JPS63307851A - Bactericidal fungicide of substituted cyanamides - 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 relates to substituted cyanamides, which are known in part as fungicides, novel substituted cyanamides and processes for their production.

It has been disclosed that certain plant diseases can be controlled by active compounds from the group of dithiocarbamates and sulfenylated arylsulfamides. Thus, for example, zinc ethylene-1,2-bisudithiorubamidete [
zineb] can be used against Venturia in fruit cultivation; dichlof 1uanid] in the genus Pyricularia in rice.
ia) [Phytopathology 33 (194
3), 1113 or German Patent Application Publication No. 1.19
3.498]. However, the action of these known compounds is not always satisfactory, especially at low active compound concentrations.

A series of substituted cyanamides have already been described in the literature [Journal of Organic Chemistry (
J. Org. Chem.) 29 (1964), 15
3-157; Synthesis l
975, l l l ” l 13 ; Bull,
Soc, Chim, France1975r395-
397; J, Chem, Res.

5ynop, 1981% 148; US Patent No. 3.
793°372]. However, nothing has been disclosed yet regarding the bactericidal and fungicidal properties of the chemical compound.

Partially known general formula (1)
Q, -R' or -P, where R3 is alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aralkenyl, aryl, heteroaryl, alkoxy, aralkoxy, aryloxy,
Alkylthio, aralkylthio, arylthio, alkylamino, cycloalkylamino, dialkylamino,
represents an optionally substituted group from the group consisting of aralkylamino and arylamino, R' represents an optionally substituted group from the group consisting of alkyl, aralkyl, aryl and heteroaryl, and Re represents Represents an optionally substituted group from the group consisting of alkyl, aryl, alkoxy, alkylthi, alkylamino and dialkylamino, R1 is an optionally substituted group from the group consisting of alkyl, alkoxy, alkylthio, alkylamino and dialkylamino and Q represents oxygen or sulfur, it has been found that substituted cyanamides exhibit strong bactericidal and fungicidal properties.

Surprisingly, the substituted cyanamides of general formula (I) exhibit considerably stronger fungicidal properties than known fungicides such as zineb or dichlofluanid with a comparable action profile.

All aliphatic groups, alone or in combination, such as alkyl, alkoxy or alkenyl, are straight-chain or branched, even if this is not specified otherwise. In the present specification, halogen alone or in combination, such as halogenoalkyl, refers to fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine,
Very particular preference is given to fluorine and chlorine.

In the present invention, preferably R1 is CI"" C4-alkyl,
or optionally halogen, cyano, nitro, C, -C.

-alkyl, 01-C2-halogenoalkyl, C1-C
1-alkoxy, cl-C1-halogenoalkoxy, C
2-C4-alkylthio, C,-C,-halogenoalkylthio% C1-C4-alkylsulfinyl, C1-C
6-alkylsulfonyl, C2-C2-halogenoalkylsulfonyl, 01-C4-alkylamino, di(C
, ~C1-alkyl)-amino, C1-C6-alkyl-carbonyl-amino and C,-C,-alcoquinecarbonyl, which may be mono to polysubstituted with the same or different substituents. represents phenyl or 7-tyl, R2 is a group -Co-R3, -5○2-R
4 or -P, in which R3 is optionally mono- to polysubstituted with the same or different substituents from the group consisting of halogen and C1-C4-alkoxy;
U~C0゜-Alkyl, optionally halogen and H01~C2-
C1-C6-cycloalkyl, which may be mono- to polysubstituted with the same or different substituents from the group consisting of alkyl, optionally mono- to polysubstituted with the same or different halogen substituents 02~CIG-
Alkenyl, C2-C3°-alkynyl, benzyl optionally optionally substituted with mono to polysubstituted halogen substituents in the ring with the same or different halogen substituents, phenylethynyl, optionally halogen, cyano, nitro, Cl-C4-aldoxy and C, Phenyl, naphthyl, furyl, chenyl, pyridyl, Cl-C3-alkoxy, benzyloxy, phenoxy, which may be mono- to polysubstituted with the same or different substituents from the group consisting of -C2-halogenoalkoxy, 01- C3-alkylthio, benzylthio,
Phenylthio, C3-C1-alkylamino, 03-C
5-cycloalkylamino, di(CI-C3-argyl)-amino, benzylamino or optionally halogen, cyano, nitro, C1-C6-alkyl, C,-C,-halogenoalkyl, 01-C1-alkoxy% C1- 02
-halogenoalkoxy, 01-C4-alkylthio, 0
1-C2-halogenoalkylthio, ClNC4-alkylsulfinyl, C1-C4-alkylsulfonyl, C
1-C2-halogenoalkylsulfonyl and C, -C,
- represents phenylamino which may be mono- to polysubstituted with the same or different substituents from the group consisting of alkoxycarbonyl, even if R4 is optionally mono- or polysubstituted with the same or different halogen substituents; Good 01-C1o-alkyl, optionally halogen, cyano, nitro, C1-C4-alkyl-C,-halogenoalkyl,
Benzyl which may be mono- to polysubstituted with the same or different substituents from the group consisting of 01-C4-alkoxy, C,-C2-halogenoalkoxy and 01-C,-alkoxy-carbonyl, optionally halogen, cyano ,
Nitro, phenyl, 01-C,-alkyl, 01-C2
-halogenoalkyl, 01~C,-alkoxy, 01~
C2-halogenoalkoxy, CI-04-alkylthio, 01-C2-halogenoalkylthio, Cl-C4-alkylsulfinyl, C1-C1 halogenoalkylsulfonyl, di(CI-02-alkyl)-aminosulfonyl and C, -C,- Phenyl optionally substituted with alkoxy-carbonyl, optionally mono- to polysubstituted with the same or different substituents from the group consisting of halogen, cyano, nitro, C1-C4-alkyl and C,-C4-alkoxy. Naphthyl, optionally halogen,
C□-C,-alkyl and C,-C4-alkoxycarbonyl, which may be mono- to polysubstituted with the same or different substituents, optionally halogen, 01-C4-alkyl and 01 pyrazolyl optionally substituted with ~C4-alkoxy-carbonyl or optionally halogen, CI-04-alkyl and CI~C
represents pyridyl which may be mono- to polysubstituted with the same or different substituents from the group consisting of 4-alkoxy-carbonyl, and R' is optionally mono- to polysubstituted with the same or different halogen substituents; may be 0
1-C4-alkyl, phenyl, 01-C4-alkoxy, 01-C4-alkylthio, 01-C, optionally mono- to polysubstituted with the same or different halogen substituents.

-alkylamino or di-CCI~C,-alkyl)
-represents amino, and R6 may optionally be mono- to polysubstituted with the same or different halogen substituents 01
~C. -Alkyl, optionally mono- to polysubstituted with the same or different halogen substituents 01-C1
Alkoxy, C, ~C, -C rulethio, 01~C4-
alkylamino or di(C+~C,-alkyl)-
The present invention relates to the use of fungicides and fungicides based on compounds of the general formula (I) in which Q represents amino and Q represents oxygen or sulfur.

Particularly preferably R1 is optionally fluorine, chlorine, bromine, methyl, ethyl, cyano, nitro, trifluoromethyl, 1
-lichloromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino, diethylamino, trifluoromethylthio, acetylamino, propionylamino, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and isopropoxy represents phenyl which may be mono- to tri-substituted with the same or different substituents from the group consisting of carbonyl, R2 is a group -Co-R3, -SQ. -R' or -P, where R3 is optionally selected from fluorine, chlorine, bromine, cyanide, nitro, methyl, ethyl, trifluoromethyl, trichloromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy and chlorodifluoromethoxy. represents phenyl which may be mono- to tri-substituted with the same or different substituents from the group consisting of R4 or optionally fluorine, chlorine, bromine, cyanide, nitro, methyl, phenyl, chloromethyl, trifluoromethyl, methoxy , ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, trifluoromethylthio, dimethylaminosulfonyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and isopropoquinecarbonyl, one to three substituted with the same or different substituents. Represents phenyl which may be substituted; R8 represents methyl, ethyl, phenyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino; R1 represents methyl, ethyl, methoxy, ethoxy, propoxy, butoxy, pentyl Oxy, hexyloxy,
Methylthio, ethylthio, propylthio, butylthio,
Compounds of formula (I) which represent methylamine, ethylamino or dimethylamino and in which Q represents oxygen or sulfur are used in the present invention.

Examples of compounds of formula (I) for use in the invention that may be mentioned include: N-(3,4-dichloro-phenyl)-N
-(ethoxy-ethylthionophosphoryl)-cyanamide, N-benzoyl-N-(3-nitro-phenyl)-cyanamide, N-benzoyl-N-(4-chloro-phenyl)-cyanamide, N-(4-methoxy -7Eniru)-
N-(4-methyl-3-ditrophenylsulfonyl)-cyanamide, N-(4-methoxy-phenyl)-N
-(4-chloro-3-nitro-phenylsulfonyl)-
Cyanamide, N-(4-chloro-phenyl) to N-(2
-Chloro-5-nitro-phenylsulfonyl)-cyanamide, N-(4-chlorophenyl)-N-(2-chloromethyl-phenylsulfonyl)-cyanamide, N-(4-chlorophenyl)-N-(2-chloromethyl-phenylsulfonyl)-cyanamide,
-Chloro-phenyl)-N-(2-chloro-phenylsulfonyl)-CyanamiF, N-(4-chlorophenyl)
-N-(4-methyl-phenylsulfonyl)-cyanamide, N-(4-chloro-phenyl)-N-(4-methyl-3-ditrophenylsulfonyl)-cyanamide I' and H-N-(4-chlorophenyl) )-N-(2-encyclo1-xyerbonyl-phenylsulfonyl)-cyanamide.

These compounds are very particularly preferred because of their pronounced bactericidal and morcidal action.

Further examples of compounds of formula (I) used in the invention are shown in Table 1 below.

NmiC-N (I) Table 1=
Examples of compounds of formula (1) C11□C1 m1 Table - Series C, I+.

C00C, l+.

7 NO! 'CI　　　　C1l.

, No□ Table 1 - Reading Table 1 - Standard Table 1 - Standard Table 1 - Standard CI C1 Table 1 - Standard Table 1 - Standard Table 1 - Standard Table 1 - Standard Table 1 - Standard Table 1 - Standard Table 1 - Reading Table 1 - Reading Table 1 - Reading Table 1 - Standard Table 1 - Standard Table 1 - Reading ゝC1εl Table 1 - Standard Table 1 - Standard 'No.

Furthermore, the present invention provides general formula (Ia) N=C-N (Ia) in which Al represents optionally substituted aryl, A2 represents a group -P, where A3 represents alkyl, aryl, represents an optionally substituted group from the group consisting of alkoxy, alkylthio, alkylamino or dialkylamino, and A4 is optionally substituted from the group consisting of alkyl, alkoxy, alkylthio, alkylamino or dialkylamino and Q represents oxygen or sulfur.

Novel compounds of formula (Ia) are of formula (II a) N=C-
N H-A' (II a) where A1
has the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, a cyanamide of formula (lna)CQ-A"
(nIa) is obtained when reacting with a compound of formula (nIa) in which A2 has the above meaning.

Basically, in the same way, the formula (I[) N = C-N H-R' (II),
R1 has the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, a cyanamide of the formula (I!I) C11-R''
(III) is obtained when reacting with a compound of formula (III) in which R2 has the above meaning.

A' is [lI halogen, cyano, nitro, C1-C4-
Alkyl, C1-C2-halogenoalkyl, C, -C,
-alcoquine, CI"" C2-halogenoalkoxy,
01-C2-alkylthio, 01-C2-halogenoalkylthio, 01-C1-alkylsulfinyl, 01-
C4-alkylsulfonyl, C1-C2 halogenoalkylsulfonyl, 01-C4-alkylamino, di(c
r-C1-alkyl)-amino, 01-C4-alkyl-carbonyl-amino and C1-C4-alkoxy-
represents phenyl or naphthyl which may be mono- to polysubstituted with the same or different substituents from the group consisting of carbonyl, A2 represents a group -P, where A3 is optionally the same or different halogen substituents; C, -C, -alkyl, which may be monosubstituted to polysubstituted,
01-C1-alkoxy, which may optionally be mono- to polysubstituted with the same or different halogen substituents, 01
~C3-alkylthio, 01-C4-alkylamino or di(cr-C1-alkyl)-amino, and A4 may optionally be mono- to polysubstituted with the same or different halogen substituents; C1-C1; -Alkyl, 01-C4-alkoxy optionally optionally substituted with mono to polysubstituted halogen substituents, 0
Novel formula (Ia) representing 1-C4-alkylthi, C--C6-alkylamino or di(C+-C3-alkyl)-amino and Q representing oxygen or sulfur
Preferred are substituted cyanamides.

A1 is fluorine, chlorine, bromine, methyl, ethyl, cyanide, nitro, trifluoromethyl, trichloromethyl,
Methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylamino,
Mono- to polysubstituted with the same or different substituents from the group consisting of ethylamino, dimethylamino, diethylamino, trifluoromethylthio, acetylamino, propionylamino, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and isopropoxycarbonyl; A3 represents methyl, ethyl, phenyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, and A4 represents methyl, ethyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, Particular preference is given to novel compounds of formula (Ia) which represent hexyloxy, methylthio, ethylthio, propylthio, butylthio, methylamino, ethylamino or dimethylamino and in which Q represents oxygen or sulfur.

If, for example, N-(4-fluoro-phenyl)-cyanamide and phosphoryl dimethyl chloride ester are used as starting materials in the process for the preparation of novel compounds of formula (Ia), the course of the reaction can be summarized by the following formula: QC)l .

Formula (II a) gives a general definition of cyanamides used as starting materials. In formula (I[a), AI is preferably or especially similar to those given as preferred or particularly preferred for A1 in the novel active compounds of formula (Ia) above. has the meaning of

Examples of starting materials of formula (I[a) that may be mentioned include -N-phenylucyanamide, N~(4-fluoro-
phenyl)-cyanamide, N-(4-chloro-phenyl)-cyanamide, N-(3-chloro-phenyl)-cyanamide, N-(2-chloro-phenyl)-cyanamide,
N-(3,,4-dichloro-phenyl)-cyanami)'
, N-(4-nitro-phenyl)-cyanami)', N-
(3-Nitro-phenyl)-/anamide, N-(4-methoxy-phenyl)-cyanamide, N-(3-methoxy-phenyl)-cyanamide, N-(4-trifluoromethyl-phenyl)-cyanamide, N -(3-trifluoromethyl-phenyl)-cyanamide, N-(4-methyl-phenyl)-cyanamide, N-(3-methyl-phenyl)-cyanamide, N-(2-chloro-5-trifluoromethyl- phenyl)-cyanamide, N-(3-acetylamino-4-methyl-phenyl)-cyanamide, N-
(2-methoxy-5-nitro-phenyl)-cyanamide, N-(4-trifluoromethoxy-7enyl)-cyanamide, N-(2-methyl-5-ditrophenyl)-
Cyanamide, N-(4-methoxycarbonyl-phenyl)-cyanamide, N-(4-anophenyl)-cyanamide, N-(4-methylthio-phenyl)-cyanamide and N-(4-trifluoromethylthio-phenyl)
-Cyanamide.

The starting materials of formula (Ila) are known [Houben-Weyl, Methods of Organic Chemistry].
Chemie), Vol. 8, pp. 172-177 and Vol. E4, pp. 981-985; Org, Syn,
, Call, Vol. 4, 172-174; see DE-A-3,538,128.1 The formula (Dla) gives a general definition of the compounds further used as starting materials.

In the formula (Iota), A2 preferably or particularly has the same meanings as are given as preferred or especially preferred for A2 in the description of the novel active compounds of the formula (Ia) above.

Examples of starting materials of formula (Ina) that may be mentioned include: dimethylphosphinyl chloride, dimethylthiophosphinyl chloride, methyl ester of methane-, ethane- and hypenzene-phosphonyl chloride, ethyl Esters, propyl esters, butyl esters, pentyl esters and hexyl esters, S-methyl esters, S-ethyl esters, S-7'-methyl esters, S-butyl esters, S-methyl esters, S-ethyl esters, S-7'-methyl esters, S-butyl esters, S-methyl esters, propyl esters, butyl esters, pentyl esters and hexyl esters.
- pentyl esters and S-hexyl esters, methanephosphonamide chloride, methylamide, ethylamide, propylamide and butyramide of methanephosphonyl chloride, 0-methyl ester, 0-ethyl ester of methane-, ethane- and benzene-thiophosphonyl chloride, 0 -Propyl ester, 0-butyl ester, 0-pentyl ester and 0-hexyl ester, methane chloride, ethane and benzene - methyl ester, ethyl ester, propyl ester of dithiophosphonyl butyl ester, pentyl ester and hexyl ester, methane chloride Methylamide, ethylamide, propylamide and butyramide of -, ethane- and benzene-thiophosphonyl, dimethyl ester, diethyl ester, diethyl ester, dibutyl ester, methyl ethyl ester, methyl propyl ester, methyl butyl ester, ethyl propyl ester, ethyl Butyl ester and propyl butyl ester, o,S-dimethyl ester of thiophosphoryl chloride, 01S-diethyl ester, O,S-'; propyl ester, 0. S-dibutyl ester, 0-methyl-5-ethyl ester, 0-methyl-8-propyl ester, O-methyl-8-butyl ester, 〇-ethyl-5-methyl ester, 0-ethyl-S-propyl ester, 〇-Ethyl-3-butyl ester, o-propyl-5-methyl ester, 〇-propyl-5-ethyl ester, O-propyl-S-butyl ester, 0-butyl-8-methyl ester, 0-butyl-8-ethyl Esters and 0-butyl-5-propyl esters, methyl esters, ethyl esters, propyl esters and butyl esters of phosporamide chloride, methyl ester methylamide of phosphoryl chloride, ethyl ester methylamide, propyl ester methylamide, butyl ester methylamide, methyl Ester ethylamide, ethyl ester ethyl amide 1:, propyl ester ethyl amide, butyl ester ethyl amide, methyl ester propyl amide, ethyl ester propyl amide, propyl ester propyl amide, butyl ester propyl amide, methyl ester butyl amide, ethyl ester butyl amide amides, propyl ester butyramide and butyl ester butyramide, S, S-dimethyl ester of dithiophosphoryl chloride, S, S-diethyl ester, S, S-dipropyl ester and S, S-dibutyl ester, S of thiophosphoryl chloride -Methyl ethyl methylamide, S-ethyl ester methyl amide, S-propyl ester methyl amide, S-methyl ester ethyl amide, S-ethyl ester ethyl amide, S-7'-methyl ester ethyl amide, S-methyl ester propyl amide , S-ethyl ester ethylamide and S-propyl ester butyramide, phosphoryl chloride bis-dimethylamide and bis-diethylamide, 0.0-dimethyl ester of thiophosphoryl chloride, 0. O-diethyl ester, o.

0-dipropyl ester, 0. o-dibutyl ester,
0-methyl-〇-ethyl ester, O-methyl-〇-propyl ester, O-methyl-〇-butyl ester, 0
-ethyl-〇-propyl ester, 0-ethyl-〇-butyl ester and O-propyl-〇-butyl ester,
02S-dimethyl ester of dithiophosphoryl chloride, 0
．． S-diethyl ester, 0.5-dipropyl ester, 0, S-'; dibutyl ester 0-methyl-5-ethyl ester, 0-methyl-8-propyl ester, ○-
Methyl-S-butyl ester, 0-ethyl-5-7' methyl ester, 0-ethyl-3-7' methyl ester, 0
-ethyl-8-methyl ester, O-propyl-8-methyl ester, 0-propyl-5-ethyl ester, 0
-propyl-5-butyl ester, 0-butyl-5-methyl ester, 0-butyl-5-ethyl ester and 0
-butyl-5-propyl ester, O-methyl ester of thiophosphoramide chloride, 0-ethyl ester, 0-
7'pyl ester and O-butyl ester, O-methyl ester methylamide of thiophosphoryl chloride, 0-ethyl ester methylamide, 0-propyl ester methylamide, 0-butyl ester methylamide, O-methyl ester ethylamide, 0-ethyl ester ethylamide, O-globil ester ethylamide, O-butyl ester ethylamide, 0-methyl ester propylamide, 〇-ethyl ester propylamide, 〇-propyl ester propylamide, 0-butyl ester propylamide, 0-Methyl ester butyramide, 〇-ethyl ester butyramide, 〇-propyl ester butyramide and Q-butyl ester butyramide, S, S-dimethyl ester of trithiophosphoryl chloride, S, S-
diethyl ester, S, S-dipropyl ester and S
.

S-dibutyl ester and thiophosphoryl bis-chloride
Dimethylamide and bis-diethylamide.

The starting materials of formula (Illa) are known (Hoben-Uniyl, Methods of Organic Chemistry, Vol. 12/1, 415-42
0 and pages 560-563, Volume 12/2, 274-29
2.405~408.607~618.621~622
and pp. 755-757, and Vol. 62, 333-68.
(See page 4).

The process for preparing the novel compounds of formula (I a) according to the invention is preferably carried out using a diluent. In this case, water and practically all inert organic solvents are suitable as diluents. These include preferably aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, chloride. ethylene, chloroform, carbon tetrachloride, chlorobenzene and 0-dichlorobenzene, ethers such as diethyl ether and dibutyl ether,
Included are glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate or nitriles such as acetonitrile and propionitrile.

All acid binders customary for such reactions can be used as acid acceptors in the process according to the invention. Preferred are alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates and alcoholades such as sodium and calcium carbonate, sodium methylate and potassium. Methylate, sodium ethylate and potassium ethylate, sodium t-
Butyrad and potassium butyrad, and also aliphatic, aromatic or heterocyclic amines such as triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1,5-diazabicyclo[
4,3,0]-non-5-ene (DBN), 1.
8-diazabicyclo-[5,4,0]-undes-7
-ene (DBU) and 1,4-diazabicyclo-[
2,2,2]-octane (DABCO).

In the process according to the invention, the reaction temperature can be varied within a relatively wide range. Generally, the reaction is carried out at a temperature between -20 and 80°C, preferably between 0 and 40°C.

The process according to the invention is generally carried out under atmospheric pressure.

When carrying out the method according to the invention, formulas (II a) and (n
The starting materials [a) are generally used in approximately equimolar amounts. The reaction mixture is stirred in each case for several hours at the required temperature. Treatment can be carried out using conventional methods. For example, the mixture is concentrated, the residue is taken up in a practically water-immiscible organic solvent such as methylene chloride, and the solution is washed with water, dried and filtered. The residue obtained after removing the solvent from the filtrate by distillation, optionally at slightly elevated temperature and reduced pressure, essentially contains the respective product of formula (I a).

The active compounds according to the invention have a strong microbicidal action (n+1c
robicidal action) and can be used in the control of practically undesirable microorganisms.

The active compounds are suitable for use as plant protection agents, in particular fungicides.

Plasmodiophoromycetes is a fungicide and fungicide for plant protection.
, Oomycetes, Chytridio-mycetes, Zygomycetes (
Z ygomycates), cystomycetes (A scom
ycetes), Basidiomycetes (Basido+nyce
tes), and Deuteromyce
tes) is used to control.

Examples of the causative organisms for the fungal and fungal diseases mentioned above may be mentioned, but are by no means limited to: Pythium species, such as seedling damping-off (
P ythiui ultimum; Phytophthora (P 11yL□phthora) species such as Phytophthora (P
hytopbth.

ra 1nfestans); Pseudoperonospora species such as downy mildew (P5eudoperonospora hu)
muli; or P5eudoperonospo
ra cubensis) ; plasmopara (P l
asmopara) species such as downy mildew (P lasmop
ara viticola) ; Peronosvora (Peronosvora);
onospora) species such as downy mildew (P aronos
pora pisi or P, brassicae)
; Erysiphe species such as powdery mildew (Erysiphe graminis)
; S phaerotheca species such as powdery mildew (S phaerotheca ful
1g1nea); Podosp
haera) species such as powdery mildew (P. haera)
era 1eucotricha); Venturia species such as V enturia
ria 1naequalis) ; Pirenohora (P
yranophora) species such as P yren
ophora Leres or p, graminea
) (conidiophore; D rechslera, synonym: Helmintbosp.

rium); Cochliobolus
lus) species such as Cochliobolus
5aLivus) (conidiospore-like: l) r6Ch
slera, synonym: Helminthosporiu
m); Uromyces species such as Uromyces appendiculatu;
s); Puccinia species such as Puccinia recondiLa
; TileLia species such as TilleLia caries ; Ustilago species such as naked smut (U
stilagonuda or Ustilago av
enae); Pellicularia
aria) species 1, such as Pelliculari
a 5asakii); Biricularia (Pyri
cularia) species such as rice blast (Pyricul
aria oryzae) ; Fusalium (Fus
arium) species such as Fusarium thalmorum (F
usarium culmorum); gray mold (
Botrytis is) species such as botrytis blight (B ot
rytis cinsrea); Cebutria (Sep
toria) species, such as Saptoria n.
odorum); Leptosphaeria (Leptosp.
haeria) species such as Leptosphaeria nodorum (
Leptosphaeria nodorum);
Cercospora (Cerc.

5pora) species such as Cercospora canescens (Ce
rcospora canescens; Alternaria species such as black spot (A
1ternaria brassicae) and P. 5eudocercosporella (P.
Rella) species such as Pseudocercosborella herphotricoides (P 5eudocercospore)
herpotrichoides).

The good tolerability of the active compounds by plants at the concentrations required for controlling plant diseases makes it possible to treat the above-ground parts of plants, the growing stems and seeds, and the soil.

In particular, the compounds according to the invention have a pronounced effect on fruit cultivation, such as Penturia sp. in apples and Viricularia sp. in rice.

Certain of the compounds of formula (I) according to the invention also exhibit bactericidal action and action against mites and insects in cultivated plants and against pests in hygiene and storage.

Depending on its special physical and/or chemical properties,
The compounds can be prepared in conventional compositions, e.g. solutions, emulsions, suspensions,
Powders, encapsulants, liniments, granules, natural and synthetic substances impregnated with active compounds in aerosols, very fine capsules and coating compositions in polymeric substances for seeds, compositions for use in combustion devices, e.g. fumigation cartridges. , fumigation cans and fumigation coils, etc., as well as ULV cold mist and warm mist compositions.

These compositions are prepared in known manner, for example, by mixing the active compounds with extenders, i.e. liquid solvents and/or solid carriers, and optionally surfactants, i.e. emulsifiers and/or dispersants and/or blowing agents. Ru. Furthermore, when water is used as an extender, for example, an organic solvent can also be used as an auxiliary solvent.

As liquid solvents, mainly aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons such as hachlorobenzene,
chloroethylene or hydrogenated methylene, aliphatic hydrocarbons such as cyclohexane, or paraffins such as mineral oil fractions, mineral and vegetable oils, alcohols such as butanol or glycols and their ethers and esters,
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water are suitable; liquefied gaseous extenders or carriers are defined as liquids which are gaseous at normal temperature and pressure. halogenated hydrocarbons and aerosol propellant bases such as butane, propane, nitrogen and carbon dioxide; as solid carriers ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite; , montmorillonite, or diatomaceous earth, as well as ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates; as solid carriers for the granules, ground and fractionated natural rocks, such as calcite,
Marble, pumice, sepiolite and dolomite as well as inorganic and organic ground synthetic granules and granules of organic substances such as sawdust,
Palm, corncobs and tobacco stalks are suitable; as emulsifiers and/or blowing agents nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycols. Ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and albumin hydrolysis products are suitable as monodispersing agents, such as lignin sulfite waste liquor and methylcellulose.

Adhesives such as carboxymethyl cellulose as well as powders,
Particulate or latex natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalin and lecithin, and synthetic phospholipids can be used in the composition.

Further additives can be 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 and metal phthalocyanine dyes and trace amounts of nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc may be used. Can be done.

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

The active compounds according to the invention can be used in preparations in mixtures with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, as well as with fertilizers and other growth regulators. can exist.

The active compounds are used as such, in the form of their preparations or in the use forms prepared from them, such as liquid solutions, suspensions, wettable powders, liniments, soluble powders, powders and granules. be able to. These are applied in the usual manner, for example by watering, spraying, atomizing, scaltering, dusting, foaming, brushing, etc. Furthermore, it is possible to apply the active compound according to ultra-low volume methods or to inject the active compound preparation or the active compound itself into the soil. It is also possible to treat plant seeds.

When treating plant parts, the active compound concentration in the application forms can be varied within a substantial range. Generally the concentration is between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

When treating seeds, generally 0.00
From 1 to 50 g of active compound are required, preferably 0.001-10 g.

When treating soil, generally o, ooooo is applied to the working area.
t~0.1% by weight, preferably 0.0001-0.02
requires an active compound concentration of % by weight.

USE EXAMPLES The following compounds were used as comparative substances in the following usage examples: I Zinc ethylene-1,2-bisudithiocarbamidate (
Zineb) [Phytobathology-33 (1943), +11
3].

N,N-dimethyl-N'-phenyl-N'-fluorodichloromethylthiosulfamide (dichlorofluanid) (
(Known from German Patent Application Publication No. 1,193°498).

Example A Pyricularia test (rice)/
Protective solvent: 12.5 parts by weight of acetone Emulsifier: Alkylaryl polyglycol ether 0.
To prepare a suitable preparation of 3 parts by weight of active compound, 1 part by weight of active compound is mixed with the above amount of solvent and the concentrate is diluted with water and the above amount of emulsifier to the desired concentration.

To test the protective activity, young rice plants were sprayed with the active compound preparation until dripping wet. After the spray coating has dried, the plant blast disease (P y
ricularia oryzae). The plants were then placed at 100% relative humidity and 25°
I placed it in a hotbed of C.

Assessment of disease infection was performed 4 days after inoculation.

In this test, Example No., (2), (3), (6
), (I3), (26), (61), (62) and (8
The compounds according to the invention shown as 3) in Table 1 exhibited a considerably better action than the comparative substance (A). The results are shown in Table A.

Lo lo lo lo.

cPIc'v (1')
M eq Practical Example V enturia test (apple) / Protective solvent: 4.71 parts of acetone Emulsifier: Alkylaryl polyglycol ether 0.
To prepare a suitable preparation of 3 parts by weight of 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 activity, young plants were sprayed with the active compound preparation until dripping wet. After the spray coating has dried, the plant is infected with apple 5cab causative.
anism (Venturia 1naequali
s)] and then inoculated with an aqueous suspension of conidiophores of 20
The device was kept in the culture room for 1 day at 100% relative humidity.

The plants were placed in a greenhouse at a temperature of about 20°C and a relative humidity of about 70%.

Evaluation was performed 12 days after inoculation.

In this test, Examples (9), (28), (38)
The compounds shown in Table 1 as (61) and (61) are the comparative substance (B
) showed a much better effect. The results are shown in Table B.

Table B Scotch disease test (apple)/protection dispatch (B) (Publicly known) C1be N C1be N C1be Manufacturing example Example 1 OC2H.

9.4 g (0.05 mol) of thiophosphoryl chloride o,0-diethyl ester dissolved in 150 mff of acetonitrile were stirred at 20'O, and then 9.8 g (0.05 mol) of N-(3-nitro-phenyl)-cyanamide was dissolved in 150 mff of acetonitrile. mol), 7 g (0,0625 mol) of potassium t-butylade and 150 mQ of acetonitrile. The reaction mixture was stirred at 2b°C for 12 hours and then evaporated. The residue was taken up in 200 n+Q methylene chloride, washed twice with in each case 200 m of water, dried over sodium sulfate and filtered. The solvent was carefully distilled off at slightly elevated temperature and under reduced pressure. and removed from the filtrate.

Refractive index nt? -1,5863 N-(3-nitro-phenyl')-N-(jethoxythiophosphoryl)-cyanamide was obtained as a brown, oily residue.

In addition, as Example Nos. 70 to 73 and 75 to 93, the first
The novel compound of formula (Ia) shown in the table was used as Example No.
It could be prepared analogously to Preparation Example 1 giving rise to the compound shown in Table 1 as 74.

Formula (I) further shown as an example in Table 1
A widely known compound was obtained in essentially the same manner.

The main features and aspects of the invention are as follows.

1. At least one general formula (I) N=C-N (I) in which R1
represents optionally substituted alkyl or aryl, and R2 represents a group -CO-R'', -SO!-R' or -PR
', where R3 is alkyl, cycloalkyl, alkenyl, aralkyl, aralkenyl, aryl, heteroaryl, alkoxy, aralkoxy, aryloxy, alkylthio, aralkylthio, arylthio, alkylamino, cycloalkylamino, dialkylamino, aralkylamino and arylamino, R4 represents an optionally substituted group from the group consisting of alkyl, aralkyl, aryl and heteroaryl, and R5 represents alkyl, aryl. , alkoxy, alkylthio, alkylamino and dialkylamino, and R@ is an optionally substituted group consisting of alkyl, alkoxy, alkylthio, alkylamino and dialkylamino. and Q represents oxygen or sulfur.
fungicide.

2. In formula (I), R1 is 01-C4-alkyl,
or optionally halogen, cyano, nitro, C,-C,-alkyl, CI'=Cz-halogenoalkyl, 01-C
1-alkoxy, 01-C2-halogenoalkoxy, 0
1-C4-alkylthio, C8-C2-halogenoalkylthio, 01-C1-alkylsulfinyl, C1-C
4-alkylsulfonyl, C1-C2 halogenoalkylsulfonyl, 01-C3-alkylamino, di(C+
~C3-alkyl)-amino, C1-C4-alkyl-
represents phenyl or naphthyl which may be mono- to polysubstituted with the same or different substituents from the group consisting of carbonyl-amino and 01-C4-alkoxycarbonyl, and R2 is a group -C O -R 3, -S O
, -R' or 1P, in which R3 may optionally be mono- to polysubstituted with the same or different substituents from the group consisting of halogen and C1-C4-alkoxy, C□-C,- alkyl, optionally mono- to polysubstituted with the same or different substituents from the group consisting of halogen and 01-C2-alkyl,
~C. C siloalkyl, optionally mono- to polysubstituted with the same or different halogen substituents, C2
~CIO-alkenyl, C2-C1. -Alkynyl, optionally benzyl optionally substituted with mono- to polysubstituted halogen substituents in the ring with the same or different halogen substituents, phenylethynyl, optionally halogen, cyano, nitro, CI-04-
phenyl, naphthyl, furyl, chenyl, pyridyl, C, -C. C decoxy, benzyloxy, phenoxy, cl-Cs-alkylthio, benzylthio, phenylthio, 01-C,-alkylamino, C. N.C. -cycloalkylamino, di(C1-C
, -alkyl)-amino, benzylamino or optionally halogen, cyano, nitro, C. ~C, -C rule, C,
~C2-halogenoalkyl, C, ~C, -C ruoxy,
CI~C,-halogenoalkoxy, 01~C,-alkylthio%Cl~C2-halogenoalkylthio, C1~C
,-alkylsulfinyl, C1-C,-alkylsulfonyl, C1-C2 halogenoalkylsulfonyl and C
, - represents a phenylamino which may be mono- to polysubstituted with the same or different substituents from the group consisting of C4-alkoxycarbonyl, and R4 is optionally mono- to polysubstituted with the same or different halogen substituents; C1-C1o-alkyl, optionally halogen, cyano, nitro, C,-C4-alkyl, 01-C. -halogenoalkyl, C. -C,-alkoxy, C, ~C,-
Benzyl, optionally halogen, cyan, nitro, phenyl, C I-C 4 optionally substituted with mono- to polysubstituted substituents from the group consisting of C-ronoalkoxy and 01-C4-alkoxy-carbonyl, the same or different substituents -Alkyl, C, ~C2-halogenoalkyl, 01~C, -
Alkoxy, 01~C2-halogenoalkoxy, 01~
C4-alkylthio, 01-C.

-halogenoalkylthio, 01-C4-alkylsulfinyl, C1-C4-halogenoalkylsulfonyl, di(01-C2-alkyl)-aminosulfonyl and C
, -C,-alkoxy-carbonyl, optionally halogen, cyano, nitro, C
8~C. -furkyl, naphthyl which may be mono- to polysubstituted with the same or different substituents from the group consisting of C1-C,-alkoxy, optionally halogen, CI-0
chenyl, optionally halogen, which may be mono- to polysubstituted with the same or different substituents from the group consisting of 4-alkyl and 01-C4-alkoxy-carbonyl;
pyrazolyl optionally substituted with CI-04-alkyl and 01-C4-alkoxy-carbonyl or optionally with the same or different substituents from the group consisting of halogen, CI-C4-alkyl and 01-C4-alkoxy-carbonyl; 01-C4-alkyl, phenyl, which may be mono- to polysubstituted pyridyl, where R' is optionally substituted with the same or different substituents, phenyl, optionally the same or different substituents represents 01-C,-alkoxy, 01-C4-alkylthio, 01-C,-alkylamino or di(C+-C,-alkyl)-amino, which may be mono- to polysubstituted, and Ra is optionally 01-C,-alkyl, which may be mono- to polysubstituted with the same or different halogen substituents; C,-C,-alkyl, which may optionally be mono- to polysubstituted with the same or different halogen substituents; The sterilization/killing agent according to 1 above, wherein C represents decoxy, 01-C,-alkylthio, 01-C,-alkylamino or di(01-C1-alkyl)-amino, and Q represents oxygen or sulfur. mold agent.

3. In formula (I), R1 is optionally fluorine, chlorine, bromine, methyl, ethyl, cyano, nitro, trifluoromethyl, trichloromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylamine, ethyl mono- to tri-substituted with the same or different substituents from the group consisting of amino, dimethylamino, diethylamino, trifluoromethylthio, acetylamino, propionylamino, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and impropoxycarbonyl; represents good phenyl, R8 is a group -Co-R", R3 is optionally fluorine,
Mono- to tri-substituted with the same or different substituents from the group consisting of chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, trichloromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy and chlorodifluoromethoxy represents phenyl, which may optionally be
trifluoromethylthio, dimethylaminosulfonyl,
R5 represents methyl, ethyl, phenyl, methoxy, ethoxy, methylthio , ethylthio, methylamino, ethylamino or dimethylamino, and R6 is methyl, ethyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, methylthio, ethylthio, propylthio, butylthio, methylamino, ethylamino or dimethylamine and Q represents oxygen or sulfur,
The bactericidal/fungicidal agent described in 1 above.

4. Use of the substituted cyanamide of formula (I) as described in 1 above in controlling fungi and molds.

5. A method for controlling fungi and mold, which comprises causing the substituted cyanamide of formula (1) described in 1 above to act on the fungus and mold and/or its environment.

6. A method for producing a bactericidal/fungicidal agent, which comprises mixing the substituted cyanamide of formula (I) described in 1 above with a filler and/or a surfactant.

7. General formula (Ia) N=C-N(Ia) In the formula, A1 represents optionally substituted aryl, A3 A3 is a group consisting of alkyl, aryl, alkoxy, alkylthio, alkylamino or dialkylamino A4 represents an optionally substituted group from the group consisting of alkyl, alkoxy, alkylthio, alkylamino or dialkylamino, and Q represents oxygen or sulfur. , substituted cyanamide.

8. In formula (Ea), A' is optionally halogen, cyano, nitro, C1-C4-alkyl, Cl-62-halogenoalkyl, Cl-04-alkoxy, 01-02-halogenoalkoxy, C, -C, - Alkylthio, Cl-
02-halogenoalkylthio, 01-C4-alkylsulfinyl, C,-C,-alkylsulfonyl, Cl-
C2 halogenoalkylsulfonyl, cl-C6-alkylamino, C(C+-C1-alkyl)-amino, C
, -C, -alkyl-carbonyl-amino and 01-C
represents phenyl or naphthyl which may be mono- to polysubstituted with the same or different substituents from the group consisting of 4-alkoxy-carbonyl, and A2 is a group -P
represents C,-, where A3 may optionally be mono- to polysubstituted with the same or different halogen substituents;
C, ~alkyl, optionally mono- to polysubstituted with the same or different halogen substituents 01-C4-
Alkoxy, 01-C4-alkylthio, C, -C, -
alkylamino or di(C+~C8-alkyl)-
01--, which represents amino, and A4 may optionally be mono- to polysubstituted with the same or different halogen substituents;
C4-alkyl, optionally mono- to polysubstituted with the same or different halogen substituents 01-C6-
Alkoxy, CI-C, -alkylthio, 01-C1-
alkylamino or di(cr~C8-alkyl)
- substituted cyanamide according to claim 7, wherein Q represents oxygen or sulfur.

9. In formula (I a), AI is optionally fluorine, chlorine,
Bromine, methyl, ethyl, cyanide, nitro, trifluoromethyl, trichloromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio,
From monosubstitution with the same or different substituents from the group consisting of ethylthio, methylamino, ethylamino, dimethylamino, diethylamino, trifluoromethylthio, acetylamino, propionylamino, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and impropoxycarbonyl represents phenyl which may be polysubstituted, A'' is a group -p, where A
3 is methyl, ethyl, phenyl, methoxy, ethoxy,
represents methylthio, ethylthio, methylamine, ethylamino or dimethylamino, and A4 is methyl, ethyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, methylthio, ethylthio,
Substituted cyanamide according to 7 above, which represents propylthio, butylthio, methylamino, ethylamino or dimethylamino, and Q represents oxygen or sulfur.

10. General formula (Ia) AINmiC-N(Ia) In the formula, AI represents optionally substituted aryl, and A3 consists of alkyl, aryl, alkoxy, alkylthi, alkylamino or dialkylamino A4 represents an optionally substituted group from the group consisting of alkyl, alkoxy, alkylthi, alkylamino or dialkylamino, and Q represents oxygen or sulfur. When producing a substituted cyanamide with the general formula % formula %
) in which A1 has the abovementioned meaning, a cyanamide of the formula (Ina)CQ-A, if appropriate in the presence of a strict receptor and if appropriate in the presence of a diluent.
(lira), wherein A2 has the above meaning, characterized in that it is reacted with a compound of the general formula (Ia
) A method for producing a substituted cyanamide.

Claims (1)

[Claims] 1. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼... (I) In the formula, R^1 represents alkyl or aryl which may be optionally substituted, and R^2 represents a group -CO-R^3, -SO_2-R^4 or ▲a mathematical formula, a chemical formula, a table, etc.▼, where R^3 is alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aralkenyl , aryl, heteroaryl, alkoxy, aralkoxy, aryloxy, alkylthio, aralkylthio, arylthio, alkylamino, cycloalkylamino, dialkylamino, aralkylamino and arylamino, which may be optionally substituted. , R^4 represents an optionally substituted group from the group consisting of alkyl, aralkyl, aryl and heteroaryl, and R^5 represents a group consisting of alkyl, aryl, alkoxy, alkylthio, alkylamino and dialkylamino. represents an optionally substituted group from the group consisting of alkyl, alkoxy, alkylthio, alkylamino and dialkylamino, and Q represents oxygen or sulfur. A bactericidal and fungicide characterized by containing at least one substituted cyanamide as shown below. 2. Use of substituted cyanamides of formula (I) according to claim 1 for controlling fungi and molds. 3. General formula (I a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I a) In the formula, A^1 represents an optionally substituted aryl, and A^2 is a group ▲Math , chemical formulas, tables, etc. ▼, where A^3 represents an optionally substituted group from the group consisting of alkyl, aryl, alkoxy, alkylthio, alkylamino, or dialkylamino, and A^4 represents Substituted cyanamides representing an optionally substituted group from the group consisting of alkyl, alkoxy, alkylthio, alkylamino or dialkylamino, and Q representing oxygen or sulfur. 4. General formula (I a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I a) In the formula, A^1 represents an optionally substituted aryl, and A^2 is a group ▲Math , chemical formulas, tables, etc. ▼, where A^3 represents an optionally substituted group from the group consisting of alkyl, aryl, alkoxy, alkylthio, alkylamino, or dialkylamino, and A^4 represents represents an optionally substituted group from the group consisting of alkyl, alkoxy, alkylthio, alkylamino or dialkylamino, and Q represents oxygen or sulfur. General formula (IIa) ▲Mathematical formulas, chemical formulas, tables, etc.▼(IIa) In the formula, A^1 has the above meaning, and the cyanamides of , if appropriate, in the presence of an acid acceptor and if appropriate, diluted. In the presence of an agent, formula (IIIa) Cl-A^2
(IIIa) wherein A^2 has the above-mentioned meaning, characterized in that it is reacted with a compound of the general formula (I
A) Method for producing substituted cyanamides.