EP0852579A1

EP0852579A1 - Fungicidal quinolines

Info

Publication number: EP0852579A1
Application number: EP96931024A
Authority: EP
Inventors: Oliver Wagner; Frank Wetterich; Karl Eicken; Gisela Lorenz; Eberhard Ammermann; Siegfried Strathmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1995-09-12
Filing date: 1996-09-04
Publication date: 1998-07-15
Also published as: AU6987096A; TW338038B; JPH11512406A; US5955473A; WO1997010215A1

Abstract

Quinolines have the formula (I), in which the substituents have the following meaning: R7 stands for hydrogen, C¿1?-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl; R?8¿ stands for hydrogen, formyl, C¿1?-C8 alkyl, C2-C8 alkenyl, C2-C8 alkinyl or C1-C8 alkylcarbonyl, whereas said groups may be partially or totally halogenated, C3-C7 cycloalkyl, or C3-C7 cycloalkenyl, whereas these radicals may be partially or totally halogenated; R?8¿ may also stand for aryl or heteroaryl, whereas these radicals may bear one to three of the following groups: nitro, halogen, cyano, C¿1?-C4 alkyl, C1-C4 halogen alkyl, C1-C4 alkoxy, C1-C4 halogen alkoxy, C1-C4 alkylthio, C1-C4 alkylamino, di-C1-C4-alkylamino, C1-C4 alkylsulfonyl, C1-C4 alkylsulfoxy, C1-C4 alkylsulfonyloxy, C1-C4 alkylcarbonyl, C1-C4 alkylcarbonyloxy, C1-C4 alkoxycarbonyl, aryl, aryloxy; R?7 and R8¿ form together a bond; and R9 stands for aryl or heteroaryl. Also disclosed are fungicides and their use to control harmful fungi.

Description

Fungicidal quinolines

description

The present invention relates to quinolines of the formula I.

R ⁸

in which the substituents have the following meaning

Ri.R ^ R ^ R ⁴ each independently of one another hydrogen, hydroxy, nitro, halogen, -CC ₄ -alkyl, -C-C ₄ -alkoxy, -C-C ₄ -haloalkyl, C ₁ -C ₄ -alkylthio, Cι- C ₄ -haloalkoxy, -C-C ₄ -haloalkylthio, -C-C ₄ -alkoxyalkyl,

R ⁵ , R ⁶ each independently of one another hydrogen, halogen, -CC ₄ -alkyl, -C-C ₄ -alkoxy, -C-C ₄ -haloalkoxy, Cχ-C ₄ -alkylthiθ;

R ^{7 is} hydrogen, C 1 -C ₄ -alkyl, formyl, C 1 -C ₄ -alkyl carbonyl, C 1 -C ₄ -alkoxycarbonyl;

R ^{8 is} hydrogen, formyl, Ci-Cg-alkyl, C ₂ -Ca-alkenyl,

C ₂ -C ₆ -alkynyl or C ₁ -C ₆ -alkylcarbonyl, where these groups can be partially or completely halogenated, C ₃ -C ₇ cycloalkyl, or C ₃ -C ₇ cycloalkenyl, where these radicals can be partially or completely halogenated ,

Aryl or heteroaryl, where these radicals may carry one to three of the following groups: nitro, halogen, cyano, C ₄ -alkyl, C ₄ haloalkyl, Cχ-C ₄ -alkoxy, C ₄ haloalkoxy, C 1 -C ₄ alkylthio, C 1 -C ₄ alkylamino, di C 1 -C ₄ alkylamino _/ C 1 -C ₄ alkylsulfonyl, C 1 -C ₄ alkylisulfoxy, Cj _. -C ₄ -Alkylsulfonyloxy, -C-C ₄ -alkylcarbonyl, Cι ~ C ₄ -alkylcarbonyloxy, -C-C ₄ -alkoxycarbonyl, aryl, aryloxy; R ⁷ and R ⁸ together form a bond; R ⁹ is aryl or heteroaryl, where these radicals may carry from one to three _H r of the following groups: nitro, halogen, cyano, ~ C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ -haloalkoxy, C 1 -C ₄ -alkylthio, C ₄ -C ₄ -alkylamino, di-C 1 -C ₄ -alkylamino, C 1 -C ₄ -alkylsulfonyl,

C 1 -C ₄ -Alkylsulfoxy, C 1 -C ₄ -alkylsulfonyloxy, C 1 -C ₄ -alkylcarbonyl, C 1 -C ₄ -alkylcarbonyloxy, Cχ-C ₄ -alkoxycarbonyl, aryl, aryloxy in which the cyclic substituents in turn one to three of the can carry the following substituents: halogen,

Nitro, cyano, C 1 -C ₄ alkyl, C _! -C ₄ -alkoxy, -C-C ₄ -haloalkoxy, Cχ-C ₄ -alkylthio, Cι-C ₄ -alkylamino, di-Cι ~ C ₄ -alkylamino, Cι-C ₄ -alkylsulfonyl, Cι ~ C ₄ - AlkyIsulfoxy, -C ~ C ₄ alkylsulfonyloxy, Cι -C ₄ alkylcarbonyl, Ci-C ₄ alkylcarbonyloxy,

Cι ~ C ₄ alkoxycarbonyl, aryl, aryloxy;

as well as the N-oxides and the acid addition salts of the quinolines of the formula I, except for the compounds according to the following definition of the radicals:

1 ad _R l, 2,3,4,5,6,7,8 - _{H; R} 9 _{= C6} H _5/ 4-ci-C ₆ H _{4 /} 2,4-di-

C1-C ₆ H ₃ , 2,4-di-Br-C ₆ H ₃ , 1 eh _R ι, 2,3,4,5,6,7,8 - _{H; R} 9 ₌ 4-ci-C ₆ H ₄ , 2, 4-di-Cl-C ₆ H ₃ each as N-oxide and HCl salt,

1 i _R 1.2.3.4.5.6.7, ^β _{= H; R} 9 = 4-Br-C ₆ H ₄ HBr salt

1 j -k R1,2,3,4,6,8 = _H. R5 = CH ₃ ; R ⁷ = H, CH ₃ ; R ⁹ = C ₆ H ₅

1 m Rl, 3,4,6,7,8 = _H. R2.5 _{= CH3} . _R 9 = C ₆ H ₅ ,

1 n R! = O-CH ₃ . R2,3,4,6,7,8 = _{H; R} 5 _{= CHa} . _R 9 = C _g ji ,. HCl-Sal _Z ,

1 oq Rl, 3,4,5,6.7.8 = _H; R2 = CH ₃ ■ ^R9 = 4-N0 ₂ -C ₆ H ₄ ; HCl salt, N-oxide

1 rs _R 1,2,4,5,6,7,8 _{= H.} _R 3 _{= C1} . _R 9 = 4-NO ₂ -C ₆ H ₄ , 4-Cl-C ₆ H ₄ tu RI, 2,3,4,6,7, ^β = _H. _R 5 _{= cl} . _R 9 = 4-cl-C ₆ H ₄ , 2, 4-di-Cl-C ₆ H ₃

1 vx RI.4.6.7 = H; R ³ = H,; R ² = H, CH ₃ 0; R ⁵ = CH ₃ R ⁸ -9 =

CH ₂ CH ₂ C1 HCl salt,

1 x Rl, 4,6,7 = _H. _R 3 = _{C1 R} 2 _{= H; R} 5 _{= CH3 R} 8.9 ₌ CH ₂ CH ₂ C1

HCl salt,

1 y _R 1.4. 6. 7 = _H ; R ³ = H; R ² = Cl; R ⁵ = HR ⁸ < ⁹ = CH ₂ CH ₂ C 1 HCl-

Sal z, 1 _ZR 1, 2, 4, 5, 6, 7, 8 = _{H; R} 3 = _{C 1; R} 9 = _C H ₂ _3_py _/

2 from RI, 2,3, ₄ , 5 ^, 6,7, a _{= H.} _R 9 = quinolin-4-yl, di-N-oxide,

2 c _R ι, 2,3,4,6,7,8 = _H. _R 5 = _CH3 . _R 9 = quinolin-4-yl, di-N-oxide, 2 do _R l, 2,3,4,5,6 = _H ; R ⁹ = C ₆ H ₅ , C ₆ H ₅ N-oxide, 4-Cl-C ₆ H ₄ , 4-Cl-C ₆ H ₄ N-oxide, 4 -Br-C ₆ H ₄ , 4-Br- C ₆ H ₄ N-oxide, 2,4-Cl-C ₆ H _3/2, 4-Cl -C ₆ H ₃ N-oxide, 2,4-Br-C ₆ H _3, 2,4-Br C ₆ H ₃ N-oxide, 4- (CH ₃ ) ₂ NC ₆ H ₄ , 4- (CH ₃ ) ₂ NC ₆ H ₄ N-oxide,

2 pq _R l, 3,6 = _{H; R} 5 = _C H ₃ , R ⁹ = C ₆ H ₅ ; R ² = OCH ₃ , R ⁴ = OCH ₃ ; 2 rs Rl.3,6 = _{H; R} 5 = _CH3 ; R ⁹ = C ₆ H ₅ ; R ² = OCH ₂ CH ₃ ; R ⁴ =

OCH ₂ CH ₃ ;

2 tv Rl, 2,3,4,6 = _H. _R 5 = Ce; R ⁹ = C ₆ H ₅ , 4-Cl-C ₆ H ₄ ,

2,4-Cl-C ₆ H _{3 /}

2 w Rl, 2,4,5,6 = _{H; R} 3 = Cl; R ⁹ = = C ₆ H ₅ , 2 X _R 1, 2,3,4,6 = _H. _R 5 = CH ₃ ^• R ⁹ = C ₆ H ₅ , 2 y Rl 2,3,4 = _H ; R ⁵ ' ⁶ = CH ₃ ^• R ⁹ = C ₆ H ₅ , 2 z _R 2,3,4,6 _{= H.} _R l, 5 - CH ₃ R ⁹ = C ₆ H _5, 3 a Rl.3,4,6 = _H. _R 2.5 = CH ₃ R ⁹ = C ₆ H ₅ , 3 b Rl.2.3.6 = _H ; R ⁴ < ⁵ = CH ₃ R ⁹ = C ₆ H ₅ , 3 c _R 2,4,6 = _H; Rl.3.5 = CH ₃ R ⁹ = C ₆ H ₅ , 3 d Rl.3.6 = _H. _R 2,4,5 = CH ₃ R ⁹ = C ₆ H ₅ .

a process for their preparation, fungicidal agents and their use for controlling harmful fungi.

From WO 94/07492 4-hydrazoquinolines and 4-hydrazoquinolines with pharmaceutical activity are known.

4-Quinoline hydrazines are known from the literature, but nothing is reported about the fungicidal activity of these compounds. (see: Ann. Chim. (Rome), 46 (1956) 1050; J. Chem. Soc, 1930, 1999; J. Chem. Soc, 1938, 1083; Yakugaku Zasshi, 65 (1945) Ed. B, 431; Farmaco, Ed. Sei., 30 (1975) 965), J.Med. Chem., 12 (1969) 801.

Various phenylazoquinolines are also described in the literature (cf. J. Heterocyclic Chem .; 21 (1984) 501; Ann. Chim. (Rome), 46 (1956) 1050; J. Chem. Soc; 1084, 1938).

From Attl. Accad. Be. Siena Fisiocrit. (1976) 8, 43-57, 4-hyrazoquinolines with microbicidal activity are known. However, a fungicidal activity against plant pathogens of these compounds is not known.

The object of the present invention was to provide quinoline derivatives with a fungicidal action.

It has now been found that compounds of the formula I have a good fungicidal activity against plant pathogens. The compounds of the present invention can be prepared by using known syntheses. The starting compounds can be obtained by known methods.

The compounds of the general formula I are obtained by condensation of the 4-chloroquinolines of the formula II with hydrazines of the formula III.

The quinolines II are known or can be obtained by known methods (Tetrahedron 41 (1985) 3033-36, Organic Syntheses, Col. Vol.3,272 (1955), EP 497371, US 5240940).

The hydrazines III are also known and can be obtained by known methods (cf. Houben-Weyl, volume 10/2, pages 1 to 71 and 169-409, in particular 396-399 and 402-405).

The compounds of the general formula I are obtained by condensation of the 4-chloroquinolines II with hydrazines of the formula III.

The 4-chloroquinolines II are preferably reacted with the corresponding hydrazines in a suitable diluent at elevated temperatures. Suitable diluents are inert organic solvents such as e.g. aliphatic hydrocarbons e.g. Petroleum ether, aromatic hydrocarbons such. Example. Toluene or o-, m-, p-xylene or alcohols, such as. Example n-, i-, t-butanol for use.

The salts of the compounds I are also part of the invention, in particular the salts of mineral acids or Lewis acids. Usually, the type of salt is not important. For the purposes of the invention, preference is given to salts which do not damage the plants, surfaces, materials or spaces to be kept free from harmful fungi and which do not impair the action of the compounds I. The salts of the compounds I are known per se, such as. For example, by reacting the corresponding quinolines I, which are accessible with acids in water or an inert organic solvent at temperatures between -80 ° to 120 °, preferably 0 ° to 60 ° C.

The N-oxides of the compounds I are also part of the invention. They can be prepared by methods known from the literature (see, for example, Ann. Chim. Rome; 46 (1956) 1050).

Compounds la in which R ⁷ , R ^{8 represent} a bond can be prepared by methods known from the literature (see Hou¬ ben-Weyl; 10/3 page 226-423), such as. For example, by coupling aromatic diazonium compounds (pp.226-311), by condensation reactions (pp. 332-355) or by dehydrogenation of the compounds of the general formula Ib, in which R ⁷ and R ^{8 are} hydrogen (pp.377 )

R9

As an oxidizing agent come inorganic and organic compounds, such as. For example, peroxides, hypohalites, nitrous acid, nitric acid, metal salts such as. Eg Fe III salts, Cu II salts, Pb IV salts, but also oxygen or air in question.

Suitable diluents are e.g. For example, water, organic and inorganic acids such as For example glacial acetic acid, sulfuric acid or nitric acid; Alcohols such as Methanol, ethanol; halogenated hydrocarbons, aromatic hydrocarbons or dimethylformamide.

The reaction temperature is generally between 0 ° and the respective boiling point of the solvent in question.

In the definitions of the compounds I given at the outset, collective terms were used which represent the following substituents: In the definition of compounds I given at the outset, collective terms were used which represent the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: straight-chain or branched alkyl groups having 1 to 8 carbon atoms, for example Ci-C _ö alkyl such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-MethyIpropyl, 2-MethyIpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 1-dimethylpropyl, 2, 2-dimethylpropyl, 1, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3, 3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methylpropyl and 1-ethyl-2-methylpropyl;

Haloalkyl or partially or completely halogenated alkyl: straight-chain or branched alkyl groups with 1 to 4 or 8

Carbon atoms (as mentioned above), in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms (as mentioned above), for example C ₁ -C ₂ -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl , Chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl , 2, 2-dichloro-2-fluoroethyl, 2, 2,2-trichloroethyl and pentafluoroethyl;

Alkoxy: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms, for example Cχ-C ₃ alkoxy such as methyloxy, ethyloxy, propyloxy and 1-methylethyloxy;

Alkoxyalkyl: straight-chain or branched alkyl groups with 1 to 8 carbon atoms (as mentioned above), which in any position carry a straight-chain or branched alkoxy group (as mentioned above) with 1 to 4 carbon atoms in the case of C 1 -C ₄ -alkoxyalkyl, such as methoxymethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl and 2-butoxyethyl;

Haloalkoxy: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above), where the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms (as mentioned above), for example C ₁ -C ₂ -haloalkoxy such as chloromethyloxy, dichloromethyloxy, tri - chloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyloxy, chlorofluoromethyloxy, dichlorofluoromethyloxy, chlorodifluoromethyloxy, 1-fluoroethyloxy, 2-fluoroethyloxy, 2, 2-difluoroethyloxy, 2, 2,2-trifluoroethyloxy, 2-chloro-2-fluoroethyloxy, 2- Chloro-2,2-difluoroethyloxy, 2, 2-dichloro-2-fluoroethyloxy, 2, 2,2-trichloroethyloxy and pentafluoroethyloxy;

Alkylthio: straight-chain or branched alkyl groups with 1 to 4 carbon atoms (as mentioned above) which are bonded to the structure via a sulfur atom (-S-), for example C 1 -C ₄ -alkyl thio such as methylthio, ethylthio, propylthio, 1- Methyl ethylthio, n-butylthio and tert-butylthio;

Alkoxycarbonyl: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above), which are bonded to the skeleton via a carbonyl group (-C0-);

Alkenyl: straight-chain or branched alkenyl groups with 2 to 8 carbon atoms and a double bond in any position, for example C ₂ -C ₆ ~ alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-l-propenyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, 2-methyl-1-propenyl, l-methyl-2- propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, l-dimethyl-2-propenyl, 1, 2-dimethyl-l-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-l-propenyl, l-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4- Hexenyl, 5-hexenyl, 1-methyl-l-pentenyl,

2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4- Methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl- 4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2,2-dimethyl-3butenyl, 2,3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 3, 3-dimethyl-1-butenyl, 3, 3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2- Ethyl-3-butenyl, 1, 1,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, l-ethyl-2-methyl-l-propenyl and l-ethyl-2-methyl- 2-propenyl; Alkynyl: straight-chain or branched alkynyl groups with 2 to 8 carbon atoms and a triple bond in any position, for example C ₂ -C ₆ -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3- Methyl-l-butynyl, 1, 1-dimethyl-2-propynyl, l-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2- pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-l-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1, l-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2- Dimethyl-3-butynyl, 3, 3-dimethyl-l-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2- propinyl;

Cycloalkyl: monocyclic alkyl groups with 3 to 7 carbon ring members, for example C ₃ -C ₇ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl;

Cycloalkenyl: monocyclic alkyl groups with 5 to 7 carbon ring members which contain one or more double bonds, for example C ₅ -C ₇ -cycloalkenyl such as cyclopentenyl, cyclohexenyl and cycloheptenyl;

non-aromatic 4- to 8-membered rings which, as ring members, contain one or two oxygen, sulfur or nitrogen atoms in addition to carbon, such as saturated 5- or 6-membered rings with 1 or 2 nitrogen and / or oxygen atoms such as 3-tetrahydrofuranyl, 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-morpholinyl and 3-morpholinyl;

Aryl: monocyclic or polycyclic aromatic groups with 6 to 10 carbon atoms, such as phenyl and naphthyl;

Arylalkyl: aryl groups (as mentioned above) which, in the case of aryl (C 1 -C ₄ ) alkyl, are bonded to the skeleton via alkyl groups having 1 to 4 carbon atoms (as mentioned above), for example phenyl (C 1 -C ₄ ) alkyl such as benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-phenylethyl, 1-phenylpropyl and 1-phenylbutyl;

Aryloxy: aryl groups (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-), such as phenoxy, 1-naphthoxy and 2-naphthoxy; Heteroaryl: aromatic mono- or polycyclic radicals which, in addition to carbon ring members, can additionally contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, for example:

5-membered heteroaryl containing 1 to 3 nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain 1 to 3 nitrogen atoms as ring members, e.g. 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl,

5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1,2, 4-triazol-3-yl and 1, 3, 4-triazol-2-yl;

5-membered heteroaryl containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur atom or oxygen atom or 1 oxygen or 1 sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 May contain sulfur or oxygen atom or 1 oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl,

2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-othsothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5- Pyrazolyl, 2-oxazolyl, 4-0xazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-oxadiazol-3-yl, 1, 2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3 4-oxadiazol-2-yl, 1, 3, 4-thiadiazol-2-yl, 1, 3, 4-triazol-2-yl;

- Benzo-fused 5-membered heteroaryl containing 1 to 3 nitrogen atoms or 1 nitrogen atom and / or an oxygen or sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or can contain 1 oxygen or a sulfur atom as ring members, and in which 2 adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group;

5-membered heteroaryl bonded via nitrogen, containing 1 to 4 nitrogen atoms, or benzo-fused 5-membered heteroaryl bonded via nitrogen, containing 1 to 3 nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, contain 1 to 4 nitrogen atoms or 1 to 3 Nitrogen atoms as ring members can contain, and in which 2 adjacent carbon ring members or a nitrogen and an adjacent carbon ring member can be bridged by a buta- 1,3-diene-1,4-diyl group, these rings being connected to the frame via one of the nitrogen ring members;

6-membered heteroaryl containing 1 to 3 or 1 to 4 nitrogen atoms: 6-ring heteroaryl groups which, in addition to carbon atoms, may contain 1 to 3 or 1 to 4 nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1, 2,4, 5-tetrazin-3-yl;

benzo-fused 6-membered heteroaryl containing 1 to 4 nitrogen atoms: 6-ring heteroaryl groups, in which 2 adjacent carbon ring members can be bridged by a buta-1, 3-diene-1, 4-diyl group, e.g. Quinoline, isoquinoline, ehinazoline and quinoxaline.

The expression "partially or completely halogenated" is intended to express that the hydrogen atoms in the groups characterized in this way can be replaced in part or in full by identical or different halogen atoms, as mentioned above.

Alkylamino: an amino group which carries a straight-chain or branched alkyl group with 1 to 6 carbon atoms as mentioned above;

Dialkylamino: an amino group which carries two independent, straight-chain or branched alkyl groups each having 1 to 6 carbon atoms as mentioned above;

Alkylcarbonyl: straight-chain or branched alkyl groups with 1 to 10 carbon atoms, which are bonded to the skeleton via a carbonyl group (-CO-);

Alkylsulfonyl: straight-chain or branched alkyl groups with 1 to 6 or 10 carbon atoms, which are bonded to the skeleton via a sulfonyl group (-S0 ₂ -);

AlkyIsulfoxy1: straight-chain or branched alkyl groups with 1 to 6 carbon atoms, which are bonded to the skeleton via a sulfoxyl group (-S (= 0) -); Alkylsulfonyl oxide: straight-chain or branched alkyl groups with 1 to 6 or 10 carbon atoms, which are bonded to the skeleton via a sulfonyl oxide group (-S0 ₂ -0);

Alkylcarbonyloxy: straight-chain or branched alkyl groups with 1 to 10 carbon atoms, which are bonded to the skeleton via a carbonyloxy group (-CO-O);

Alkoxycarbonyl: straight-chain or branched alkyl groups with 1 to 6 carbon atoms, which are bonded to the skeleton via an oxycarbonyl group (-0C (= O) -);

With regard to their biological action against harmful fungi, compounds I are preferred in which

R ^1, R ^2, R ^3, R ⁴ are each independently hydrogen, halogen, Cχ-C ₄ -alkyl, C ₄ alkoxy, Cι ~ _{C4-haloalkyl,} _{Cι-C4-alkylthio,} Cι-C ₄ haloalkoxy, Cχ-C ₄ halo-alkylthio, Cι-C ₄ alkoxyalkyl, R ⁵ and R ⁶ are each independently hydrogen, Cχ-C ₂ alkyl or halogen

R ⁷ and R ⁸ each independently of one another hydrogen, Ci-Cβ-alkyl, -C-C ₃ alkylcarbonyl, formyl

R ⁷ R ⁸ together represent a bond

R ⁹ is aryl or heteroaryl, where these radicals may carry one to three of the following groups: nitro, halogen, cyano, C ₄ alkyl, Cχ-C ₄ -alkoxy, C ₄ haloalkoxy,

C 1 -C ₄ -alkylthio, C 1 -C ₄ -alkylamino, di-C C-C ₄ -alkylamino, Cι-C ₄ -alkylsulfonyl, Cι-C ₄ -alkylsulfoxy, Cχ-C ₄ -alkylsulfonyloxy, Cι-C ₄ -Alkylcarbonyl, Cι ~ C ₄ -alkylcarbonyloxy, Cχ-C ₄ -alkoxycarbonyl, aryl, aryloxy in which the cyclic substituents on their part can carry one to three of the following substituents: halogen, nitro, cyano, Cχ-C ₄ - alkyl, _{Cχ-C4-alkoxy,} _{Cχ-C4-haloalkoxy,} _{Cχ-C4-alkylthio,} Cχ-C ₄ alkylamino, di-Cχ-C ₄ alkylamino, Cχ-C ₄ alkyl sulfonyl, Cχ- C ₄ alkyl sulfoxy, Cχ-C ₄ alkyl sulfonyloxy,

Cχ-C ₄ alkylcarbonyl, Cχ-C ₄ alkylcarbonyloxy, Cχ-C ₄ alkoxycarbonyl, aryl, aryloxy.

Compounds I are particularly preferred in which the radicals have the following meanings, individually or in combinations: two of the radicals R ^ R ^ R ^ R ^{4 are} hydrogen;

three of the radicals R ^ R ^ R ^ R ^{4 are} hydrogen;

R ³ = cyano, halogen, Cχ-C ₃ alkyl, Cχ-C ₃ alkyloxy, Cχ-C ₃ alkylthio, Cχ-C ₃ haloalkoxy; preferably halogen, Cχ-C ₃ alkyl, especially chlorine and methyl;

R ⁵ and R ^{6 are} hydrogen, halogen, methyl, especially hydrogen;

R ^{5 is} hydrogen, methyl, chlorine, especially hydrogen;

R ^{6 is} hydrogen;

R ^{7 is} hydrogen, methyl, formyl, Cχ-C ₂ alkylcarbonyl, especially hydrogen;

R ⁷ and R ^{8 are} hydrogen, Cχ-Ce-alkyl, C ₄ -C ₆ cycloalkyl, formyl, Cχ-C ₂ alkylcarbonyl.

R ^{8 is} hydrogen, formyl, Cχ-C ₂ alkylcarbonyl, Cχ-C ₄ alkyl, C ₄ -C ₆ cycloalkyl; particularly preferably hydrogen, formyl, CH ₃ C0, Cχ-C ₄ alkyl; further preferably hydrogen, Cχ-C ₄ alkyl, particularly preferably hydrogen, methyl, ethyl, i-propyl, n-butyl, especially hydrogen;

R ⁷ and R ⁸ particularly preferably form a common bond;

R ⁹ aryl, where these radicals can carry one to three of the following groups: nitro, halogen, cyano, Cχ-C ₄ -alkyl, Cχ-C ₄ -alkoxy, Cχ-C ₄ -haloalkoxy, Cχ-C ₄ -alkylthio, Cχ-C ₄ -alkylamino, di-Cχ-C ₄ -alkylamino, Cχ-C ₄ -alkylsulfonyl, Cχ-C ₄ -alkylsulfoxy, Cχ-C ₄ -alkylsulfonyloxy, Cχ-C ₄ -alkylcarbonyl, Cχ-C ₄ -alkylcarbonyl ¬ oxy, Cχ-C ₄ alkoxycarbonyl, aryl, aryloxy in which the cyclic substituents in turn one to three of the following

Can carry substituents: halogen, nitro, cyano, Cχ-C ₄ alkyl, Cχ-C ₄ alkoxy, Cχ-C ₄ haloalkoxy, Cχ-C ₄ alkylthio, Cχ-C ₄ alkylamino, di-Cχ -C ₄ -alkylamino, Cχ-C ₄ -alkylsulfonyl, Cχ-C ₄ -alkyl-sulfoxy, Cχ-C ₄ -alkylsulfonyloxy, Cχ-C ₄ -alkylcarbonyl, Cχ-C ₄ -alkylcarbonyloxy, Cχ-C ₄ - Alkoxycarbonyl, aryl, aryloxy;

preferably aryl, where these radicals can carry one to three of the following groups: nitro, halogen, cyano, Cχ-C ₄ alkyl, Cχ-C ₄ alkoxy, Cχ-C ₄ haloalkoxy, Cχ-C ₄ alkylthio, phenyl , Phenyl oxy. Also preferred are compounds I in which R ¹ and R ^{3 have} the following meaning, R ¹ and R ³ = halogen, Cχ-C ₃ alkyl.

With regard to their use, particular preference is given to the compounds lc compiled in the tables below, and to their hydrochlorides and N-oxides.

R ⁸

R5, R ⁶ = H

Table 1 R ⁸ = H

Furthermore, the following compounds of the formula Ic are particularly preferred:

the compounds 1.1a - 1.192a, which differ from the corresponding compounds 1.1 - 1.192 in Table 1 in that the substituent R ^{8 is} CH ₃ .

the compounds 1.1b - 1.192b, which differ from the corresponding compounds 1.1 - 1.192 in Table 1 in that the substituent R ^{8 is} C ₂ H ₅ .

the compounds 1.1c - 1.192c, which differ from the corresponding compounds 1.1 - 1.192 in Table 1 in that the substituent R ^{8 is} iC ₃ H ₇ .

- The compounds ID-1.192d, which differ from the corresponding compounds 1.1-1.192 in Table 1 in that the substituent R ^{8 is} CC ₅ H ₉ .

the compounds 1. le-1.192e, which differ from the corresponding compounds 1.1-1.192 in Table 1 in that the substituent R ^{8 is} CH ₂ -C ₆ H ₅ .

the compounds I.lf-1.192f, which differ from the corresponding compounds 1.1-1.192 in Table 1 in that the substituent R ^{8 is} COCH3. Table 2

The new compounds of formula I are suitable as fungicides.

The new compounds, or the compositions containing them, can be sprayed, for example in the form of directly sprayable solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules. Nebulization, dusting, scattering or pouring can be used. The forms of application depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The plants are normally sprayed or dusted with the active compounds or the seeds of the plants are treated with the active compounds.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where in the case of water as diluent other organic solvents can also be used as auxiliary solvents. The following are essentially suitable as auxiliaries: solvents such as aromatics (for example xylene), chlorinated aromatics (for example chlorobenzenes), paraffins (for example petroleum fractions), alcohols (for example methanol, butanol), ketones (for example cyelohexanone), amines (for example ethanolamine) , Dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin-,

Phenolic, naphthalene and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octyl iso-phenyl ether, ethoxylated octylphenol -, Octyl or nonylphenol, alkylphenol, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, iso-tridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol ester cellulose, sorbite ester cellulose, lignin sulfate, lignin sulfate, lignin sulfate ester, lignin.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers , such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as grain flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

Examples of such preparations are:

I. a solution of 90 parts by weight of a compound I according to the invention and 10 parts by weight of N-methyl-2-pyrrolidone, which is suitable for use in the form of tiny drops;

II. A mixture of 10 parts by weight of a compound I according to the invention, 70 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt dodecylbenzenesulfonic acid, 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil; A dispersion is obtained by finely distributing the solution in water.

III. an aqueous dispersion of 10 parts by weight of a compound I according to the invention, 40 parts by weight of cyelohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the Addition product of 40 mol ethylene oxide with 1 mol castor oil;

IV. An aqueous dispersion of 10 parts by weight of a compound I according to the invention, 25 parts by weight of cyclohexanol, 55 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C. and 10 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil;

V. a mixture of 80 ground in a hammer mill

Parts by weight, preferably a solid compound I according to the invention, 3 parts by weight of the sodium salt of di-isobutylnaphthalene-2-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight powdered silica gel; a spray mixture is obtained by finely distributing the mixture in water;

VI. an intimate mixture of 3 parts by weight of a compound I according to the invention and 97 parts by weight of finely divided

Kaolin; this dust contains 3% by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of a compound I according to the invention, 62 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which was sprayed onto the surface of this silica gel; this preparation gives the active ingredient good adhesion;

VIII. A stable aqueous dispersion of 40 parts by weight of a compound I according to the invention, 10 parts by weight of the

Sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which can be further diluted;

IX. a stable oily dispersion of 20 parts by weight of a compound I according to the invention, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde con densates and 50 parts by weight of a paraffinic mineral oil.

The new compounds are distinguished by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Deuteromycetes,

Ascomycetes, Phycomycetes and Basidiomycetes. You are for Partly systemically effective and can be used as leaf and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, lawn, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetable plants such as cucumbers, beans and Pumpkin family, as well as on the seeds of these plants.

The compounds are used by treating the fungi or the seeds, plants, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds.

It is used before or after the infection of the materials, plants or seeds by the fungi.

The new compounds are particularly suitable for combating the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and turf, Ustilago sugar species on cereals, Ustilago sugar on cereals, Ustilago varieties on cereals, Ustilago sugar varieties on cereals, Ustilago varieties on cereals, Ustilago varieties inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryza , Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species on various plants, Plasmopara viticola on vines, Alternaria species on vegetables and fruits.

The new connections can also be used in material protection (wood protection), e.g. against Paecilomyces variotii.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.

Depending on the type of effect desired, the application rates are between 0.025 and 2, preferably 0.1 to 1 kg of active ingredient per ha In the case of seed treatment, amounts of active compound of 0.001 to 50, preferably 0.01 to 10 g per kg of seed are generally required.

The agents according to the invention can also be present in the use form as fungicides together with other active ingredients, e.g. with herbicides, insecticides, growth regulators, fungicides or even with fertilizers.

When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:

Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc ethylene diamine bis-dithiocarbamate, tetramethylthiurondiamide dithi disamide, ), Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thio¬ carbamoyl) -disulfide;

Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-see-butyl-4, 6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-iso-propyl carbonate, 5-nitro -iso-phthal ^■ acid-di-iso-propyl ester;

heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-l- [bis - (dimethylamino) -phosphinyl] - 3-phenyl-l, 2,4-triazole, 2,3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4, 5-b] quinoxaline, Methyl 1- (butylcarbamoyl) -2-benzimidazole-carbamate, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1, 1,2, 2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N ', N' -dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanomethylthiobenzothiazole, 1,4-dichloro-2, 5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-

2-thione-l-oxide, 8-hydroxyquinoline or its copper salt, 2,3-di-hydro-5-carboxanilido-6-methyl-l, 4-oxathiin, 2, 3-dihydro- 5-carboxanilido-6-methyl-l, 4-oxathiin-4, 4-dioxide, 2-methyl-5, 6-dihydro-4H-pyran-3-carboxylic acid anilide, 2-methyl-furan-3-car- bonic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid anilide, 2,4, 5-trimethyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid cyclohexylamide, N-cyclohexyl-N-methoxy-2, 5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2, 2-trichloroethyl acetal, piperazine-1,4- diylbis- (1- (2,2, 2-trichloroethyl) formamide, 1- (3, 4-dichloroanilino) -1-formylamino-2, 2,2-trichloroethane,

2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert-butylphenyl) -2- methylpropyl] cis-2, 6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-l , 3-dioxolan-2-yl-ethyl] - 1H-1, 2,4-triazole 1- [2- (2,4-dichlorophenyl) -4-n-propyl-l, 3-dioxolan-2- yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-tri-chlorophenoxyethyl) -N'-imidazol-yl-urea, 1- (4th -Chlorphenoxy) - 3, 3-dimethyl-l- (1H-1,2, 4-triazol-1-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine- methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido ) -benzene, 1, 2-bis- (3-methoxycarbonyl-2-thioureido) -benzene, [2- (4-chlorophenyl) ethyl] - (1, 1-dimethylethyl) -1H-1,2,4 -triazol-l-ethanol, 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxiran-2-yl-methyl] - 1H-1, 2,4-triazole and

various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethylphenyl) -N-furoyl (2) -alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) -alanine-methyl ester, N- (2,6-dimethylphenyl) -N -chloroacetyl-D, L-2-aminobutyrene-acton, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) -alanine methyl ester, 5-methyl-5-viny1-3- (3, 5- dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 3- [(3,5-dichlorophenyl) -5-methyl-5-methoxymethyl-1,3-oxazolidin-2,4-dione, 3- (3, 5-dichlorophenyl) -1-iso-propylcarbamoyl-hydantoin, N- (3, 5-dichlorophenyl) -1, 2-dimethylcyclopropane-1, 2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-meth-oximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H-1 , 2, 4-triazolyl-1-methyl) -benzhydryl alcohol, N- (3-chloro-2, 6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1- ((bis- (4-fluoropheny l) -methylsilyl) -methyl) -lH-1,2,4-triazole, Strobilurins such as methyl-E-methoximino- [α- (o-tolyloxy) - o-tolyl] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyridimin-4-yloxy] phenyl} -3-methoxyacrylate, methyl-E-methoximino- [α- (2,5-dimethyloxy) -o-tolyl] acetamide.

Anilino-pyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl-6- cyclopropyl-pyrimidin-2-yl) aniline.

Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile.

Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acrylic acid morpholide.

7-chloro-4- (N'- (3-fluorophenylhydrazino) quinoline hydrochloride

5 g (0.026 mol) of 4,7-dichloroquinoline, 4.72 g (0.029 mol) of 3-fluorophenylhydrazine hydrochloride are refluxed in 50 ml of i-butanol until no further starting compound can be detected (HPLC control).

After cooling, the precipitate formed is filtered off, washed with diisopropyl ether and dried. 5.9 g (70%) of the title compound are obtained.

7-chloro-4- (3-fluorophenylazo) quinoline

4.34 g are added to 3.6 g (0.011 mol) of 7-chloro-4- (N'- (3-fluorophenylhydrazino) quinoline hydrochloride in 50 ml of glacial acetic acid

(0.027 mol) of ferric chloride and added and refluxed for 30 min. After cooling, it is poured onto 500 ml of ice water and brought to pH 10 with ammonium hydroxide solution. The resulting precipitate is filtered off and extracted several times with ethanol. Water is added to the ethanolic phase and the precipitate formed is suction filtered.

1.6 g (51%) of the azo compound are obtained. (Mp. 145-147 ° '

Table 3

(Physical data: IR [cm ^-1 ] - ¹³ C [ppm against tetramethylsilane], mp. [*> C]) R ⁸

x acid

10

Table 4

R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ = H

Table 5

R ² , R ' ¹ , R ⁵ , R ⁶ , R ⁷ , R ⁸ = H

Table 6

Table 7

(Physical data: IR [cm ^-1 ] ^'13 C [ppm against tetramethylsilane], mp. [ ^«» C])

i) N-oxide on the nitrogen atom "*" ² ) N-oxide on the nitrogen atom "**"

³ ) N-oxide on the nitrogen atom "*" and on the nitrogen atom "**"

Application example 1

Efficacy against powdery mildew

Leaves of "early gold" wheat seedlings grown in pots were sprayed with aqueous spray liquor, which contained 80% active ingredient and 20% emulsifier in the dry substance, and 24 hours after the spray coating had dried on, with oidia (spores) of the powdery mildew (Erysiphe graminis) var. trictici) pollinated. The test plants were then placed in the greenhouse at temperatures between 20 and 22 ° C. and 75 to 80% relative atmospheric humidity. The extent of mildew development was determined after 7 days.

Rating:

Percentage of leaf area affected

Table 10

Claims

claims

1. Quinolines of the formula IR ⁸

in which the substituents have the following meaning:

Ri, R ^2, R ^3, R ⁴ are each independently hydrogen, hydroxy, nitro, halo, Cι ~ C ₄ -alkyl, C ₄ -alkoxy, C ₄ haloalkyl, Cι ~ C ₄ alkyl thio , Cι ~ _C4 haloalkoxy, Cι-C hio ₄ -Halogenalkylt-, Cι ~ C ₄ alkoxyalkyl,

Lied to R ^5, R ⁶ are each independently hydrogen, Ha¬, Cι-C ₄ -alkyl, C ₄ alkoxy, halo-Cι ~ _C4 alkoxy, _{Cι-C4-alkylthio;}

R ^{7 is} hydrogen, C 1 -C ₄ -alkyl, formyl, C 1 -C ₄ -alkyl carbonyl, C 1 -C ₄ -alkoxycarbonyl,

R ⁸ is hydrogen, formyl, Cι-C ₈ alkyl, C ₂ -C _θ alkenyl, C ₂ -C _θ alkynyl or Cι-C ₈ -alkylcarbonyl, where these groups may be partially or fully defined haloge¬, C ₃ -C ₇ cycloalkyl, or C ₃ -C ₇ cycloalkenyl, where these radicals can be partially or completely halogenated,

Aryl or heteroaryl, where these radicals may carry one to three of the following groups: nitro, halogen, cyano, Cχ-C ₄ -alkyl, C ~ ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ haloalkoxy, C ₁ -C ₄ -alkyl thio, C ₁ -C ₄ -alkylamino, di-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylisulfonyl, Cs-C ₄ -alkylsulfoxy, C _! -C ₄ -Alkylsulfonyloxy, -C-C ₄ -alkylcarbonyl, Ci-C ₄ -alkylcarbonyloxy, Cι-C ₄ -alkoxycarbonyl, aryl, aryloxy;

R ⁷ and R ⁸ together form a bond; R ⁹ is aryl or heteroaryl, where these radicals may carry one to three of the following groups: nitro, halogen, cyano, C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ - Halogenalkoxy, Cχ-C ₄ alkyl thio, C ~ C ₄ alkylamino, di-Cι-C ₄ alkylamino,

C 1 -C ₄ alkylsulfonyl, C 1 -C ₄ alkylsulfoxy, C 1 -C ₄ alkylsulfonyloxy, C 1 -C ₄ alkylcarbonyl, C 1 -C ₄ alkylcarbonyloxy, C 1 -C ₄ alkoxycarbonyl, aryl, aryloxy in which the cyclic substituents may carry one to three of the substituents in turn folic constricting: halogen, nitro, cyano, C ₄ -alkyl, C ₄ -alkoxy, C ₄ haloalkoxy, _{Cχ-C4-alkylthio,} Cι ~ C ₄ -Alkylamino, Di-Cι ~ C ₄ -alkylamino, Cι ~ C ₄ -alkylsulfonyl, Cχ-C ₄ -alkylsulfoxy,

Cχ-C ₄ alkylsulfonyloxy, C ₁ -C ₄ alkylcarbonyl, Cι ~ C ₄ alkylcarbonyloxy, Cχ-C ₄ alkoxycarbonyl, aryl, aryloxy;

1 ad _R 1, 2, 3, 4, 5, 6, 7, 8 = _{H; R} 9 = _C6 H _5I 4-ci-C ₆ H ₄ , 2,4-di-C1-C ₆ H ₃ , 2,4-di-Br-C ₆ H ₃ ,

1 eh _R 1, 2, 3, 4, 5, 6, 7, 8 - _{H; R} 9 ₌ 4-Cl-C ₆ H ₄ , 2, 4-di-Cl-C ₆ H ₃ each as N-oxide and HCl salt,

1 i _R 1, 2, 3, 4, 5, 6, 7, 8 _{= H; R} 9 = 4-Br-C ₆ H ₄ HBr salt

1 jk _R 1, 2, 3,4, 6, 8 = _H. R5 = CH ₃ ; R ⁷ = H, CH ₃ ; R ⁹ = C ₆ H ₅ I m Rl, 3,4,6,7,8 = _H; R2.5 _{= CH3} ; R9 = C ₆ H ₅ ,

1 n R ^{1 =} O-CH ₃ . R2,3,4,6,7,8 = _H; R5 _{= C} H ₃ . _R 9 = _{CgH5 HC1} _

Salt, 1 oq Rl, 3, 4, 5, 6, 7, 8 _{= H} ; R2 = CH3 ' ^{* R9} = 4-N0 ₂ -C ₆ H ₄ ; HCl salt,

N-oxide 1 rS Rl, ² , 4,5,6, ⁷ , 8 _{= H} ; R ³ = Cl; R ⁹ = 4-NO ₂ -C ₆ H ₄ , 4-Cl-C ₆ H ₄

1 do Rl, 2,3, ₄ , 6,7,8 = _H. R5 _{= C1} . _R 9 = 4-Cl-C ₆ H _{4 /} 2,4-di-

C1-C ₆ H ₃ 1 vx R1,4,6,7 = _{H; R} 3 = _{H /} . _R 2 = H, CH ₃ 0; R ^s = CH ₃ R ⁸ - ⁹ =

CH ₂ CH ₂ C1 HCl salt, IX Rl, 4,6,7 = _H. _R 3 = _{C1 R} 2 = _H. _R 5 = _C H ₃ R8.9 ₌

CH ₂ CH ₂ C1 HCl salt, 1 y Rl 4.6.7 = _H. _R 3 = _H. _R 2 = _{C1; R} 5 _{= HR} 8.9 ₌ CH ₂ CH ₂ C1

HCl salt,

1 _Z Rl, 2, 4, 5, 6, 7, 8 = _{H; R} 3 _{= C1} . _R 9 = _CH2 _ ₃ _ _{py /} 2 from _R ι, 2, 3, 4, 5, 6, 7, 8 _{= H.} _R 9 = quinolin-4-yl, di-N-oxide,

2 c _R ι, 2, 3, 4, 6, 7, 8 _{= H.} _R 5 = _C H ₃ ; R ⁹ = quinolin-4-yl, di-

N-oxide, 2 do _R 1, 2, 3, 4, 5,6 = _H. _R 9 - _{C6HS / C6H5} N-oxide, 4-Cl-C ₆ H ₄ ,

4-Cl-C ₆ H ₄ N-oxide, 4-Br-C ₆ H ₄ , 4-Br-C ₆ H ₄ N-oxide,

2,4-Cl-C ₆ H ₃ , 2,4-Cl-C ₆ H ₃ N-oxide, 2,4-Br-C ₆ H ₃ ,

2, 4-Br-C ₆ H ₃ N-oxide, 4 - (CH ₃ ) ₂ NC ₆ H ₄ , 4 - (CH ₃ ) ₂ NC ₆ H ₄

N-oxide,

2 pq RL ³ - ⁶ = H; R ⁵ = CH ₃ , R ⁹ = C ₆ H ₅ ; R ² = OCH ₃ , R ⁴ =

OCH ₃ ; 2 rs Rl- ³ ' ⁶ = H; R ⁵ = CH ₃ ; R ⁹ = C ₆ H ₅ ; R ² = OCH ₂ CH ₃ ; R «=

OCH ₂ CH ₃ ; 2 tv _R l, 2,3,4,6 - _H. _R 5 _{= Ce} . _R 9 ₌ Q ^^ 4-Cl-C ₆ H ₄ ,

2,4-Cl-C ₆ H ₃ ,

2 w _R l, 2,4,5,6 = _H. _R 3 = _C1 . _R 9 = _{CsH5 /} 2 X _R l, 2,3,4,6 _{= H.} _R 5 = _CH3 R ⁹ C ₆ H ₅ , 2 y _R 1, 2,3,4 = _{H; R} 5.6 = _CH3 R ⁹ C ₆ H ₅ , 2 z _R 2,3,4,6 = _{H; R} l, 5 = _{CH 3} R ⁹ C ₆ H _5, _R 3 a l, 3,4,6 = _{H; R} 2.5 _{= CH3} R ⁹ C ₆ H ₅ , 3 b _R 1, 2.3.6 = _H. _R 4.5 _{= CH3} R ⁹ C ₆ H ₅ , 3 c _R 2,4,6 = _{H; R} l, 3.5 = _CH3 R ⁹ C ₆ H ₅ , 3 d Rl ' ³ ' ⁶ = H; R ² '«' 5 - _CH3 R ⁹ C ₆ H ₅ .

Quinolines of formula I according to claim 1, in which the substituents have the following meaning:

Lied Rl, R ^2, R ^3, R ⁴ are each independently hydrogen, Ha¬, Cι-C ₄ -alkyl, ~ C ₄ alkoxy, halo-Cι ~ _C4 alkyl, _{Cι-C4-alkylthio,} Cχ -C ₄ haloalkoxy, _{Cι-C4-haloalkylthio,} Cι-C ₄ alkoxyalkyl,

R ⁵ , R ⁶ each independently of one another hydrogen, -CC ₂ alkyl or halogen;

R ⁷ and R ^{8 are} each independently hydrogen, Ci-Cβ-alkyl, Ci-Cs-alkylcarbonyl, formyl;

R ⁷ , R ⁸ together form a bond;

R ⁹ is aryl or heteroaryl, where these radicals may carry one to three of the following groups: nitro, halogen, cyano, C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ - Haloalkoxy, C 1 -C ₄ -alkyl thio, C 1 -C ₄ -alkylamino, di-Cχ-C4-alkylamino, C 1 -C ₄ -alkylsulfonyl, Cχ-C ₄ -alkylsulfoxy, Cι ~ C ₄ -alkylsulfonyloxy, Cι ~ C ₄ -alkylcarbonyl, C 1 -C ₄ -alkylcarbonyloxy, C 1 -C ₄ -alkoxycarbonyl, aryl, aryloxy in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, Nitro, cyano, ~ C ₄ -alkyl, C ₄ alkoxy, Cι ~ _C4 haloalkoxy, Cι-C ₄ alkylthio, Cι ~ C ₄ alkylamino, di-Cι ~ C ₄ alkylamino, Cχ- C ₄ alkylsulfonyl, C ~ C ₄ alkylsulfoxy, C ~ C ₄ alkylsulfonyloxy, Cχ-C ₄ alkyl carbonyl,

-C ~ C ₄ alkylcarbonyloxy, -C -C ₄ alkoxycarbonyl, aryl, aryloxy.

3. quinolines of the formula I according to claim 1, in which the substituent R ^{3 has the} following meaning:

R ³ cyano, halogen, C _! -C ₃ alkyl, -C-C ₃ alkyloxy,

Cι-C ₃ alkylthio, Cι ~ C ₃ haloalkoxy.

4. Quinolines of formula I according to claim 1, in which the

Substituents R ¹ and R ^{3 have} the following meaning:

R ¹ and R ³ = halogen, -C-C ₃ alkyl.

5. Quinolines of formula I according to claim 1, in which two of the substituents R ¹ , R ² , R ³ or R ^{4 are} hydrogen.

6. quinoline of the formula Ia according to claim 1,

in which the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{9 have} the meaning given in claim 1.

7. Quinolines of the formula Ia according to Claim 6, in which the substituents have the following meanings:

R ^! , R ^2, R ^3, R lied ⁴ are each independently hydrogen, Ha, Cι-C ₄ -alkyl, C ₄ alkoxy, _Cχ-C4 halo-alkyl, Cι ~ C ₄ alkylthio, Cι- C ₄ haloalkoxy, _{Cι-C4-haloalkylthio,} Cχ-C ₄ alkoxyalkyl;

R ⁵ and R ^{6 are} each independently hydrogen, -CC ₂ alkyl or halogen; R ⁹ is aryl or heteroaryl, where these radicals may carry one to three of the following groups: nitro, halogen, cyano, C ₄ -alkyl, C ₄ -alkoxy, C ₄ haloalkoxy, Cι-C ₄ - Alkylthio, C 1 -C ₄ -alkylamino, di-C 1 -C ₄ -alkylamino,

Cι-C ₄ alkylsulfonyl, Cι-C ₄ alkylsulfoxy, Cι-C ₄ alkylsulfonyloxy, _C! -C ₄ -alkylcarbonyl, -C-C ₄ -alkylcarbonyloxy, -C-C ₄ -alkoxycarbonyl, aryl, aryloxy in which the cyclic substituents can in turn carry one to three of the following substituents: halogen, nitro, cyano, Cι-C ₄ -Alkyl, -C ~ C ₄ -alkoxy, Cι-C ₄ -haloalkoxy, Cχ-C ₄ -alkylthio, Cι-C ₄ -alkylamino, di-Cχ-C ₄ -alkylamino, Cχ-C ₄ alkylsulfonyl, Cι-C _4- alkyl sulfoxy,

Cχ-C ₄ -alkylsulfonyloxy, Cι-C ₄ -alkylcarbonyl, Cι-C ₄ -alkylcarbonyloxy, Cι-C ₄ -alkoxycarbonyl, aryl, aryloxy.

8. Use of the quinolines of the formula I or one of their N-oxides or acid addition salts according to claim 1, including the compounds Ia to 3d, for combating harmful fungi.

9. A process for the preparation of the quinolines of the formula I according to claim 1, characterized in that 4 -haloquinoline lines of the formula II are reacted with hydrazines of the formula III,

wherein the substituents R ⁱ to R ^{9 have} the meaning given in claim 1 and Hal is J, Br, Cl or F.

10. A process for the preparation of the quinolines of the formula Ia according to claim 5, characterized in that the quinolines of the formula Ib are oxidized with an oxidizing agent p9

wherein the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{9 have} the meaning given in claim 1.

11. Fungicidal compositions comprising a fungicidally effective amount of at least one quinoline of the formula I or one of its N-oxides or acid addition salts according to claim 1, except for compounds la to 3d.

12. A method of combating harmful fungi, characterized gekenn¬ characterized in that the harmful fungi, their habitat or the plants, areas, materials or spaces to be kept free of them with a fungicidally effective amount of a compound of general formula I or one of its N-oxides or Acid addition salts as claimed in claim 1, including compounds Ia to 3d, or a fungicidal composition containing a quinoline of the formula I as claimed in claim 11.