DD156940A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to fungicidal compositions comprising a solid or liquid traegerstoff and an N-substituted 2-methylnaphthylamide of the general formula wherein R is high 1 - C - R high 3 group, wherein R is high 3 hydrogen or C deep 1 - C. 4 is alkoxy and furthermore R 1 is a -CH- OR 4-membered group, where R 4 is high and R 5 is independently an optionally substituted C 1 - C deep 4-alkyl radical or R 4 is high and R 5 is high together form an alkylene group which, together with the radical of which they are substituents, forms a 5- or 6-membered heterocyclic ring optionally substituted by C 1-C deep 4 alkyl or aryl, and R 2 is optionally fluorine , Chlorine, bromine, iodine, C deep 1 - C deep 4 - alkoxy, C deep 1 - C 4 - alkylthio, 1 - imidazolyl, 1 - pyrazolyl, 1,2,4 - triazolyl - (1) or oxo (= 0 ) -substituted C deep 1-C deep 4-alkyl, furthermore a C deep 2-C deep 5-alkenyl, C deep 2-C deep 5-alkynyl, C deep 3-C deep 7-cycloalkyl, C4-C7 cycloalkenyl, C1-C5 alkoxy, an optionally substituted phenyl or optionally substituted heteroaryl and X is hydrogen, methyl, chlorine or bromine.

Description

^ Fungicides <

Field of application of the invention

The new fungicides can be applied in agriculture as a fungicidal agent.

Characteristic of the known technical solutions

It is already known to use zinc ethylene-l, 2-bisdithiocarbamidatj the N-trichloromethylthiophthalimide and N-trichloromethylthio-tetrahydro-phthalimid ^ as fungicides in agriculture and horticulture. The compounds mentioned are good agents for controlling fungal diseases (see R. Wegler, "Chemistry of Crop Protection and Pest Control", Volume 2, pages 65 to 66 and 109 and Volume 4, pages 139 and 191, Berlin / Heidelberg / New York, (1970) and (1977)).

Aim of the invention

"The aim of the invention is the development of fungicidal agents with improved efficacy in fungi, but crops are not damaged.

DESCRIPTION OF THE INVENTION The object of the invention is to provide novel chemical compounds with fungicidal activity.

It has been found that new N-substituted 2-methylnaphthylamides of general formula I,

I I ii f. J ΙΛ -Vi

CH-R

C-R

R is a -CR ^ρ group, where R ^ is hydrogen or

1 4

CCij-Alkoxy means and further R is a -CH-OR group ¹⁴ ic

0R ^D

4 5, where R and R independently of one another

4 optionally substituted C.-C ^ -alkyl radical or R and R together represent an alkylene group which, together with the radical whose substituents they are, one optionally substituted by Cx-Ch-alkyl or aryl-substituted 5 or 6-membered two oxygen atoms heterocyclic

and R is optionally substituted by fluorine, chlorine, bromine, iodine, C ₁ -C ₁₊ -alkoxy, C ₁ -C ₁₄ -alkylthio, 1-imidazolyl, 1-pyrazolyl, l, 2, 4-triazolyl- (I) - or oxo (= O) - substituted C ₁ -C 12 alkyl, furthermore a C 9 -C 12 alkenyl, C 9 -C 20 alkynyl, C ₁ -C 6 cycloalkyl, C ₁ -C 4 alkyl, C ^ -Cycloa'lkenyl-, C ₁ -C _t ^-? "alkoxy group, an optionally substituted phenyl or optionally substituted heteroaryl and X is hydrogen, methyl, chlorine or bromine, exhibit strong fungicidal properties.

In the formula I, R preferably represents an unbranched or branched C ₁ -C _t -alkoxy radical, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert. Butoxy, n-pentyloxy or iso-pentyloxy, or represents an optionally substituted by fluorine, chlorine, bromine, iodine, methoxy, ethoxy, butoxy, methylthio, ethylthio, '1-imidazolyl, 1-pyrazolyl or 1,2,4'- Triazolyl- (1) sub-

1 3 .3-

'' It itii th, branched or unbranched C ^ -C ^ alkyl- rest, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or tert .-butyl.

2 '

§ R is furthermore, for example, vinyl, 1-propenyl, 2-propenyl, allyl, ethynyl or, for example, a cyclic alkyl or alkenyl radical having 3 to 7 ring carbon atoms, for example cyclopropyl, cyclopentyl, cyclohexyl or cyclohexene-2-yl, furthermore, for example, an optionally substituted phenyl radical or _{v represents} an optionally substituted heteroaryl radical having 5 to 6 ring atoms and 1 to 3, in particular - 1 to 2 heteroatoms in the ring, which may be identical or different and preferably oxygen, nitrogen or

} g are sulfur, such as a furan, thiophene, Isoxazol ™ or pyridine.

As preferred substituents of the above-explained, for

R standing aromatic _r and heteroaromatic radicals may be mentioned, for example:

Halogen, in particular fluorine, chlorine or bromine; nitro; a straight-chain alkyl radical having 1 to 4 carbon atoms; an alkoxy or alkylthio radical having 1 to 4 carbon atoms, for example a methoxy, ethoxy or a methylthio, ethylthio or n-propylthio group; a haloalkyl, haloalkoxy, haloalkylthio having up to M carbon atoms and up to 8 halogen atoms, in particular fluorine and chlorine, for example a trichloromethyl, trifluoromethyl or tetrafluoroethoxy radical; a cyano, alkylcarbonyl or alkoxycarbonyl group, for example a methoxycarbonyl, acetyl or propionyl radical; an optionally substituted phenyl or phenylcarbonyl radical.

"Ir is in particular hydrogen and a branched or unbranched C 1-8 alkoxy radical, e.g. Methoxy, ethoxy, n-propoxy, iso -propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert -butoxy.

S '

h R and R are, for example, an optionally substituted unbranched or branched alkyl radical having up to 4 carbon atoms, for example methyl, ethyl, n-propyl, iso-propyl, η-butyl or iso-butyl. Further, R and R together represent, for example, an alkylene group having 2 or 3 carbon atoms, which may optionally be substituted by alkyl of up to 4 carbon atoms, for example methyl or ethyl.

X is preferably hydrogen, methyl, chlorine or bromine.

The new N-substituted 2-methylnaphthylamides of the formula I have a chiral carbon atom with H, CH, R and -N- as ligands and, depending on the nature of the

2 3 4 5 R, R, R, and R are other centers of chirality.

By customary methods, the optically pure enantiomers or the diastereomers can be obtained. The present invention also covers these compounds in pure form or as mixtures. As fungicides, both the pure enantiomers or the uniform diastereomers and the mixtures usually obtained in the synthesis are effective.

Furthermore, it has been found that the novel compounds of the general formula (I) are obtained when a 2-methyl-naphthylamine of the "formula II- ...

CH-R "

II

in which

1 R and X have the meanings given above,

a) with an acid halide of the formula III

R - C-Hal

III

or

b) with an acid anhydride of the formula IV

20 25 30

0 0

Rc ρ a η ο ¹ -

IV

35

in which

R has the abovementioned meaning and shark chlorine or bromine, if appropriate in the presence of a solvent or diluent, optionally with the addition of an inorganic or organic base and optionally with the addition of a reaction accelerator, at temperatures between -10 and 100 C. This reaction is preferred. As preferred solvents or diluents inert to the reactants, e.g. aliphatic or aromatic hydrocarbons such as pentane, cyclohexane, petroleum ether, benzene, toluene or xylenes; Halogenated hydrocarbons, for example methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene; Ketones such as acetone and methyl ethyl ketone; Ethers, such as diethyl ether,

Dimethoxyethane, tetrahydrofuran or dioxane; Esters, such as ethyl acetate; Nitriles such as acetonitrile used sulfoxides such as dimethyl sulfoxide or corresponding mixtures.

Suitable inorganic or organic bases which may optionally also be used as acid-binding agents in the reaction are, for example, alkali metal and alkaline earth metal carbonates, such as sodium or potassium bicarbonate, sodium or potassium carbonate, calcium carbonate; Borates such as sodium borate; Phosphates such as sodium or potassium di- or triphosphate or amines such as triethylamine, N, N-dimethylaniline, Ν, Ν-dimethylcyclohexylamine, N-methylpiperidine or pyridine .. However, other conventional bases can be used. , ·

'

The reaction accelerators are preferably metal halides such as sodium bromide or potassium iodide, azoles such as imidazo! or 1,2,4-triazole or pyridines such as 4-dimethylaminopyridine in question.

20

The reactions of the invention take place for example at temperatures between -10 and +100 ⁰ C, preferably between 0 and + 40 C, under atmospheric or superatmospheric pressure, continuously or discontinuously.

·. · .- ·. .. ·. ' , It has also been found that compounds of the formula I are obtained by reacting a 2-methylnaphthylamide of the formula Ia

30

Ia

35

in which * · * Ρ 4

R and X have the abovementioned meanings and R and R independently of one another have an optionally substituted

Ii ierten C, -C., ~ Alkyl radical, by cleavage of R

-5 ^{x H} § and, R to the corresponding aldehyde or by reaction

4 5 4 5

with a diol HO-R-R-OH, wherein R and R together represent an alkylene group, to the corresponding cyclic acetal, optionally in the presence of a diluent and optionally with the addition of an acidic catalyst, is reacted. ·

The diol mentioned above includes, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,3-butanediol,

4 5 tandiol and neopentyl glycol. The cleavage of R and R is carried out, for example, by catalytic amounts of strong protic or Lewis acids such as hydrogen chloride (or hydrochloric acid), hydrogen bromide, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethylsulfonic acid, zinc chloride, zinc bromide or boron trifluoride etherate at temperatures of 0 ⁰ C and up to the boiling point of the split-off alcohols Rj, -OH and R ^ -OH act. The reaction with a 1,2- or 1,3-diol is carried out, for example, by passing the alcohols Rh-OH and R ^ -OH from the reaction mixture by distillation in vacuo or under atmospheric pressure or with the aid of an inert gas such as nitrogen or argon, removed. Suitable solvents or diluents are the abovementioned liquids or water, or the 1,2- or 1,3-diols themselves when used in stoichiometric amount or in excess.

; "

; Suitable acid catalysts are Lewis "or protic acids, for example, BP ,, AlCl, or ZnCl ₂ or mineral acids or sulfonic acids.

 - 8th -

Furthermore, compounds of the general formula I are obtained by reacting a 2-methylnaphthylamide of the formula Ib

10

ib

in which ·

R and X have the meanings given above, Hal is a halogen atom and R is hydrogen, a C ₁ -C ₅ -alkyl, Cg-Cjj-alkenyl, C ₅ -C ₇ -cycloalkyl or C ₁ -C ₅ -alkoxy means with a nucleophilic compound of the formula V

20 25

NuH

, V

wherein Nu is a C ^ -C ^ alkoxy or C ^ C ^ alkylthio or 1-imidazolyl, 1-pyrazolyl or 1,2,4-triazolyl (1) radical, optionally in the presence of a solution or diluent, if appropriate in the presence of an inorganic or organic base and if appropriate with the addition of a reaction accelerator at temperatures between -10 and +100 C.

Further compounds of the general formula I are obtained if, depending on the functional nature of

12 R and R makes usual chemical follow-up reactions.

35

The 2-methylamino naphthylamines of the formula II used as starting materials for the preparation of the compounds of the formula I.

/ / h Μ {i

'' is obtained when a 2-methylnaphthylamine of the formula VI

CH-

VI

wherein X has the meaning given above,

V -

a) with a 2-halo-propionic acid ester of the formula VII

VII

shark

in swe Hai chlorine or bromine, or with a 2-halo-propanaldialkylacetal of the formula III

CH, --CH- CH -OR ,, VIII

Hal OR- ³

wherein Hal is chlorine or bromine and R and R ^ have the meanings given above; possibly

in the presence of a solvent or diluent, if appropriate in the presence of an inorganic or organic .Base and optionally with the addition of a reaction accelerator at temperatures 3Q between -10 and +130 ⁰ C reacted.

Preferred solvents and diluents, inorganic or organic base and reaction accelerators include the above-mentioned compounds.

It has also been found that the compounds of the general formula II is obtained when

a) a 2-methylnaphthylamine of the formula Hb with a pyruvic acid ester of the formula IX '

CH 1 -C -COOC ₁ -C ₁₁ alkyl IX .Pm. ih

or a methylglyoxal acetal of the formula XI 10

it is CH-j-C-CHf OR

3 κ t 5

0 OR XI

4 5 wherein R or R have the meanings explained above

have, implements and. , ·

b) hydrogenating the Schiff base obtained as a reaction product, e.g. with complex metal hydrides or catalytically with hydrogen.

The preparation of Schiff's base is carried out, for example, by reacting 1 mol of the 2-methylnaphthalamine of the formula VI with 0.9 to 1.5 mol of the pyruvic acid ester of the formula IX or of the methylglyoxal acetal of the formula XI in a solvent, if appropriate with addition of a reacted acid catalyst and separated at a temperature of 40 to 200 ⁰ C, preferably 50 to 120 ⁰ C water by distillation. Appropriately used, under the reaction conditions inert and simultaneously with water azeotrope-forming solvent for the reaction. Examples of suitable solvents are aromatic hydrocarbons, for example benzene, toluene, ethylbenzene, o-, m-, p-xylene, isopropylbenzene, methylnaphthalene; aliphatic or cycloaliphatic hydrocarbons, for example heptane, nonane, pinane, gasoline fractions within a boiling point

Cycle interval from 70 to 190 ⁰ C, cyclohexane, methylcyclohexane, decalin, ligroin, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane, 2,3 ^ -Trimethylpentan, octane and corresponding mixtures.

Suitable for the hydrogenation are both the reduction with complex Hydride'n as NaBH ₂ ^ and catalytic hydrogenation with hydrogen.

The reduction with sodium borohydride is generally carried out by heating in a solvent the Schiff base with 0.2 mol to 1 mol of sodium borohydride per mole of vessel. Base at a temperature between -20 and + * ^{0 0} C converts.

In the catalytic hydrogenation, such amounts of hydrogen are fed to the reaction mixture at the beginning and in the course of the reaction that a corresponding reaction temperature is always present at the reaction temperature.

pressure, suitably between 150 and 300 bar, sets. The reaction is generally carried out at a temperature of 20 to 200 ⁰ C, preferably from 25 to l60 ° C, batchwise or continuously. For appropriate pressure adjustment, inert gases such as nitrogen can also be used. , ·

For both process variants of the hydrogenation, particularly suitable solvents are cycloolanols and cycloalkanols, for example n-propanol, isopropanol, n-butanol, isobutanol, glycol, ethylene glycol monoethyl ether, glycerol, "amyl alcohol, cyclohexanol", 2- Methyl-1-yl-pentanol, 2-ethylhexanol, and especially methanol, ethanol; cyclic ethers such as tetrahydrofuran and dioxane.

To the catalytic! Hydrogenation, the catalyst is usually used in an amount of 5 to 30 weight percent, based on the Schiff base. It may be mixed with a suitable support material for the reaction, e.g. Silicon dioxide, 'wherein suitably the amount of the catalyst is 10 to 40 weight percent of the mixture of catalyst and carrier.

Conveniently used Kupferchromitkatalysatoren, z. Copper chromium oxide catalysts such as the copper chromites used by H. Adkins (see, Houben-Weyl, Methoden der organischen Chemie, Vol. 4/2, pages 180 to 183 and J. Applied Chem. 5, 289-295 (1955)). They contain, for example, copper-chromium spinel (CuCr ₂ O) or mixtures in the ratio 5 CuO: 4 Cr ₃ OJ. or assume such compounds and may contain other oxides, mainly those of alkaline earth metals such as magnesium, calcium or barium.

The following process descriptions illustrate the preparation of 2- * methylnaphthylamines of the formula II:

a) Direct alkylation of 1-amino-2-methyl-naphthalene

CH,

NH CH-COOCH-

CH,

V-OT-OOOOH ₃ - - ^ΗΒΙ Λ ° 1 ° T "" ³

144.2 g of 1-amino-2-methylnaphthalene (0.92 mol) are treated with 90.2 g (1.08 mol) of sodium bicarbonate and 460 g (2.76 mol) of methyl bromopropionate at 120 to 125 ^° C. for 18 hours touched. After cooling

the precipitate is filtered off with suction and the filtrate is concentrated in vacuo. The residue is distilled in vacuo. This gives 188 g (83.7 % of theory) of N ~ (2-methyl-1-naphthyl) -alanine methyl ester as a colorless oil. Bp .: 138-140 ° C / O, 2 mbar.

b) Schiff base of 1-amino-2-methylnaphthalene

N = C-C00C _o H _c .CH,

(2)

+ CH ₃ .CO COOC ₂ H ₅

g 1-amino-2-methylnaphthalene (2 moles), 232 g of ethyl pyruvate (2 mol) and 0.4 g of p-toluenesulfonic acid are refluxed in 1000 ml of cyclohexane for 4 hours until 36 g of water are distilled off azeotropically and from the Distillate are separated. Then the cyclohexane is distilled off in vacuo and the residue reacted directly.

Yield: 494.7 g (97 % of theory) of vessel see base.

CH ₃ N = C-CH (OCH ₃ ) ₂

+ CH ₃ -CO-CH (OCH ₃ O ₂

314 g of 1-amino-2-methylnaphthalene, 236 g of methylglyoxaldirnethylacetal and 0.4 g of p-toluenesulfonic acid are reacted analogously to process b, equation (2).

, H ₅ Η, NH ^0H 3. COOC, 'COOC. CH CH ₃ CH _{3 5} H ₅

" Yield: 493 g (96 % of theory) of Schiff's base.

c) Hydrogenation of the Schiff base

Catalytic hydrogenation ''

N C

<L o d.D

UH-2-CH-2

(4)

_c , A hydrogenation autoclave of volume 1l is charged with 200 g of Schiff's base of 1-amino-2-methylnaphthalene and methyl pyruvate dissolved in 500 parts of tetrahydrofuran and 15 parts

Ig copper chromite (Kupferehromit in powdered form) filled ". The autoclave is heated to 150 ⁰ C and hydrogen until reaching a pressure of 200 bar pressed" Once the hydrogen terminated on would take, and a constant pressure is reached (after ca 9 hours), is cooled, the catalyst is filtered off with suction and the filtrate is distilled in vacuo.

This gives 142 g (71 % of theory) of N- (2-methyl-1-naphthyl) -: -alanine ethyl ester as a colorless oil of bp. 144-145 ° C / O, 15 mbar.

Reduction "with NaBH ₁ ,

490 g of the Schiff's base of 1-amino-2-methylnaphthalene and methylglyoxal dimethyl acetal are dissolved in 1500 ml of methanol and treated at ⁰ ° C. in portions with 60 g of sodium borohydride. After stirring overnight, the methanol is distilled off, the residue dissolved in 1000 ml of methylene chloride and

Stirred for 30 minutes with 500 ml 10 # iger potassium hydroxide solution and the organic phase separated. After washing three times with 200 ml of water and drying over sodium sulfate, the methylene chloride is distilled off and the residue is distilled in vacuo.

This gives 367 g (7 ¹ J % of theory) of 2- (N-2 ^f ~ methyl- ¹ -naphthyl) = aminopropanaldimethy! Acetal of bp 140-145 ⁰ C / 0.3 mbar

 10

2-N - [(1-pyratolyl) acetyl] -N- (2- ^t- methyl-1-naphthyl) alanine methyl ester,

2-N - [(l-pyrazolyl) acetyl] -N- (2'-methyl-l'-naphthyl) -Ala

Nin-ethyl ester, 2-Nt (1, 2 _J 4-triatolyl (1)) -acetyl] -N- (2'-methyl- ^1- naphthalene)

thyl) -alanine methylester,

2-N - [(l, 2 _i i | -Triazolyl- (l)) - acetyl] RN- (2 -'- methyl-l ^t -naphthyD-alanine ethyl esters,

2-N ~ cyclopropyl "" carbonyl-N- (2-methyl-1-naphthyl) alanine methyl ester,

2-N-cyclopropylcarbonyl-N- (2-methyl-1-naphthyl) alanine ethyl ester,

2-N-cyclopentylcarbonyl-N- (2-methyl-l-naphthy1) alanine

methyl ester,

2-N-cyclohexylcarbonyl-N- (2-methyl-1-naphthyl) alanine methyl ester,

2-N ~ methoxycarbonyl-N ~ (2-methyl-1-naphthyl) alanine methyl ester,

2-N-Ethoxycarbony1-N- (2-methy1-1-naphthy1) -alanine methylester ,,

2-N-Ethoxycarbony1-N- (2-methy1-1-naphthyD-alanine ethyl ester,

2-N-propoxycarbonyl-N- (2-methyl-1-naphthyl) -alanine methyl ester,. '.

' ^f 2-N-allyloxycarbonyl-N- (2-methoxy-1-naphthyl) alanine methyl ester,

2-N-butoxycarbonyl-N- (2-methoxy-l-naphthyl) -alanine-raethyl-

ester, § 2-N-methoxalyl-N- (2-methoxy-1-naphthyl) -alanine methyl ester,

2 ~ N-ethoxalyl-N- (2 ~ methoxy-l ~ naphthyl) -alanine-methyl-

ester,.

2-N-Ethoxalyl-N- <2-methyl-1-naphthyl) alanine ethyl ester, 2-N-acetoacetyl-N- (2-methyl-1-naphthyl-alanine methyl ester, 2-N-, (4 Oxo-pentanoic 1) -N- (2 '»methyl 1-1 ^! -Naphthyl-1) alanine methyl ester,

.2-N- (3-Hydroxybuty.ry 1) -N- ^(2-methyl-f l-naphthy 1) alanine

methyl ester j __.

2-N-Benzoyl-N "(2-methyl-1-naphthyl) -alanine methyl ester, 2-N- (2 ° chlorobenzoy1) -N- (2'-methyl-1'-naphthyl) alanine methyl ester,

2-N "(2-bromo-benzoyl) -N- (2'-methyl-1'-naphthyl) -alanine-methyl ester,

2 "N- (2-iodo - = - benzoyl)" N- (2'-methyl-l ^f naphthyl) alanine methyl ester,

2-N- (2-methylbenzoyl) -N- (2-methyl-l ^{t t} naphthyl) alanine methyl ester,

2-N- (2-trifluoromethyl-benzoyl) -N- (2'-methyl-1'-naphthyl) -alanine methyl ester,

2-N- (2-methoxybenzoyl) -N- (2'-methyl-1'-naphthyl) alanine methyl ester,

2-N- (2 "thiophene-carbonyl) -N - ="(2'-methyl-1-1'-naphthyl) -alanine methyl ester, 2-N- (2-furan carbonyl) -N- (2 "^f" -methyl 1'-naphthyl) alanine methyl ester,

2-N- (2-Purancarbonyl) -N- (2'-methyl-1'-naphthyl) -alanine-ethyl ester,

2-N- (2-methyl-furan-3-carbonyl) -N- (2'-methyl-1'-naphthyl) -alanine methyl ester,

2-N- (2,5-Dimethylfuran · 3-carbonyl) -N- (2'-methyl-1-1-methyl-1'-naphthyl) -alanine methyl ester, 2-N- (2, ¹ J, 5-Trimethy If uran-3-car bony 1) -N- (2'-methy 1-1 '-

-naphthyl-alanine methyl ester, S 2-N- (3-isdxazolyl-carbonyl) -N- (2'-methyl- ^1- naphthyl) alanine methyl ester,

2-N- (3-Isoxatolyl-carbonyl) -N- (2'-methy1-1'-naphthyl) alanine ethyl ester,

2-N- (3-Methylisoxazoly1-5-carbonyl) -N- (2'-methyl-l'-naphthyl) = alanine methylester,

2-N-Micotinoyl-N- (2-methyl-1-naphthyl) -alanine methyl ester; 2-N- (2-chloro-nicotinoyl) -N- (2'-methyl-1'-naphthyl) -alanine - methyl ester,

2-N-acryloyl-N- (2-methyl-1-naphthyl) alanine methyl esteri 2-N- (2-methylacryloyl) -N- (2-methyl-1-naphthyl) alanine methyl ester,

2-N-phenoxycarbonyl-N- (2-methy1-1-naphthyD-alanine methylester,

2-N- (M-chlorophenoxycarbonyl) -N- (2'-methyl-1-naphthyl) alanine methyl ester,

2- [N- (2-methyl-1-naphthyl) -N-acetyl] -aminopropanol dimethyl acetal

2- [N- (2-methyl-1-naphthyl) -N-propionyl] -aminopropanedimethyl acetal, 2- [N- (2-methyl-1-naphthyl) -N-butyryl] -aminopropanedimethyl acetal,

2- [N- (2-Methy1-1-naphthyl) -N-chloroacetyl] -aminopropanaldimethylacetal,

Chloroacetic acid N- [1- (1,3-dioxolan-2-yl) -e-ethyl] -N- ^2f - 3Q- methyl-1-naphthylamide,

Chloroacetic acid N-] 1- (4'-methyl-1 ', 3'-dioxolane-2- ^f- yl) - ethyl] -N-2 "-methyl-1-naphthylamide _} 2- [N- (2 Methyl 1-1-naphthyl 1) -N-bromoacetyl '] - aminopropanaldi-

methyl acetal, 3S

^r 2- [N- (2-methyl-1-naphthyl) -N-iodoacetyl] -aminopropanaldi-

methy! acetal, ·

2- [N- (2-methyl-1-naphthyl) -N-methoxyacetyl] ~ -aminopropa

dimethyl acetal,. , -

g methoxyacetic acid ~ N - [1 _J 3 - dioxolan-2-yl) "ethyl" ~ N-2- ^t -methyl-1'-naphthylamide,

Methoxyacetic acid-N- [1- (4'-methy1-1 ', 3'-dioxolan-2'-yl) - -ethyl3-N-2-methyl-l ^{ll ll} naphthylamide, Methoxye isigsäure £ ~ N- [1 - (4 ', 5' -dimethyl-1 ', 3'-dioxolan-2'-yl) ethyl] -N-.2 "-methyl-l ^{n-naphthylamide,} 2- [N- (2-methyl -l-naphthyl) -N ~ ethoxyacetyl] ™ arainopropanaldimethylacetal,

2- [N- (2-methyl-1-naphthyl) -N-methylthioacety1] -aminopro-

panaldimethy! acetal,

^ g 2- [N- (2-methyl-1-naphthyl) -N- (2'-chloropropionyl)] - aminopropanaldimethylacetal,

2- [N- (2-methyl-1-naphthyl) -N- (1'-imidazolylacetyl)] - amino ™ propanoldiraethylacetal,

2- [N- (2-methyl-1-naphthyl) ^ - N- (1'-pyrazoly lacety 1)] -amino-2Q-propanaldimethylacetalj

2- [N- (2-methyl-naphthyl) -N- (1 ', 2', M'-triazolyl-U'-acetyl)] - aminopropanaldime thy lace tal, 2 "[N- (2-Me thy 1-1-naphthyl) - N -cyclophenylcarbony1] -aminopropanaldimethylacetal, 2- [N- (2-methyl-1-naphthyl) -N-cyclohexylcarbonyl] -aminopropanaldimethylacetal,

2- [N- (2-methyl-1-naphthyl) -N-methoxycarbonyl] -aminopropanaldimethylacetal,

2- [N- (2-methyl-1-naphthyl) -N-ethoxycarbonyl] -aminopropanal-3Q dimethylacetal,

2- [N- (2 "-methyl-1-naphthyl) -N-butoxycarbonyl] -aminopropanaldimethylacetalj

2- [N- (2-methyl-1-naphthyl) -N-allyloxycarbonyl] -aminopropanaldimethylacetal,

; - ^: ·, _ν · .- / · ν> - - - 19 - \ λ - ·, · ',

2- [N- (2-methyl-1-naphthyl) -N-methoxy-1] -aminopropanedimethylacetal, 2- [N- (2-methyl-1-naphthyl) -N-ethoxalyl] -aminopropanaldimethylacetal,

§ 2- [N- (2 "methyl-1-naphthyl) -N-acetoacetyl] -aminopropanaldimethylacetal,.

Acetoacetic acid N- {1- (1,3-dioxolan-2-yl) -ethyl] -N-2'-methyl-1'-naphthylamide, 2- [N- (2-methyl-1-naphthyl) - N- (3'-hydroxybutyryl)] - aminopropanaldimethylacetal,

2- [N- (2-Methy1-1-naphthyl) -N-benzoyl] -aminopropanaldimethylacetal,

2- [N- (2-methyl-1-naphthyl) -N- (2'-chlorobenzoyl)] - aminopropanedimethyl acetal,

2- [N- (2 ~ methyl-l-naphthyl) -N- (2'-bromobenzoyl)] - aminopropanaldimethylacetalj

2- [N- (2-methyl-1-naphthyl) -N- (2'-trifluoromethyl-benzoyl)] - aminopropanedimethyl acetal, 2- [N- (2-methyl-1-naphthyl) -N- (2 ' methoxy-benzoyl)] - amino

propanaldimethylacetal,

2- [N- (2-methyl-1-naphthyl) -N- (2-furancarbonyl)] - aminopropanedimethyl acetal,

2-Purancarbonsäure-N- _[l} 3-dioxolan-2-yl) ethyl] -N-2 ^f -methyl- -1'-naphthylamide,

2- [N- (2-methyl-1-naphthyl) -N- (2'-methyl-furan-3'-carbonyl)] - -aminopropanaldimethylacetal,

2- [N- (2-Methyl-1-naphthyl) -N- (2 ', _: 4', 5'-trimethyl-1-furan-3'-carbonyl)] - amanopropane dimethyl acetal, 2- [N- (2 ~ Methyl (naphthyl) -N- (3 ^f -isoxazolylcarbonyl)] - aminopropanaldimethylacetal,

', 2- [N- (2-methyl-1-naphthyl) -N- (3'-methylisoxazol 1-5'-carbonyl)] - aminopropanaldimethylacetal,

2- [N- (2-methyl-1-naphthyl-N-nicotinoyl] -aminopropanedimethyl acetal, 35 '.

* 2- [Ν- (2-methyl-1-naphthyl) -Ν- (2 "-chlornieotinoy1)] - aminopropanaldimethy acetal!

2- [N- (2-methyl-l-napthyhl) -N-acryloyl] -aminopropanaldimethy! Acetal,

2 "[N- (2-methyl-1-naphthyl) -N- (4-chlorophenoxy-carbonyl)] - -aminopropanaldimethylacetal,

N- (2-furancarbonyl) -N- (2 ^{f-methyl-4'-bromo-l-naphthyl)} alanine methylester,

N-methoxyacetyl-N- (2-methyl-4-bromo-1-naphthyl) alanine

methyl ester, -

2- [N- (2-methyl-1-naphthyl) -N-bromoacetyl] aminopropionaldehyde, 2- [N- (2-methyl-1-naphthyl) - = N -methoxyacetyl] .- aminopropion-

aldehyde. ..... · -

The preparation of the new compounds is illustrated by the following examples:

example 1 CH CH, • 7 j -N J \ ₍ r \ : o-CH ₃ (Ο) CH-COOCH ₃ / \

A mixture of 30.7 g (0.12 mol) of N- (2-methyl-1-naphthyl) -α-lanine methyl ester, 9.5. g pyridine (0.12 mol), 5 g of 4-dimethylaminopyridine and 50 ml of acetic anhydride is stirred at 80 C for 8 hours, then cooled and concentrated in vacuo, the residue is mixed with 250 ml of ethyl ether and with 250 ml of water. The organic phase is separated off, washed with 100 ml of 1N hydrochloric acid, then with 100 ml of water, decolourised with carbon and concentrated. The residue is admixed with 30 ml of a 5: 1 petroleum ether: ether mixture

J η M Ί ι 4, UJ 1 «J **

- 21 -

¹ O ⁰ C stirred, allowed to crystallize for 4 hours at 0 ° C and filtered with suction. This gives 23.6 g (69% of theory) of N-acetyl-N- (2-methyl-1-naphthyl) -alanine methyl ester as white crystals of melting point 119-121 ⁰ C.

Example 2

COOCH,

CO-CH ₂ -Br

To a well-stirred suspension of 14 g of sodium bicarbonate (0.17 mol) and 20 g of sodium sulfate in 150 ml of dry toluene are added 19.4 g (0.09 mol) of N- (2-methyl-1-naphthyl) alanine methyl ester and then a solution of 24.2 g (0.12 mol) of bromoacetyl bromide in 50 ml of toluene in 1 hour at + 15 ° C was added dropwise. After five hours of stirring at 25 C, the precipitate is filtered off with suction and washed with 50 ml of toluene. The filtrate is washed twice with 100 ml of 1N sodium hydroxide solution, once with 50 ml of 2N hydrochloric acid and finally with 100 ml of water, dried, decolorized with carbon and evaporated in vacuo. The remaining oily residue is dried for 3 hours at 50 C and 0.1 mbar. This gives 22.5 g (77.3 % of theory) of N-bromoacetyl-N- (2-methyl-1-naphthyl) alanine methyl ester as a light yellow oil.

IR spectrum (film): 3035, 2970, 2935, 1730, 1652, 1440, _w 1415, 1360, 1200, 1132, 1095, 812,

782, 744 cm " ¹ .

Example 3

CH,

CH-

/ CH COOCH ₃ .

CO-CH

13 g (Ο, Ο3β mol) of N-bromoacetyl-N ~ (2-methyl-1-naphthyl) -alanine methyl ester (Example 2) are dissolved in 6O ml of dry dimethylformamide and with 6.8 g (0.1 mol ) Imidazole. The mixture is stirred for 10 hours at 60 ⁰ C and concentrated in vacuo. The residue is extracted by shaking with 150 ml of methylene chloride and 50 ml of VJasser, the or-IS ganic layer separated and washed twice with 50 ml of water. The organic solution is dried, decolorized with carbon and concentrated. After cleaning of the crude product by filtration of its solution in Essigester over silica gel obtained by evaporation of the ^r Essigesters as a residue 9.6 g of resin.

: Cal.. ^: 'C 68.4 H 6.0 N 12.0 %. Found: C 68.0 H 6.4 N 11.9 %,

Example 4

CH-

CH

CH-COOCH ₃

24.3 g (0.1 mol) of N- (2-methyl-1-naphthyl) alanine methyl ester and 0.5 ml of triethylamine in 50 ml of dry toluene

are at "80" to 90 with 9 g ⁰ C -having "stirring (0.1 mol)

Diketen added drop by drop. After three hours of stirring at 95 ⁰ C, the mixture was cooled, washed once with 50 ml of '2N hydrochloric acid and once with water, dried and concentrated. After purifying the crude product by filtration of its solution in ethyl acetate on silica gel, the residue obtained by evaporating off the ethyl acetate as the residue gives 29.7 g of analytically pure oil (yield 90 % of theory).

IR spectrum (film): 3042, 2980, 2940, 1740, 1720, 1β50, Γ 1650, 1455, 1370, 1310, 1195, 920,

815, 786, 746 cm " ¹ .

Example 5

> 3

'.CH-COOCH ₃

Br- ^ Π V-N;

20

22.2 g (0.066 mol) of N- (2-furancarbonyI) -N- (2-methyl-1-naphthyl) -alanine methyl ester (Example 21) and 6 g (0.07 mol) of anhydrous sodium acetate in 150 ml 'Acetic acid are mixed with 11 g (0.067 mol) of bromine and stirred at 35 ° C for 24 hours. The mixture is then stirred into 700 ml of ice-water and the product is extracted three times with 100 ml of ether each time. The combined ethereal extracts are washed once with 100 ml of 1N sodium hydroxide solution and once with water, dried and concentrated.

30

17 g is obtained (62% of theory) N- (2-furancarbonyl) -N- (2'-methyl-4 .'- ^bromo-l? -Naphthyl) -alanine methyl he read. as a colorless resin.

3S

• TR spectrum (film): 3035, 2930, 1730, 1640, 1450, 136O,

1235, 1190, 1126, 1092, 908, 810.

Example 6

20

14.2 g (0.04 mol) of 2- [N- (2-methyl-1-naphthyl) -N- (2-furan-carbonyl)] -aminopropanal-dimethylacetal (Example No. 23) 3 ml of ethylene glycol and 0.2 g of p-toluenesulfonic acid in 80 ml of toluene are stirred at 80 C for 8 hours. The resulting methanol in a weak stream of nitrogen is constantly expelled from the reaction mixture. After cooling and washing three times with 60 ml of water, the organic solution is decolorized with carbon and concentrated in vacuo. The residue crystallizes after addition of 10 ml

cold ether. This gives 9 g (.64 % of theory) of 2-purancarboxylic acid N- [1- (1,3-dioxolan-2-yl) -2-methyl-1-ethyl-1] -N-2'-methyl- -l'-naphthylamide as white crystals of melting point 129-131 ^O C.

Example 7

30

CH ₃

CH, I

t *> CH-CHO

CO-CH ₂ Br

3S

lib a ι ό

- 25 -

Ύ, 6 g (0.02 mol) of 2- [N- (2-methyl-1-naphthyl) -N-bromoacetyl] - aminopropanedimethyl acetal (Example No. 12) dissolved in 50 ml of methylene chloride are mixed with 100 ml for 1 hour 2N hydrochloric acid stirred vigorously at room temperature. The organic phase is separated, washed with 100 ml of water, dried and concentrated. This gives 5.3 g (80 % of theory) of 2- [N- (2-methyl-1-naphthyl) -N-bromoacetyl] - »aminopropionaldehyd as a light yellow oil.

IR (film): 3038, 2970, 2820, 2710, 1720, 1645, 1 ^ 90, 1365,

1203, 810, 778, 7 ^ 2, 640 cm " ¹ .

The following compounds are prepared analogously: 15

Table 1

CH-R

ο Η

example X -CH (OCH) _? COOCH, ν "C R '\ tt / o r -CH ₂ -Cl Mp. > oil IR (FiIm) 298ο [cm- ¹ ] 10 No j R ^{2 0} C 1448 8th H oil 3042, 1148 , 2930, -CH 1645, 945, , 1360, 1295, 747th , 1120, 15 -CH (OCH,) _p -CH (OCH) ₂ -CH ₂ Cl 80-82 1062, 2928 814 COOCH -0 ~ CH resin 786, 1365 9 H ί oil 2972, 1θ8θ , 1642, -C ₂ H ₅ 1445, 811, , 1256, 1120 , 1060, 20 952 2980 783, 744, respectively. 1622 10 H 3042, 1240 , 2940, 1740, 1050 , 1505, 1365, 748th , 1200, 25 1105 , 815, 783, 2940 11 H 1690 12 - H 3040, 1190 , 2910, 30 1732, 810 , 1430, 1325, 742nd , 1066, 1025, 785, 772,

1 3

"Example X No. Pp

⁰ C

IR (.Pilm) [cm " ¹ ]

16

H »COOCH

CH (OCH ₃ ) ₂ -CH ₂ Br resin 3018, 2912, 2810-

1645, 1585, 1556,

1415, 1256, 1235,

1138, IO85, 810, 780,

-C ₂ H ₅ oil 3045, 2972, 1720,

1648, 1440, 1390,

1260, 1170, 1130,

1075, 812, 780, 644 oil

H -COOCH., -CH 2 -O-CH.

3042, 2935, 1732, 1664, 1440, 138O, 1280, 1190, 1125, 812, 784, 746.

H -COOCH.

-QH ₂ -O-CH 107-109

-CH ₂ -S-CH

H is -COOCH ^ -CH ₀ -N

"COOCH.

Oil 3035, 2975, 2935, 1730, 164o, 1440, 1359, 1210, 1185, 1100, 1043, 978, 810, 780, 744.

106-108

Oil 3040, 298O, 2938, 1712, I63O, 1548, 146, 1400, 1304, 1246, II90, 1098, 1010, 814, 78O, 762.

Example no.

22

23

24

25

26

R Pp.

IR (FiIm) [cm " ¹ ]""

-COOC ₀ Hr

H -COOCH.

CH (OCH) ₂

H -COOCH.

-CH (OCH) J ~ \

Oil 3130, 2982, 2935, 2900, 1710, 1630, 1550, 1450, 1402, 1302, 1240, 1095, 1070, 812, 7 ..

 760th

oil 2968, 2925, 1625, 1555, 1455, 1376, 1305, 1174, 1100, 1058, 8L0 _s 795, 779, 750th

Resin 3108, 3038, 2935, 1726, 1635, 1532, 14 .., 1330, 1200, 1100, 1042, 875, 856, 810, 796, 778, 758, 742.

Resin 3105, 3θ4θ, 2930, 1640, 1544, 1438, Ι8θ, 1200, 1100, 1058, 835, 810, 795, 778, 75, 743.

Resin 3038, 2970, 2935, 2908, 1725, 1615, 156., 1420, 13ΙΟ, 1292, 1200, ΙΙ30, 1022, 810, 782, 763, 745.

15 20 25 30

Example no.

Pp.

Or.

IR (FiIm) [cm " ¹ ]

27

H -COOCH.

35

Resin 3030, 2932, 1728, 1640, 1560, 1430, 1135, 1290, 1210, 1188, 810, 779, 745.

The new active ingredients show a strong fungitoxic activity against phytopathogenic fungi, in particular from the class of Phycomycetes. The novel compounds are therefore, for example, suitable for controlling Phytophthora infestans on tomatoes and potatoes, Phytophthora parasitica on strawberries, Phytophthora cactorum on apples, Pseudoperonospora cubensis on cucumbers, Pseudoperonosppora humuli on hops, Peronospora destructor on onions, Peronospora sparsa on roses, Peronospora tabacina on tobacco, Plasmopara viticola on vines, Plasmopara halstedii on sunflower, Sclerospora macrospora on corn, Bremia lactucae on salad, Mucor mucedo on fruits, Rhizopus nigricans on beets, Erysiphe graminis on cereals, Uncinu-la necator on vines., Podophaera leucotricha on apples , Sphaerotheca fuliginea on roses, Erysiphe cichoriacearum on cucumbers. The fungicidal compositions contain 0.1 to 95 % (weight percent) of active ingredient, preferably 0.5 to 90 %. The application rates are depending on the nature of the desired effect between 0 _s l and 5 kg of active ingredient per ha. Part of the active ingredients shows curative properties, ie the application of the funds can be made even after the infection of the plants by the pathogens to a safe control success to achieve. Active ingredient particles with a particle size smaller than 5 / U show a good fungicidal action.

In addition, many of the new compounds are systemically effective, so that over the root canal also protection of aerial plant parts is possible.

§ The active compounds according to the invention can also be used together with other active substances, e.g. Herbicides, insecticides, growth regulators and fungicides or mixed with fertilizers and applied. In many cases, the mixture with fungicides also increases the fungicidal activity spectrum; in a number of these fungicide mixtures, synergistic effects also occur, i. the fungicidal activity of the combination product is greater than that of the added activities of the individual components. A special.

Ig favorable enlargement of the effect spectrum is achieved with the following fungicides:

manganese ethylenebisdithiocarbamate

Manganese zinc ethylene bisdithiocarbamate Ammonium complex of zinc (N, N-ethylene-bis-dithiocarbamate) N-trichloromethylthio-tetrahydrophthalimide N-trichloromethyl-phthalimide

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole 2-Methoxycarbonylaminobenzimidazole 2-Rhodanemethylthiobenzothiazole

l, 4-Dichloro ~ 2,5-dimethoxybenzene

2,3-dichloro-6-methyl-1,4-oxathiin-5-carboxylic acid anilide 2-methyl-5,6-dihydro-4-H-pyran-3-carboxylic acid anilide 2,4,5-trimethyl-furan 3-carboxylic acid urethanilide 2-methyl-furan-3-carboxylic acid anilide. .-. 2,5-Dimethyl-furan-3-carboxylic acid cyclohexylamide.

N-cyclohexyl-N-methoxy-2,5 ~ dimethyl-'furan-3-carboxylic acid amide

 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-l, 3-oxazolidin

3- (3,5-dichlorophenyl) -5-methyl »5-niethoxymethyl-l, 3-oxazolidine-2,4 ~ dione

The following list of fungicides with which the compounds according to the invention can be combined is intended to illustrate, but not limit, the possible combinations. ,

Fungicides which can be combined with the active compounds according to the invention are, for example:

Dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate

Zinc dimethyldithiocarbamate zinc ethylenebisdithiocarbamate

Tetramethylthiuramdisulfide

Zinc "(Ν, Ν-propylene-bis-dithiocarbamate) ammonia complex of zinc-CN ^ N'-propylene-bis-dithiocarbamate) and N, N'-polypropylene-bis (thiocarbamoyl) -disulfide

Nitroderivate, like

Dinitro- (1-methylheptyl) -phenylcrotonate 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethacrylate 2-sec-butyl-4,6-dinitrophenyl-isopropylcarbonate

heterocyclic structures, such as 2-heptadecyl-2-imidazoline acetate 2, M-dichloro-6- (o-chloroanilino) -s-triazine, 0, 0-diethyl-phthalimidophonothioate, 5-amino-1- (bis (dimethylamino) - phosphinyl) -3-phenyl-1,2,4-triazole)

2,3-dicyano-1,4-dithiaanthraquinone 2-thio-1,3-dithio (4,5-b) quinoxaline. '

l "(butylcarbamoyl) -2-benzimidazole-carbaminsäuremethyl ~

-ester "'.

4- (2-Chlorphenylhydrazono) -3-methyl-5-isoxazolone

Pyridine-2-thio-l-oxide.

S 8-hydroxyquinoline or its copper salt, 2,3 "dihydro ~ 5-carboxanilido ~ 6 ~ _methyl-l> 4-oxath.iin-

-4,4-dioxide '.

2 _i 3-Dihydro-5 "^> carboxanilido-6-methyl-1,4-oxathiin 2- (Pury) .- (2)) benzimidazole piperazine-1,4-diylbis- (1- (2,2,2 trichloroethyl) -formamide 2- (thiazolyl- (4) -benzimidazole

5-butyl-2 ™ dimethylamine "4" -hydroxy-6-ethyl-pyrimidine Bis (p-chlorophenyl) -3-pyridinemethanol

l, 2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene 1S l, 2-bis (3-methoxycarbonyl-2-thiour ^> eido) -benzene and various fungicides, such as

dodecylguanidine acetate

3- (3- (3,5-Dimethyl-2-oxycyclohexyl) -2 »hydroxyethyl) glutarimide hexachlorobenzene

N-dichlorofluoromethylthio-N ', N ¹ -dimethyl-N-phenyl-sciiwefelsäurediamid

2,5-Dimethyl-furan-3-carboxylic acid anilide 2-Methyl-benzoic acid anilide 2-Iodo-benzoic acid anilide

1- (3 _s' 4-di-chloro anilino) -1-f ormy lamino-2,2,2-tr ichlor et han 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2 _J 6 "Dimethyl -N-cyclododecyl-morpholine bzvr its salts l- (4 ^ chlorophenoxy) -3 _s 3-dimethyl-l- (lH »l _i 2 _s 4-triazol-1-yl) -2-butanone

l- (4-chlorophenoxy) -3,3-dimethyl-.l- (lH-l, 2,4-triazol-l-yl) -

-2-butanol - (2-chlorophenyl) -.- (4-chlorophenyl) -5-pyrimidine-methane

nol

 · -

ZZD3! ό

The new active ingredients are, for example in the form of directly sprayable solutions, powders, suspensions, and highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules, by spraying, atomizing, dusting, scattering, pickling or Pouring applied. The Aufwendungsformeη depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the new active ingredients. The particle size can influence the fungicidal action of the active ingredient in the sense that an improvement in the fungicidal activity is determined with increasing fineness of the active ingredient particles.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils, etc., and oils. vegetable or animal origin, aliphatic,. cyclic and aromatic hydrocarbons, for example, benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, e.g. Methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., strong polar solvents, e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. into consideration.

-j .

Aqueous application forms can be prepared from emulsion concentrates, bases or wettable powders (spray powders), oil dispersions by addition of water. For the preparation of emulsions, pastes or oil dispersions, the substances as such or in an oil or. Solvents are dissolved, homogenized by means of wetting agents, adhesives, dispersants or emulsifiers in water. It

'' But can also be prepared from v / effective substance, wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water. S

Suitable surface-active substances are: alkali metal, alkaline earth metal, ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, alkali metal and alkaline earth metal salts of dibutyinaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, fatty alkali and alkaline earth salts, salts of sulfated hexadecanols, heptadecanols, octadecanols , Salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene-octylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonyphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkali aryl polyether alcohols, isotridecyl alcohol , Fatty alcohol-ethylene oxide condensates, ethoxylated castor oil, poly (ethylene alkyl) ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, so rbitester, lignin, liquors and methylcellulose

loose.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coating, impregnation and homogeneous granules j 'can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, attaclay, limestone,

Chalk, talc, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flours, bark, hull and nutshell flours, cellulose powders and other solid carriers.

For the following experiments, the following compounds were used as known comparative agents.

c- '. ...

N-trichloromethylthio-phthalimide (Compound A) N-trichloromethylthio-tetrahydrophthalimide (Compound B). Zinc-ethylene-1,2-bis-dithiocarbamate (Compound C). 15

Trial 1 .

Efficacy against casseroles on peas

LOO-g samples "Senator" pea seeds are carefully pickled in glass flasks for about 5 minutes with 300 mg (= 0.3% by weight ) of pickling agent preparations containing 40 % active ingredient in the dry matter. Then, 100 seeds each are seeded in seed boxes 3 cm deep and 3 to 5 cm apart in a compost soil that has a strong natural contamination with the fungi Pythium spec, Aphanpmyces spec, and Pus ar oum oxysporum. Die.Kästen be placed in the greenhouse at temperatures of 17 to 20 ⁰ C. After a test period of 21 days, the number of healthy pea plants is determined.

'' healthy plant after

(Mordant preparation) 21 days in compost soil

2 86 10 84 16. 92 19 90 20 88   21 85 Compound B (comparative agent) 70 Control (untreated) 18

infected compost soil

Control (untreated) 92 sterilized compost

Versuc_h_2

Efficacy against Erysiphe graminis on wheat

Leaves of potted wheat seedlings of the "Jubilar" variety are mixed with aqueous suspensions of 80 % . (Percent by weight) of active ingredient and 20 % emulsifier.

"E sprays and dusted after drying the spray coating with Oidien (spores) of wheat powdery mildew (Erysiphe graminis var. Tritici). The test plants are then placed in the greenhouse at temperatures between 20 and 22 ⁰ C and up to 8o % relative humidity "

2Q 10 days, the extent of mildew fungus development is determined.

active substance infestation (Untreated) the leaves after injections 5 0.006. With x # active ingredient broth 4 X = Oj 025 0.012. 3-4 5 5 0 2 0 8th 1 1 3-4 12 0 0 1 ¹⁶ 7 0 1 26 ^_-:; , 1 1 10 control

0 =. no fungal attack, graded to 5 - total infestation

Trial 3

Efficacy against ^ Phytophthora infestans on tomatoes

Leaves of potted plants of the variety "large beef tomato" are sprayed with aqueous suspensions containing 0.025 % (weight percent) of active ingredient. After the spray coating has dried on, the leaves are treated with a zoospore suspension of the fungus Phytophthora infestans

infected. The plants are then placed in a water vapor-saturated chamber at temperatures between 16 and 18 ⁰ C. After 5 days, the disease on the untreated but infected control plants has developed so strongly that the fungicidal activity of the substances can be assessed.

sg

Active ingredient Infestation of the leaves after spraying with 0.025% active ingredient broth.

4 0 a • 8th .' , 0 17 ι · 20 '· * ... ". 0 21; 1-2 24 1 . 10 Compound C (comparative agent) 2-3 Control (untreated) 5

0 = no fungal attack, graded to 5 = total infestation. - ._ 15

Trial 4 ;

Efficacy against Plasmopara viticola on vines

ir

Leaves of potted vines of the variety "Müller-Thurgau" are sprayed with aqueous suspensions containing 0.025 % (weight percent) .. Active ingredient, sprayed. To assess the duration of action of the active ingredients, the plants are after

-On drying the spray coating 10 days in the greenhouse set up. Only then are the leaves infected with a zoospore suspension of Plasmopara viticola (vine peronospora). Afterwards, the vines are first placed in a steam-saturated chamber at 24 ^° C. for 16 hours.

3Q closing for 8 days in a greenhouse with temperatures between 20 and 30 ⁰ C. After this time, the plants are again placed in the humid chamber for 16 hours to accelerate the Sporangienträgerausbruch. Then, the extent of the mushroom outbreak is assessed on the undersides of the leaves. _ ..

1 3 -3. ; ^:

S3

• Active ingredient Infestation of the leaves after spraying ⁿ

with O, O25 # iger drug broth

.0

21 0

Compound A (Comparative Agent) 2

Control (untreated) 5

0 = no fungal attack, graded to 5 = total infestation «

Embodiments · ic examples of preparations are:

I. 90 parts by weight of compound 1 are mixed with

10 parts by weight of N-methyl-alpha-pyrrolidone and obtains a solution which is suitable for use in the form of very small 2Q drops. ,

II. 10 parts by weight of compound 2 are dissolved in a mixture which comprises 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of α-lacto-N-mono-

ethanolamine, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.

"

III. 20 parts by weight of compound 3 are in one

Mixture dissolved consisting of HO parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of 'ground. product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the

^r solution into 100 000 parts of water gives an aqueous dispersion which comprises 0.02 -. containing% of V / irkstoffs.

IV. 20 parts by weight of compound 1 are in one

Mixture dissolved, consisting of 25 parts by weight of cyclohexanone ,. 65 parts by weight of a mineral oil fraction of boiling point 210 to 28O ⁰ C and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02 wt .- % of the active ingredient.

V. · 20 parts by weight of compound 2 are well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite liquor and 7 parts by weight of powdered silica gel and mow in a hammer mill. By finely distributing the mixture in water, a spray mixture is obtained.

VI. 3 parts by weight of compound 3 are intimately mixed with 97 parts by weight of finely divided kaolin. Obtained in this way, a dusting agent which contains 3.% ~ Containing the active ingredient.

VII. 30 parts by weight of compound 1 are with a

Mixture of 92 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, intimately mixed. This gives a preparation of the active substance with good adhesive properties.

- speed. -

226913 3

ΎΐΙΙ. 40 parts by weight of compound 2 are intimately mixed with 10 parts of sodium salt of phenol sulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. You get a 5! stable aqueous dispersion. By diluting with 100,000 parts by weight of water gives an aqueous dispersion which 0.04 wt -.% Containing the active ingredient.

IX. 20 parts of compound 3 are intimately mixed with 2 parts CaI-10 cium salt of dodecylbenzenesulfonic acid, 8 parts _v Pettalkohol polyglycol ether, 2 parts of sodium salt of phenol sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

Claims (2)

Claim of invention . , , ι Fungicidal agent, characterized by a content of a solid or liquid carrier and a 2-Methyl naphthylamide of the general formula where 0 R is a -C-R group, wherein R is hydrogen or C.-Ci.-alkoxy and further R is a -CH-OR group, R and R independently t. * ® from each other an optionally substituted i {5
C ₁ -C ₁ J-AIkYlTeSt or R and R together represent an alkylene group which, together with the radical whose substituents they are, a 5- or 6-membered radical which is optionally substituted by C ₁ -C -alkyl or aryl- ' forms two oxygen atoms containing heterocyclic ring and ρ
R is optionally substituted by fluorine, chlorine, bromine, iodine, C ₁ -C ₂ J-alkoxy, C ₁ -C ₄ -alkylthio, 1-imidazolyl, 1-pyrazolyl, 1,2, -triazolyl- (I) or oxo ( = 0) -substituted C ₁ -C ₄ -alkyl-, furthermore a C ₁ -C ₄ -alkenyl, C ₂ -C ₅ -alkynyl, C ₃ -C ₇ -cycloalkyl-C, C _A -C ₇ -cycloalkenyl -, RC ^ alkoxy, an optionally substituted phenyl or optionally substituted heteroaryl. means and
X is hydrogen, methyl, chlorine or bromine.