DD150842A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

1. Claims for the Contracting States : BE, CH, LI, DE, FR, GB, IT, LU, NL, SE A 2-(N-aryl-n-acyl)-aminopropanal-acetal of the general formula I see diagramm : EP0019745,P23,F3 where X**1 , X**2 and X**3 independently of one another are oxygen or sulfur, Y is oxygen, sulfur or NR**7 , n is 0 or 1, R**1 is C1 -C4 -alkyl, R**2 is hydrogen, halogen, C1 -CV4 -alkyl or C1 -C4 -alkoxy, R**3 is hydrogen, halogen or C1 -C4 -alkyl, R**4 and R**5 independently of one another are unsubstituted or substituted alkyl or arylalkyl or together are alkylene and form part of a 5-membered or 6-membered heterocyclic ring which may or may not be substituted by alkyl or aryl, R**6 is unsubstituted or substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or heteroaryl, with the exception of chloromethyl and acetylmethyl, and if n is 1, R**6 may also be unsubstituted or substituted alkynyl, aryl, arylalkyl or heteroarylalkyl, and R**7 is hydrogen, alkyl or alkoxy. 1. Claims for the Contracting State : AT A fungicide containing a 2-(N-aryl-n-acyl)-aminopropanalacetal of the formula see diagramm : EP0019745,P27,F1 where X**1 , X**2 , and X**2 independently of one another are oxygen or sulfur, Y is oxygen, sulfur or NR**7 , n is 0 or 1, R**1 is C1 -C4 -alkyl, R**2 is hydrogen, halogen, C1 -C4 -alkyl or C1 -C4 -alkoxy, R**3 is hydrogen, halogen or C1 -C4 -alkyl, R**4 and R**5 independently of one another are unsubstituted or substituted alkyl or arylalkyl or together are alkylene and form part of a 5-membered or 6-membered heterocyclic ring which may or may not be substituted by alkyl or aryl, R**6 is unsubstituted or substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or heteroaryl, with the exception of chloromethyl and acetylmethyl, and if n is 1, R**6 may also be unsubstituted or substituted alkynyl, aryl, arylalkyl or heteroarylalkyl, and R**7 is hydrogen, alkyl or alkoxy.

Description

' ~ ^Λ " Ο.Ζ.0050 / 033867

fungicidal e 'agent.

Field of application, the invention

The new fungicides can be used in agriculture as fungicides.

Characteristic of the known technical solutions

It is known that N-trichloromethylthiotetrahydrophthalimide is a good fungicide for combating fungal plant diseases, in particular for controlling the false mildew of the vines. (Chemical Week 1972, June 21, p. 63). Its effect, however, is against other phycomycetes, e.g. Phytophthora infestans in tomatoes or potatoes unsatisfactory. It is also known that substituted chloroacetanilides which carry a 1,3-dioxolan-2-yl-methyl group have a herbicidal action (DE-OS 2,405,510).

Object of the invention

The aim of the invention is the development of fungicidal agents with improved efficacy but not harming crops.

Explanation of the essence of the invention

The invention has for its object to provide new chemical compounds with fungicidal activity.

It has now been found that novel 2- (N-aryl, N-acyl) - aminopropanal acetals of the formula I

221137

- 2 - O. Z: OO5O / O3386.7

wherein

12?

X, X and X are independently oxygen or sulfur,

Y is oxygen, sulfur or NR ', η is 0 or 1,

R ^{1 is} C ₁ -C, -alkyl,

2 R is hydrogen, halogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,

R _{3 is} hydrogen, halogen or C ₁ -C ₁ -alkyl,

ti ~ \

R and R independently of one another are optionally substituted alkyl or arylalkyl radicals or together form, as the alkylene group, part of an optionally substituted by alkyl or aryl-substituted 5- or 6-membered heterocyclic ring, R is an optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, heteroaryl

or AzoIyIalkyl rest with the exception of the chloromethyl radical and the acetylmethyl radical and in the event that η = 1, R in addition to the above meanings an optionally substituted alkynyl, aryl, arylalkyl or heteroaryl

arylalkyl group and ν

R 'is hydrogen, an alkyl or alkoxy group, have strong fungicidal properties.

ι

In formula I, Tr is a C.sub.1 -C.sub.18 alkyl radical, in which

, J.H

O. Z. 0050/033857

For example, methyl, ethyl, n-propyl, iso-propyl or

ρ butyl. R is hydrogen, halogen, e.g. Fluorine, chlorine or bromine, for a C -C alkyl group, e.g. Methyl, ethyl, propyl or butyl, or a C ^ -C ^ alkoxy, for example methoxy, ethoxy, propoxy or butoxy. R 1 is hydrogen, halogen, e.g. Fluorine, chlorine or bromine, or for a C 1 -C 4 -alkyl radical, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl. R and R ^ are preferably optionally substituted unbranched or branched alkyl. radicals having up to 4 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, η-butyl or isobutyl, or optionally substituted arylalkyl radicals, for example benzyl or 2-phenylethyl-1.

4 c

R and R are in particular also an alkylene group having 2 or 3 carbon atoms, which may optionally be substituted by aryl, for example phenyl, or by alkyl having up to 4 carbon atoms, for example methyl, ethyl or propyl.

R is, for example, an optionally substituted alkyl radical which is, for example, unbranched and contains 1 to 20 carbon atoms, for example methyl, ethyl, η-butyl, n-decyl or n-heptadecyl, or is branched and contains 3 to 15 carbon atoms, for example isoproyl , , pyl, tert-butyl, 2-methylbutyl-1 or 2-ethylhexyl-1. R ⁶ is, for example, also a straight-chain or branched alkenyl radical having 2 to 15 carbon atoms, for example vinyl, propen-1-yl, 2-methylpropen-1-yl, hexen-1-yl or undecen-3-yl or, for example, a cyclic one Alkyl or alkenyl radical having 3 to 10 ring carbon atoms, for example, cyclopropyl, cyclobutyl, cyclohexyl or cyclohexene-2-yl, further, for example, an optionally substituted heteroaryl radical with 5

- 4 - O. Z. 0050 / 0338β7

to 6 ring atoms and 1 to 3> in particular 1 to 2 heteroatoms in the ring, which may be identical or different and are preferably oxygen, nitrogen or sulfur, for example in a furan, thlophene, isoxazole or pyridine radical. In addition, R preferably represents an optionally substituted azolylalkyl radical having 1 to 2 carbon atoms in the alkyl and, for example, pyrazolyl, imidazolyl or triazolyl as the azolyl radical. In the event that η = 1, R additionally represents an optionally substituted alkynyl radical having 3 to 6 carbon atoms, for example, propin-2-yl-1 or

l, l-Dimethyl-propyn-2-yl-l. '

In addition, R then preferably represents an optionally substituted aryl radical, for example a phenyl or naphthyl radical, or an optionally substituted arylalkyl or heteroarylalkyl radical having 1 to 2 carbon atoms in the aryl ring or with 5 to 6 ring atoms in the heteroaryl moiety, of which 1 to 3> in particular 1 and 2, heteroatoms such as oxygen, nitrogen or sulfur, such as in a thiophene, isoxazole or pyridine ring.

Examples of preferred substituents of the radicals described above for R are: halogen, in particular fluorine, chlorine or bromine; nitro; a straight-chain alkyl radical having 1 to 4 carbon atoms; a branched or cyclic alkyl radical having 3 to 6 carbon atoms; ' an alkoxy, alkoxyalkoxy or alkylthio radical having from 1 to 8 carbon atoms, for example a methoxy, rethoxy or isopropoxy group or a methylthio, ethylthio or n-butylthic group; a haloalkyl, haloalkoxy, haloalkylthio or haloalkylsulfonyl radical having up to 4 carbon atoms and up to 9 halogen atoms, in particular

- fluorine or chlorine, for example a trichlorme-

L. - ¹

1137

- 5 - O. Z. 0050 / 0338βγ

a methyl, cyano or thiocyanato group, an alkoxycarbonyl, alkoxysulphonyl, alkylcarbonyl, alkylcarbamoyl, amino, acylamino or an alkylaminosulphonyl radical having 2 to 10 carbon atoms, for example, a methoxycarbonyl, acetyl, propionyl, Ν, Ν-dimethylcarbamoyl or a butyrylamino radical; an alkylamino, dialkylamino or an azolyl radical, for example a methylamino, diethylamino, pyrazolyl, imidazolyl or triazolyl radical; substituted phenyl or phenylcarbonyl radical having 6 to 11 carbon atoms, an aryloxy or arylalkyloxy radical which is optionally substituted in particular in the 4-position, for example a 4-chlorophenoxy or a 2,4-dichlorophenoxy radical, an optionally substituted arylthio, arylsulfinyl or an aryl sulphone radical;

7 phonyl radical. R is hydrogen or an alkyl or alkoxy radical having 1 to M carbon atoms.

The new 2- (N-aryl, N-acyl) amino-propanal acetals in the carbon atom 2 of the propane have an asymmetric center and, depending on the nature of R, additional centers of asymmetry. The optically pure enantiomers or the diastereomers can be obtained by customary methods

^ become. The present invention also encompasses these compounds. As fungicides, it is possible to use both the pure enantiomers or the uniform diastereomers, as well as the mixtures usually obtained in the synthesis.

The anilines of the formula II required for the preparation of the new compounds,

D-

O. Z. 0050/03385?

II

in which R ¹ , R ² , R ^, R, R ⁵ , X ² and X ^ have the meanings explained above, are known in some cases. Thus, M. Chastrette (Ann. Chim. (Paris) 7, 643-668 (1962)) described the synthesis of 2- (N-2'-methylphenyD-aminopropanaldiethylacetal (ibid., P. 654, Table II, 4 Row) by reaction of 2-Brompropanaldiethylacetal with 2-methylaniline (ibid p 656, 657, yield 24 %) or by reaction of methylmagnesium iodide with N-phenyliminoglyoxyl diethyl acetal (ibid p 658, yield 72 JS).

Furthermore, part of the anilines of the formula II used as starting materials is the subject of DE-OS 2,802,211. There, an aniline having a cyclic acetal structure is described, namely the 2- (N-2-methyl-6-ethylphenyl) aminopropanalethylene glycol acetal.

It has now been found that the anilines of the formula XII

XII

- 7 - O. Z. 0050 / 0338o7

in which R ¹ , R ² , R 1, X ² and X 1 have the meanings explained above.

Q IQ

and R and R independently of one another are optionally substituted alkyl or arylalkyl radicals, advantageously obtained when a methylglyoxalacetal of the formula XIII

^CH -

ρ X

^X CH XIII

\ _Y 3

with an aniline of formula XIV

(UhNH, xiv

and hydrogenating the Schiff base obtained as a reaction product, e.g. with complex hydrides or by catalytic means.

O "i rs

In formula XII, R 1 and R 3 preferably represent optionally substituted unbranched or branched alkyl radicals having up to H carbon atoms, for example methyl, ethyl, n.-propyl, isopropyl, n-butyl or iso-Bu. tyl, or optionally substituted arylalkyl radicals, for example the benzyl or the 2-phenylethyl-l radical.

In the process according to the invention, the formation of inorganic salts is avoided which are formed as by-products in large quantities in the known reaction of -halopropanal acetals with anilines by reacting the resulting hydrogen halide with inorganic auxiliary bases. In addition, the new process is easier to

2 2113 7

-. 8 - O.Z. 0050/033867

Since absolutely dry reaction conditions, as required by the known Grignard reaction, can be dispensed with, the process according to the invention is more environmentally friendly and simpler than the known processes.

A further advantage of the novel process is that it is possible to produce the anilines of the formula XII on a larger scale than on the laboratory scale according to the following procedure:

1. Preparation of the Schiff base of the general formula XV

XV

by heating the reaction mixture at reflux and Wasserauskreisung and

2. subsequent hydrogenation.

The first reaction step - the production of the Schiff's base - is carried out, for example, by reacting 1 mol of the .Anilins of formula XIV with 0.9 to 1.5 mol of methylglyoxal acetal of the formula XIII in a solvent, optionally with the addition of a catalyst

So reacted and the reaction at a temperature of from ⁰ to 200 ⁰ C, preferably from 50 to 120 ⁰ C, without pressure or under pressure, continuously or discontinuously carried out. It is expedient to use inert solvents under the reaction conditions. As a solvent come, for example in. Question:

- 9 - O. Z. 0050/033867

'"Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, o-, m-, p-xylene, isopropylbenzene, methylnaphthalene, aliphatic or cycloaliphatic hydrocarbons, for example heptane, pinane, nonane, petroleum fractions within a boiling point interval from 70 to 190 ⁰ C, cyclohexane , Methylcyclohexane, decalin, hexane, ligroin, 2,2,4-trimethylpentane,

, 2,2,3-trimethylpentane, 2,3-trimethylpentane, octane; and corresponding mixtures. Suitably, the solvent is used in an amount of 150 to 10,000 weight percent, preferably from 300 to 600 weight percent, based on starting material XIV.

The reaction can be carried out as follows: A mixture of the starting materials XIII, XIV and the solvent are kept at the reaction temperature for 2 to 15 hours. Advantageously, the resulting water can be continuously added during the reaction, e.g. by azeotropic distillation, with a suitable solvent such as cyclohexane. Then the Schiff base can be prepared from the mixture in a conventional manner, e.g. By fractional distillation, separated and seen with the isolated, purified vessel base the second step of the reaction can be carried out. However, this procedure will usually not be chosen for economic reasons, but advantageously see after the preparation of the ship base distill off the solvent, add a suitable for hydrogenation solvent and perform the hydrogenation at the reaction temperature.

For the hydrogenation, both the reduction with complex hydrides such as NaBH are suitable. or LiAlH. as well as the catalytic hydrogenation.

The reduction with sodium borohydride is generally so

  that in a solvent the vessel

- ίο - o.'z. 0050/033867

* ° see bases with 0.2 mol to 1 mol, preferably 0.25 to "* 0.5 mol, sodium borohydride per mole of Schiff base at a temperature between -20 and +20 ⁰ C without pressure or under pressure, continuously or discontinuously In the catalytic hydrogenation, the reaction mixture is fed at the beginning and in the course of the reaction with such amounts of vaporizer that a corresponding reaction pressure, suitably between 150 and 300 bar, is always established at the reaction temperature The reaction ] q is generally carried out at a temperature from 20 to 200 ⁰ C, preferably from 25 to l60 ° C, batchwise or continuously. For the corresponding pressure setting also inert gases such as nitrogen can be used..

Suitable solvents for both process variants are those which are inert under the reaction conditions, such as alkanols and cycloalkanols, e.g. n-butanol, isobutanol, tert-butanol, glycol, glycerol,, n-propanol, isopropanol, amyl alcohol, cyclohexanol, 2-methyl-A-pentanol, ethylene glycol monoethyl ether, 2-ethylhexanol, methyl glycol and especially ethanol, methanol; cyclic ethers such as tetrahydrofuran or dioxane. Also suitable are the solvents already mentioned for the first reaction step.

Preferably, the solvent amounts mentioned for the first reaction step are used.

For catalytic hydrogenation, the catalyst is usually used in an amount of 5 to 30 percent by weight, based on the Schiff base. It may be mixed with a suitable support material for the reaction, e.g. The amount of catalyst used is about 10 to 40 percent by weight of the catalyst / support mixture

is.

ι ι t. -inn O Γ 'r \ η, -Ί

ο. ζ. 0050/033867

Conveniently, copper chromite catalysts, e.g. corresponding copper-chromium oxide catalysts such as those of

H. Adkins used copper chromites. They contain, for example, copper-chromium spinel (CuCr ₂ O.) or mixtures in the ratio 5 CuO: 4 Cr _? 0 "or assume such compounds and may contain other oxides, mainly those of the alkaline earth metals such as barium, calcium or magnesium.

Regarding the production of copper chromite catalysts, reference is made to Houben-Weyl, Methoden der Organischen Chemie, Vol. 4/2, pages 180 to 183 and Journal of Applied Chemistry, Vol. 5 (1955), pages 289 to 295.

The following process description illustrates the preparation of anilines of the formula XII:

1.

reaction step

CH,

+ O = C

121 parts (parts by weight) of 2,6-dimethylaniline, 118 parts of methylglyoxal dimethyl acetal and 0.2 parts of p-toluenesulfonic acid are refluxed in 500 parts of cyclohexane for 4 hours until 18 parts of water are distilled off azeotropically and separated from the distillate. Then, the solvent is distilled off and the residue reacted directly

Yield: 212 parts (96 %) of Schiff's base.

.- 12 -

Ο · ² · ΟΟ5Ο / Ο33867

2nd reaction step

a) Catalytic hydrogenation

N = C

CH ₃

^^ Γ * TT

0-CH.

CH O-CKL

A hydrogenation autoclave having a volume of 1000 parts by volume is charged with 200 parts of the Schiff's base of 2,6-dimethylaniline and methylglyoxaldehymethylacetal dissolved in 500 parts of tetrahydrofuran and 15 parts of Adkins catalyst (copper chromite in powdered form).

Subsequently, the autoclave is heated to θβθ C and hydrogen is pressed until reaching a pressure of 200 bar. As soon as the hydrogen absorption is finished and a constant pressure is reached (after approx. 7 hours), it is cooled down and worked up.

The catalyst is separated from the reaction mixture by filtration. Ηigung be ~ 129 parts obtained 2- (N-2 ', 6'-dimethylphenyl) -aminopropanal -.- dimethylacetal, bp = 90-91 ⁰ C, by distillative Re i from the filtrate. The yield is 64 % d. Th.

Reduction with NaBH ₁

220 parts of the ship see base of 2,6 »dimethylaniline and Methylglyoxaldlmethylacetal are dissolved in 1000 parts of methanol and treated at ⁰ ° C in portions with 57 parts of sodium borohydride. After stirring overnight, the solution is

OO5O / O33867

distilled off, the residue dissolved in 1000 parts of water and the solution extracted four times with 300 parts of methylene chloride.After distilling off the methylene chloride remain as a residue 205 parts of crude product which is distilled at 8l ° C / 0, l mm

Yield: 182 parts (81 %).

The following anilines of the formula XII can be prepared analogously:

Table I

O-.CH

R-

kp

mbar

CH, H H O ₂ H ₅ H H CH, C ₂ H ₅ H ^0H 3 H 5-tert-C ₄ H ₉ C ₂ H ₅ C ₂ H ₅ H CH ₃ Cl H OH ₃ CH ₃ 4-C H OH CH ₃ 3-CKL

75 / 0.1 84 / 0.1 86-88 / 0.1 100-102 / 0.1 92-93 / 0.1 90-92 / 0.1

115 / 0.3 94 / 0.4

22 1137

- IH - OZ ΟΟ5Ο / Ο33867

The novel compounds of the general formula I can be prepared by reacting an aniline of the formula II

1 'P "5 ii ^ P ·?' · ~

wherein R, R, R, R, R, X and X ^{J have} the meanings given above,.

a) with an acid halide of the formula III X ¹

R ⁶ [γ] C-Hal III

or

b) with an acid anhydride of the formula IV

O O

R ⁶ ^ COCR ⁶ "IV

or

c) with an isocyanate of the formula V

iT_ _{N == c =}

in which X, Y, η and R have the abovementioned meanings, if appropriate in the presence of a solvent or diluent, if appropriate with addition of an inorganic or organic base and, if appropriate, with addition of a reaction accelerator,

1137

• - 15 - ° ' ^Ζ · ΟΟ5Ο / Ο33867

_Γ ο

at temperatures between 0 and 120 C. Preferred solvents or diluents include halohydrocarbons, for example methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene; aliphatic or aromatic hydrocarbons such as cyclohexane, petroleum ether, benzene, toluene or xylenes; Esters such as ethyl acetate; Nitriles such as acetonitrile; Sulfoxides, such as dimethylsulfoxide; Ketones such as acetone or methyl ethyl ketone; Ethers such as diethyl ether, tetrahydrofuran or dioxane or corresponding mixtures.

It is expedient to use the solvent or diluent in an amount of 100 to 2000% by weight, preferably 100 to 1000% by weight, based on the starting materials II or III, IV or V.

Suitable inorganic or organic bases which may optionally also be used as acid-binding agents in the reaction are, for example, alkali metal carbonates such as potassium or sodium carbonate, alkali metal hydrides such as sodium hydride or tertiary amines such as Tr in ethylamine, triethylamine, N, N-dimethylaniline, Ν, Ν-dimethylcyclohexylamine, N-methylpiperidine or pyridine; azoles such as 1,2,4-triazole or imidazole, but other common bases may be used.

Preferred reaction accelerators are metal halides such as sodium bromide or potassium iodide, azoles such as imidazole or 1,2,4-triazole or pyridines such as 4-dimethylaminopyridine or combinations of these reaction accelerators.

2 113 7

• - 16 - ° · ^Ζ · ΟΟ5Ο / Ο33867

The reaction is generally carried out at temperatures between 0 and 120 ⁰ C in a period of 1 to 60 hours, without pressure or under pressure, continuously or discontinuously.

The procedure is generally carried out by adding to 1 mol of the

, bond II in each case 0.9 to 1.3 mol of the compounds III or IV or V and 0.5 to 2 moles of base and optionally 0.01 mol to 0.1 mol of a reaction accelerator.

In a preferred form of the process according to the invention, the starting material II is optionally mixed with a base and optionally with a diluent, then the starting material III or IV, or V and optionally a Reaktionsbeschieuniger and keeps the reaction mixture for 0.5 to 12, preferably 1 to 6 hours, at the reaction temperature, which may be between 0 and 120 ⁰ C.

To isolate the new compounds, the diluent is optionally removed, the residue dissolved in a suitable solvent and washed with aqueous, dilute acid, then with dilute aqueous solution and with water to remove the excess base and starting materials II, III, IV and V to remove.

The remaining products after distilling off the solvent generally require no further purification, but can, if necessary, be further purified by known methods such as recrystallization, extraction or chromatography.

- 17 - O. Z. OO5O / O33867

^r It has further been found that one can make a subset of the compounds of formula I of the invention by reacting an aniline of the formula II

II

Α-ί ^Ν υ 10

wherein R ¹ , R ² , R ³ , R, R ⁵ , X ² and X ^{3 have} the meanings described above, first

15 a) with a phosgene of the formula VI

X ¹ = CCl ₂ VI

In which X has the meaning indicated above, to give a compound of the formula VTI

^25th / 17th century

or 30

- 18 - ^αζ · ΟΟ5Ο / Ο33867

^r b) with a compound of the formula VIII

R ⁸ -CH-Lal Hai

wherein R is hydrogen or has the meanings given for R and Hai means a halogen atom, to give a compound of formula IX 10

( O VN H CH ₀ IX

μηα then the compounds of the formulas VII or IX with nucleophilic compounds of the formula X.

R ⁶ - YH X

wherein R and Y have the meanings described above, if appropriate in the presence of a solvent or diluent, if appropriate in the presence of an inorganic or organic base, if appropriate with addition of a reaction accelerator at temperatures between -20 and +100 ⁰ C.

Preferred solvents or diluents and inorganic or organic bases include those discussed above.

221137

, - 19 - ° · ^Ζ · ΟΟ5Ο / Ο33867

The inventive reaction is carried out for example at temperatures between -20 and +100 ⁰ C, under atmospheric or superatmospheric pressure, continuously or discontinuously,

 5

The above explanations apply to the isolation of the final products.

Another subgroup of the compounds of the general formula I according to the invention is obtained by reacting compounds of the formula XI

  FT ^ CH XI

wherein R ¹ , R ² , R ³ , R ⁶ , R ^9,. R ¹⁰ , X ¹ , X ² , X ³ , Y and η have the meanings described above with 1,2- or 1,3-diols, dithiols or -Mercaptoalkoholen to cyclic acetals at temperatures between 0 and 120 C, optionally in the presence a solvent or diluent and optionally with the addition of a reaction accelerator umacetalisiert.

The above-mentioned 1,2- or 1,3-diols, dithiols or mercaptoalcohols include, for example, ethylene glycol, mercaptoethanol, ethanedithiol-1,2, propylene glycol-1,2, propanediol-1,3, propanedithiol-1, 3, 2-methyl, 2-phenylpropanediol-1, 3j 2-methyl-2-mercaptoethanol-1, butanediol-1,3, butanediol-2,3 and neopentyl glycol.

- 20 - ° · ^ζ · ΟΟ5Ο / Ο33867

Suitable solvents or diluents are the abovementioned liquids or the 1,2- or 1,3-diols, dithiols or mercaptoalcohols when used in a stoichiometric amount or in excess. Suitable reaction accelerators are Lewis or protic acids, for example ZnCl, AlCl 3 or BP_ or mineral acids or sulfonic acids. The above explanations apply to the isolation of the final products.

Further subgroups of the compounds of the general formula I according to the invention are obtained by carrying out customary customary chemical reactions, depending on the functional nature of R.

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

Example 1 20

33.5 parts (parts by weight) of 2- (N-2 ·, 6'-dimethylphenyl) - aminopropanaldimethylacetal are dissolved in 300 parts of toluene and treated with 2 5 parts of triethylamine. Upon addition of 20 parts of furan-2-carboxylic acid chloride the temperature rises to 30 ⁰ C. Then the reaction mixture for 2 hours at 70 ° C is stirred. After cooling, the reaction mixture is washed twice with 100 parts of 2N hydrochloric acid, twice with 100 parts of 2N sodium hydroxide solution and twice with parts of water. After drying, the

- 21 - ° · ^ζ · ΟΟ5Ο / Ο33867

Distilled off solvent. The remaining residue is recrystallized from n-pentane. This gives 28 parts (59 % of theory ) of 2- (N-2 ', 6'-dimethylphenyl, N-2 "-furancarbonyl) -aminopropanaldimethylacetal of melting point 75 to 77 °.

Example 2

CH ₀ 0 -CH ₀ ι 3 ι 3

^IU CH_C-CH

r \ ³ / ^v H \

O) 0-CH

1 C-CHg-N

30 parts of 2- (N-2 ', 6'-dimethylphenyl, N-chloroacetyl) -aminopropanaldimethylacetal, 20.4 parts of imidazole, 50 parts of dioxane and 20 parts of V / asser are heated for 8 hours at reflux temperature. After evaporation in vacuo, the residue is dissolved in 100 parts of methylene chloride, washed three times with 50 parts of water, dried over sodium sulfate and concentrated. After purifying the crude product by filtration of the solution in ethyl acetate on silica gel to isolate 18.1 parts of uniform oil.

Ber. : C 65, 2 H 7 , 6 N 12 6 Gef .: C 64 8th H 7 ,8th N 12 1.

- 22 - 0.2. OO5O / O33867

Example 3

25

10

a) To a solution of 45 parts by weight of phosgene in 200 parts of toluene at -10 ⁰ C, a solution of 85 parts of 2 (N-2 ', 6'-dimethylphenyl) -aminopropanaldimethylacetal in 150 parts of toluene was added dropwise.

The mixture is stirred for 4 hours, with the temperature rising to room temperature. Then the solvent is distilled off. There remain 120 parts of N (2,6-dimethylphenyl) -N- (l ', 1' -dimethoxy-2 '-propyDcarbaminsäurechlorids back as a brown oil, whose UR spectrum no NH band has more.

b) To a solution of 30 parts of sodium 4-chlorophenolate in 200 parts of tetrahydrofuran is added a solution of 54 parts of N- (2,6-dimethylphenyl) -N- (I *, 1'-dimethoxy-2'-propyl). Carbamic acid added dropwise in 100 parts of tetrahydrofuran and stirred overnight t.

The reaction mixture is concentrated, in methylene

2 2 1 13 "/

- 23 - ° · ^ζ · ΟΟ5Ο / Ο33867

Dissolved chloride, washed twice with water, dried and concentrated. The remaining oil is purified by chromatography on silica gel with cyclohexane with increasing addition of ethyl acetate as eluent. 10 parts of the O- (4-chlorophenyl) -N- (2 ', 6'-dimethylphenyl) -N- (1 ", 1" -dimethoxy-2 "-propyl) -carbamate are obtained as analytically pure oil; ° = 1.5425.

Example 4

0-CH ₃

To a solution of 61.4 parts of 2,6-dimethyl-N- (l ', l' .- dimethoxy-2'-propyD-acetoacetanilld in 500'Teilen methanol at 0 to +5 ⁰ C in portions 7.6 parts After stirring overnight, 40 parts of glacial acetic acid are added and the reaction mixture is concentrated to dryness The residue is dissolved in 500 parts of diethyl ether and 400 parts of aqueous sodium carbonate solution 100. The organic phase is separated, dried and concentrated.

This gives 50.2 parts (8l % of theory) of 2,6-dimethyl-N-. - (I ¹ , l-dimethoxy-2'-propyl) -3 "-hydroxybutyranilide as an analytically pure oil.

The starting 2,6-dimethyl-N- (1 ', 1'-dimethoxy-2'-propyl) -acetoacetanilide is prepared as follows:

- 24 -. ° · ^ζ · ΟΟ5Ο / Ο33867

^r To a solution of 111.5 parts of 2- (N-2 ^f, 6'-dimethylphenyl) amino-propanaldimethylacetal in 250 parts toluene and 3 parts of triethylamine at 80 to - 90 ⁰ C, with stirring, 39.5 parts of diketene was added dropwise. The mixture is then stirred for 3 hours. The cooled reaction mixture is washed once with 2 normal hydrochloric acid and twice, washed with water, dried and concentrated. This gives 121.8 parts (78.8 % of theory) of 2,6-dimethyl-N- (1 ^!, 1'-dimethoxy-2'-propyl-acetoacetanilide as analytically pure oil

Example 5

CH-CH (OCiL) _o

<O> - < ^{3 2}

'' \ / ^ C-CH - (OC ₉ H ₁₁ ), - OCH,

CH ₃

To e: L solution of 36.5 parts of 2- (N-2-methyl-6-chlorophenyl) -aminopropanaldimethylacetal in 200 parts of methylene chloride are added 16.5 parts of triethylamine. With stirring and cooling, 29.4 parts of 3,6,9-trioxadecanoic acid chloride are added dropwise and the mixture is stirred overnight. The precipitate is filtered off with suction, the organic phase is washed three times with water, dried and concentrated. There remain 30 parts (2-methyl-6-chloro-N- (1'-dimethoxy-2'-propyl) -) - 2,6,9-troxohexanoic acid anilide as an analytically pure oil (n = 1.5042) ,

2 1137

O. Z. OO5O / O33867

Analogously, the following compounds are produced:

table

R-

1V '

CH,

χ ·

2 9 1 1 ^ 7

.- 26 -

° · ^ζ - ΟΟ5Ο / Ο33867

OJ Q

VO

»Η

CNCC

CVI

35 '

in cn

CVI

in

su cd

S- O O CD OO O O O ε in in in O cn

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cn

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cn

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2 2 113 7

° · ^Ζ · ΟΟ5Ο / Ο33867

OJ Q

ro

cc:

CM

r-l

35 C

LPV

O LPv

33 °° O O OO 33 33 OJ O O O O CM OJ 33 t-i-4 O O

O O

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O O

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ΟΟ5Ο / Ο33867

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co cc Ü co cc O co cc Ü co cc O co co il en

22 1137

O.Z. OO5O / O33867

cvi Q

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0.2. OO5O / O33867

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22 1

O.Z. OO5O / O33867

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° · ^ζ · ΟΟ5Ο / Ο33867

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co co co co

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co

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SC O

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SC O

frco

co co

22 1137

O. Z.

OO5O / O33876

OJ Q

Cu

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co

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dc cc

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221137

- 35 - ° ' ^Ζ · ΟΟ5Ο / Ο33867

Example 99

31.7 parts of 2- (N-2 ', 6'-dimethylphenyl, N-furan-2 "-carbonyl) -amlno-propanaldimethylacetal (corresponding to Example 1) with 9 parts of 2-mercaptoethanol and a 0.5 parts p-toluenesulfonic acid is stirred for k hours at 70 ° C. The reaction mixture is then dissolved in 300 parts of methylene chloride and washed twice with saturated sodium bicarbonate solution and twice with water After drying and distilling off the solvent, 18 parts of oil which crystallizes from diisopropyl ether remain ,

This gives 10.2 parts puran-2-carboxylic acid-N- (l- (l, 3-oxathiolan-2-yl) ethyl-2 ', 6'-dimethylanil id of melting point 128-132 ⁰ C.

Accordingly, the following compounds were prepared: 25

2 113 7

° · ² · 0050/033867

OJ Q C

VD cc

cn

OJ

in cc

sr CC

CO cc

VD OO

VD

O pH V_j to in O CTN co O ITV OO on rh I 0 · OJ σ \ I co in . = R in OJ OO co r-l rh rh OJ rh

v co co 1 EC EC O O O O • O OJ I I OJ OJ ϋ EC. EC · I O Ü

EC

EC

EC

OJ OJ I OJ OJ I OJ OJ I OJ OJ I OJ OJ OJ OJ I in \ ^. • τ * EC EC EC EC EC EC   EC EC EC EC OJ EC T O O Ü O Ü O O Ü O Ü Ü O EC OJ OJ I I I I I I I I I I I I Ü O EC I ' Ü I OJ ^ - \ EC O I V T in OJ EC EC OJ O O

OJ " CO co in CO CO CO CO CO CO CC U EC EC EC EC EC EC EC EC EC Z O O OJ Ü O Ü O O O O CO rh EC co CO co co O CO CO co co ^ CO EC EC EC OJ EC EC EC EC O O O O EC O Ü O O O O O JO O rh OJ co . = R in VD co CD O O O O O O O O rh rh rh rh rh rh rh rh rh

° · ^ζ · ΟΟ5Ο / Ο33867

CVJ Q

VD

OO

CJ

in

CS

r CC

OO

(K

cc

O ro O rh O O in t-. m t rh O OJ in OO I I OO ro OJ in m in OJ in m in rh

33

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O. Z. OO5O / O33867

OJ

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O O

O O

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I OJ OJ OO CO I co I OJ OJ I OJ OJ I OJ OJ OJ I OJ OJ OJ I OJ OJ • CO I OJ OJ I OJ CO I OJ OJ OJ I OJ OJ I I EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC CV O O O I O co O O O O O O co O O OO O O O O O O O O O O O O 'O ln EC I I I EC I I I I I I I I I I I. I EC O O EC O O OJ , -N VD I m O ln EC ln EC EC O cc; EC I O EC O EC EC H- O · I I OJ EC I OJ OO EC EC I EC EC EC ec EC O O O EC O CO CO ν I O EC I O OI co co EC "-ΓΙ C OJ C 1-1-4 rh EC EC EC co O O EC »- O O O O EC EC I , -ν O I / - " CO O m OO EC EC EC = r O O OJ EC O CC I O EC CO O O EC I CO I O OJ EC EC O O I co EC cc CO OJ EC cc O

CO O CO O OO O CO EC O CO O CO EC O OO EC O CO EC O CO EC O OO EC O CO EC O OO EC O OO EC O (EC O 120 121 122 123 124 ιη OJ ιΗ 126 Γ- OJ rH 128 129 130 131 132 133

O.Z. OO5O / O33867

ο co OJ ln OJ OO O t OJ co O in vo O OJ OJ Q  sr cc iT cc cc co cc co OO co OO VO C  = r O rh O O iH rh O rh rh rh co OO \ in ln O ln in ln in ln in in • sr rh rh M-I rh rh rh rh rh iH rh OJ OO O OO CC O cc Ü Ü O O bDC IN THE OJ CO OJ O Ü CC OO , - ,, I -Z vo OO ST O cc .ra- r ^ CD ln CC CC O O CC I o co CC O OJ O OJ cc OJ I O cc O O O O O OJ co O O O I Ü cc I I  sr I O O T cc OJ OJ OJ cc cc CC O Ü O Ü

ro

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- 40 - ° · ^Ζ · ΟΟ5Ο / Ο33867

^r The active ingredients according to the invention exhibit a powerful fungitoxic action. They do not damage crops in concentrations necessary to combat fungi and bacteria. For these reasons they are for use as plant protection products to combat

Mushrooms suitable. ·. ,

The new active ingredients show a strong fungolytic activity against phytopathogenic fungi, in particular from the class of Phycomycetes. The claimed compounds are therefore suitable, for example, for controlling Phytophthora infestans on tomatoes and potatoes, Phytophthora parasitica on strawberries, Phytophthora cactorum on apples, Pseudoperonospora cubensis on cucumbers, Pseudoperonospora.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 lettuce, Mucor mucedo on fruit, Rhizopus nigricans on beet. The funglziden means 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 0.1 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 in order to achieve a safe control success. In addition, many of the current compounds are systemically effective, so that the root canal treatment also provides protection of aboveground plant parts. Furthermore, fungi that cause seedling and casserole diseases, such as Pythium and Aphanomyces species on legumes and cotton, can also be controlled with the new compounds. The application rates are per 100 kg of seed

2 2 113 7

τ 41 - ° · ^ζ · ΟΟ5Ο / Ο33867

Up to 200 g of active substance, applied in the form of seed dressing.

The compounds are applied by spraying or dusting the plants with the active ingredients or treating the seeds of the plants with the active ingredients. The application takes place before or after the infection of the plants or seeds by the fungi.

The substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The forms of application depend entirely on the intended use; they should in any case ensure a fine and even distribution of the active substance. The formulations are prepared in a known manner, e.g. by stretching the active substance with solvents and / or excipients, if appropriate using emulsifiers and dispersants, wherein in the case of using water as a diluent, other organic. Solvent can be used as Hilfslösungsmlttel. Suitable auxiliaries are essentially: solvents such as aromatics (e.g., xylene, benzene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., petroleum fractions), alcohols (e.g., methanol, butanol), amines (e.g., ethanolamine, dimethylformamide), and water; Carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin, liquors and methylcellulose.

.- 42 - O.Z. OO5O / O33867

^r The agents and the ready to use preparations prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, scattering, dressing or watering.

embodiments

Examples of such preparations are:

I. Mixing 90 parts by weight of the compound of

Example 1 with 10 parts by weight of N-methylpyrrolidone and obtains a solution which is suitable for use in the form of very small drops.

II. 20 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct. from 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecyl benzenesulfonic acid and 5 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.

III. 20 parts by weight of the compound of Example 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide with 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, which contains 0.02 Gew.Ji of the active ingredient.

2 2113 7

- 43 - ° · ^ζ · ΟΟ5Ο / Ο33867

* "IV. 20 parts by weight of the compound of Example 1 are dissolved in a mixture which consists of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 28O ⁰ C and 10 parts by weight of AnIagerungsProduktes of 40 mol of ethylene oxide to 1 mol of castor oil. By Pouring and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.02% by weight of the active ingredient

V. 20 parts by weight of the compound of Example 2 with 3 parts by weight of the sodium salt of diisobutylnaphthalene-c-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a SuI-fitablauge and 60 weight points of powdered silica gel, well milled and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water to obtain a spray, broth containing 0.1 wt.% Of the active ingredient.

VI. 3 parts by weight of the compound of Example 3 are intimately mixed with 97 parts by weight of finely divided kaolin. This gives a dust containing 3 wt. % Of the active ingredient.

VII. 30 parts by weight of the compound of Example 1 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. This gives a preparation of the active substance with good adhesion.

VIII. 40 parts by weight of the compound of Example 2 are mixed with 10 parts of sodium salt of a phenolsulfone

.- 44 - ° · ^ζ · ΟΟ5Ο / Ο33867

acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water intimately mixed. A stable aqueous dispersion is obtained. By diluting with 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.04 wt.% Active ingredient.

IX. 20 parts of the compound of Example 3 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyhydric alcohol, 2 parts of sodium salt of phenol sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. This gives a stable oily dispersion.

The agents according to the invention may also be present together with other active substances in these application forms, e.g. Herbicides, insecticides, growth regulators and fungicides, or mixed with fertilizers and applied. In the case of mixing with fungicides, in many cases an enlargement of the fungicidal activity spectrum is obtained.

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 compounds according to the invention are, for example:

Dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylenebisdithiocarbamate,

Manganese zinc ethylendiamln bisdithiocarbamate,

a /

- 45 - ° · ^Ζ · ΟΟ5Ο / Ο33867

Zinc ethylenebisdithiocarbamate, tetramethylthiuram disulphide,

Ammonia complex of zinc-CN ^ N-ethylene-bis-dithiocarbamate) and

NjN'-polyethylenebis-cthiocarbamoyD disulphide, zinc-iNjN'-propylene-bls-dithiocarbaraat), ammonia complex of zinc-CNjN'-propylene-bis-dithiocarbamate) and

NjN' polypropylene-bis-ithiocarbamoylJ-dlsulfid; 10

Nitroderivate, like

Dinitro (1-methylheptyl) -phenylc rotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl-isopropylcarbonate;

heterocyclic structures, such as

N-trichloromethylthio-tetrahydrophthaliTiid, N-trichloromethylthio-phthalimide,

2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -B-triazine _> 0.0-diethyl-phthalimidophosphonothioate, 5-amino-1- (bis (dimethylamino) - phosphoryl) -3-phenyl-1,2,4-triazole,

S-ethoxy-S-trichloromethyl-1'-thiadiazole, 2,3-dicyano-1,4-dithioanthraironone,

2-thio-l, 3-dithio (4,5-b) quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid, 2-methoxycarbonylamino-benzimidazole, 2-Rhodanmethylthio-benzthlazole, 4- (2-Chlorphenylhydrazono ) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide,

8-Hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-l _> 4-oxathiin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4 -oxathiin,

- 46 - O.Z. ΟΟ5Ο / Ο33867

^f * 2- (furyl (2)) benzimidazole,

Piperazine-1, 4-diyl-bis (1- (2,2,2-trichloroethyl) -formamide), 2- (thiazolyl- (4)) -benzimidazole,

5-Butyl-2-dimethylamino-4-hydroxy-6-methyl-pyulidine, bis-Cp-chlorophenyl-S-pyridinemethanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, l, 2 bis- (3-methoxycarbonyl-2-thioureido) -benzene

and various fungicides, such as dodecylguanldin acetate,

3- (3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) -glutarimide,

hexachlorobenzene,

N-dichlorofluoromethylthio-N ^f, N'-dlmethyl-N-phenyl-schwefelsäuredlamid,

2,5-Dimethyl-furan-3-carboxylic acid cyclohexylamide, 2-methylbenzoic acid anilide, 2-iodo-benzoic acid anilide,

l- (3,4-dichloroanilino) -1-formylamino-2,2,2-trlchloräthan, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts.

DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) alaninate, DL-N- (2,6-Dimethyl-phenyl) -N- (2 -methoxyacetyl ¹⁾ alanine methyl ester,

Di-isopropyl 5-nitro-isophthalate, 1- (1 ', 2', V-triazolyl-1 ') - [1- (4'-chlorophenoxy)] -3,3-di-

methylbutan-2-one,.

1- (1 ^!, 2 ', il'-triazolyl-l ¹ ) - [1- (4'-chlorophenoxy)] -3,3-dimethylbutan-2-ol,

N- (2,6-Dirnethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone,

N- (ri -propyl) -N- (2,4,6-trichlorophenoxyethyl) -N ^t -imidazolylurea,

· ^Ζ · ΟΟ5Ο / Ο33867

* N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide, 2, i (, 5-trimethyl-furan-3-carboxylic acid anilide, 5-methyl-5-vinyl-3- (3,5 -dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 5-methoxymethyl-5-methyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, N- [ 3- (p-tert-butylphenyl) -2-methyl-propyl] -cis-2,6-dimethylmorpholln.

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

CH

3 /

/ ^CH 2 " ^CH N ^X

CH,

CH

C-CH Cl Ji ^d

3 0

N-S-CCI.

•Attempt

(Compound A)

known from DE-OS 24 05 510

(Compound B)

known from Chem. Week 1972, June 21, page 63,

Fungicidal activity against Phytophthora infestans on tomatoes

Leaves of tomato plants of the cultivar "Professor Rudioff" are sprayed with aqueous suspensions containing 80 % (by weight) of the active substance to be tested and 20 % sodium lignosulfonate in the dry matter. It

2 2 113

• - 48 - O. Z. OO5O / O33867

""0> 025 and 0.012 # (wt. %) spray liquors (calculated on the dry substance) are used. After the spray coating has dried on, the leaves are infected with a .Zoosporenauf flushing of the fungus Phytophthora infestans.

  5 The plants are then placed in a steam-saturated chamber at temperatures between 16 and 18 ° 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:

0 = no fungal attack, graded to 5 = total infestation (control) '' '·

2 2 113 7

O. Z. 0050/033867

'drug

Infestation of leaves after spraying with. ./Siger active ingredient broth

0,025

0,012

20

2 6 9

34 104-111

24 ·

80 10.1 102 117 118 119

Control (untreated)

0 0 0 0 0 0 0 1 1 1 0 1 0 0 1 0

2 2-3

2 2-3

25

Trial 2

30

35

Fungicidal activity against casseroles on peas

100 g samples "Senator" pea seeds are carefully shaken in glass bottles for about 5 minutes with 300 mg (= 0.3% by weight) of pickling preparations containing 40 % (by weight) of active ingredient in the dry matter. Then 100 seeds each in seed boxes are 3 cm deep

1025

30

221137

- 50 ° · ² · OO5O / O33367

"" and at a distance of 3 to 5 cm in a compost earth, which has a strong natural contamination with the fungi Pythium spec, Aphanomyces spec, and Fusarium oxysporum.The boxes are 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.

Active ingredient ..% healthy plants after 21 days

in compost soil

20 96

42 96

78 94

A (known) 15

B (known) 63

Control (untreated) '8

Control 98

(sterilized compost soil)

20

35

Claims (1)

AP A 01 N / 221 137 57 35? * "12 22 1137 _ 51 - Invention claim A fungicidal composition characterized by a content of a solid or liquid carrier and a 2- (N-aryl, N-acyl) -ininopropanal acetal of general formula I. X, X and X ^ are independently oxygen or sulfur, Y oxygen, sulfur or NR ⁷ , η 0 or 1 R ^{1 is} C ₁ -C ₄ -alkyl, R is hydrogen, halogen, C ₁ -C 4 -alkyl or C ₁ -C -alkoxy, R 1 is hydrogen, halogen or C 1 -C 4 -alkyl, 4 5. τ 4 "* R and R independently of one another are optionally substituted alkyl or arylalkyl radicals or together form, as the alkylene group, part of an optionally substituted by alkyl or aryl-substituted 5- or 6-membered heterocyclic ring, - .52 - O. Z. 0050/033367 R is an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl radical with the exception of the chloromethyl radical and R is hydrogen, an alkyl or alkoxy group.