represents nitrogen or a group ^ ^" ^ .C - R 3, wherein

R ³ for hydrogen, halogen, cyano, nitro, trifluoromethyl, thiocarb-

NH amoyl, thiocyanato or the group \ where

S - R

R ^{4 represents} alkyl, YR ^{6 stands} for one of the following groupings ^so ₂ ^{~ R} , P, in which

R ⁷

Y represents oxygen or sulfur,

for an optionally substituted, unsaturated heterocyclic

Rest stands,

R ° and R 'independently of one another for alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyl, haloalkenyl, alkenyloxy, alkenylthio, alkynyl, alkynyloxy, alkynylthio, optionally substituted by alkyl, cycloalkyl or aryl, optionally substituted aryl, optionally substituted aryl Aryloxy, optionally substituted arylthio, optionally substituted cycloalkyl, optionally substituted cycloalkyloxy, optionally substituted cycloalkylthio or represent an optionally substituted, saturated or unsaturated heterocyclic radical, or

R and R ^ together with the phosphorus atom to which they are attached represent an optionally substituted heterocyclic radical,

as well as their acid addition salts and metal salt complexes.

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkynyl, are also linked to heteroatoms, as in

Alkoxy, alkylthio or alkylamino, in each case straight-chain or branched.

Furthermore, it was found that fused azole derivatives of the formula (I) and their acid addition salts and metal salt complexes are obtained if

a) Azoles of the formula in which

R *, R ^ and G have the meanings given above,

with halides of the formula

AX ¹ (III)

in which

A has the meaning given above and

χl represents halogen,

if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,

or if you

b) cyanimidazoles of the formula

in which

Rl, R ^ and A have the meanings given above, with hydrogen sulfide, if appropriate in the presence of a base and if appropriate in the presence of a diluent, or if

c) thiocarbamoylimidazoles of the formula

in which

Rl, R ^ and A have the meanings given above,

with an alkylating agent of the formula

R ⁴ -X ² (IV)

in which

R ^{4 has} the meaning given above and

X ^{2 represents} a leaving group,

and optionally adding an acid or a metal salt to the compounds of formula (I) thus obtained.

Finally, it was found that the fused azole derivatives of the formula (I) and their acid addition salts and metal salt complexes have very good microbicidal properties. possess properties and can be used both in crop protection and in material protection.

Surprisingly, the substances according to the invention show a better fungicidal activity than 1- (3,5-dimethyl-isoxazole-4-sulfonyl) -1H-benzotriazole, which is a constitutionally similar, known active ingredient with the same direction of action.

The substances according to the invention are generally defined by the formula (I).

Rl and R ² together with the carbon atoms to which they are attached are preferably a 5- or 6-membered heterocyclylic ring which contains one, two or three identical or different heteroatoms, such as oxygen, sulfur and / or nitrogen, and can be monosubstituted to trisubstituted, identical or different, by halogen, cyano, nitro, hydroxy, amino, formyl, carboxy, carbamoyl, thiocarbamoyl, alkyl having 1 to 4

Carbon atoms, alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, Cycloalkyl with 3 to 6 carbon atoms,

Haloalkylsulfinyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkylamino with 1 to 4 carbon atoms, hydroxyalkylamino with 1 to 4 carbon atoms, dialkylamino with 1 to 4 carbon atoms in each alkyl group, alkylcarbonyl with 1 to 4 carbon atoms in the alkyl part, hydroximinoalkyl with 1 to 4 carbon atoms in the alkyl part, alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, alkylcarbonyloxy with 1 to 4 carbon atoms in the alkyl part and / or haloalkylcarbonyloxy with 1 to 4 carbon atoms in the

Haloalkyl group and 1 to 5 identical or different halogen atoms,

or R ² together with the carbon atoms to which they are attached preferably represent a benzo-fused 5- or 6-membered heterocyclic ring which contains one or two identical or different heteroatoms, such as oxygen, sulfur and / or nitrogen, and is simple can be substituted up to three times, in the same way or differently, by halogen, cyano, nitro, hydroxy, amino, formyl, carboxy, carbamoyl, thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 up to 5 identical or different halogen atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, cycloalkyl with 3 to 6 carbon atoms, haloalkylsulfinyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkylsulfonyl having 1 to 4 carbon atoms and 1 to 5 identical or r different halogen atoms,

Alkylamino with 1 to 4 carbon atoms, hydroxyalkylamino with 1 to 4 carbon atoms, dialkylamino with 1 to 4 carbon atoms in each alkyl group, alkylcarbonyl with 1 to 4 carbon atoms in the alkyl part, hydroximinoalkyl with 1 to 4 carbon atoms in the alkyl part, alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, alkylcarbonyloxy with 1 to 4 carbon atoms in the alkyl part and / or haloalkylcarbonyloxy with 1 to 4 carbon atoms in the haloalkyl group and 1 to 5 identical or different halogen atoms,

in the event that the heterocyclic ring or the benzo-fused heterocyclic ring contains more than one oxygen atom, the oxygen atoms are not adjacent.

also preferably represents nitrogen or a group ^R R ³ preferably represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, trifluoromethyl, thiocarbamoyl, thiocyanato or the NH group

R ⁴ preferably represents alkyl having 1 to 4 carbon atoms.

A also preferably represents one of the following groupings: ^so ₂ ^{~ R} ,

YR ⁶ - P

V

Y also preferably represents oxygen or sulfur.

R5 preferably represents an unsaturated heterocyclyl radical with 5 or 6 ring members and 1 to 3 identical or different heteroatoms, such as nitrogen, oxygen and / or sulfur, where each of the heterocyclyl radicals can be mono- or disubstituted, identical or different, by halogen, Cyano, nitro, hydroxy, amino, formyl, carboxy, carbamoyl, thiocarbamoyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkoxy with 1 to 4 Carbon atoms and 1 to 5 identical or different halogen atoms,

Alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, cycloalkyl with 3 to 6 carbon atoms, haloalkylsulfinyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkylamino with 1 to 4 carbon atoms, hydroxyalkylamino with 1 to 4 carbon atoms, dialkylamino with 1 to 4 carbon atoms in each alkyl group, alkylcarbonyl with 1 to 4 carbon atoms in the alkyl part, hydroximinoalkyl with 1 to 4 carbon atoms in the alkyl part, alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 Carbon atoms in the alkyl part, alkylcarbonyloxy with 1 to 4 carbon atoms in the alkyl part and / or haloalkylcarbonyloxy with 1 to 4 carbon atoms in the haloalkyl group and 1 to 5 identical or different halogen atoms.

R ^ independently of one another preferably represent straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, straight-chain or branched haloalkoxy 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, straight-chain or branched haloalkylthio having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkenyl having 2 to 4 carbon atoms , straight-chain or branched haloalkenyl with 2 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkenyloxy with 2 to 4 carbon atoms, straight-chain or branched alkenylthio with 2 to 4 carbon atoms, straight-chain or branched alkynyl having 2 to 4 carbon atoms, straight-chain or branched alkynyloxy having 2 to 4 carbon atoms, straight-chain or branched alkynylthio having 2 to 4 carbon atoms, optionally single or double, identical or different from alkyl having 1 to 4 carbon atoms, cycloalkyl with 3 to 7 carbon atoms or phenyl-substituted amino,

or for phenyl, phenoxy, phenylamino or phenylthio, where each of these radicals can be substituted once to three times, identically or differently, by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine , Chlorine and / or bromine atoms, alkoxy with 1 to 4 carbon atoms and / or haloalkoxy with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, or for cycloalkyl with 3 to 7 carbon atoms, cycloalkyloxy with 3 to 7 carbon atoms, cycloalkylthio with 3 to 7 carbon atoms, cycloalkylamino with 3 to 7 carbon atoms, pyrrolidinyl, piperidinyl or morpholinyl, each of these radicals being one to three times, may be substituted in the same way or differently by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms,

or for a saturated or unsaturated heterocyclyl radical with 5 or 6 ring members and 1 to 3 identical or different heteroatoms, such as

Nitrogen, oxygen and / or sulfur, where each of these radicals can be substituted once or twice, identically or differently, by halogen, cyano, nitro, hydroxy, amino, formyl, carboxy, carbamoyl, thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxy by 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, cycloalkyl with 3 to 6 carbon atoms, haloalkylsulfinyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkylamino with 1 to 4 carbon atoms, hydroxyalkylamino with 1 to 4 carbon atoms, dialkylamino with 1 up to 4 carbon atoms in each alkyl group, alkylcarbonyl with 1 to 4 Carbon atoms in the alkyl part, hydroximinoalkyl with 1 to 4 carbon atoms in the alkyl part, alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, alkylcarbonyloxy with 1 to 4 carbon atoms in the alkyl part and / or haloalkylcarbonyloxy with 1 to 4 carbon atoms in the haloalkyl group and 1 to 5 identical or different halogen atoms.

R6 and R ^ together with the phosphorus atom to which they are attached are preferably a 5- or 6-membered heterocyclyl radical which contains one or two further identical or different heteroatoms, such as oxygen, Sulfur and / or nitrogen, and can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms and / or haloalkoxy having 1 to 4 carbon atoms and 1 up to 5 fluorine, chlorine and / or bromine atoms.

Rl and R ² together with the carbon atoms to which they are attached are in particular furandiyl, thiophendiyl, pyrroldiyl, oxazole diyl, thiazole diyl, imidazole diyl, isoxazole diyl, isothiazole diyl, pyrazole diyl, 1,2,3-oxadiazole diyl, 1,2,3- Thiadiazole diyl, 1,2,3-triazole diyl, pyridinediyl, pyridazinediyl, pyrazinediyl,

Pyrimidinediyl, 1,2,4-triazinediyl, indole-2,3-diyl, benzofuran-2,3-diyl, benzothiophene-2,3-diyl, quinoline-2,3-diyl, quinazoline-2,3- diyl, benzo [1,4] dioxin-2,3-diyl, benzo [1,4, dithiine-2,3-diyl, 4H-benzo [1,4, oxazine-2,3-diyl, 4H-benzo [ 1,4] thiazine-2,3-diyl, where these radicals can be substituted once or twice, in the same way or differently, by fluorine, chlorine, bromine,

Cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy , Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylamino, ethylamethyl, ethylamino, or iamethylaminoamino, ethylamethylamino, ethylamethylamino, ethylamethylamino, ethylamethylamino, ethylamethylamino, ethylamethylamino, ethylamethylamino, ethylamethylamino, ethylamethylamino, or iamifluoromethylamino, ethylamethylamino, ethylamethylamino, or iamethylaminoamino, ethylamethylamino, ethylamethylamino, or iodomethylamino, ethylamethylamino, ethylamethylamino, ethylamethylamino, or iamethylaminoamino , Propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyloxy, ethylsulfonyloxy, hydroxyiminomethyl, hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl, methoxyiminoethyl and / or ethoxyiminoethyl,

or

R ^{1 and} R ² together represent a radical of the formula N CH ₂ CH ₂

- H - CH, 2- CH5-CH52- -O- CH, - CH, - N- ^{2 2} H or ^- N CH ₂ CH ₂ N _> where each of these radicals can be substituted once or twice by methyl.

G also particularly stands for nitrogen or a grouping P ^R

R ³ also represents in particular hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, trifluoromethyl, thiocarbamoyl, thiocyanato or the grouping

R ⁴ stands in particular for methyl or ethyl.

A also particularly stands for one of the following groupings: ^so ₂ ^{~ R} ,

YR ⁶ - P

V

Y also particularly stands for oxygen or sulfur.

R5 stands in particular for pyrrolyl, furyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, pyridyl, Pyrimidyl, pyrazinyl or pyridazinyl, where each of these radicals can be substituted once or twice, in the same way or differently, by fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethyl, difluoromethoxy , Trifluoromethoxy, difluoromethylthio, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methylamino, ethylamino, n- or i-propylamino, Dimethylamino, diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyloxy, ethylsulfonyloxy, hydroxyiminomethyl, hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl, methoxyiminoethyl and / or ethoxyiminoethyl.

R ^ independently of one another are in particular methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n- or i-propoxy, n-, i -, s- or t-butoxy, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, allyl, n- or s-butyl; Allyloxy, n- or s-butenyloxy; Allylthio, n- or s-butenylthio; Propargyl, n- or s-butinyl; Propargyloxy; Propargylthio; Amino; Methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino; Dimethylamino, diethylamino, di-n- or i-propylamino, methylethylamino, methyl-n-propylamino, methyl-i-propylamino, cyclopropylamino, phenylamino or methylphenylamino,

for phenyl, phenoxy or phenylthio, where each of these radicals can be substituted once to three times, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-

Propoxy, trifluoromethyl and / or trifluoromethoxy; or

for cyclopropyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclopentylamino, cyclohexylamino, 1-pyrrolidinyl, 1-pipidridinyl, and 1-morphololinyl, each of which is simple to may be substituted identically or differently by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and / or trifluoromethyl, or

for pyrrolyl, furyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl,

Oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, pyridyl, pyrimidyl, pyrazinyl or pyridazinyl, each of these radicals being single or double, similar or different can be substituted by fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, Methoxy, ethoxy, n- or i-propoxy, methyl-thio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy,

Difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl or trifluoromethanesulfonic thylsulfonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyloxy, ethylsulphonyloxy, hydroxyiminomethyl, hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl, methoxy - Iminoethyl and / or ethoxyiminoethyl, or for pyrrolidinyl, piperidinyl, morpholinyl or piperazinyl which is optionally mono- or disubstituted by methyl.

R6 and R ^ together with the phosphorus atom to which they are attached also represent in particular a 5- or 6-membered heterocyclyl radical which contains one or two further identical or different heteroatoms, such as oxygen, sulfur and / or nitrogen can and can be mono- to trisubstituted, identical or different, by methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, chlorine and / or trifluoromethyl.

The general or preferred radical definitions given above apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation.

Preferred compounds according to the invention are also addition products of acids and those fused azole derivatives of the formula (I) in which R ^, B -, G and A have those meanings which have been mentioned as preferred for these radicals.

The acids which can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, sulfuric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids, such as p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid, saccharin and thiosaccharin.

In addition, preferred compounds according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. As well as IV. To NHL subgroup of the Periodic Table of the Elements and those fused azole derivatives of the formula (I) in which Rl , R ² , G and A have those meanings which have been mentioned as preferred for these radicals.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to physiologically tolerable addition products. Particularly preferred acids of this type are the hydrohalic acids, e.g. the hydrochloric acid and the

Hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.

Examples of substances according to the invention are the fused azole derivatives listed in Tables 1 to 11 below:

Table 1

where A stands for the following substituents:

Table 2

where A stands for the substituents mentioned in Table 1. Table 3

where A stands for the substituents mentioned in Table 1.

Table 4

where A stands for the substituents mentioned in Table 1.

Table 5

where A stands for the substituents mentioned in Table 1.

Table 6

where A stands for the substituents mentioned in Table 1. Table 7

where A stands for the substituents mentioned in Table 1

Table 8

where A stands for the substituents mentioned in Table 1

Table 9

where A stands for the substituents mentioned in Table 1

Table 10

where A stands for the substituents mentioned in Table 1 Table 11

where A stands for the substituents mentioned in Table 1.

If, for example, 2-bromo-1H-imidazo [4,5-b] pyridine and thiophene-2-sulfonyl chloride are used as starting materials, the course of process (a) according to the invention can be illustrated by the following formula:

Formula (II) provides a general definition of the azoles required as starting materials for carrying out process (a) according to the invention. In this formula (II), R, R ² and G preferably or in particular have those meanings which have already been given as preferred or as particularly preferred for R ² and G in connection with the description of the compounds of the formula (I) according to the invention .

The azoles of the formula (II) are known (compare, for example, Chem. Ber. 85_ (1952) 1012, 1020; Arch. Pharm. 290 (1957) 20, 31; Chem. Ber. 60 (1927), 773; and FR- A

2 542 742).

Formula (III) provides a general definition of the halides which are further required as starting materials for carrying out process (a) according to the invention. In this formula (III), A preferably or in particular has the meaning which is already in connection with the description of the compounds according to the invention of formula (I) has been indicated as preferred or as particularly preferred for A. χl is preferably chlorine.

The halides of the formula (III) are known or can be prepared by processes known per se (see, for example, J. Heterocyclic Chem. 1981. 997-

1006).

Suitable diluents for carrying out process (a) according to the invention are all inert organic solvents. Aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin can preferably be used; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or

Anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methyl-pyπ-olidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones, such as sulfolane, or amines, such as pyridine.

Suitable acid binders for carrying out process (a) according to the invention are all customary inorganic or organic bases. Alkaline earth metal or alkali metal hydrides, hydroxides,

amides, alcoholates, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate , Potassium hydrogen carbonate or sodium hydrogen carbonate, also ammonium compounds, such as ammonium hydroxide,

Ammonium acetate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmo holin, N, N-dimethylaminopyridine, diaza- bicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 120 ° C.

To carry out process (a) according to the invention, 1 to 15 mol, preferably 1 to 2 mol, in particular, are generally employed per mol of azole of the formula (II)

1 to 1.3 mol of halide of the formula (III). The processing takes place according to usual methods.

If, for example, l- (thiophene-2-sulfonyl) -lH-imidazo [4,5-b] pyridine-2-carbonitrile is used as the starting material and hydrogen sulfide as the reaction component, the course of process (b) according to the invention can be shown by the following formula illustrate:

Formula (Ia) provides a general definition of the cyanimidazoles required as starting materials for carrying out process (b) according to the invention. In this formula, *, R ² and A preferably or in particular have those meanings which have already been given as preferred or as particularly preferred for R *, R ² and A in connection with the description of the compounds of the formula (I) according to the invention. The cyanimidazoles of the formula (Ia) are compounds according to the invention and can be prepared by process (a) according to the invention.

Suitable diluents for carrying out process (b) according to the invention are all customary inert organic solvents and also water

Consideration. Aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether,

Diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Amines like

Pyridine; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with Water or pure water.

Suitable bases for carrying out process (b) according to the invention are again all customary inorganic or organic acid binders. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, are preferably usable. Sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate, furthermore ammonium compounds, such as ammonium hydroxide, ammonium acetate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N , N-dimethylbenzylamine,

Pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). The reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 120 ° C.

To carry out process (b) according to the invention, generally 1 to 1000 mol, preferably 1 to 50 mol, of hydrogen sulfide are used per mole of cyanimidazole of the formula (I-a). The implementation and processing are carried out using customary methods.

If, for example, l- (thiophene-2-sulfonyl) -lH-imidazo [4,5-b] pyridine-2-thiocarboxamide and iodomethane are used as starting materials, the course of process (c) according to the invention can be illustrated by the following formula:

Formula (Ib) provides a general definition of the thiocarbamoylimidazoles required as starting materials for carrying out process (c) according to the invention. In this formula, R 1, R ² and A preferably or in particular have those meanings which have already been given as preferred or as particularly preferred for R 1, R ² and A in connection with the description of the compounds of the formula (I) according to the invention.

The thiocarbamoylimidazoles of the formula (Ib) are compounds according to the invention and can be prepared by process (b) according to the invention. Formula (IV) provides a general definition of the alkylating agents which are further required as starting materials for carrying out process (c) according to the invention. In this formula, R ⁴ preferably or in particular has those meanings which have already been given as preferred or as particularly preferred for R ⁴ in connection with the description of the compounds of the formula (I) according to the invention. X ² preferably represents halogen, methanesulfonyloxy, toluenesulfonyloxy, R -0-S0 ₂ -0- or R ⁴ -0-CO-0-.

The alkylating agents of formula (IV) are common laboratory chemicals.

Suitable diluents for carrying out process (c) according to the invention are all inert organic solvents. Aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene,

Dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides like

N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; or amines such as pyridine.

Suitable acid binders for carrying out process (c) according to the invention are all customary inorganic or organic bases. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, can preferably be used Sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate, furthermore ammonium compounds, such as ammonium hydroxide, Ammonium acetate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out process (c) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 120 ° C.

To carry out process (c) according to the invention, 1 to 10 mol, preferably 1 to 5 mol, of alkylating agent of the formula (IV) are generally employed per mol of thiocarbamoylimidazole of the formula (I-b). The processing takes place according to usual methods.

The processes (a), (b) and (c) according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.

The fused-on azole derivatives of the formula (I) can be converted into acid addition salts or metal salt complexes.

For the preparation of acid addition salts of the compounds of the formula (I), preference is given to those acids which have already been associated with the

Description of the acid addition salts according to the invention have been mentioned as preferred acids.

The acid addition salts of the compounds of formula (I) can be easily prepared by conventional salt formation methods, e.g. by disconnecting the

Formula (I) in a suitable inert solvent and adding the acid e.g.

Hydrochloric acid can be obtained and in a known manner, for example by filtering off trieren, isolated and optionally cleaned by washing with an inert organic solvent.

For the preparation of metal salt complexes of the compounds of formula (I), preference is given to those salts of metals which have already been mentioned as preferred metal salts in connection with the description of the metal salt complexes according to the invention.

The metal salt complexes of the compounds of formula (I) can be obtained in a simple manner by conventional methods, e.g. by dissolving the metal salt in

Alcohol, e.g. B. ethanol and adding to compounds of formula (I). Metal salt complexes can be prepared in a known manner, e.g. by filtering, isolating and, if necessary, cleaning by recrystallization.

The substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.

Fungicides can be used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and

Use Deuteromycetes.

Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans; Erwinia species, such as, for example, Erwinia amylovora; Pythium species, such as, for example, Pythium ultimum; Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or

Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola; Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P. brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca Fülliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha; Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea

(Conidial form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: Drechslera, Syn: Helminthosporium); Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum; Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil. The active compounds according to the invention can be used with particularly good success to combat diseases in wine, fruit and vegetable cultivation, such as, for example, against Phytophthora species.

The active compounds according to the invention are also suitable for increasing the crop yield.

They are also less toxic and have good plant tolerance.

Depending on their respective physical and / or chemical properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols,

Fine encapsulation in polymeric materials and in coating compositions for seeds, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or Glycol and its ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. The following are suitable as solid carriers: for example, natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. As solid carriers for granules come in Question: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersants are, for example, lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

Depending on their respective physical and / or chemical properties, the active compounds can be converted into the customary formulations, such as

Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm mist formulations.

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In many cases you get it synergistic effects, ie the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

Fungicides:

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,

Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazon, chlorfenazole, chloroneb,

Chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofüram,

Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,

Diniconazol-M, Dinocap, Diphenylamine, Dipyrithione, Ditalimfos, Dithianon, Dodemorph, Dodine, Drazoxolon,

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, Fenapanil, Fenarimol, Fenbuconazol, Fenfüram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Fluφrimidolutin, Flusilimidol, Flusulfimidol, Flusulfimidol, Flusulfimidol, Flusulfimidol, Flusulfimidol, Flusulfilidol, Flusulfinidol, Flusulfilidol, Flusulfinidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusulfilidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusulfilidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusulfilidol, Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis,

Furmecyclox,

Guazatin, Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan,

Isovaledione,

Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfüroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,

Nickel dimethyldithiocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,

Paclobutrazole, pefürazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb,

Propanosine sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxy for,

Quinconazole, quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, dioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutichl, triazoxid, triazoxid, triazoxid, triazoxide

Tridemorph, triflumizole, triforin, triticonazole,

Uniconazole, Validamycin A, ninclozolin, viniconazole,

Zarilamid, Zineb, Ziram as well

Dagger G,

OK-8705, OK-8801, α- (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1H-1, 2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) - β-fluoro-b-propyl-1H-1, 2,4-triazole-1-ethanol, - (2,4-dichlorophenyl) -ß-methoxy-a-methyl-1H-1, 2,4-triazole-1 -ethanol, - (5-methyl-1,3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] - 1 H-1,2,4-triazol-1-ethanol ,

(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (lH-l, 2,4-triazol-l-yl) -3-octanone,

(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,

{2-methyl- 1 - [[[[- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid -

1-isopropyl ester, 1 - (2,4-dichlorophenyl) -2- (1 H-1, 2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) oxime,

1 - (2-methyl-1-naphthalenyl) - 1 H-pyrrole-2, 5-dione, l- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione, l- [ (Diiodomethyl) sulfonyl] -4-methyl-benzene,

1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole, l - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl ] -lH-l, 2,4-triazole, l- [l- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -lH-imidazole, l-methyl-5-nonyl- 2- (phenylmethyl) -3-pyrrolidinol,

2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide, 2,2-dichloro-N- [1 - (4-chlorophenyl) -ethyl] -1-ethyl-3-methyl-cyclopropanecarboxamide,

2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate,

2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide,

2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole, 2 - [(l-methylethyl) sulfonyl] -5- (trichloromethyl) -l, 3,4-thiadiazole,

2 - [[6-Deoxy-4-0- (4-0-methyl-ß-D-glycopyranosyl) -aD-glucopyranosyl] -amino] -4- methoxy-lH-pyrrolo [2,3-d] pyrimidine- 5-carbonitrile, 2-aminobutane,

2-bromo-2- (bromomethyl) pentandinitrile,

2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1 H-inden-4-yl) -3-pyridinecarboxamide,

2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide, 2-phenylphenol (OPP),

3,4-dichloro-1 - [4- (difluoromethoxy) phenyl] -1 H-pyrrole-2,5-dione,

3, 5-dichloro-N- [cyan [(1-methyl-2-propynyl) -oxy] -methyl] -benzamide,

3 - (1,1-dimethylpropyl-1-oxo-1 H-indene-2-carbonitrile,

3- [2- (4-chloro-phenyl) -5-ethoxy-3-isoxazolidinyl] pyridine, 4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) - 1H-imidazole-1 - sulfonamide,

4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,

8- (l, l-dimethylethyl) -N-ethyl-N-propyl-l, 4-dioxaspiro [4 5] decane-2-methanamine,

8 -hydroxy quinoline sulfate,

9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, ice-1 - (4-chloro-phenyl) -2- (1 H-1, 2,4-triazole-1-yl) cycloheptanol, cis-4- [3- [4- (l, l-dimethylpropyl) phenyl -2-methylpropyl] -2,6-dimethyl-moφholin hydrochloride,

Ethyl - [(4-chlθφhenyl) azo] cyanoacetate, potassium hydrogen carbonate,

Methane tetrathiol sodium salt,

Methyl l- (2,3-dihydro-2,2-dimethyl-lH-inden-l-yl) -lH-imidazole-5-carboxylate,

Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,

Methyl-N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate, N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexane carboxamide

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,

N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,

N- (4-cyclohexylphenyl) - 1, 4,5,6-tetrahydro-2-pyrimidinamine, N- (4-hexylphenyl) - 1, 4, 5, 6-tetrahydro-2-pyrimidinamine,

N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide,

N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,

N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide, N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide, N-formyl-N-hydroxy-DL-alanine sodium salt,

O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate, O-methyl-S-phenyl-phenylpropylphosphoramidothioat, S-methyl-1, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] - 1 -Benzopyran-2, 1 '(3' H) -isobenzofüran] -3'-one.

Bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin,

Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, 4-bromo-2- (4-chloro-phenyl) -1 - (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3-carbonitrile, bendiocarb, benufracarb, bensultap, betacyfluthrin, bifenthrin, BPMC , Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,

Cadusafos, Carbaryl, Carbofüran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos,

N - [(6-chloro-3-pyridinyl) methyl] -N'-cyano-N-methyl-ethanimidamide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, Cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon,

Dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathione, disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,

Fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,

Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenarbx, Furathi

HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lamda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,

Naled, NC 184, Nitenpyram,

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrachl

Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,

Quinalphos,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozide, Tebufenpyrad, Tebupiri iphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiome- thon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, trichlorofon, triflumuron, trimethacarb,

Vamidotbion, XMC, xylylcarb, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil. It can also do that

Seeds of the plants are treated.

When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

The preparation and use of substances according to the invention are illustrated by the following examples. Manufacturing examples:

example 1

Procedure (a:

0.3 g (10 mmol) of sodium hydride (80% mineral oil suspension) are added to a solution of 2.5 g (15 mmol) of 1H-imidazo [4,5-b] pyridine in 40 ml of absolute tetrahydrofuran. The mixture is stirred at 20 ° C for 10 minutes. Then you give

3.0 g (15 mmol) of 3,5-dimethylisoxazole-4-sulfonyl chloride are added and the mixture is stirred at 20 ° C. for a further 20 hours. The reaction mixture is added to 200 ml of water. The resulting mixture is extracted twice with 150 ml of diethyl ether each time. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on silica gel using diethyl ether.

1.3 g (46% of theory) of l- (3,5-dimethyl-isoxazole-4-sulfonyl) -1H-imidazo [4,5-b] pyridine are obtained as a white solid with a melting range of 77 to 80 ° C. .

Example 2

Procedure (a):

1.4 g (10 mmol) of potassium carbonate are added to a solution of 1.2 g (10 mmol) of 1H-imidazo [4,5-c] pyridine in 30 ml of acetonitrile and the mixture is stirred at 20 ° C. for 10 minutes. Thereafter, 1.9 g (10 mmol) of 3,5-dimethylisoxazole-4-sulfonyl chloride are added and the mixture is stirred at 20 ° C. for 20 hours. The reaction mixture is then added to 150 ml of water. The resulting mixture is extracted twice with 70 ml of ethyl acetate. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is stirred with 20 ml of petroleum ether, the solid formed is filtered off and dried.

1.6 g (57% of theory) of 1- (3,5-dimethyl-isoxazole-4-sulfonyl) -1H-imidazo [4,5-c] pyridine are obtained as a yellow solid with a melting point of 130-135 ° C. .

The substances listed in Table 12 below are also produced by the methods given above.

Table 12:

Table 12: (continued)

) The 1H NMR spectra were recorded in deuterochloroform (CDCI3) or hexacheuterodimethyl sulfoxide (DMSO-dg) with tetramethylsilane (TMS) as the internal standard. The chemical shift is given as a δ value in ppm. Examples of use

Example A

Plasmopara test (vine) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, it is mixed

1 part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the

The plants are sprayed with an aqueous spore suspension of Plasmopara viticola and then remain in an incubation cabin at about 20 ° C. and 100% relative atmospheric humidity for 1 day. The plants are then placed in a greenhouse for 5 days at approx. 21 ° C and approx. 90% humidity. The plants are then moistened and placed in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active substances, application rates and test results are shown in the following table Table A

Plasmopara test (vine) / protective

Active ingredient Application rate of effectiveness Active ingredient in g / ha in%

According to the invention:

(6) known from DE-A 19523446:

Example B

Venturia test (apple) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen Venturia inaequalis and then remain for 1 day at approx.

20 ° C and 100% relative humidity in an incubation cabin.

The plants are then placed in the greenhouse at approx. 21 ° C. and a relative humidity of approx. 90%.

Evaluation is carried out 12 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active ingredients, application rates and test results come from the following

Table. Table B

Venturia test (apple) / protective

Active ingredient application rate of efficiency

Active ingredient in g / ha in%

According to the invention:

known from DE-A 195 23 446:

Claims

claims

1. Annellated azole derivatives of the formula

^A in which

R1 and R2 together with the carbon atoms to which they are attached represent an optionally substituted heterocyclic ring or an optionally substituted benzo-fused heterocyclic ring,

G represents nitrogen or a group ^ ^ .C - R 3, wherein

R represents hydrogen, halogen, cyano, nitro, trifluoromethyl, thiocarbamoyl, thiocyanato or the grouping

NH

\. where S - R ⁴

R ^{4 represents} alkyl,

YR ⁶

5

A stands for one of the following groupings S0 ₂ - R _} P _^ ,

V in which

Y represents oxygen or sulfur,

R5 represents an optionally substituted, unsaturated heterocyclic radical, and R6 and R ^ independently of one another for alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkenyl, haloalkenyl, alkenyloxy, alkenylthio, alkynyl, alkynyloxy, alkynylthio, amino optionally substituted by alkyl, cycloalkyl or aryl, optionally substituted aryl optionally substituted aryloxy, optionally substituted arylthio, optionally substituted cycloalkyl, optionally substituted cycloalkyloxy, optionally substituted cycloalkylthio or represent an optionally substituted, saturated or unsaturated heterocyclic radical, or

R6 and R ^ together with the phosphorus atom to which they are attached represent an optionally substituted heterocyclic radical,

as well as their acid addition salts and metal salt complexes.

2. A process for the preparation of fused azole derivatives of the formula (I) according to claim 1 and of their acid addition salts and metal salt

Complexes, characterized in that one

a) Azoles of the formula

in which

R, R2 and G have the meanings given above, with halides of the formula

AX ¹ (III) in which

A has the meaning given above and

χ represents halogen,

optionally in the presence of an acid binder and optionally in

In the presence of a diluent,

or

b) cyanimidazoles of the formula

in which

Rl, R2 and A have the meanings given above,

with hydrogen sulfide, optionally in the presence of a base and optionally in the presence of a diluent, or

c) thiocarbamoylimidazoles of the formula

in which

R, R2 and A have the meanings given above,

with an alkylating agent of the formula

R ⁴ -X ² (IV)

in which

R ^{4 has} the meaning given above and

χ represents a leaving group,

optionally in the presence of an acid binder and optionally in

In the presence of a diluent,

Microbicidal agents, characterized by a content of at least one fused azole derivative of the formula (I) according to claim 1 or of an acid addition salt or metal salt complex of a fused azole derivative of the formula (I) in addition to extenders and / or surface-active substances.

Use of fused azole derivatives of the formula (I) according to Claim 1 or of their acid addition salts or metal salt complexes as microbicides in crop protection and in material protection.

Process for combating undesirable microorganisms in crop protection and in material protection, characterized in that fused azole derivatives of the formula (I) according to Claim 1 or their acid additive tion salts or metal salt complexes on the microorganisms and / or their habitat.

6. A process for the preparation of microbicidal agents, characterized in that fused azole derivatives of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes are mixed with extenders and / or surface-active substances.

Annellated azole derivative according to claim 1, characterized by the formula

8. Annelated azole derivative according to claim 1, characterized by the formula

9. Annelated azole derivative according to claim 1, characterized by the formula

0. Annelated azole derivative according to claim 1, characterized by the formula