JPS61286363A - N alpha-(2-cyano-2-alkoxyiminoacetyl)-amino acid derivative and e-isomer of peptide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel N-(2-cyano-2-alkoxyiminoacetyl)-amino acid derivatives and peptides.
- isomerism, some methods of its preparation and its agents for com-bating
ests), especially fungicides (fun-gicides)
e).

Certain compounds, such as N~trichloromethylthio-
It is a known fact that tetrahydrophthalimide, zinc ethylene-1゜2-bis-dithiocarbamate, and N-ethylaminocarbonyl-2-cyano-2-methoxyiminoacetamide have good bactericidal and fungicidal effects. (
For example, U.S. Patent Specification No. 2.553.770, U.S. Patent Specification No. 2.457.674 and DE-O8
(cf. West German Publication No. 2.312.956) 0 However, the action of these compounds is not always completely satisfactory, especially when used in small amounts and at low concentrations. .

General formula (I) in which R represents alkyl, alkenyl, alkynyl, cyanoalkyl, azolylalkyl or optionally substituted phenylalkyl, or represents optionally substituted cycloalkyl, R1 represents hydrogen, alkyl, optionally substituted phenyl or optionally substituted benzyl, or represents alkoxycarbonylamino, R2 represents hydrogen or alkyl, R1 represents hydrogen, alkyl, alkoxycarbonylalkyl , represents hydroxycarbonylalkyl, aminocarbonylalkyl, azolylalkyl, cyanoalkyl, hydroxyalkyl, alkenyl, alkynyl or optionally substituted cycloalkyl, or
represents optionally substituted phenyl or phenylalkyl, or the group R'-8On-Z- in which R4 represents hydrogen, alkyl or optionally substituted phenylalkyl, and 11 represents a number 011 or 2
, and Z represents a straight or branched alkylene chain), or 1Yiho and Ra, together with the nitrogen atom and carbon atom to which they are bonded, are 5- or 6-membered different atoms. represents a node ring, or R1 and Ha together with the carbon atom to which they are bonded,
cycloalkylidene, X is a group 10RI or NR11R" [In these groups, R1 represents hydrogen, alkyl or alkenyl,
or represents alkynyl, R11 represents hydrogen or alkyl; represents dialkylaminocarbonylalkyl, cyanoalkyl, optionally substituted phenylalkyl, optionally substituted phenyl or optionally substituted cycloalkyl, or represents an acylamino group; -N=C)I-R■ (where HfV represents alkyl or optionally substituted phenyl), or RI and R1 are substituted together with the nitrogen atom to which they are bonded. E- of novel N-(2-cyano-2-alkoxyiminoacetyl)-amino acid derivatives and peptides of Isomers and their physiologically acceptable, possibly substituted ammonium, alkali metal and alkaline earth metal salts and metal salt complexes have been found.

If R2 and Ra have different meanings, the compound of formula (I) has an asymmetric carbon atom and can therefore also exist in the form of optical isomers (D- and L-configurations), the image form being Obtained in various quantitative ratios. is most often obtained as a racemate.

Furthermore, in the formula (f), R represents alkyl, alkenyl, alkynyl, cyanoalkyl, azolylalkyl, or optionally substituted phenylalkyl, or optionally substituted cyclo alkyl, R1 represents hydrogen, alkyl, optionally substituted phenyl or optionally substituted benzyl, or represents alkoxycarbonylamino, R2 represents hydrogen or alkyl, R3 represents hydrogen , alkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, azolylalkyl, cyanoalkyl, hydroxyalkyl, alkenyl, alkynyl or optionally substituted cycloalkyl or can be substituted Phenyl also represents phenylalkyl or the group R'-8On-Z- (in which R4 represents hydrogen, alkyl or optionally substituted phenylalkyl, n represents the number 0.1 or 2); , 2 represents a linear or branched alkylene chain), or R1 and R3, together with the ♀ elementary atom and carbon atom to which they are bonded, represent a 5- or 6-membered heteroartic ring. or R2 and R1 together with the carbon atoms to which they are bonded,
represents cycloalkylidene, X is a group -OR- or N
RIIR1 ■ [In these groups, Rf represents hydrogen, alkyl or alkenyl,
or represents alkynyl, RI represents hydrogen or alkyl, Rj is hydrogen, alkyl, alkenyl, alkynyl, halogenoalkyl, alkoxyalkyl, dialkylaminoalkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, alkylaminocarbonylalkyl, dialkylaminocarbonylalkyl, cyanoalkyl, optionally substituted phenylalkyl, optionally substituted phenyl or optionally substituted cycloalkyl, or represents an acylamino group; -N=CH-R■ (where HIV represents alkyl or optionally substituted phenyl), or R11,! N a (2-cyano- (2-alkoxyiminoacetyl)-E-isomers of amino acid derivatives and peptides and their physiologically acceptable, optionally substituted ammonium, alkali metal and alkaline earth metal salts and metal salt complexes ( a) Formula (II) ■ HNR dish-c-CO-X(n) woS In the formula, R1, R'', R8 and X are the amino acid derivatives having the above meanings. optionally in the presence of a catalyst, optionally in the presence of an acid binder, and optionally in the presence of a diluent, or still (b) The carboxyl-activated derivative of the E-isomer of a carboxylic acid of formula (N) in which R has the meaning given above is first prepared by formula (IV) H2NR' (IV) where R1 has the meaning given above. , then an amine having the formula (v) R1-Co-R" (V), in which R2 and R1 have the meanings of -F, and finally a carbonyl rust conductor of the formula (Vl) CN-LRI (
Vl) in which RI represents alkyl, alkenyl, alkynyl, cycloalkyl or alkoxycarbonylargyl, or represents cycloalkyl, phenylmodyzyl or phenylalkyl, which may still be substituted, with isonitrile and optionally a diluent. It can also be reacted in the presence of the carboxyl-activated derivative of the E-isomer of the amino acid of the formula (Ia), where R1 R, R'' and R1 have the meanings given above, in the presence of the formula (Vll) H- NRIIRI wherein R and R1 have the above-mentioned meanings; react with the amine of (d) Formula (Ib) 41 The E-isomer of the amino acid derivative of the formula (V Rib H-NRI'
It has also been found that R1(vn) can be obtained by a method in which R and R11 in the formula are reacted with the amine (2) having the above meanings in the presence of an appropriate diluent.

The thus obtained compounds of formula (I) in which X represents a hydroxyl group include hydroxides, carbonates, and hydrogen carbonates of amines and alkali or alkaline earth metals;
It can also form salts with ammonium hydroxide, and can also form metal salt complexes with heavy metal salts.

Finally, new N"-(2-cyano-2-alkoxyiminoacetyl)-amino acid derivatives and E-isomers of the peptides of formula (I) and their optionally substituted ammonium, alkali metal and alkaline earth It has now been found that ferric salts and metal salt complexes have particularly strong fungicidal and fungicidal properties.Surprisingly, the compounds according to the invention have a structure known from the prior art. Compounds that are closely related in terms of physical or action,
For example, N-)lichloromethylthiotetrahydrophthalimide, zinc ethylene-1,2-bis-dithiocarbamate and N-ethylaminocarbonyl-2-cyano-
It shows stronger action than 2-methoxyiminoacetamide. The materials described in this invention thus represent an enrichment of the art.

Formula (I) provides a general definition of the E-isomer of the N-(2-cyano-2-alkoxyiminoacetyl)-amino acid derivatives and peptides according to the invention.

Preferred compounds of formula (I) are those in which R is straight-chain or branched alkyl having 1 to 8 carbon atoms, or alkenyl or alkynyl having in each case 2 to 4 carbon atoms; , cyanoalkyl having 1 to 4 carbon atoms in the alkyl moiety, 1,2,4-triazol-1-yl-alkyl or pyrazole-1, in each case having 1 to 6 carbon atoms in the alkyl moiety -yl-alkyl; or phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety and which may be -, di- or tri-substituted in the phenyl moiety by the same or different substituents; Preferred substituents include halogen, cyanogen, nitro, hydroxyl, alkyl, alkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl having in each case 1 to 4 carbon atoms, and the same or different substituents. phenyl, which may be substituted with -, di- or tri-substituted by halogen substituents; or cyfuroalkyl, which may be trisubstituted, in which preferred substituents are halogen or alkyl having 1 to 4 carbon atoms, and R1 is hydrogen or 1 to 4 carbon atoms; represents a straight-chain branched alkyl having atoms or phenyl or benzyl which may be -, di- or trisubstituted in each case by the same or different substituents; and the preferred possible substituents are the phenyl substituents already mentioned for R, or alkoxycarbonylamino having 1 to 4 carbon atoms in the alkyl part, and R1 is hydrogen or 1 to 4 carbon atoms; represents a straight-chain or branched alkyl having 4 carbon atoms; R1 represents hydrogen or a straight-chain or branched alkyl having 1 to 6 carbon atoms; Straight-chain or branched hydroxyalkyl having 1 to 4 carbon atoms; both K in the alkyl and alkoxy moieties each include alkoxycarbonylalkyl having 1 to 4 carbon atoms; hydroxycarbonylalkyl and aminocarbonylalkyl having from 1 to 6 carbon atoms in the alkyl moiety; -triazol-4-ylalkyl, imidazol-4-ylalkyl and pyrazol-1-ylalkyl, representing cyanoalkyl having 1 to 4 carbon atoms in the alkyl moiety, or in each case 2 to 4 represents alkenyl or alkynyl having 3 to 7 carbon atoms, or cycloalkyl having 3 to 7 carbon atoms, which may be mono-, di- or trisubstituted by the same or different substituents; The preferred substituted group 46 represents one in which one of the groups 7 is an alkyl having 1 to 4 carbon atoms, or furthermore, the alkyl moiety has 1 to 4 carbon atoms. and phenyl or phenylalkyl, which may be -, di-, or tri-substituted with identical but L< on the phenyl moiety, in each case preferred possible substituents. represents a substituent of phenyl as already mentioned for R, or the group R'-8On-Z- (in which R4 represents hydrogen or is still a straight chain with 1 to 4 carbon atoms) or branched alkyl, or has 1 to 4 carbon atoms in the alkyl moiety and is substituted -, di- or tri-substituted in the phenyl moiety by the same or different substituents. represents a phenylalkyl in which the possible substituents are the phenyl substituents already listed for R, n represents the number 011 or 2, 2 is a straight chain having 1 to 4 carbon atoms, or R1 and R8, together with the nine atoms and carbon atoms to which they are bonded, represent a 5- or 6-membered heterocyclic ring, or R' and Rs together with the carbon atoms to which they are bonded,
represents a cycloalkylidene having 3 to 6 carbon atoms; or alkenyl or alkynyl in each case having 2 to 4 carbon atoms;
or represents a branched alkyl; R1 represents hydrogen or a straight-chain or branched alkyl having 1 to 4 carbon atoms; or in each case having 2 to 4 carbon atoms; alkenyl or alkynyl, or halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, or alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy and alkyl moieties; or dialkylaminoalkyl having up to 4 carbon atoms in each alkyl moiety; hydroxycarbonylalkyl having 1 to 4 carbon atoms in each alkyl moiety, or aminocarbonylalkyl, alkylaminocarbonylalkyl or dialkylaminocarbonylalkyl having 1 to 4 carbon atoms in each alkyl moiety in each case or cyanoalkyl having 1 to 4 carbon atoms in the alkyl moiety, having 1 to 4 carbon atoms in the alkyl moiety and with the same or different substituents on the phenyl moiety; phenyl, which may be substituted, S phenylalkyl, or -, di- or trisubstituted by the same or different substituents, in which case the possible substituents are already present for R; represents a substituent of the listed phenyl or has 3 to 7 carbon atoms,
and cycloalkyl, which may be substituted by the same, if different, substituents, the preferred possible substituents being halogen and alkyl having 1 to 4 carbon atoms; or in each case the alkyl or alkoxy moiety represents alkylcarbonylamino or haalkoxyluponylamino having 1 to 4 carbon atoms;
: 1, and in the case of Istl, 1 is also added to each alkyl moiety.
to aminocarbonylamino having 4 carbon atoms,
Alkylaminocarbonylamino, dialkylaminocarbonylamino, only formylamino, or the group -N=CH-Rff (wherein HIV is a straight-chain, or branched, group having 1 to 4 carbon atoms) represents an alkyl or phenyl which may be -, di- or tri-substituted with the same, if different, substituents, the possible substituents being the substituents of phenyl already listed for R); or R11 and R1 may contain oxygen or nitrogen as another heteroatom together with the nitrogen atom to which they are bonded, such as cyano, halogen, alkyl having 1 to 4 carbon atoms. , hydroxycarbonyl, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, in each case substituted by aminocarbomyl, alkylaminocarbonyl and dialkylaminocarbonyl having 1 to 4 carbon atoms in each alkyl moiety represents a 5- or 6-membered heterocyclic ring which may be

Particularly preferred compounds of formula (I) are those in which R is straight-chain or branched alkyl having 1 to 4 carbon atoms, the alkyl moiety, haplobargyl, cyanomethyl, cyanoethyl, in each case the alkyl moiety is 1,2.4- having 1 to 4 carbon atoms
represents triazol-1-yl-alkyl or pyrazol-1-yl-alkyl or has 1 to 2 carbon atoms in the alkyl moiety and is substituted with - or di by the same or different substituents in the phenyl moiety; Phenylalkyl, which may be substituted,
In particular, substituents that can be mentioned are 1. be mono- or di-substituted with the same or different substituents selected from the group consisting of fluorine, chlorine, cyano, nitro, hydroxyl, methyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, and fluorine and chlorine; cyclopropyl, which may also be substituted by the same or different substituents selected from the group consisting of fluorine, chlorine and methyl in each case; , cyclobutyl, cyclopentyl, cyclobutyl or hacyclohexyl, R1 represents hydrogen, methyl or ethyl, or in each case phenyl, which may be - or disubstituted by the same or different substituents; or benzyl, in which the possible substituents are, in particular, the phenyl substituents already mentioned for R, or additionally methoxycarbonylamino or ethoxycarbonylamino, in which the R value is hydrogen, methyl or ethyl, R1 is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, hydroxymethyl or 1-hydroxyethyl, methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonyl ethyl, hydroxycarbonylmethyl, hydroxycarbonylethyl, aminocarbonylmethyl,
aminocarbonylethyl, 1,2゜4-)lyazol-1-yl-alkyl, 1゜2,4-)lyazol-4-yl, in each case having 1 to 4 carbon atoms in each alkyl moiety; -Alkyl, imidazol-4-yl-
represents alkyl and pyrazol-1-ylalkyl, cyanomethyl, cyanoethyl or represents allyl or represents propargyl or in each case the same selected from the group consisting of fluorine, chlorine and methyl. or cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, which may be substituted or disubstituted by different substituents, or which further has 1 to 2 carbon atoms in the alkyl moiety and the phenyl moiety phenylalkyl, which may be - or disubstituted with the same or different substituents, or phenyl, which may be - or disubstituted with the same or different substituents, in which the possible substituents represents a substituent of phenyl as already mentioned for R, or in addition represents a group R'-8On-Z-, in which R' represents hydrogen, methyl or ethyl, having 1 to 2 carbon atoms, with the same, ' or different substituents on the phenyl moiety -
or phenylalkyl, which may be disubstituted, in which the possible substituents are, in particular, the phenyl substituents already mentioned for R, n represents the number 011 or 2, 2 is 1 represents a linear or branched alkylene chain having 2 to 2 carbon atoms, or R1 and R3, together with all the elementary atoms and carbon atoms to which they are bonded, are 5- to 6-membered Represents a heterocyclic ring, or R1 and R1 together with the carbon atom to which they are bonded represent cyclopropylidene, and X is a group -0RI or -NRIIRl [In these groups, RI is hydrogen, methyl, represents ethyl, allyl or propargyl, R11 represents hydrogen, methyl or ethyl, I- represents hydrogen, methoxyethyl, n-propyl, isopropyl, n-
Butyl, isobutyl, 8ee, -butyl, tert, -
butyl, allyl or propargyl, 1 to 2 carbon atoms and 1 to 3 same or different).
halogenoalkyl with halogen atoms, such as fluorine and chlorine atoms; alkoxyalkyl with 1 or 2 carbon atoms in each alkoxy and alkyl moiety; dialkylaminoalkyl with 1 or 2 carbon atoms in each alkyl moiety; or,
alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, in each case having 1 or 2 carbon atoms in each alkyl moiety;
represents alkylaminocarbonylalkyl or dialkylaminocarbonylalkyl, or cyanoalkyl, or furthermore, the alkyl moiety has 1 or 2
represents phenylalkyl having 5 carbon atoms and which may be - or disubstituted in the phenyl moiety by the same or different substituents or - or disubstituted by the same or different substituents; represents a phenyl in which the possible substituents are in each case the substituents of phenyl already listed for R, or in each case from the group consisting of fluorine, chlorine and methyl. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexylmody, cycloheptyl, which may be substituted or disubstituted by the same or different selected substituents, or in each case an alkyl or alkoxy moiety; represents carbonylamino or alkoxycarbonylamino having 1 or 2 carbon atoms, or aminocarbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, dimethylaminocarbonylamino, diethylaminocarbonylamino, methylethyl represents aminocarbonylamino or formylamino, or also the group -N=CH-R (where RIV represents methyl or ethyl or can be - or disubstituted by the same or different substituents) represents a phenyl whose possible substituents are the phenyl substituents already listed as preferred for R, or RIl and RI together with their bonding base atoms , may contain oxygen or 9 atoms as other heteroatoms, cyanide, fluorine, chlorine, bromine, iodine, methyl, ethyl, l-propyl, hydroxycarbonyl,
methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl and methylethylaminocarbonyl, and It is something.

N-(2-cyano-2-alkoxyiminoacetyl)-amino acids and peptide derivatives of the formula (f) in which X represents a hydroxyl group and R1R1, R1 and R1 have the meanings already given for these substituents. Alkali metal, alkaline earth metal and sometimes substituted ammonium salts of the E-isomer are also preferred compounds according to the invention.

Alkali metal and alkaline earth metal hydroxides, carbonates or bicarbonates or amines and ammonium hydroxide can be used for the salt formation. These include, preferably, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, calcium hydroxide and barium hydroxide; ammonia; primary amines such as methylamine and inpropylamine; Secondary amines such as dimethylamine and dicyclohexylamine; tertiary amines such as triethylamine, pyridine and N,N-dimethylbenzylamine and ammonium hydroxides such as benzyltrimethylammonium hydroxide.

■～■of the main family, and ■Seyo and ■and ■～Vl
salts of metals of the subgroup and substituted N-(2-cyanoalcogysiimino- (acetyl)-amino acids and addition products with peptide derivatives are also preferred compounds according to the invention.

Here, copper, zinc, manganese, magnesium, tin,
Particularly preferred are iron and nickel salts. Possible anions for these salts are those derived from acids that result in physiologically acceptable addition products. In this connection, particularly preferred acids of this type are hydrohalic acids, such as hydrochloric acid and hydrobromic acid, as well as phosphoric acid, nitric acid and sulfuric acid.

For example, glycine ethyl ester and 2-cyano-2 chloride
-methoxyiminoacetyl is used as a starting material, the process of process (a) according to the present invention can be represented by the following formula.

For example, if 2-cyano-2-methoxyiminoacetic acid, benzylamine, isobutyraldehyde and ethyl isocyanoacetate are used as starting materials, the process of process (b) according to the invention can be represented by the following formula.

CNO For example, if N-(2-cyano-2-methoxyimino'acetyl)-glycine ethyl ester and methylamine are used as starting materials, the process (c) according to the invention
The process can be expressed by the following equation.

Formula (II) provides a general definition of the amino acid conductor used as starting material for carrying out the process (a) according to the invention. In this formula, R1, R'', R1 and X have the meanings already given for these substances in connection with the description of the substances of formula (I) according to the invention.

The amino acid derivatives of formula (I) are in some cases known substances (for example as described by Houben-Weyl).
yl), Methods of Organic Chemistry
Chemie, volume XV, parts 1 and 2, published by Georg Thime.
emeVerlag, Stuttgart) 197
4: and heppar (R, C, 5heppar
d), ASpecialist Peri
Amino acids, peptides and proteins, Royal Society of Chemistry (Royal 5ociet)
y of Chemistry, Burli-ngt
on House, London) l 978, and Greenstein (I,P.
n) and Winitz),
Chemistry of Amino Acids
o Ac1d), Wiley Zands (I, Wiley
5ons Inc., New York.

London) 1961: as well as Schroeder (
g.

5chr8der) and Lubkke (K, Lubk
e), The Peptides Volume 1, -f-) J Demikkubus vs. Academic P
ress, New York.

London 1965) or by the methods described herein.

Formula (I) also comprises the process (a) according to the present invention,
and likewise gives a general definition of the carboxyl-activated derivatives of the carboxylic acid E-isomers used as starting materials for carrying out the preparation (I)). In this formula, R
-1: has the following meaning.

The carboxy-activated conductor of the carboxylic acid E-isomer of formula (I) is the E-isomer of 2-cyano-2-methoxyiminoacetic acid (Belasco, I, J. and Baude, F. J.). ), Pesticide Science (Pestle, Sci, ), 12.27.198
1) are not known substances. The carboxyl-activated derivatives of the carboxylic acids of formula (I) can be prepared according to well-known methods and have the formula (Vl) CNRO-N=C-C-ORDing (picture), where R has the above meaning; R? represents an alkyl, preferably methyl or ethyl, first with an alkali metal hydroxide, such as sodium hydroxide, then with an acid, such as hydrochloric acid or sulfuric acid, or with an acidic ion exchanger, a diluent, For example, in the presence of water, alcohols, ethers, or mixtures of alcohols or ethers with water,
It is obtained by a reaction step at a temperature of 0 to 80°C, preferably 20 to 40°C.

Hydrolysis is preferably carried out using potassium hydroxide in water/
The reaction mixture is evaporated in vacuo at 20° C. and the potassium salt formed is reacted with, for example, oxalyl chloride to give the corresponding acid chloride (see also Preparation Examples 66). ).

Carboxylic acid esters of formula (vi) are in some cases known substances (Velasco and Baudet, Pestic, Set, 12.27.198
1) or by the methods described in the above-mentioned documents, the formula (IX) N MO-N=C-C-OR? (■) I R in the formula? has the abovementioned meaning, and M represents hydrogen, sodium or potassium, preferably sodium. and W is a halogen or a sulfonyldioxy or sulfonyloxy group, such as preferably chlorine, bromine, iodine, -0SO,0CHs, -08O,QC2H,, -0S
0 to 120° C. with a compound of O2CHs-7, 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. It is obtained through a reaction process at a temperature of .

The E-isomer of the carboxylic acid ester of formula (■) is a known substance (for example, Kinast) (G, Kinast) Liebigs Ann, Chem.
, 1981.1561: :ry Schiller (M, Co
nrad) and Schulze x (A, 5chulze
), Annual Report of the German Chemical Society (Ber.

dtsch, chem, Ges, ), 42.735
．． 1909) and can be obtained by the method described herein.

Formula (The rumored compound is a well-known alkylating agent.

Possible carboxylic acid carboxyl-activated derivatives of formula (I) include all carboxyl-activated derivatives, such as acid halides such as acid chlorides, acid azides, and symmetrical and mixed anhydrides, such as mixed 0-alkyl carbonic anhydrides. , as well as active esters such as p-nitrophenyl ester or N-hydroxysuccinimide ester, as well as active forms of carboxylic acids prepared in the presence of condensing agents, such as dicyclohexylcarbodiimide or carbonyldiimidazole.

Acid chlorides corresponding to carboxylic acids of formula (I) are preferably used. These can be produced by reacting a carboxylic acid of formula <1) or a salt thereof with a halogenating agent such as phosphorus pentachloride, thionyl chloride or oxalyl chloride in a known manner. The use of oxalyl chloride with the sodium or potassium salt of the carboxylic acid of formula (sub) is preferred because isomerization is minimized under these conditions.

Acylation with carboxyl activated derivatives can be carried out in aqueous or non-aqueous media. Suitable media here include ketones, such as acetone; esters, such as ethyl acetate; amides, such as dimethylformamide; nitriles, such as acetonitrile; chlorohydrocarbons, such as methylene chloride; hydrocarbons, such as toluene; or esters, such as tetrahydrofuran, or mixtures thereof.

Acylation with acid chlorides can be carried out in the presence of acid binders, such as preferably tertiary amines such as triethylamine or pyridine, or inorganic bases such as sodium carbonate or calcium carbonate.

Formula (vl) gives a general definition of the isonitriles used as starting materials for carrying out the process ()1) according to the invention. In this formula, R5 is preferably 1 to 4
represents a straight-chain or branched alkyl having 2 to 4 carbon atoms r-, or in each case represents an alkenyl or alkynyl having 2 to 4 carbon atoms r-, or in the alkyl moiety represents sia7alkyl having 1 to 4 carbon atoms, or represents alkoxycarbonylalkyl having 1 to 4 carbon atoms r in both the alkoxy and alkyl moieties, or further represents 3 to 7 cycloalkyls having 1 to 4 carbon atoms r and which may be -, di- or El-substituted by the same or different substituents, which may be mentioned as preferred substituents are halogen and 1 to 4 carbon atoms represents an alkyl having a carbon atom, or has 175 to 4 carbon atoms r in the alkyl moiety, and is substituted with -, - or trisubstituted in the phenyl moiety by the same or different substituents phenylalkyl, or phenyl, which is mono-, di- or tri-substituted by the same or different substituents, the preferred possible substituents being in each case already as preferred for R. Represents a substituent of the listed phenylalkyl.

Isonitriles of formula (Vf) are in some cases known substances (e.g. Isonitrile Chemistry),
Academic Press
ss, N e+u Y ork), 1971), or by analogy, the corresponding formylated primary amines are combined with, for example, phosgene or phosphorus oxychloride, and a tertiary amine, such as pyridine or It can be produced by reacting in the presence of triethylamine while separating water.

Formula (IV) or (V) gives a general definition of the amines and carbonyl derivatives which are also used as starting materials for carrying out the process (b) according to the invention. In this formula, Rl or R2 and R3 have the meanings given in 7h.

Amines of formula (IV) and carbonyl derivatives of formula (V) are well-known substances in organic chemistry.

Formula (Ia) provides a general definition of the amino acid derivatives which are used as starting materials for carrying out the process (c) according to the invention and which are also part of the invention.

In this formula, R, R2 and R3 preferably have the meanings already given for these substances in connection with the description of the substances of formula (I) according to the invention.

Possible acylating agents corresponding to the amino acid derivatives of formula (I a) are all carboxyl-activated derivatives already mentioned in connection with the acylating agents corresponding to the carboxylic acid derivatives of formula (II), preferably and, 0 - an activated derivative prepared in the presence of an alkyl carbonic anhydride and a cyclohexyl grouponimide.

The amino acid derivative of formula (Ia) is a compound disclosed by the present invention and can be produced by the production method (a) described in the present invention.

Formula (■) also provides a general definition of the amine used as starting material for carrying out the process (c) according to the invention. In this formula, R11 and 1111
has the above meaning.

Amines of formula (■) are well-known compounds in organic chemistry.

Formula (Ib) provides a general definition of the amino acid derivatives used as starting materials for carrying out the process (d) according to the invention. In this formula, 'R, R2 and R3 are preferably in the context of the description of the substances of formula (I) according to the invention;
These substitutions have the meanings already given. R6 preferably represents methyl or ethyl.

Amino acid derivatives of formula (Ia) are compounds disclosed by the present invention.

Possible diluents for the preparation m(a) according to the invention are water and inert organic solvents. These include ketones, such as acetone or methyl ethyl ketone; estenos, such as ethyl acetate or methyl acetate; amides, such as dimethylformamide; nitriles, such as acetonitrile; chlorohydrocarbons, such as methylene chloride or carbon tetrachloride; , such as toluene; or ethers, such as tetrahydro7rane; or mixtures thereof.

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

The production method (a) according to the invention is suitably carried out in the presence of a catalyst. Examples that may be mentioned are 4-tumethylaminopyridine, 1-
Hydroxybenzotriazole or dimethylformamide.

When carrying out process (a), the temperature can be varied within a considerable range. This manufacturing method is generally -60 to +120
It is carried out at a temperature of -20°C to +4°C, preferably -20°C to +4°C.

Equimolar amounts are preferably used when carrying out the production method (a) according to the present invention.

The amino acid derivatives of formula (I1) are used here both as pure optically isomers (form D or I4) and as racemates.

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

When carrying out process (b) according to the invention, the temperature can be varied within a considerable range. The process is carried out at a temperature of -20 to +40°C, preferably 0 to 20°C.

When carrying out the process (b) according to the invention, preferably equimolar amounts are used.

Possible diluents, catalysts and acid binders for process (c) according to the invention correspond to those for process (a).

When carrying out process (c) according to the invention, the temperature can be varied within a considerable range. This process is carried out at -60 to +120°C, preferably -60 to +40°C.

When carrying out the process (c) according to the invention, preferably equimolar amounts are used.

Possible diluents for process (d) according to the invention are preferably alcohols, such as methanol, ethanol or impropatol.

When carrying out the process (cl) according to the invention, the temperatures can be varied within a considerable range. This manufacturing method is generally -2
It is carried out at a temperature of 0 to +60°C, preferably 0 to 20°C.

When carrying out the production method (d) according to the present invention, the formula (lb)
Preference is given to using 1 to 10 mol of amine of formula (■) per mole of compound.

Metal salt complexes of compounds of general formula (I) are easily obtained by conventional methods, for example by dissolving the metal salt in an alcohol, such as ethanol, and adding a solution of the compound of general formula (I). This metal salt complex can be isolated by known techniques, for example by filtration, and optionally purified by recrystallization.

76 - The active compounds according to the invention exhibit a strong microbicidal action,
It can be put to practical use in controlling undesirable microorganisms. The active compounds are suitable for use as pest control agents.

In the field of plant protection, fungicides and fungicides are used, for example, in the field of plant protection.
eLes), Oomycetes M, Chytridiowycekes, Zygomycetes@
(Z yI?omycetes), Asco
mycetes), Basidiomycetes
etes) and Deuteromu 1i (D euteromu
eetes).

Fungal and fungal diseases included in the above genus names (fungal d
Some of the disease pathogens are included by way of example and not by way of limitation.

7 Pythium+n species, such as Pythium ultium
; P hytophthora species,
For example, Phytophthora infestans (Phytophthora infestans)
phthorainfestans); Bushudoperonospora (P 5eudoperono
spora) species, such as Bushudovero/Spora 7
Pseudoperonospora hu+
nul i ) or Bushudo r (Pseudoperonospora cub
ense)
a) Species - for example Mopala viticola (r' 1
asIIIol+ara viticola); Peronospora species, such as r'eronospora pisi
) or P, brassicae:
Powdery mildew (Erisipl+e) species, such as Erysipl+egrah+1
nis); S7 aerotheca (S pl+aeroLheca) species,
For example, S 7 Aeroteca 7 Riginea (S pbaer
oLbeca fuliginea); Podosphaera species, such as Podosp.
l+aera 1eucotricl+a); V enturia species, r also known as V enturia inaecaris (V enturia 1
naequal is)”.

Pyrenophora species, such as Pyrenophora teres
a Leres) or P.

Graminea (P, graω1nea) (conidial type: Drechslera, synonym: ITe1minthosporiu+
o)); Cochliobolus
species, such as Cochliobolus sativus (Cochli
Uromyces species, such as Uromyces apendiculatus ([1romyces
appendjculatus; Puccinia species, such as Brassinia recond
it, a): Namagsacropokin (T 1lleLia)
) species, such as Cirretia caries (T 1llet
ia caries)'.

LJstilago species, such as Ustilago nuda or rJstilago ave
nae); Pellicularia
a) Species, such as Berricularia sasakii (r'el
licularia 5asaki): licularia (
P yricularia) species, such as r' yricularia oryz
ae); 7 thalium (F'usariu+o) species, such as 7 thalium φ curmorum (F”usarium
cu1moru+a): Botrytis (BotryLi
s) species, such as Botrytis cinerea (r3oLry
tis cinerea); Septoria (S epl
oria) species, such as Septoria φ7 dorum (S e
L eptosphaeria species, such as L eptosphaeria 7 dorum (r, eptosphae
ria nodorum); Cercospora species, such as Cercospora canescens (Cercospora c
anence)'.

Alternaria species, such as A 1ternaria
a brassicae); P 5 eudocerc
opore11a) species, such as Pseudocercosborella herpetotrichoides
cosporella herptotrichoi
des).

The good tolerance of plants to the concentrations of active compounds required for plant disease control makes it possible to treat the above-ground parts of plants, asexually propagated plants and seeds, as well as the soil.

As pest control agents, the active compounds according to the invention can be used with particularly good results for the control of fungal species, such as Buchsmopara viticola on grapes, and Phytophthora infestans, such as phytophthora infestans, such as Toma F. It should be particularly emphasized that the active compounds according to the invention not only exhibit a protective activity, but also have a therapeutic effect in certain cases, i.e. when used after being contaminated with fungal spores. be. It should also be pointed out that the substance in question has a partially intrarhizomatic action. It is therefore possible to protect plants from attack by fungi and fungi by supplying the active compounds to the soil-L part of plants via the soil and roots or via seeds.

The active compounds can be prepared in conventional formulations, e.g. solutions, emulsions,
Suspension agents, powders, foams, pastes, granules, aerosols,
In natural and synthetic materials impregnated with active compounds, microcapsules in polymeric substances and in coated compositions for seeds, and also in formulations for use with combustion devices, such as fumigation cartridges, fumigation cans, fumigation coils. etc., as well as T.T.
i, V can be converted to cold mist 1 and warm mist mixing machining.

These formulations are prepared in a known manner, for example by combining the active compounds with extenders, i.e. liquid solvents, pressurized liquefied gases and/or solid carriers, optionally with surfactants, i.e. emulsifiers and/or dispersants and/or initiators. Obtained by mixing with a foaming agent. If water is used as an extender, it is also possible, for example, to use organic solvents as auxiliary solvents.

Principal suitable liquid solvents include: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes; chlorine-substituted aromatic or chlorine-substituted aliphatic hydrocarbons such as chlorobenzenes, polytetraethylenes or methylene chloride; cyclohexane or paraffins. aliphatic hydrocarbons such as mineral oil fractions; alcohols such as butanol or glycols and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; highly polar solvents such as dimethylformamide and dimethyl sulfoxide; There's water.

By liquefied gas extender or carrier is meant a liquid that is a gas at normal temperature and pressure, such as aerosol propellants such as halogen-substituted hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers include: kaolin,
There are mills of natural minerals such as clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and mills of synthetic minerals such as highly dispersed silicic acid, alumina and silicates.

Suitable solid carriers for the granules include: crushed and fractionated natural rocks such as, for example, calcite, marble, pumice, ceviolite and dolomite; and synthetic granules of inorganic and organic powders; and organic materials. Examples include sawdust, coconut husk, corncob and tobacco stalk granules.

Suitable emulsifiers and/or foaming agents include: for example polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonic acids. There are nonionic and anionic emulsifiers such as salts and albumin hydrolysis products.

Suitable dispersants include, for example, lignin-benzosulfate waste liquor and methylcellulose.

Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in powdered, granular or latex form, such as gum arabic, polyvinyl alcohol, vinyl acetate, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids are also used in the formulations. It is possible. Other possible additives are mineral and vegetable oils.

Colorants such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes and metal-7 talocyanine dyes may also be used as trace nutrients such as iron, manganese, boron, copper, copper, etc. It is also possible to use salts of molybdenum and zinc.

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

The active compounds according to the invention can be used in formulations or in the various forms of use in combination with other known active compounds, such as fungicides, bactericides, etc.
insecticide
, acaricides, nematicides, herbicides, avian deterrents, growth factors, plant nutrients and soil structure improvers.

The active compounds can be used as such, in their formulations or in use forms prepared by further dilution of the formulations, such as formulated solutions, emulsions, suspensions, powders, pastes and granules. These are conventional methods such as liquid dispersion, dipping, spraying, atomization, misting, evaporation, pouring, slurry formation, brushing, dusting, granulating, dry coating,
Use as moist coating, wet coating, slurry coating or crust formation.

When treating plant parts, the active compound concentration in the use form can be varied within a considerable range. Generally 1
to (I, (I001 weight % 1 preferably C), 5 to (I, (I01 weight %).

When treating seeds, use 0.0 () per 1 kg of seeds.
Amounts of active compound from 1 to 5() g, preferably from 0.01 to 10 g, are generally required.

For the treatment of soil, 0.00001 to 0.1% by weight, preferably 0.0n (I1 to 0.02
A concentration of active compound of 10% is required.

Si! unrealistic example Example 1 (gJ1 Law a) Glycine ethyl ester hydrochloric acid t360.5g (O.

427 mol) was suspended in 4.5 (I+1) methylene chloride, 86.2[1 (0,853 mol) of triethylamine and 5.2 g (0°043
mol) and the reaction mixture was heated to 15 mol at 20°C.
After stirring for a minute, a solution of 62.5 g (0,427 mol) of 2-cyano-2-methoxyiminoacetyl chloride (E-isomer) was added at 0° C. over a period of 1 hour. The reaction mixture was then stirred at 0°C for 1 hour and then at room temperature for 5 hours,
This solution is left at room temperature for 2 days. 1M hydrochloric acid (3001
6A each), saturated sodium bicarbonate solution (200
After washing with 2×30 OuA) and water (2×30 OuA), the solution is dried over sodium sulfate and evaporated in vacuo.

N-(2-cyano-2-methoxyiminoacetyl)-
81.0 g (89% of theory) of glycine ethyl ester (E-isomer) are obtained as a brown oil with a refractive index of 1.4699.

Out l-substance-Ω, □l! i- a) CN Cll3(')-rlJ-(nee C(')C2Hs2-
164 g of ethyl cya 7-2-hydroxyiminoacetate (I
mole), sodium chloride (Kinast, Liel+igs Ann, Chen,), 19
81.1561) and powdered potassium carbonate 138[1] were suspended in 1.52 ton of acetate, 61 g (I, 25 mol) of dimethyl sulfate (98% pure N) was added at 30 g.
It is added in portions and the reaction mixture is heated under reflux for 3 hours. After cooling, filter through diatomaceous earth and evaporate.

124.8 g of ethyl 2-cyano-2-methoxyiminoacetate (E-isomer) are obtained as a reddish-brown oil with a purity of 85% (gas chromatogram). This yield corresponds to 68% of the theoretical amount. Five passes of chromatography on silica gel 60 and chloroform give a pale yellow oil with a purity of 93%.

b) CN No. CH, 0-N=C-C-0K Ethyl 2-cyano-2-methoxyiminoacetate (E-isomer N 24.8s (0,672 mol) with purity of 84% in 500 mj! of ethanol A solution of 45.Ig (0,806 mol) of potassium hydroxide dissolved in 500 g of water is added to the dissolved solution at 20° C., and the reaction mixture is stirred at 40° C. for 1 hour.

The solution was evaporated in vacuo at 40°C, the residue was stirred with methanol for 30 minutes, filtered off in a suction oven, ethanol and
Wash with acetonitrile and methylene chloride and dry at room temperature.

58.6 g (53% of theory) of the kaliuno salt of 2-cyano-2-methoxyiminoacetic acid (E-isomer) are obtained.

c) CN C'H,0-N=C-C-C1 20 g (0.12 mol) of the potassium salt of 2-cyano-2-methoxyiminoacetic acid (E-isomer) are suspended in 250 ai1 of dry ether. After adding several drops of dimethylformamide, oxalyl chloride 76.2H ('0.6 mol) was added neatly at 0°C. The reaction mixture is stirred for 2 hours at 0° C., filtered and the filtrate is evaporated in vacuo at room temperature.

13.5 g (77% of the amount of fill) of 2-thia-7-2-methoxyiminoacetyl chloride (E-isomer) are obtained as a yellow oil, which is reacted further immediately.

Example 2 (Production method a) Glycine diethylamide 5.8 g (0.02 mol), triethylamine 5.05 g (0.05 mol) and 4-
Tsumethylaminopyrinone 0.61g (0,005mol)
751111 in methylene chloride, 2-benzyloxyimino-2-cyanoacetyl chloride (E
A solution of 11.1 g (0.05 mol) of the isomer) dissolved in 50 ω2 methylene chloride is added neatly at 0° C., and the reaction mixture is stirred at 0° C. for 1 hour and at room temperature for 20 hours.

The reaction mixture is diluted with 50 Ill of methylene chloride, washed with 1M hydrochloric acid, 10% strength sodium bicarbonate solution and water, dried over magnesium sulphate and evaporated in vacuo.

The residue is recrystallized from ligroin/ethyl acetate.

N-(2-benzyloxyimino-2-cyanoacetyl)-glycine diethylamide (melting point 76-81°C)
4.0 g (25% of theory) of E-isomer) are obtained.

Example 3 ShiIl, Shii.

9l- (V method b) 2-cyano-2-methoxyiminoacetic acid (E-isomer) 1
5.3 g ((I, 12 mol), isobutyraldehyde 8
．． 65 g (0.12 mol) and benzyl 7 mi 712.
85 g (0.12' mol) of ethyl isocyanoacetate (
Hotzpe (I'), Tlop+]e) and Scholkopf (IJ, 5chollkop, f), Liebig Annals of Chemistry (I-, Ieb 1g5Ann, Chen+
, L, '7-6-3-, 1.1972N 3. 6g (
A solution of 0.12 mol) dissolved in 1001 methanol is added neatly at 0°C. The reaction mixture was warmed to room temperature and stirred at 20°C for 13 hours. The solvent was evaporated in vacuo, the residue was partitioned between 30011112 parts of water and ethyl acetate, and the organic phase was dissolved in 200i parts of 1M hydrochloric acid, 10
% strength sodium bicarbonate solution and water, dry over sodium sulfate and evaporate in vacuo. N-[2
-Benzyl-N-(2-cyano-2-methoxyiminoacetyl)-DC-valyl 1-glycine ethyl ester (E-isomer) 14.4. g (30% of theory) are obtained as a brown oil.

uJ'01-Quality-Q-Ken1-N CH,0-N=C-C-OH I ethyl 2-cyano-2-methoxyiminoacetate (E-isomer) 83[1 (0.5 mol) 550 tml (0.55 mol) of IM sodium hydroxide solution are added neatly to the mixture with 25 ouQ of water at 20-30 DEG C. and the reaction mixture is stirred at room temperature for 318 hours. The solution was washed with ether and washed with Lewatit S 100 (H+ form,
(previously washed with acetone) Pour into column 1e. The column is eluted with acetone and acetonitrile, both 1e, and the eluent is evaporated in vacuo at 30-40°C. 63.2 g (99% of theory) of 2-cyano-2-methoxyiminoacetic acid (E-isomer) with a melting point of 48-49 DEG C. are obtained.

Example 4 0 0C113 \[:'' ■ (Production method b) 2-cyano-2-methoxyiminoacetic acid ((cou isomer)
6.4 g (0, (I5 moles), methyl carbanate 4.
A solution of 5.5 g (I, 05 mol) of cyclohexyl isocyanide was added to a solution of 5B (I1, (I5 mol)) and 3.6 g (I, 5 mol) of isobutyraldehyde dissolved in 7511 Ij! of methanol. 1 and the mixture was stirred at room temperature for 24 hours.

The solvent was distilled off in vacuo, and both residual aromas were removed from 2001Ile.
Partition the organic phase between ethyl acetate and water, and reduce the organic phase to 1
5 (Img of 1M hydrochloric acid, 10% strength sodium bicarbonate solution and water, dried over sodium sulfate and concentrated in vacuo.

N-(2-cyano-2-methoxyiminoacetyl)-N-meroxycarbonylamino-D L-valine cyclohexylamide (E-isomer) with melting point 132-134°C9. Og (47% of theory) is obtained.

Example 5 (Production method C) N-(2-cyano-2-methoxyimino-a-7tyl)-
Glycine ethyl ester (E-1 form) 11.8g (0
, 0553 mol) dissolved in 50 mJ of methanol was added a 6.8 M methanol solution of methylamine (24.5 mol) in 50 mJ of methanol.
m1 (0,166 mol) are added directly at 0°C. The reaction mixture is allowed to warm to room temperature and stirred at 20° C. for an additional hour. After cooling to 10°C, the crystalline precipitate is separated in a suction oven, washed with a small amount of cold ethanol and dried at 40°C.

N-(2-cyano2-mer1.
N-diiminoacetyl)-glycine methylamide (T:
-isomer) 7.0 g (64% of theory) are obtained.

Example 6 (Production method C) 7.1 g (0°035
6 moles) to 1011Il! f) E) Concentrated hydrochloric acid 7. og(o, (I71
A solution of 2 mol) dissolved in 10 mg of tetrahydro7rane is added, and isoamylnitrile (97% purity)5.
15 g (0,042 mol) are added dropwise at -20°C.

After stirring this mixture at -20°C for 15 minutes, 10.8 g (0,107 mol) of triethylamine was added to 15+ a
j! of dimethylformamide is dissolved in 20
4.2 g of benzylamine (0
, 0392 mol) dissolved in 3.5 mg of dimethylformamide is added. The reaction mixture was kept at 0 °C for 65 h, stirred at 20 °C for 24 h, then
Pour into 0mQ water. This mixture was mixed with ethyl acetate (I
The extract was washed with 1001 1M citric acid, 10% strength sodium bicarbonate solution and water, dried over sodium sulfate,
Concentrate in vacuo.

N-(2-cyano-2-methoxyiminoacetyl)-glycinebencylamide (E-
6.2 g (64% of theory) of the isomer) are obtained.

N-(2-cyano-2-methoxyiminoacetyl)-chrysin ethyl ester (EM trunk) 30 g (0,1
15.5 g (0°31 mol) of hydrazine hydrate was added to a solution of 55 mol) dissolved in 150 ml of ethanol.
It is added dropwise at ˜30° C. and the reaction mixture is stirred at room temperature for 4 hours. After cooling to 10° C., the crystalline precipitate is filtered off with suction, washed with 2001 ether and dried at room temperature.

28.1 g (91% of theory) of N-(2-cyano-2-methoxyiminoacetyl)-glycine hydrazide (E-isomer) having a melting point of 167 DEG-168 DEG C. are obtained.

The following E-isomers of the compounds of general formula (I) are likewise obtained by the process described in the invention.

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I (U.S. Pat. No. 3,957.'847) Example A Plasmopara test (grape)/Protection Solvent: 4.7 parts by weight of 77 tons Emulsifier: 0.3 part by weight of furkylaryl To prepare a suitable formulation of polyglycol ether active compound, 1 part by weight of active compound is mixed with the above amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test the protective effect, young seedlings are sprayed with the active compound formulation until dripping wet. After the spray coating has dried, the seedlings are coated with P lasmoparaviticol.
Inoculate with an aqueous suspension of spores of a), then 20 to 2
High humidity room at 2℃ and 100% relative humidity.
(eha+ober) for one day and night. Next, the seedlings are placed in a greenhouse at 22° C. and a relative temperature of about 80% for 5 days. Next, moisten this cloth and place it in a high humidity room for a night.

Evaluation is carried out 70 days after inoculation.

In this test, a clearly superior activity compared to the prior art is shown, for example, by the compound described in Preparation Example 5.

Phytophthora test (grapes) / Protective effect I (A) (known) Example B Phytophthora test (tomato) / Therapeutic effect Solvent: 4.7 parts by weight A7Tone emulsifier: 0.3 parts by weight To prepare a suitable formulation of the furkylaryl polyglycol ether active compound, one part of the active compound is mixed with the above amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test the therapeutic efficacy, young adults were treated with Phytophthora infestans (Phytophthora 1n).
festans) in an aqueous suspension of spores.

The seedlings are left in an incubator at 20° C. and 100% relative humidity for 7 hours. After a short drying time, the seedlings are sprayed with the active compound formulation until dripping wet.

The seedlings are placed in an incubator at 100% relative humidity and approximately 20°C.

Evaluation takes place 311 days after inoculation. 'In this test, a clearly superior activity compared to the prior art is shown, for example, by the compounds of Preparation Examples 1 and 5.

pB Pigeon test (tomato) / Towards therapeutic effect (B) (known) υ N Example C Pigeon test (tomato) / Solvent acting in rhizome: 4.
To make a suitable formulation of 7 parts by weight of acetone emulsifier and 0.3 parts by weight of furkylaryl polyglycol ether active compound, 1 part by weight of active compound is mixed with 1 part of solvent and emulsifier. , dilute this concentrate with water to the desired concentration.

To test the rhizomatic properties, young seedlings prepared for the test are grown and a standard soil is sprayed with the active compound formulation. Three days after this treatment, the seedlings are inoculated with an aqueous suspension of Phytophthora infestans spores.

The seedlings are placed in an incubator at 100% relative humidity and approximately 20°C.

Evaluation is performed 3rd day after inoculation.

In this test, a clearly superior activity compared to the prior art is shown, for example, by the compound described in Preparation Example 5.

Cloth-9 Ekibyokin test (tomato)/Intrarhizome action (C) (known)

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the formula, R is alkyl, alkenyl, alkynyl, cyanoalkyl, azolylalkyl, or may be substituted. represents phenylalkyl or optionally substituted cycloalkyl, R^1 represents hydrogen, alkyl, optionally substituted phenyl or optionally substituted benzyl, or represents alkoxycarbonylamino, R^2 represents hydrogen or alkyl, R^3 represents hydrogen, alkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, azolylalkyl, cyanoalkyl, hydroxyalkyl, alkenyl, alkynyl or represents optionally substituted cycloalkyl, or represents optionally substituted phenyl or phenylalkyl, or represents a radical R^4-SOn-Z- in which R^4 is hydrogen, represents alkyl or optionally substituted phenylalkyl, n represents the number 0, 1 or 2, Z represents a linear or branched alkylene chain), or R^1 and R^3, together with the nitrogen atom and carbon atom to which they are bonded, represent a 5- or 6-membered heterocyclic ring, or R^2 and R^3, together with the carbon atom to which they are bonded, , cycloalkylidene; In the expression, R^III is hydrogen, alkyl, alkenyl, alkynyl,
Halogenoalkyl, alkoxyalkyl, dialkylaminoalkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl,
represents alkylaminocarbonylalkyl, dialkylaminocarbonylalkyl, cyanoalkyl, optionally substituted phenylalkyl, optionally substituted phenyl or optionally substituted cycloalkyl, or represents an acylamino group mosquito,
or represents the group -N=CH-R^IV (where R^IV represents alkyl or optionally substituted phenyl), or the combination of R^II and R^III N^α (2-cyano-2-alkoxyiminoacetyl)-amino acid derivatives and E-isomers of peptides and their physiologically acceptable, optionally substituted ammonium, alkali metal and alkaline earth metal salts and metal salt complexes. 2. In the formula R is straight-chain or branched alkyl having 1 to 8 carbon atoms, or in each case alkenyl or alkynyl having 2 to 4 carbon atoms, 1 in the alkyl moiety cyanoalkyl having from 4 carbon atoms, in each case from 1 to 6 in the alkyl moiety
1,2,4-triazole-1- with carbon atoms
represents yl-alkyl or pyrazol-1-yl-alkyl; or has 1 to 4 carbon atoms in the alkyl moiety and is mono-, di- or trisubstituted in the phenyl moiety by the same or different substituents and phenylalkyl, which may be mentioned as preferred substituents: halogen, cyano, nitro, hydroxyl, alkyl, alkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl, in each case having 1 to 4 carbon atoms. or phenyl, which may be mono-, di- or tri-substituted with the same or different halogen substituents; or having 3 to 7 carbon atoms and with the same or different halogen substituents; cycloalkyl, which may be mono-, di- or tri-substituted, preferred substituents being halogen and alkyl having 1 to 4 carbon atoms; or represents straight-chain or branched alkyl having 1 to 4 carbon atoms, which may in each case be mono-, di- or trisubstituted by the same or different substituents. represents phenyl or benzyl, the preferred possible substituents being the substituents of phenyl already mentioned for R, or represents alkoxycarbonylamino having 1 to 4 carbon atoms in the alkyl part, R^ 2 represents hydrogen or a straight-chain or branched alkyl having 1 to 4 carbon atoms; R^3 represents hydrogen or a straight-chain or branched alkyl having 1 to 6 carbon atoms; or straight-chain or branched hydroxyalkyl having 1 to 4 carbon atoms; alkoxycarbonylalkyl having 1 to 4 carbon atoms in each of the alkyl and alkoxy moieties; hydroxycarbonylalkyl and aminocarbonylalkyl having 1 to 4 carbon atoms in the alkyl moiety,
1,2,4-triazol-1-ylalkyl, 1,2,4-triazol-4-ylalkyl, imidazol-4-ylalkyl, in each case having 1 to 6 carbon atoms in the alkyl moiety; pyrazol-1-ylalkyl, in the alkyl part represents cyanoalkyl having 1 to 4 carbon atoms, or in each case representing alkenyl or alkynyl having 2 to 4 carbon atoms, or Cycloalkyl having 3 to 7 carbon atoms, which may be mono-, di- or trisubstituted with the same or different substituents, which may be mentioned as preferred substituents are halogen and 1- to 7-carbon atoms. represents an alkyl having 4 carbon atoms or, in addition, having 1 to 4 carbon atoms in the alkyl moiety, mono-, di- or trisubstituted in the phenyl moiety by the same or different substituents; phenyl or phenylalkyl, in each case a preferred possible substituent being R
represents a substituent of phenyl as already mentioned for , or the group R^4-SOn-Z-, in which R^4 represents hydrogen or a straight chain having 1 to 4 carbon atoms. or branched alkyl or having 1 to 4 carbon atoms in the alkyl moiety and which may be mono-, di- or tri-substituted in the phenyl moiety by the same or different substituents; represents alkyl whose possible substituents are the phenyl substituents already mentioned for R, n represents the number 0, 1 or 2, and Z represents a straight chain having 1 to 4 carbon atoms; , or a branched alkylene chain), or R^1 and R^3, together with the nitrogen atom and carbon atom to which they are bonded, represent a 5- or 6-membered heteroartic ring, or, R^2 and R^3 together with the carbon atom to which they are bonded represent a cycloalkylidene having 3 to 6 carbon atoms, and X is a group -OR^I or -NR^IIR^III [these In the radicals R^I represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms, or in each case alkenyl or alkynyl having 2 to 4 carbon atoms; R^II represents hydrogen or a straight-chain or branched alkyl having 1 to 4 carbon atoms; R^III represents hydrogen or a straight-chain or branched alkyl having 1 to 4 carbon atoms; represents alkyl or alkenyl or alkynyl in each case having 2 to 4 carbon atoms or halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms , or alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy and alkyl moieties, or dialkylaminoalkyl having up to 4 carbon atoms in each alkyl moiety; alkoxycarbonylalkyl, both having from 1 to 4 carbon atoms, hydroxycarbonylalkyl, having from 1 to 4 carbon atoms in the alkyl moiety, or in each case having from 1 to 4 carbon atoms in each alkyl moiety; or cyanoalkyl having 1 to 4 carbon atoms in the alkyl moiety, phenyl identical in part,
or phenylalkyl, which may be mono-, di- or tri-substituted with different substituents, or phenyl, which may be mono-, di- or trisubstituted with the same or different substituents, where the possible substituents are In each case it represents a substituent of phenyl as already mentioned for R, or it has 3 to 7 carbon atoms and may be substituted by the same or different substituents. cycloalkyl, the preferred possible substituents of which are halogen and alkyl having 1 to 4 carbon atoms, or in each case on the alkyl moiety or on the alkoxy moiety 1 to 4 represents alkylcarbonylamino or alkoxycarbonylamino having 4 carbon atoms;
or, in addition, in each case 1 on each alkyl moiety
to aminocarbonylamino having 4 carbon atoms,
represents alkylaminocarbonylamino, or dialkylaminocarbonylamino or formylamino, or represents a group -N-CH-R^IV, where R^IV is a straight-chain or branched group having 1 to 4 carbon atoms; phenyl which may be mono-, di- or tri-substituted by the same or different substituents, the possible substituents being the phenyl substituents already listed for R) Alternatively, R^II and R^III may contain oxygen or nitrogen as other heteroatoms together with the nitrogen atom to which they are bonded, and may include cyano, halogen, 1 to 4 carbon atoms. alkyl, hydroxycarbonyl, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, aminocarbonyl, alkylaminocarbonyl and dialkylaminocarbonyl, in each case having 1 to 4 carbon atoms in each alkyl moiety; represents a 5- or 6-membered heterocyclic ring which may be substituted by
) of N^α-(2-cyano-2-alkoxyaminoacetyl)-amino acid derivatives and E-isomers of peptides and their physiologically acceptable, optionally substituted ammonium, alkali metal and alkali Earth metal salts and metal salt complexes. 3. In the formula R is a straight-chain or branched alkyl having 1 to 4 carbon atoms, allyl or propargyl, cyanomethyl, cyanoethyl, in each case with 1 to 4 carbon atoms in the alkyl moiety; has 1,2,4-
represents triazol-1-yl-alkyl or pyrazol-1-yl-alkyl or has 1 to 2 carbon atoms in the alkyl moiety and is mono- or di-substituted in the phenyl moiety by the same or different substituents; phenylalkyl, which may be fluorine, chlorine, cyano, nitro,
represents phenyl, which may be mono- or di-substituted by the same or different substituents selected from the group consisting of hydroxyl, methyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, and fluorine and chlorine; or, in addition, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, which in each case may be mono- or di-substituted by the same or different substituents selected from the group consisting of fluorine, chlorine and methyl. R^1 represents hydrogen, methyl or ethyl, or phenyl or benzyl, which may be mono- or di-substituted in each case by the same or different substituents, and the possible substitutions the group is in particular a substituent of phenyl as already mentioned for R, or in addition represents methoxycarbonylamino or ethoxycarbonylamino, R^2 represents hydrogen, methyl or ethyl, R^3 is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, hydroxymethyl or 1
-Hydroxyethyl, methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, hydroxycarbonylmethyl, hydroxycarbonylethyl, aminocarbonylmethyl, aminocarbonylethyl, in each case 1 to 4 alkyl moieties 1,2,4- with carbon atom
represents triazol-1-yl-alkyl, 1,2,4-triazol-4-yl-alkyl, imidazol-4-yl-alkyl and pyrazol-1-ylalkyl, cyanomethyl, cyanoethyl or allyl; or represents propargyl, or
represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, which in each case may be mono- or di-substituted by the same or different substituents selected from the group consisting of fluorine, chlorine and methyl, or , furthermore having 1 to 2 carbon atoms in the alkyl moiety and which may be mono- or di-substituted in the phenyl moiety by the same or different substituents or phenyl, which may be disubstituted, represents one in which the possible substituents are the substituents of phenyl already mentioned for R, or in addition represents a group R^4-SOn-Z- (in which R^4 represents hydrogen, methyl or ethyl, or phenyl having 1 to 2 carbon atoms in the alkyl moiety and which may be mono- or di-substituted in the phenyl moiety by the same or different substituents; alkyl, where the possible substituents are in particular the phenyl substituents already mentioned for R, n represents the number 0, 1 or 2, and Z has 1 to 2 carbon atoms; represents a linear or branched alkylene chain), or R^1 and R^3 together with the nitrogen atom and carbon atom to which they are bonded represent a 5- to 6-membered heterocyclic ring. or, R^2 and R^3 together with the carbon atom to which they are bonded represent cyclopropylidene, and X is a group -OR^I or -NR^IIR^III [In these groups, R^ I represents hydrogen, methyl, ethyl, allyl or propargyl; R^III represents hydrogen, methyl or ethyl; R^II
I is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. -butyl, tert. -butyl, allyl or propargyl, halogenoalkyl having 1 or 2 carbon atoms and 1 to 3 identical or different halogen atoms, such as fluorine and chlorine atoms, 1 or 2 in each case in the alkoxy and alkyl moieties; alkoxyalkyl having carbon atoms, dialkylaminoalkyl having 1 or 2 carbon atoms in each alkyl moiety, or alkoxycarbonylalkyl having in each case 1 or 2 carbon atoms in each alkyl moiety; , hydroxycarbonylalkyl, aminocarbonylalkyl, alkylaminocarbonylalkyl or dialkylaminocarbonylalkyl or cyanoalkyl having 1 or 2 carbon atoms in the alkyl part, or furthermore 1 or 2 carbon atoms in the alkyl part phenylalkyl, which may be mono- or di-substituted by the same or different substituents on the phenyl moiety, or phenyl which is mono- or di-substituted by the same or different substituents; In each case, the possible substituents represent those which are the phenyl substituents already mentioned for R, or in each case the same substituents selected from the group consisting of fluorine, chlorine and methyl. or in each case one or two on the alkyl or alkoxy moiety; represents alkylcarbonylamino or alkoxycarbonylamino having a carbon atom, or aminocarbonylamino, methylaminocarbonylamino,
represents ethylaminocarbonylamino, dimethylaminocarbonylamino, diethylaminocarbonylamino, methylethylaminocarbonylamino or formylamino, or the group -N=CH-R^IV, where R^IV represents methyl or ethyl. or phenyl, which may be mono- or di-substituted with the same or different substituents, and the possible substituents are R
or R^II and R^III, together with the nitrogen atom to which they are bonded, represent oxygen or May contain a nitrogen atom, such as cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, i-propyl, hydroxycarbonyl, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylamino Represents a 5- or 6-membered heteroartic ring optionally substituted with carbonyl, diethylaminocarbonyl, and methylethylaminocarbonyl]
The formula (I
) of N^α-(cyano-2-alkoxyiminoacetyl)-amino acid derivatives and E-isomers of peptides and their optional ammonium, alkali metal and alkaline earth metal substitutions. Salts and metal salt complexes. 4. (a) Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) In the formula, R^1 is hydrogen, alkyl, phenyl that may be substituted, or benzyl that may be substituted. or represents alkoxycarbonylamino, R^2 represents hydrogen or alkyl, R^3 is hydrogen, alkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, azolylalkyl, cyanoalkyl, hydroxyalkyl , represents alkenyl, alkynyl or optionally substituted cycloalkyl or represents optionally substituted phenyl or phenylalkyl, or represents a radical R^4-SOn-Z- (in which R^4 represents hydrogen, alkyl or optionally substituted phenylalkyl, n represents the number 0, 1 or 2, Z represents a straight or branched alkylene chain), or R ^1 and R^3, together with the nitrogen atom and carbon atom to which they are bonded, represent a 5- or 6-membered heterocyclic ring, or R^2 and R^3, together with the nitrogen atom and carbon atom to which they are bonded, together with the atom represents cycloalkylidene; Represents alkyl, R^III is hydrogen, alkyl, alkenyl, alkynyl,
Halogenoalkyl, alkoxyalkyl, dialkylaminoalkyl, alkoxycarbonylalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl,
represents alkylaminocarbonylalkyl, dialkylaminocarbonylalkyl, cyanoalkyl, optionally substituted phenylalkyl, optionally substituted phenyl or optionally substituted cycloalkyl, or represents an acylamino group mosquito,
or represents the group -N=CH-R^IV (where R^IV represents alkyl or optionally substituted phenyl), or the combination of R^II and R^III The amino acid derivative of formula (III) represents a heterocyclic ring which may be substituted and may contain other heteroatoms along with the nitrogen atom in the formula (III). III) E- of a carboxylic acid in which R represents alkyl, alkenyl, alkynyl, cyanoalkyl, azolylalkyl or optionally substituted phenylalkyl, or represents optionally substituted cycloalkyl; an isomeric carboxyl-activated derivative, optionally in the presence of a catalyst, optionally in the presence of an acid binder,
(b) Formula (III) ▲ Numerical formula, chemical formula, table, etc. ▼ (III) In the formula, R is E of a carboxylic acid having the above meaning. - The carboxyl-activated derivative of the isomer is first converted to an amine of the formula (IV) H_2NR^1(IV) where R^1 has the meaning given above and then to an amine of the formula (V) R^2-CO-R^3 (V) where R^2 and R^3 have the above meanings, and finally formula (VI) CN-R^5 (VI) where R^5 is alkyl, alkenyl, alkynyl, cyclo cycloalkyl representing alkyl or alkoxycarbonylalkyl or optionally substituted;
React with isonitrile representing phenyl or phenylalkyl in the presence of an appropriate diluent, or (c) Formula (I a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I a) In the formula R, R^ 2 and R^3 are the carboxyl-activated derivatives of the E-isomer of the amino acid with the meanings given above and are represented by the formula (VII
) H-NR^IIR^III (VII) where R^II and R^III are as defined above, in the presence of an amine having the above meaning, optionally in the presence of a catalyst, and optionally in the presence of an acid binder, and (d) Formula (I b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I b) In the formula, R, R^2 and R^3 have the above meanings. and R^6 represents alkyl having 1 to 4 carbon atoms. The E-isomer of the amino acid derivative has the formula (VII) H-NP^IIR^III where R^II and R^III are Ammonium, alkali metal or alkaline earth metal salts, which may be substituted by reaction with amines having the meaning above, optionally in the presence of diluents, and then optionally with these products. or a metal salt complex (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the formula, R, R^1, R^2, R^3 and X have the above meanings. E-isomers of N^α-(2-cyano-2-alkoxyiminoacetyl)-amino acid derivatives and peptides and their physiologically acceptable, optionally substituted ammonium, alkali metals and alkaline earths. Method for producing similar metal salts and metal salt complexes. 5. Formula (I) described in claims 1 to 4
A pest control agent comprising at least one N^α-(2-cyano-2-alkoxyimino-acetyl)-amino acid derivative and an E-isomer of a peptide. 6. Formula (I
) of N^α-(2-cyano-2-alkoxyiminoacetyl)-amino acid derivatives and E-isomers of peptides for controlling pests. 7. Formula (I
1. A method for controlling pests, which comprises applying a N^α-(2-cyano-2-alkoxyiminoacetyl)-amino acid derivative and an E-isomer of a peptide to pests and/or their environment. 8. Formula (I
)-(2-cyano-2-alkoxyiminoacetyl)-amino acid derivative and the E-isomer of the peptide are mixed with a filler and/or a surfactant. Method. 9. N^α- of formula (I) described in claim 6
Use of (2-cyano-2-alkoxyiminoacetyl)-amino acid derivatives and E-isomers of peptides for controlling fungi and molds.