DD247370A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The invention relates to pest control agents containing the novel E-isomers of Na- (2-cyano-2-alkoximino-acetyl) -aminosahe derivatives and peptides of general formula (I), RONCN RONCCO-NR1CCOX (I) R3 in which R, R1, R2 , R3 and X have the meanings given in the description, as active ingredients. The new E isomers of Na (2-cyano-2-alkoximinoacetyl) amino acid derivatives and peptides have particular fungicidal effects.

Description

in which

R is alkyl, alkenyl, alkynyl, cyanoalkyl, azolylalkyl, optionally substituted phenylalkyl or for

optionally substituted cycloalkyl; R ^{1 is} hydrogen, alkyl, optionally substituted phenyl, optionally substituted benzyl or

Alkoxycarbonylamino; R ^{2 is} hydrogen or alkyl; R ^{3 is} hydrogen, alkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, azolylalkyl, cyanoalkyl, hydroxyalkyl, alkenyl, alkynyl, optionally substituted cycloalkyl, optionally substituted phenyl and

Phenylalkyl or for the group R ⁴ -SO _n -Z-

stands, where

R ^{4 is} hydrogen, alkyl or optionally substituted phenylalkyl; η is the numbers 0,1 or 2 and Z is a straight or branched alkylene chain;

R ¹ and R ³ together with the nitrogen atom and the carbon atom to which they are attached for a 5- or

6-membered heterocycle;

R ² and R ^3, together with the carbon atom to which they are attached, represent cycloalkylidene and X represents the grouping-OR ¹ or NR ¹¹ R ¹ ", where

R ^{1 is} hydrogen, alkyl, alkenyl or alkynyl; R "represents hydrogen or alkyl;

R ¹ "is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, dialkylaminoalkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, alkylaminocarbonylalkyl, dialkylaminocarbonylalkyl, cyanoalkyl, optionally substituted phenylalkyl, optionally substituted phenyl, optionally substituted cycloalkyl, an acylamino radical, or the moiety

-N = CH-R ^IV

stands, where

R ^{lv represents} alkyl or optionally substituted phenyl; or R "and R ¹ " together with the nitrogen atom to which they are attached, optionally

substituted heterocycle, which may contain other heteroatoms,

and their physiologically acceptable optionally substituted ammonium, alkyl and alkaline earth salts and metal salt complexes, in addition to extenders and / or surface-active agents.

2. Use of Ε-isomers of N ^a - (2-cyano-2-alkoximinoacetyl) -amino acid derivatives and peptides of the formula (I) according to item 1, characterized in that they are used for the Bekämfpung of pests and fungi.

3. A method for combating pests, characterized in that Ε-isomers of IT (2-cyano-2-alkoximinoacetyl) -amino acid derivatives and peptides of the formula (I) according to point 1 on pests and / or their habitat act ,

4. A process for the preparation of Schädlingsb'ekämpfungsmitte, characterized in that Ε isomers of N "- (2-cyano-2-alkoximinoacetyl) -amino acid derivatives and peptides of the formula (I) according to item 1 with extenders and / or surface-active Mixtures mixed.

Field of application of the invention

The present invention relates to pesticides containing novel Ε-isomers of N "- (2-cyano-2-alkoximinoacetyl) -amino acid derivatives and peptides as active ingredients.

Characteristic of the known technical solutions

It is already known that certain compounds such as, for example, N-trichloromethylthio-tetrahydrophthalimide, zinc ethylene-1,2-bis-dithiocarbamate and N-ethylaminocarbonyl-cyano-methoximino-acetamide have good fungicidal activity (cf., for example, US Pat. US-PS 2457674 and DE-OS 2312956). The effect of these compounds, however, is not always fully satisfactory, especially at low application rates and concentrations.

Object of the invention

Surprisingly, the compounds according to the invention have a higher activity than the compounds known from the prior art, such as N-trichloromethylthio-tetrahydrophthalimide, zinc ethylene-1,2-bis-dithiocarbamate and N-ethylaminocarbonyl-2-cyano-2-one. methoximinoacetamide, which are constitutionally or functionally obvious compounds. The substances according to the invention thus represent an enrichment of the art.

Explanation of the essence of the invention

There are new Ε-isomers of N ^a - (2-cyano-2-alkoximino-acetyl) -amino acid derivatives and peptides of the general formula (I)

RO CN

/ 2

N = C FT.

CO-Nf ^ -OCOX R ³

in which

R is alkyl, alkenyl, alkynyl, cyanoalkyl, azoalylalkyl, optionally substituted phenylalkyl and optionally

substituted cycloalkyl; R ^{1 is} hydrogen, alkyl, optionally substituted phenyl, optionally substituted benzyl and

Alkoxycarbonylamino; R ^{2 is} hydrogen or alkyl; R ^{3 is} hydrogen, alkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, azolylalkyl, cyanoalkyl, hydroxyalkyl, alkenyl, alkynyl, optionally substituted cycloalkyl, optionally substituted phenyl and

Phenylalkyl and for the grouping

R ⁴ -S0 _n -Z-

stands, where '

R ^{4 is} hydrogen, alkyl and optionally substituted phenyalkyl; η is the number O, 1 or 2 and Z is a straight or branched alkylene chain;

R ¹ and R ³ together with the nitrogen atom and the carbon atom to which they are attached, for a 5 or

6-membered heterocycle;

R ² and R ³ together with the carbon atom to which they are attached stand for cycloalkylidene and X stands for the grouping -OR ¹ or NR ^II R ¹ ", where

R ^{1 is} hydrogen, alkyl, alkenyl or alkynyl; R "represents hydrogen or alkyl;

R ¹ "is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, dialkylaminoalkyl, alkoxycarbonylalkyl, hydroxycarbonylalky ^ aminocarbonylalkyl.alkylaminocarbonylalkyl, dialkylaminocarbonylalkyl, cyanoalkyl, optionally substituted phenylalkyl, optionally substituted phenyl, optionally substituted cycloalkyl, an acylamino radical or the grouping

-N = CH-R ^IV , where

R ^{lv is} alkyl or optionally substituted phenyl,

R "and R ¹ " together with the nitrogen atom to which they are attached, for an optionally substituted

Heterocycle, which may contain further heteroatoms,

and their physiologically tolerated optionally substituted ammonium, alkali and alkaline earth metal salts and metal salt complexes.

The compounds of the formula (I) have, in the case where R ² and R ^{3 have} different meanings, an asymmetric carbon atom; They can thus also be present as optical isomers (D and L configuration), which can be obtained in different proportions. Most of them are obtained as racemates.

Furthermore, it has been found that the Ε-isomers of N "- (2-cyano-2-alkoximinoacetyl) -amino acid derivatives and peptides of the formula (I)

CN R ²

¹ 1 '

RO-N = C-CO-NR ¹ -C -COX (D.

, R ³

in which

R is alkyl, alkenyl, alkynyl, cyanoalkyl, azolylalkyl, optionally substituted phenylalkyl and optionally

substituted cycloalkyl; R ^{1 is} hydrogen, alkyl, optionally substituted phenyl, optionally substituted benzyl, as well as

Alkoxycarbonylamino; R ^{2 is} hydrogen or alkyl; R ^{3 is} hydrogen, alkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, azolylalkyl, cyanoalkyl, hydroxyalkyl, alkenyl, alkynyl, optionally substituted cycloalkyl, optionally substituted phenyl and

Phenylalkyl as well as the grouping

R ⁴ -S0 _n -Z-, where

R ^{4 is} hydrogen, alkyl and optionally substituted phenylalkyl; η is 0, 1 or 2, and Z is a straight or branched alkylene chain; R ¹ and R ³ together with the nitrogen atom and the carbon atom to which they are attached, for a 5 or

6-membered heterocycle;

R ² and R ³ together with the carbon atom to which they are attached stand for cycloalkylidene and X stands for the grouping -OR ¹ or NR "R '", where

R ^{1 is} hydrogen, alkyl, alkenyl or alkynyl; R "is hydrogen or alkyl, R ¹ " is hydrogen, alkyl, alkenyl, alkynyl, haloalky ^ alkoxyalkyldialkylaminoalkyljalkoxycarbonylalkyl, hydroxycarbonylalkyLAminocarbonylalkyl, alkylaminocarbonylalky ^ dialkylaminocarbonylalkyl, cyanoalkyl, optionally substituted phenyalkyl, optionally substituted phenyl, optionally substituted cycloalkyl, acylamino radical or the grouping

-N = CH-R ^IV , where

R ^{lv is} alkyl or optionally substituted phenyl, or

R "and R ¹ " together with the nitrogen atom to which they are attached, for an optionally substituted

Heterocyclic us, which may contain other heteroatoms,

and their physiologically tolerated optionally substituted ammonium, alkali metal or alkaline earth metal salts and metal salt complexes obtained when (a) amino acid derivatives of the formula (II)

r2

HNR ¹ -C-CO-X I

in which R ¹ , R ² , R ³ and X have the meanings given above, with the carboxy-activated derivatives of the Ε-isomers of the carboxylic acids of the formula (III),

RO CN

N = C (HD ·

COOH

in which R has the abovementioned meaning, if appropriate in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,

(b) carboxy-activated derivatives of the Ε-isomers of carboxylic acids of the formula (III)

RO CN

COOH in which R has the meaning given above, first with amines of the formula (IV)

H ₂ NR ¹ , (IV)

in which R ^{1 has} the abovementioned meaning, then with carbonyl derivatives of the formula (V)

R ² -CO-R ³ , (V)

in which R ² and R ^{3 have} the meanings given above, and finally with isonitriles of the formula (VI)

CN-R ⁵ ₁ (VI)

in which

R ^{5 is} alkyl, alkenyl, alkynyl, cyanoalkyl, alkoxycarbonylalkyl or optionally substituted cycloalkyl, phenyl or

Phenylalkyl,

if appropriate in the presence of a diluent, or (c) carboxy-activated derivatives of the Ε-isomers of amino acids of the formula (Ia)

RO CN

\ /

N = CR ²

\ I (la)

CO-NH-C-COOH

in which R, R ² and R ^{3 have} the meanings given above, with amines of the formula (VII)

H-NR ¹¹ R '", (VII) j

in which R "and R ¹ " have the meanings given above,

optionally in the presence of a catalyst and optionally in the presence of an acid binder and optionally

in the presence of a diluent,

(d) Ε isomers of amino acid derivatives of the formula (I b)

RO CN

N = CR ²

N.j (ib)

CO-NH-C-COOR ⁶

in which R, R ² and R ^{3 have} the meanings given above,

R ^{6 is} alkyl having 1 to 4 carbon atoms, with amines of the formula (VII)

H-NR ¹¹ R ¹ "(VII)!

in which R "and R ¹ " have the abovementioned meanings, if appropriate in the presence of a diluent.

The compounds of the formula (I) in which X is a hydroxy group can thus form salts with amines and alkali metal or alkaline earth metal hydroxides, carbonates or bicarbonates and also ammonium hydroxide

form metal complexes with heavy metal salts.

Finally, it has been found that the new Ε-isomers of N ^a - (2-cyano-2-alkoximinoacetyl) -amino acid derivatives and peptides of the formula (I) and their optionally substituted ammonium, alkali metal and alkaline earth metal salts and Metailsalz -

Complexes have particularly strong fungicidal properties.

The Ε-isomers of N "- (2-cyano-2-alkoximinoacetyl) -amino acid derivatives and peptides according to the invention are characterized by

Formula (I) generally defined. Preference is given to compounds of the formula (I) in which

R is straight-chain or branched alkyl having 1 to 8 carbon atoms, alkenyl or alkynyl having in each case 2 to 4 carbon atoms, for cyanoalkyl having 1 to 4 carbon atoms, for 1,2,4-triazol-1-ylalkyl having in each case 1 to 6 carbon atoms in the alkyl moiety , for optionally in the phenyl moiety monosubstituted to trisubstituted by identical or different substituents phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, preferably being mentioned as substituents: halogen, cyano, nitro, hydroxy, alkyl, alkoxy, alkylsulfinyl and alkylsulfonyl, alkylthio each with 1 to 4 carbon atoms and optionally mono- to trisubstituted by identical or different halogen-substituted phenyl; or represents optionally monosubstituted to trisubstituted by identical or different cycloalkyl having 3 to 7 carbon atoms, wherein as substituents preferably halogen and alkyl having 1 to 4 carbon atoms may be mentioned;

R ^{1 is} hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, each optionally mono- to trisubstituted by identical or different substituents phenyl or benzyl, preferably as substituents in R already mentioned phenyl substituents in question, or for alkoxycarbonylamino with 1 to 4 carbon atoms in the alkyl portion;

R ^{2 is} hydrogen or straight chain or branched alkyl of 1 to 4 carbon atoms;

R ^{3 is} hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched hydroxyalkyl having 1 to 4 carbon atoms, alkoxycarbonylalkyl having in each case 1 to 4 carbon atoms in the alkoxy part and in the alkyl part, for hydroxycarbonylalkyl and aminocarbonylalkyl each having 1 to 4 carbon atoms in the Alkyl part, for 1,2,4-triazol-1-ylalkyl, 1,2,4-triazol-4-ylalkyl, imidazol-4-ylalkyl and pyrazol-1-ylalkyl each having 1 to 6 carbon atoms in the alkyl moiety, for cyanoalkyl with 1 to 4 carbon atoms, alkenyl or alkynyl having in each case 2 to 4 carbon atoms, optionally mono- to trisubstituted by identical or different substituents cycloalkyl having 3 to 7 carbon atoms, wherein as substituents preferably halogen and alkyl having 1 to 4 carbon atoms may be mentioned, further for optionally in the phenyl moiety monosubstituted to trisubstituted by identical or different substituents phenyl or phenylalkyl having 1 to carbon atoms in the alkyl moiety, wherein as substituents in each case preferably already mentioned in R phenyl substituents come into question, or for the grouping

R ^{4 is} -SOn-Z-, where

R ^{4 represents} hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety which is monosubstituted to trisubstituted by identical or different substituents in the alkyl moiety, suitable substituents being the phenyl substituents already mentioned for R,

η is the number 0.1 or 2 and Z is a straight or branched alkylene chain of 1 to 4 carbon atoms;

R ¹ and R ³ together with the nitrogen atom and the carbon atom to which they are attached stand for a 5-membered or lower-membered heterocycle; ,

R ² and R ^3, together with the carbon atom to which they are attached, are cycloalkylidene of 3 to 6 carbon atoms;

X stands for the groupings-OROder-NRW, where

R ^{1 is} hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, alkenyl or alkynyl having in each case 2 to 4 carbon atoms;

R "is hydrogen or straight chain or branched alkyl of 1 to 4 carbon atoms;

R "'is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, alkenyl or alkynyl having in each case 2 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, for alkoxyalkyl each having 1 to 4 Carbon atoms in the alkoxy moiety and in the alkyl moiety, for dialkylaminoalkyl having up to 4 carbon atoms in the individual alkyl moieties, for alkoxycarbonylalkyl each having 1 to 4 carbon atoms in the alkoxy moiety and in the alkyl moiety, hydroxycarbonylalkyl having 1 to 4 carbon atoms in the alkyl moiety, aminocarbonylalkyl, alkylaminocarbonylalkyl or dialkylaminocarbonylalkyl each having 1 to 4 carbon atoms in each alkyl moiety, for cyanoalkyl of 1 to 4

Carbon atoms in the alkyl moiety, optionally in the phenyl moiety monosubstituted to trisubstituted by identical or different substituents, phenylalkyl having from 1 to 4 carbon atoms in the alkyl moiety or simply to trisubstituted by identical or differently substituted phenyl, substituents being in each case the phenyl substituents already mentioned for R, for optionally identically or differently substituted cycloalkyl having 3 to 7 carbon atoms, suitable substituents being preferably halogen and alkyl having 1 to 4 carbon atoms, for alkylcarbonylamino or alkoxycarbonylamino having in each case 1 to 4 carbon atoms in the alkyl part or in the alkoxy part, furthermore for aminocarbonylamino, Alkyiaminocarbonylamino and Dialkylaminocarbonylamino each having 1 to 4 carbon atoms in the individual alkyl moieties as well as formylamine or the moiety

-N = CH-R ^IV , where

R ^{lv represents} straight-chain or branched alkyl having 1 to 4 carbon atoms or optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents being the phenyl substituents already mentioned for R,

R "and R ¹ " together with the nitrogen atom to which they are attached stand for a 5- or 6-membered heterocycle which may optionally contain oxygen or nitrogen as further heteroatoms and optionally by cyano, halogen, alkyl having 1 to 4 carbon atoms, hydroxycarbonyl , Alkoxycarbonyl having 1 to 4 carbon atoms in Alkoxytei ^ aminocarbonyl and alkylaminocarbonyl and dialkylaminocarbonyl each having 1 to 4 carbon atoms in the individual alkyl moieties may be substituted.

Particular preference is given to those compounds of the formula (I) in which

R is straight-chain or branched alkyl having 1 to 4 carbon atoms, allyl, propargyl, cyanomethyl, cyanoethyl, 1,2,4-triazol-1-ylalkyl and pyrazol-1-ylalkyl having 1 to 4 carbon atoms in the alkyl moiety, optionally in the phenyl moiety monosubstituted or disubstituted, identically or differently substituted phenylalkyl having 1 or 2 carbon atoms in the alkyl moiety, particular mention being made of substituents: fluoro, chloro, cyano, nitro, hydroxy, methyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl and optionally once or twice, identical or different phenyl or fluorine-substituted phenyl; furthermore, in each case optionally monosubstituted or disubstituted by identical or different fluorine, chlorine or methyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl;

R ^{1 represents} hydrogen, methyl, ethyl, in each case optionally monosubstituted or disubstituted by identical or different substituents, phenyl or benzyl, suitable substituents being in particular the phenyl substituents already mentioned for R; further represents methoxycarbonylamino or ethoxycarbonylamino;

R ^{2 is} hydrogen, methyl or ethyl;

R ^{3 is} hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, hydroxymethyl, 1-hydroxyethyl, for methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, hydroxycarbonylmethyl, hydroxycarbonylethyl, aminocarbonylmethyl, aminocarbonylethyl, for 1,2,4-triazol-1-ylalkyl , 1,2,4-triazol-4-ylalkyl, imidazol-4-ylalkyl each having 1 to 4 carbon atoms in the alkyl moiety, for cyanomethyl, cyanoethyl, allyl, propargyl, each optionally optionally mono- or disubstituted by identical or different fluorine , Chloro or methyl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl; furthermore phenyl which may be monosubstituted or disubstituted by identical or different substituents and phenyl which has 1 or 2 carbon atoms in the alkyl moiety or phenyl which is monosubstituted or disubstituted by identical or different substituents, suitable substituents being the phenyl substituents already mentioned for R, and furthermore for the moiety

R ⁴ -SO _n -Z-, where

R ^{4 is} hydrogen, methyl, ethyl or optionally mono- or disubstituted in the phenyl moiety, gleiph or differently substituted phenylalkyl having 1 or 2 carbon atoms in the alkyl moiety, where as substituents in particular the already mentioned in R phenyl substituents come into question, η for the numbers 0.1 oder2stehtund

Z is a straight or branched alkylene chain having 1 or 2 carbon atoms; R ¹ and R ³ together with the nitrogen atom and the carbon atom to which they are attached represent a 5- to 6-membered heterocycle;

R ² and R ^3, together with the carbon atom to which they are attached, represent cyclopropylidene, and X represents the groupings -OR ¹ or -N''- ¹ ', where

R ^{1 is} hydrogen, methyl, ethyl, allyl and propargyl;

R "is hydrogen, methyl or ethyl;

R ¹ "is hydrogen, methyl, ethyl, n-propyl, i-propyl, η-butyl, i-butyl, sec-butyl, tert-butyl, allyl, propargyl, for haloalkyl having 1 or 2 carbon atoms and 1 to 3 identical or different halogen atoms, such as fluorine and chlorine atoms, for alkoxyalkyl having in each case 1 or 2 carbon atoms in the alkoxy moiety and in the alkyl moiety, for dialkylaminoalkyl having 1 or 2 carbon atoms in the individual alkyl moieties, for alkoxycarbonylalkyl, hydroxycarbonylalky ^ aminocarbonylalkyl, alkylaminocarbonylalkyl or dialkylaminocarbonylalkyl each having 1 or Furthermore phenyl optionally substituted once or twice, identically or differently substituted phenylalkyl having 1 or 2 carbon atoms in the alkyl moiety, monosubstituted or disubstituted by identical or different substituents, where as substituents in each case the phenyl substituents already mentioned for R. for each possibly single or double, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl which is identical or different with fluorine, chlorine or methyl, for alkylcarbonylamino or alkoxycarbonylamino having in each case 1 or 2 carbon atoms in the alkyl part or in the alkoxy part, for aminocarbonylamino, methylaminocarbonyl.amino, ethylaminocarbonylamino, dimethylaminocarbonylamino, diethylaminocarbonylamino, Methylethylaminocarbonylamino, as well as formylamino or for grouping

-N = CH-R ^IV , where.

R ^{lv is} methyl, ethyl, optionally phenyl mono- or di-substituted by identical or different substituents, wherein

suitable substituents are the phenyl substituents which are preferably already mentioned for R; or R "and R ¹ " together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocycle which may optionally contain oxygen or nitrogen as further heteroatoms and optionally substituted by cyano, fluorine, chlorine, bromine, iodine, Methyl, ethyl, i-propyl, hydroxycarbonyl, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl and methylethylaminocarbonyl.

Preferred compounds according to the invention are also the alkali, alkaline earth and optionally substituted ammonium salts of the Ε-isomers of those N "- (2-cyano-2-alkoximinoacetyl) -amino acid - and -peptide derivatives of the formula (I) in which X. represents a hydroxy group and R, R ¹ , R ² and R ^{3 have} the meanings already mentioned for these substituents.

For this salt formation alkali and alkaline earth hydroxides, carbonates or bicarbonates or amines and ammonium hydroxide can be used. These preferably include sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, calcium hydroxide, barium hydroxide; Ammonia; primary amines * such as methylamine and isopropylamine; secondary amines such as dimethylamine and dicyclohexylamine; tertiary amines such as triethylamine, pyridine and N, N-dimethylbenzylamine and ammonium hydroxides such as benzyltrimethylammonium hydroxide. Other preferred compounds of the invention are addition products of salts of metals of II. To IV. Main and the I. and II., And IV. To VIII. Subgroup and those substituted N "- (2-cyano-alkoxaminoacetyl) -amino acid and peptide derivatives of the formula (I) in which the substituents R, R ¹ , R ² , R ³ and X have the meanings which have already been mentioned for these substituents.

Here, salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Suitable anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition products. Particularly preferred such acids in this context are the hydrohalic acids, such as. Hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulfuric acid.

If, for example, glycine ethyl ester and 2-cyano-2-methoximino-acetyl chloride are used as starting materials, the course of process (a) according to the invention can be represented by the following formula scheme:

CN OO

I Il I!

CH ₃ ON = C C-Cl + H ₂ N-CH ₂ -C-OC ₂ H ₅

-HCl

CN O 0

I! !!

CH ₃ ON = C C -NH-CH ₂ -C-OC ₂ H ₅

If, for example, 2-cyano-2-methoximinoacetic acid, benzylamine, isobutyraldehyde and ethyl isocyanate are used as starting materials, the course of process (b) according to the invention can be represented by the following formula scheme:

CN 0 0 O

I Il / -χ - Il Il

CH ₃ ON = C C-OH + C V -CH ₂ -NH ₂ + CH + CN-CH ₂ -C-OC ₂ H ₅ *

CH ₃

CN CHo 0 0

I Il Il

CH ₃ ON = C CN-CH-C-NH-CH ₂ -C-OC ₂ H ₅

0 CH CH ₃ CH ₃

If, for example, N- (2-cyano-2-methoximinoacetyl) glycine ethyl ester and methylamine are used as starting materials, the course of process (c) according to the invention can be represented by the following formula scheme:

CN O

I!

CH ₃ ON = C-NH-CH ₂ -C-OC ₂ H ₅ + CH ₃ -NH ₂

-C ₂ H ₅ OH 0

CN

CH ^ O-N = C-C-NH-CHO-C-NH-CH-,

³ Il

The amino acid derivatives to be used as starting materials for carrying out the process (a) according to the invention are generally defined by the formula (II). In this formula, R ¹ , R ² , R ³ and X have the meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention for these substituents. The amino acid derivatives of the formula (II) are known in some cases (cf., for example, Houben-Weyl, Methods of Organic Chemistry, Volume XV, Parts 1 and 2, Georg Thieme Verlag, Stuttgart 1974, and RCSheppard, A Specialist Periodical Report, Amino-acids, Peptide Sand Proteins, The Royal Society of Chemistry, Burlington House, London 1978, and IP Greenstein and M. Winitz, Chemistry of Amino Acids, I. Wiley sons Inc., New York, London 1961, and E, respectively Schröder and K. Lübke, The Peptides Vol. I, Academic Press, New York, London 1965) or can be obtained by the methods given therein. The addition for carrying out the process (a) and also of the process (b) as starting materials to be used carboxy-activated derivatives of the Ε-isomers of the carboxylic acids are generally defined by the formula (III). In this formula, R has the above meaning.

The carboxy-activated derivatives of the E-isomers of the carboxylic acids of the formula (III) are, with the exception of the Ε-isomer of 2-cyano-2-methoximino-acetic acid (compare IJBelasco and FJ Baude, Pestic.Sci., 12,27 , 1981) not known. The carboxy-activated derivatives of the carboxylic acids of the formula (III) are obtained when the carboxylic esters of the formula (VIII) are obtained by generally known processes.

CN RO-N = CC-OR ⁷

(VIII)

in which

R has the meaning given above and

R ^{7 is} alkyl, preferably methyl or ethyl,

first with an alkali hydroxide, such as sodium hydroxide, and then with an acid, such as hydrochloric acid or sulfuric acid, or with an acidic ion exchanger in the presence of a diluent, such as water, alcohols, ethers or mixtures of alcohols or ethers with water, at temperatures between 0 and 80 ⁰ C, preferably between 20 and 40 ° C, reacted.

Preferably, the saponification is carried out with potassium hydroxide in the presence of a water / ethanol mixture, the reaction mixture being evaporated at 20 ° C in vacuo and the resulting potassium salt extracted with e.g. Oxalylchloridzum to the corresponding acid chloride is reacted (see also the preparation examples).

The carboxylic acid esters of the formula (VIII) are known in some cases (compare IJBelasco and FJ Baude, Pestic, Sci., 12, 27, 1981) or can be obtained by the process described therein, in which the Ε-isomers of the carboxylic esters of formula

CN MO-N = CC-OR ^{7 (IX)}

Il

in which

R ^{7 has} the abovementioned meaning and

M is hydrogen, sodium or potassium, preferably sodium, with a compound of the formula (X)

R-W, (X)

in which

R has the abovementioned meaning and W is halogen, a sulfonyldioxy or sulphonyloxy radical, such as preferably chlorine, bromine, iodine, -OSO ₂ OCH ₃ , -OSO ₂ OC ₂ H ₅ ,

-OSO ₂ CH ₃ or

-OSO ₂

stent,

optionally in the presence of a base, such as potassium carbonate, triethylamine or diazabicycloundecane (DBU), and in the presence of a solvent, such as acetone, dimethylformamide, dimethyl sulfoxide or acetonitrile, at temperatures between 0 and 12O ⁰ C reacted.

The Ε-isomers of the carboxylic acid esters of the formula (IX) are known (compare, for example, Kinast, Liebigs Ann. Chem., 1981, 1661, M. Conrad and A. Schulze, Berschitsch Chemical Ges., 42, 735, 1909) and can be obtained by the methods described therein. The compounds of the formula (X) are generally known alkylating agents.

Suitable carboxy-activated derivatives of the carboxylic acid of the formula (III) are all carboxy-activated derivatives such as acid halides, such as. As acid chlorides, acid azides, further symmetrical and mixed anhydrides, such as the mixed O-Alkylkohlensäureanhydride, further activated esters such. For example, p-nitrophenyl ester or N-Hydroxisuccinimidester and condensing agents such. As dicyclohexylcarbodiimide or carbonyldiimidazole, in situ generated activated forms of the carboxylic acids.

-9- Z4 / 3 / U

The acid chlorides corresponding to the carboxylic acids of the formula (III) are preferably used. They can be prepared by reacting the carboxylic acids of formula (III) or salts thereof with a halogenating agent such as phosphorus pentachloride, thionyl chloride or oxalyl chloride in a well-known manner. Preference is given to the use of oxalyl chloride together with the sodium or potassium salt of the carboxylic acid of the formula (III), since the isomerization is minimal under these conditions.

The acylation with the carboxy-activated derivatives can be carried out in aqueous or nonaqueous medium; suitable media are ketones, such as. Acetone; Esters, such as ζ. Ethyl acetate; Amines, such as B. dimethylformamide; Nitriles, such as ζ. For example acetonitrile; Chlorinated hydrocarbons, such as ζ. As methylene chloride, hydrocarbons, such as. For example, toluene; or ethers, such as. B.

Tetrahydrofuran or mixtures thereof.

The acylation with an acid halide can be carried out in the presence of an acid binder, such as preferably a tertiary amine, such as. For example, triethylamine, pyridine, or an inorganic base such. For example, sodium carbonate or calcium carbonate.

The isonitriles to be used as starting materials for carrying out the process (b) according to the invention are generally defined by the formula (VI). In this formula, R ⁵ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, alkenyl or alkynyl having in each case 2 to 4 carbon atoms, cyanoalkyl having 1 to 4 carbon atoms, in the alkyl moiety, for alkoxycarbonylalkyl each having 1 to 4 carbon atoms in the alkoxy moiety and in the alkyl moiety, further optionally substituted once or three, identically or differently, substituted cycloalkyl having 3 to 7 carbon atoms, preferably being halogen and alkyl having 1 to 4 carbon atoms as substituents, or optionally substituted in the phenyl moiety monosubstituted to trisubstituted by identical or different substituents Phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety or phenyl which is monosubstituted to trisubstituted by identical or different substituents, in which case preferably the phenylalkyl substituents already mentioned for R are preferably suitable substituents.

The isonitriles of the formula (VI) are known in some cases (cf., for example, I.Ugi, Isonitrile Chemistry, Academic Press, New York, 1971) or can be prepared in an analogous manner by generally known processes by reacting the corresponding formylated primary amines for example, with phosgene or phosphorus oxychloride in the presence of a tertiary amine, such as. B.

Pyridine or triethylamine, with elimination of water.

The amines and carbonyl derivatives also to be used as starting materials for carrying out the process (b) according to the invention are generally defined by the formula (IV) or (V). In these formulas, R ¹ or R ² and R ^{3 have} the abovementioned meanings.

The amines of the formula (IV) and the carbonyl derivatives of the formula (V) are generally known compounds of organic chemistry.

The amino acid derivatives to be used as starting materials for carrying out the process (c) according to the invention, which are part of the invention, are generally defined by the formula (Ia). In this formula, R, R ² and R ³ preferably have the meaning which has already been mentioned in connection with the description of the substances of the formula (I) according to the invention for these substituents.

Suitable acylating agents corresponding to the amino acid derivatives of the formula (Ia) are all carboxy-activated derivatives which have already been mentioned in connection with the acylating agents corresponding to the carboxylic acid derivatives of the formula (III), preferably azides, O-alkylcarbonic anhydrides and also dicyclohexylcarbodiimide in situ generated activated derivatives.

The amino acid derivatives of the formula (Ia) are compounds according to the invention and can be prepared according to process (a) according to the invention.

The amines also to be used as starting materials for carrying out the process (c) according to the invention are generally defined by the formula (VII). In this formula, R "and R ¹ " have the meanings given above.

The amines of the formula (VII) are generally known compounds of organic chemistry.

The amino acid derivatives to be used as starting materials for carrying out the process (d) according to the invention are generally defined by the formula (I b). In this formula, R, R ² and R ³ preferably have the meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention for these substituents. R ⁶ is preferably methyl or ethyl.

The amino acid derivatives of the formula (I b) are compounds according to the invention.

Suitable diluents for the process (a) according to the invention are water and inert organic solvents.

These include ketones, such as acetone or ethyl methyl ketone; Esters such as ethyl or methyl acetate; Amides such as dimethylformamide; Nitriles such as acetonitrile; Chlorohydrocarbon, such as methylene chloride or carbon tetrachloride; Hydrocarbons, such as toluene; or ethers, such as tetrahydrofuran; or mixtures thereof.

Suitable acid binders for the process (a) according to the invention are customary inorganic and organic acid binders. These preferably include tertiary amines, such as triethylamine, pyridine or N-methylmorpholine; and inorganic bases, such as sodium carbonate or calcium carbonate.

If appropriate, the process (a) according to the invention is carried out in the presence of a catalyst. Examples which may be mentioned are 4-dimethylaminopyridine, 1-hydroxybenzotriazole or dimethylformamide.

The temperatures can be varied within a substantial range when carrying out the process (a). In general, one works between -60 to +120 ^c C, preferably at -20 to + 40 ° C.

In carrying out the process (a) according to the invention, preference is given to working in equimolar amounts.

The amino acid derivatives of the formula (II) are used as pure optical isomers (D or L form) or as racemates.

Suitable diluents for the process (b) according to the invention are all customary inert organic solvents. These include, preferably, alcohols, such as methanol or ethanol; Ethers, such as diethyl ether; chlorinated hydrocarbons, such as chloroform or carbon tetrachloride; as well as ketones, such as acetone.

When carrying out the process (b) according to the invention, the temperatures can be varied within a substantial range. In general carried out between -20 to + 4O ⁰ C, preferably at 0 to 20 ⁰ C.

When carrying out the process (b) according to the invention, preference is given to working in equimolar amounts.

The diluents, catalysts and acid binders which are suitable for process (c) according to the invention correspond to those of process (a).

Difi Tffmnpratiirpn knnnen hpi nor Πι irrhfühn inn Hoc orfinHi inncnemäRon Vorfahronc LT \ in oinom nrnfloran raral ^ ht / ^ i-üor +

When carrying out the process (c) according to the invention, preference is given to working in equimolar amounts.

Suitable diluents for the process (d) according to the invention are preferably alcohols, for example

Methanol, ethanol or isopropanol.

In carrying out the process (d) according to the invention, the temperatures can be varied within a substantial range

become. In general, it is carried out between -20 and + 60 ° C, preferably at 0 to 2O ⁰ C.

When carrying out the process (d) according to the invention, preference is given to using 1 mol of the compounds of the formula

(Ib) 1 to 10 moles of the amine formula (VII).

The metal salt complexes of compounds of general formula (I) can be obtained in a simple manner by conventional methods, such. B. by dissolving the metal salt in alcohol, eg. As ethanol and adding to compounds of general formula (I). One can metal salt complexes in a known manner, for. B. by filtration, isolate and optionally by

Clean recrystallization.

The active compounds according to the invention have a strong microbicidal action and can be used to combat

be used practically undesirable microorganisms. The active ingredients are suitable for use as pesticides.

For example, fungicidal agents are used in crop protection to combat Plasmodiophoromycetes, Oomycetes,

Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Exemplary but not limiting are some pathogens of fungal diseases, which are listed below

Generic terms fall, called ..

Pythium species, such as Pythium ultimum; Phytophthora species, such as Phytophthora infestans;

Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubense;

Plasmopara species, such as Plasmopara viticola; Peronospora species such as Peronospora pisi or P. brassicae; Erysiphe species, such as Erysiphe graminis; Sphaerotheca species, such as Sphaerotheca fuliginea; Podosphaera species, such as Podosphaera leucotricha; Venturia species, such as Venturia inaequalis; Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium);

Uromyces species, such as Uromyces appendiculatus; Puccinia species, such as Puccinia recondita; Tilletia species, such as Tilletia caries; Ustilago species such as Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as Pyricularia oryzae; Fusarium species such as Fusarium culmorum; Botrytis species, such as Botrytis cinerea; Septoria species such as Septoria nodorum; Leptosphaeria species, such as Leptosphaeria nodorum; Cercospora species, such as Cercospora canescens; Alternaria species, such as Alternaria brassicae; Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the concentrations necessary for controlling plant diseases

allows treatment of above-ground parts of plants, planting and seed, and the soil.

As pesticides, the active compounds according to the invention can be used with particular success for controlling Plasmopara species, such as Plasmopora viticola, on vines and Phytophthora species, such as Phytophthora infestans, on tomatoes. Particularly noteworthy is that the active compounds of the invention not only develop a protective effect, but also partially curative effective, so when applied after contamination with the spores of the fungus. Furthermore, the partial systemic effect of the substances should be pointed out. That's how it works. Protecting plants against fungal attack, if you divide the active ingredient over the soil and the root or over the seeds of the above-ground parts

feeds the plants.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in seed coating compositions, furthermore in formulations with Fuel packs, such as smoke cartridges, cans,

Spirals and the like, as well as ULV KaIt and warm mist formulations.

These formulations are prepared in a known manner, for. Example, by mixing the active compounds with extenders, that is liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. As petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; by liquefied gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and under normal pressure,

z. B. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers are: z. Natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates; as solid

Carriers for granules come into question: z. For example, crushed and fractionated natural rocks ₍ such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates;

Dispersants are suitable: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and

be vegetable oils.

It can dyes such as inorganic pigments, eg. For example, iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and Metallphthalocyaninfarbstoffe and trace nutrients such as salts of iron, manganese, boron, copper, cobalt,

Molybdenum and zinc are used.

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

The active compounds according to the invention can be present in the formulations or in the various application forms in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth substances, plant nutrients and soil conditioners.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application is done in customary, z. BV. by pouring, dipping, spraying, spraying, atomizing, vaporizing, injecting, silting, spreading, dusting, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or

Encrusting.

In the treatment of parts of plants, the drug concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001%.

In the seed treatment, in general, amounts of active ingredient of 0.001 to 50g per kilogram of seed, preferably

0.01 to 10 g needed.

When treating the soil, active ingredient concentrations of from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight.

%, required at the site of action.

Preparation Examples example 1

CN O

I Il

CH ₃ ON = C-NH-CH ₂ -C-OC ₂ H ₅

O

(Method a)

60.5 g (0.427 mol) of glycine ethyl ester hydrochloride are suspended in 450 ml of dichloromethane, 86.2 g (0.853 mol) of triethylamine and 5.2 g (0.043 mol) of 4-dimethylaminopyridine are added, the reaction mixture is kept at 20 ° for 15 minutes C stirred and a solution of 62.5 g (0.427 mol) of 2-cyano-2-methoximino-acetyl chloride (Ε-isomer) is added dropwise at 0 ⁰ C in one hour. Subsequently, the reaction mixture is stirred for one hour at ⁰ ° C. and then for 5 hours at room temperature, and the solution is allowed to stand at room temperature for 2 days. After washing with 1 M hydrochloric acid (2 times per 300 ml), saturated sodium bicarbonate solution (2 times 200 ml each time) and water (2 times in each case 300 ml), the solution is dried over sodium sulfate

and steamed in vacuo.

This gives 81.0 g (89% of theory) of N "- (2-cyano-2-methoximino-acetyl) glycine ethyl ester (Ε-isomer) as a brown oil with the

Refractive index n "= 1.4699.

Preparation of the starting product CN

CH ₃ ON = CC-OC ₂ H ₅

To a suspension of 164 g (1 mol) of ethyl 2-cyano-2-hydroxyiminoacetate, sodium chloride (G. Kinast, Libiegs Ann. Chem., 1981, 165) and 138 g of powdered potassium carbonate in 1.51 of acetone are added 161 g (1.25 mol ) Dimethyl sulfate (98%) was added dropwise in 30 minutes and the reaction mixture heated under reflux for 3 hours. After cooling, it is filtered through diatomaceous earth and

evaporated.

This gives 124.8 g of 2-cyano-2-methoximino-acetic acid ethyl ester (Ε-isomer) as a red-brown oil of 85% purity (GC). The yield is therefore 68% of theory. After chromatography on five times the amount of silica gel 60 with chloroform

you get a 93% light yellow oil ^ __

cii

CH ₃ ON = C-O OK

In a solution of 124.8 g (0.672 mol) of 84% 2-cyano-2-methoximino-acetic acid ethyl ester (Ε-isomer) in 500 ml of ethanol at 20 ° C, a solution of 45.1 g (0.806 mol) of potassium hydroxide in 500 Added dropwise water and the reaction mixture was stirred at 40 ⁰ C for one hour. The solution is evaporated in vacuo at 4O ⁰ C, the residue is stirred with methanol for 30 minutes suction filtration, washed with ethanol, acetonitrile and Dichlörmethan and dried at room temperature. This gives 58.6 g (53% of theory) of the potassium salt of 2-cyano-2-methoximino-acetate (E-isomer).

CN

c) CH ₃ ON = C-Cl

20 g (0.12 mol) of the potassium salt of 2-cyano-2-methoximinoacetat (E-isomer) are suspended in 250 ml of dry ether and after addition of a few drops of dimethylformamide at 0 ° C dropwise with 76.2 g (0.6 mol ) Oxalyl chloride added. The reaction mixture is stirred for 2 hours at 0 ⁰ C, filtered and the filtrate evaporated in vacuo at room temperature. This gives 13.5 g (77% of theory) of 2-cyano-2-methoximinoacetyl chloride (E-isomer) as a yellow oil, which is immediately reacted further.

Example 2

CN OC ₂ H ₅

H ₇ -ON = CC-NH-CH ₇ -CN

² Il

(Method a)

To a solution of 5.87 g (0.02 mole) of glycine diethylamide, 5.05 g (0.05 mole) of triethylamine and 0.61 g (0.005 mole) of 4-dimethylaminopyridine in 75 mL of dichloromethane is added at OT a solution of 11.1 g ( 0.05 mol) of 2-benzyloximino-2-cyanoacetyl chloride (E-isomer) in 50 ml of dichloromethane, and the reaction mixture was stirred for one hour at ⁰ ° C. and for 20 hours at room temperature. The reaction mixture is diluted with 50 ml of dichloromethane, washed with 1 M hydrochloric acid, 10% sodium bicarbonate solution and water, dried over magnesium sulfate and evaporated in vacuo. The residue is recrystallized from ligroin / ethyl acetate.

This gives 4.0 g (25% of theory) of N ^a - (2-benzyloximino-2-cyano-acetyl) -glycindiethylamide (E-isomer) with the melting point 76-81 ° C.

Example 3

CN CH ₇ O

I L Il

CH ₃ ON = CCN-CH-C-NH-CH ₂ -C-OC ₂ H ₅ O CH

(Method b)

To a solution of 15.3 g (0.12 mol) of 2-cyano-2-methoximinoacetic acid (^ isomer), 8.65 g (0.12 mol) of isobutyldehyde and 12.85 g (0.12 mol) of benzylamine in 150 ml Methanol are added dropwise at 0 ° C. to a solution of 13.6 g (0.12 mol) of ethyl isocyanacetate (D. Hoppe and U. Schollkopf, Liebigs Ann. Chem., 763, 1, 1972) in 100 ml of methanol. The reaction mixture is allowed to come to room temperature and stirred for 13 hours at 20 ° C. The solvent is distilled off in vacuo, the residue partitioned between 300 ml of water and ethyl acetate, the organic phase washed with 200 ml of 1 M hydrochloric acid, 10% sodium bicarbonate solution and water, dried over sodium sulfate and evaporated in vacuo. This gives 14.4 g (30% of theory) of N- [N ^< "-Benzyl-N ^t " - (2-cyano-2-methoximino-acetyl) -DL-valyl] -glycine ethyl ester (E-isomer) as a brown oil ,

Preparation of the starting product

CH ₃ ON = CC-OH

IL o

In a mixture of-83g (0.5 mol) of 2-cyano-2-methoximinoessigsäureethylester (Ε-isomer) and 250 ml of water is added dropwise at 20-30 ⁰ C 550 ml (0.55 mol) 1 M sodium hydroxide solution and the reaction mixture Stirred for 2 hours at room temperature. The solution is washed with ether and applied to a column of 11 LewatitS 100 (H ⁺ form, washed with acetone before). With 11 acetone and acetonitrile is eluted and the eluate is evaporated at 30 ^ 10 ⁰ C in vacuo. This gives 63.2 g (99% of theory) of 2-cyano-2-methoximino-acetic acid (Ε-isomer) with the melting point 48-49 ° C.

Example 4

OCH ₃

CN NH

oO-N = C-C-N-CH-C-NH-

³ I! I

0 CH

CH ₃ CH ₃

(Method b)

In a solution of 6.4 g (0.05 mol) of 2-cyano-2-methoximinoacetic acid (Ε-isomer), 4.5 g (0.05 mol) of methyl carbazate and 3.6 g (0.05 mol) of isobutyraldehyde in 75 ml of methanol is added dropwise at ^{0 0} C, a solution of 5.5 g (0.05 mol) of cyclohexyl isocyanide and stirred for 24 hours at room temperature. The solvent is distilled off in vacuo, the residue partitioned between 200 ml of ethyl acetate and water, the organic phase washed with 150 ml of 1 M hydrochloric acid, 10% sodium bicarbonate solution and water, dried over sodium sulfate and concentrated in vacuo. This gives 9.0 g (47% of theory) of N "- (2- (cyano-2-methoximino-acetyl) -N" -methoxycarbonylamino-DL-valincyclohexylamide (Ε-isomer) with the melting point of 132-134 ° C.

Example 5

CN O

I! I

Choo-N = C-NH-CH ₉ -C-NH-CH-,

³ Il ³

(Method E)

To a solution of 11.8 g (0.0553 mol) of n- (2-cyano-2-methoximino-acetyl) glycine ethyl ester (Ε-isomer) in 50 ml of methanol at 0 ⁰ C 24.5ml (0.166 mol) of a , 8M solution of methylamine in methanol. The reaction mixture is allowed to come to room temperature and stirred for a further hour at 2O ⁰ C. After cooling to 1O ⁰ C, the crystalline precipitate

filtered off, washed with a little cold ethanol and dried at 40 ⁰ C.

This gives 7.0 g (64% of theory) of N ^a - (2-cyano-2-methoximino-acetyl) -glycinmethylamid (Ε-isomer) with the melting point

140-141 ⁰ C.

Example 6

CN O. ,

CH ₃ ON = C-NH-CH ₂ -C-NH-CH ₂

(Method c)

A solution of 7.0 g (0.0712 mol 5 ml of concentrated hydrochloric acid in 10 ml of tetrahydrofuran and 5.15 g (0.042 mol) of isoamylnitrile (97%) added dropwise at -20 ° C. After stirring for 15 minutes at -2O ⁰ C, a solution of 10.8 g (0.107 MoDTriethylamin'in 15ml dimethylformamide Czugetropft ⁰ and then added a solution of 4.2 g (0.0392 mole) of benzylamine in 3.5 ml of dimethylformamide. The reaction mixture is kept for 65 hours at 0 ⁰ C, 24 hours at 20 ⁰ C and then stirred at -20 in It is extracted with ethyl acetate (2 × 150 ml portions), the extract is washed with 100 ml 1 M citric acid, 10% sodium bicarbonate solution and water, dried over sodium sulphate and concentrated by evaporation in a vacuum.

This gives 6.2 g (64% of theory) of N ° - (2-cyano-2-methoximino-acetyl) glycine benzylamide (Ε-isomer) with the melting point 101-102 ° C.

Preparation of the starting product

CN O

CH ₃ ON = C-NH-CH ₂ -C-NH-NH ₂

In a solution of 30 g (0.155 IVfol) N- (2-cyano-2-methoximino-acetyl) glycine ethyl ester (Ε-isomer) in 150 ml of ethanol is added dropwise at 24-30 ⁰ C 15.5 g (0.31 mol) of hydrazine hydrate and the reaction mixture stirred for 4 hours at room temperature. After cooling to 10 ⁰ C, the crystalline precipitate is filtered off with suction, washed with 200 ml of ether and at room temperature

dried.

This gives 28.1 g (91% of theory) of N ^a - (2-cyano-2-methoximino-acetyl) -glycinhydrazid (Ε-isomer) with the melting point

167-168 ⁰ C.

In an analogous manner and according to the inventive method, the following Ε-isomers of

Compounds of the general formula (I)

RO CN

ν. y

N = CR ²

CO-NR ¹ -C-COX

R ³

receive:

CU- si

Φ ι

in co

U.

η X U O

* Φ CVJ - o (M U) I U) ι ι CM so "Η α " O " α f-l α η Q α [Χ. O U. C Ex. U) X og ~ υ / \ ο > ι O = U I χ J (Sl π η X χ χ χ X T U CJ U U O U O Z X ¥ ι ι ι Z ι ι

 χ

Π V * η X υ X U) I CJ X O ι

χ χ

η CD Γ) η X I X X I X U / " ¹ VU υ A «Ν U

X U

X U

CO

Ex 4 Nos. R

^RJ

R ² R ³

Physical constant

13 -CH-

H -CH-

-OCH ₃

Fp! 67-71 "C

14 -CH-

H -CH ₂ OH

-OCH

FpS 73-74 * C (L-shape)

15 -CH-

-CH-

H H

^C 2 ^H 5 ^C 2 ^H 5

n ²⁰ : 1.5190 D

16 -CH-

-C ₂ H ₅ -C ₂ H ₅

-NH-

Mp: 70-74 "C

17 -CH <

CH-

CH-

H H

-OC ₂ H ₅

FpS 74-76 "C

18 -CH-

H H

-OC ₂ H ₅

n ²⁰ ! 1,5175 D

19 -CH-

H -CH <

CH-

CH-

-OCH

FpS 67-71 "C

α C ^ i ffl

UJ β>. C SZ Oα. se

• ft · Φ u

Ci. ι

"* U

U)

O N Q

I O

CJ

CJ

vo - ι ε

U) O

ct

au

Ix. χ '

CJ

ΙΩ I

approx

α (ζ.

cn η η η χ χ η χ X χ X U U X ο CJ U U O ι U ο O O ι X ι X ι ι Z X Z ι Z I I

Π   χ U) cn X cn χ cn η k / O η χ U υ X X CJ X X Cj I I U CJ Y CJ U U Y CJ X ι Y O U U I cn I I CS

O CJ

CJ

cn

CJ

CJ

U) CJ

CJ

At sp.

No.

R ² R ³

physical

constant

27 -CH <

CH-

CH-H H

-NH-CH ₃ Fp: 102-104 * C

H H

-OC ₂ H ₅

FpS 47-50 ^# C

H H

-NH-CH ₃ FpSl35-140 * C

30 -CH.

H -CH-

-NH-CH ₃ FpSl77-181 * C

31 -CH-

H H

-O

FpSll9-120'C

32 -CH ₂ - <f% H

H is S0 ₂ -CH ₂ - <^ __ 3> -OC ₂ H ₅

Mp: 105-107'C (L-shape)

-C CJ υ ο • o U υ a CO CO LO η • ψ * O η σ " CM ο ul 00 »Η 1-· »Η "- · α C I ι 1 I I ι U. <8 CM. ΙΛ J ^ ts. ^ CM η CO CM U) N te β>. C £ O ί a. m α. α α α α α ti. fa. it. Dc fa.

CC

CM

• Η · φ U03 Z

η χ χ U CJ

CJ

U ι

LO

co

CO Γ)

• w tu ^ jα c

α is * C Λ ο Cu *

"OS

CSJCS

CQ Z

LO O

• -ι O

(Ζ.

cn

O CJ U 9 α ο ο U ο r-4 cn O "Γ I ι Cx. LO Φ ο * ι O CVJ »Η • Η .- .. α α α Cx. Cx. Cx.

CJ

6 ι CO L η ^^ O [Χ, ·· I αα α Cx. <- < Cx.

U O Cx. ι

LO CVJ X X CJ Z U ι X X O Z ι. ι

cn

LO (VJ X X U Z ι Z ι

η χ υ

XO

X U ι

X U I

η η X X χ U α U ι ι 1

η χ χ U U ι ι

If)

8th β PJ J = j ω υ C • Ο a α  ν ψ * α ^ t C α O χ. O α 03 Q >> C J = O.

U U ο α t>. • CNJ U) α ω * t CO N Γ5 "Η * -ι "Η α νθ ·· Γ3 · " N ·· CJ η OJ Q η fNl Q C OJ Q α α C C Lx. (Χ.

"IO

Γ)

CM O CNJ IA

O OY Q.

CNJ OJ η Π IA η Π X X χ X X X X η Z Z ο U OJ U U χ ι ι O ο. O O O υ ι ι ι ι O Z I

η ιη X X U CNJ η ι U Q. I η IA χ X U CM OJ ι U

Γ)

X U

η η η X χ X U U U ι ι ι

U X U

χ υ

χ η χ U χ U ι U I ι

Γ3 X U

CO

O tA

IA

IA

IA

Ex-No. R

Physical constant

-CH-

-OCH

Mp: 40-45 * C

-CH-

-NH-N = (

Fpt204-206 "C

57 -CH

Cl H

-OC ₂ H ₅

n ²³ : 1.5346

-NHCH ₃

No. l65-168 ^# C

-CH-

-CH (CH ₃ > 2

-NHCH-

oil

-CH-

-CH-

-NHCH-

Oil

NJ Et

υ CD Ü CJ :O in U U) O O O O fH C so i-l cn CO m fs. Js. LO co m ^ J I I ·> I U) * 3 * CT * in l-i C N so co U) O " ·· O rj α α WQ α QU It C is.

: O «D

U ^ 3

in X cn U in in π in SC O SC Il X X CVJ I CJ SC CVJ CM CJ CVJ U O U U U I U O I I O O 5C O I CV] I I 2 I K I U I SC 2 I

cn X U

η X U

cn

CJ

η ac ο

(VJ

cn

yQ

LD

cn X U

CVJ SC cn X U X U 111 U Il CJ I SC I O CVJ I X Π CVJ U X OC I U U I I

so

CO

Ex -

No. R

Phys ical constant

" ^C 2 ^H 5 -CH ₂ -CH = CH ₂ H -CH ₂ -C = CH-CH- -CH,

CH.

-CH-

-CH

-CH

H H H H H H H H H H H H H H -CH (CH ₃ J ₂

-CH

-CH (CH ₃ ) ₂

-CH-

-CH-:

-CH ₂ -OH

-NH-CH ₃ Fp: 144 ^° C

-NH-CH ₃ Fp: 133 ^° C

-NH-CH ₃ mp: 148-150 ⁰ C.

-NH-CH ₂ -CO-OC ₂ H ₅ Fp! 123-125 ⁰ C

-NH-CH ₃ Fp! 130 ⁰ C

-NH-CH '

-NH-CH ₃

• Fp! 50 ⁰ C

Fp! 130 ⁰ C

-NH-NH-CO-NH-CH ₃ Fp! 178 ⁰ C

(L-Forra)

-NH-NH-CO-NH-CH

Fp! 135 ⁰ C (DL-form)

-NH-NH-CO-NH-CH ₃ Fp! 219 ⁰ C

Ex ♦ -No. Physical consoles

CH.

-CH-

CH,

CH,

Cl

-CH ₃ HH

_-CH3 H

-C (CH ₃ J ₃

-CH-

-CH

CH,

^C 2 ^H 5

-CH ₂ -CH (CH ₃ ) ₂ '

-CH

-NH ₂ Fp! 219-223 ⁰ C

-NH-CH ₃ mp: 198-200 ⁰ C.

-NH-CH ₃ mp: 118-120 ⁰ C.

-NH-CH ₂ -CO-NH-CH ₃ Fp! 212-214 ⁰ C -OCH ₃ oil

-NH-CH ₃ oil

-NH-CH ₃ Fp! 125-126 ⁰ C

^C 2 ^H 5

Λ υ ιο

• Μ φ

ID C ύί Λ

to ω> · * CJC O Cu ϊέ

QS

QS

• Η · φ UCQ 2

CJ

Il

(NJ

CM

X U ι

 U

U ι

* - * O % O CO O O O in in  q * O 1-1 i-l .-Η 1 I I I r-t CO CO in in ^ ⁴ ON »Η a α a a fa. fa. [Ι. fa.

cn π η η X X ac O U U U 1 ι ι ι K X X 2 2 2 2 ι ι ι ι

in the ο cn , Η ο cn in cn CM "-I .-Ι I I CM I .- < CM ιη CM , -4 in CM cn CM * - * U -V i-l a a a O fa. fa. 2 It. ι CM CM cn X y. cn cn U cn X K cn ι X CJ U CM U I I U X X U 2 2 U ι U I I ι X I X 2 2 1 2 ι I cn X U ι CM O W

cn cn cn cn cn cn cn cn Γ X X X X X X U U U U U U ü U U t I I I I I I I I

CO

co

CO CO

σ "

At sp, no.

^RJ

-CH-

97 3 H H H 98 -CH ₃ H H H 99 -CH ₃ H H H 100 -chō H H H

-CH-

-CH-

H H H

H H H

Physical constant

-NH-CH ₂ -CH ₂

-NH-CH

CH ₃

-NH-CH ₂ -CH ₂ -Cl -NH-CH (CH ₃ ) ₂ -NH-C (CH ₃ ) ₃ -NH-CH ₂ -CH (CH ₃ ) ₂

Mp 92-95 ⁰ C

Fp! 96-98 ⁰ C.

Mp: 91-94 ⁰ C

Mp: 86-88 ⁰ C

Mp: 80-81 ⁰ C

Mp: 100-102 ⁰ C

-NH-CH-CH ₂ -CH ₃ -NH-CH ₂ -CH ₂ -O-CH ₃ -NH-CH ₃ κ 1/2 CuCl ₂

Mp: 111-112 ⁰ C Fp! 102-105 ⁰ C mp: 160-165 ⁰ C

use Examples

In the following examples of use, the following substances are used as comparative compounds:

CH ₇ -NH-CS

² χ

Zn CH ₇ -NH-CS

Il

(C) NC-C-CO-NH-CO-NH-C ₇ Hc-O

Il ²

NO ₃

(us 3.957.0 ^ 7)

Example A

Plasmopara test (vines) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

To test for protective activity, young plants are sprayed with the preparation of the active ingredient until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticoia and then left for 1 day in a humid chamber at 20 to 22 ° C and 100% relative humidity. The plants are then placed 5 days in the greenhouse at 22 ⁰ C and about 80% humidity. The plants are then moistened and placed in a humid chamber for 1 day.

7 days after the inoculation the evaluation takes place.

Clear superiority in efficacy over the prior art is demonstrated in this test, e.g. the compound according to Preparation Example 5.

Example B

Phytophthora test (tomato / curative

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

To test for curative efficacy, young plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants remain for 7 hours at 20 ⁰ C and 100% relative humidity in an incubation cabin. After a short drying time, the plants are sprayed dripping wet with the preparation of active compound.

The plants are placed in an incubation cabin with 100% relative humidity and about 20 ° C.

3 days after the inoculation the evaluation takes place.

A clear superiority in the effectiveness over the prior art show in this test z. B. the compounds according to Preparation Examples: 1 and 5.

Example C

Phytophthora test (tomato) / systemic

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

To test for systemic properties, the preparation of active compound is poured onto unit soil containing young plants ready for experimental use. 3 days after treatment, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans.

The plants are placed in an incubation cabin with 100% relative humidity and about 2O ⁰ C.

3 days after the inoculation the evaluation takes place.

Clear superiority in efficacy over the prior art is demonstrated in this test, e.g. the compound according to Preparation Example 5.

Claims (1)

Invention claim: 1. Pesticidal composition, characterized by a content of at least one Ε-isomer of l \ T- (2-cyano-2-alkoximino-acetyl) -amino acid derivative and peptide of the general formula (I) RO CN - R ²
NR ^Χ -C-COX ^ "> R ³ ""'