DD247371A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to herbicidal agents for use in agriculture. The aim of the invention is the provision of new agents with a strong herbicidal action and good Nutzpflanzenvertraeglichkeit. According to the invention, new 5-amino-4-cyano-1-pyridyl-pyrazoles of the formula (I) are used as active ingredient in the novel herbicidal compositions, in which, for example: R 1 is hydrogen, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl and the like. R2; hydrogen, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl and the like; a.; Pysubstituted pyridyl but not 5-nitro-2-pyridyl or 3-chloro-5-trifluoro-methyl-2-pyridyl residue. Formula (I)

Description

R ¹ and R ² together with the nitrogen atom to which they are bonded, for each optionally optionally one to four times, identically or differently by methyl, ethyl, η- or i-propyl substituted heterocycle of the formula

or

stand and

Py represents in each case one to four times, identically or differently substituted 2-pyridyl, 1,3-pyridyl or 4-pyridyl, suitable substituents being in each case: cyano, nitro, fluorine, chlorine, bromine, iodine, methyl, ethyl, η- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, difluorochloromethyl, chloromethyl, dichloromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl, difluorodichloroethyl, trifluorodichloroethyl, entachloroethyl Trifluoromethoxy, richlormethoxy, dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy, dichloromethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluorochloroethoxy, trifluoroethoxy, difluorodichloroethoxy, trifluorodichloroethoxy, pentachloroethoxy or a radical -S (O) _m -R ⁴ , where

R ^{4 is} methyl, ethyl, amino, methylamino, ethylamino, dimethylamino, diethylamino, fluorodichloromethyl, difluoromethyl, tetrafluoroethyl, trifluorochloroethyl, trichloromethyl or trifluoromethyl and

m stands for a numberO, 1 or 2,

Py, however, does not stand for the S-nitro-pyridyl radical or the S-chloro-S-trifluoromethyl-pyridyl radical.

4. A method for controlling weeds, characterized in that is allowed to act on weeds and / or their habitat an ö-amino ^ cyano-i-pyridyl-pyrazoi of the formula (I) according to the items 1 to 3. ·

5. Use of B-amino-cyano-i-pyridyl-pyrazoles of the formula (I) according to the items 1 to 3, characterized in that they are used for controlling unwanted plant growth.

6. A process for the preparation of herbicidal agents, characterized in that mixing 5-amino-4-cyano-1-pyridyl-pyrazoles of the formula (I) according to points 1 to 3 with extenders and / or surface-active agents.

Field of application of the invention

The invention relates to herbicidal compositions containing new B-amino-cyano-i-pyridyl-pyrazoles, several processes for their preparation and their use as herbicides.

-4- 247 Characteristic of the known technical solutions

It is already known that certain 4-cyano-i-arylpyrazoles, such as the 4-cyano-5-propionamido-1 - (2,3,4-trichlorophenyl-pyrazole, or certain 4-cyano-1-pyridyl-pyrazoles have herbicidal properties (see, for example, DE-OS 3226513, DE-OS 3408727).

However, the herbicidal activity of these previously known compounds against weeds, as well as their compatibility with important crops, is not always completely satisfactory in all fields of application.

Furthermore, 5-nitropyridyl-pyrazoles are known (see Rev. Latinoam Quim 13, 102-103 [1982] which can be used as intermediates in the preparation of novel heterocyclic systems, but an application of these compounds in agriculture is not mentioned.

Object of the invention

The aim of the invention is the provision of new agents with a strong herbicidal action and good compatibility with crops.

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties that are suitable as active ingredient in herbicidal compositions.

According to the invention, as active ingredient in the novel herbicidal compositions, new B-amino-cyano-i-pyridyl-pyrazoles of the general formula (I)

CN ·

R ¹

i ^N S

Py R

applied in which

R ^{1 is} hydrogen, in each case optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl or a radical ·

-CR _stand ' _ti

R ^{2 is} hydrogen, each optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl, or a radical * '-''* R, wherein

X stands for oxygen or sulfur and

R ^{3 is} hydrogen, alkyl, alkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl, haloalkyl, alkenyl, alkynyl, each optionally

substituted cycloalkyl, aryl, aryloxy, arylthio or arylamino, is alkylamino or dialkylamino or R ¹ and R ² together with the nitrogen atom to which they are attached, an optionally substituted

Heterocycle of the formula y-V

-N ι -N \ or -N

O ö Ö

stand and

Py represents substituted pyridyl, but does not represent the 5-nitro-2-pyridyl or the 3-chloro-5-trifluoromethyl-2-pyridyl radical

 Furthermore, it has been found that the new 5-amino-4-cyano-1-pyridyl-pyrazoles of the general formula (I)

iii ζ * ¹

R ² Py ^H

in which

R ^{1 is} hydrogen, in each case optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl or a radical

• CR ³ stands,

R ^{2 is} hydrogen, in each case optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl or a radical -CR ^stent '

X is oxygen or sulfur and R ^{3 is} hydrogen, alkyl, alkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl, haloalkyl, alkenyl, alkynyl, each optionally

substituted cycloalkyl, aryl, aryloxy, arylthio or arylamino, al kylamino or dialkylamino or R ¹ and R ² together with the nitrogen atom to which they are attached, an optionally substituted

Heterocycle of the formula

-N y, -N \ or

stand and

Py represents substituted pyridyl, but does not represent the 5-nitro-2-pyridyl or the 3-chloro-5-trifluoromethyl-2-pyridyl radical, can be prepared by the following procedure: (a) the 5-amino according to the invention 4-cyano-1-pyridyl-pyrazoles of the formula (I),

if

5-Halogeno-4-cyano-1-pyridyl-pyrazoles of the formula (II) ₍

(II)

in which shark stands for halogen and

Py has the abovementioned meaning, with amino compounds of the formula (III)

HN

(HD

in which

R ¹ and R ^{2 have} the abovementioned meaning, if appropriate in the presence of a diluent, or (b) the 5-amino-4-cyano-1-pyridyl-pyrazole derivatives of the formula (I b) according to the invention are obtained;

nV ^^ (Ib)

Py

in which

Py has the abovementioned meaning when pyridylhydrazines of the formula (IV)

Py-NH-NH ₂ (IV)

in which

Py has the abovementioned meaning, with acrylonitrile derivatives of the formula (V)

CN A-CH = C < ^v)

 \ CN

in which A is halogen, hydroxyl, alkoxy or dialkylamino, first in a 1st stage, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, converted to the pyridylhydrazine derivatives of the formula (VI),

/ CN

Py-NH-NH-CH = C (VI)

\ CN

in which Py has the meaning given above,

and optionally cyclized in a second stage in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or (c) the 5-amino-4-cyano-1-pyridyl-pyrazole derivatives of the formula (Ic) according to the invention,

in which R ² " ^{1 represents} in each case optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl or represents a radical -CR ^ and

R ¹ , R ³ , Py and X have the abovementioned meaning, if 5-amino-4-cyano-1-pyridyl-pyrazoles of the formula (Ik)

T. (Ik)

j NH-E ¹ Py

in which R ¹ and Py have the abovementioned meaning, with compounds of the formula (VII)

R ^{2 "1} -A ^r '(VII)

in which R ² " ^{1 represents} in each case optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl or represents a radical -CR, where

R ³ 'and X have the abovementioned meaning and A ^{1 is} an electron-withdrawing leaving group, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, or (d) the 5-amino-4-cyano-1 according to the invention pyridyl-pyrazoles of the formula (Id)

(Ld)

in which R ³ " ^{1 is} alkyl or optionally substituted aryl, Y is oxygen, sulfur, a (-NH-) or a {N-alkyl) group and Py has the abovementioned meaning, if N, N-bis (phenoxycarbonyl) amino] -1-pyridyl-pyrazoles of the formula (II) _s

Py

in which Py has the abovementioned meaning, with compounds of the formula (VIII)

R ³ - ¹ -YH,

in which R ³ "" ^{1 is} alkyl or optionally substituted aryl and Y is oxygen, sulfur, an (-NH -) or (N-alkyl) group, optionally in the presence of a diluent and optionally in the presence of a basic Reactive reactant, orman receives (e) the S-amino ^ cyano-i-pyridyl-pyrazole derivatives of the formula (I e) according to the invention,

(VIII)

(Ie)

2-2

in which R ² " ^{2 is} in each case optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl and Py has the abovementioned meaning, if 5- (N-acylamino) -4-cyano-1-pyridyl-pyrazoles of the formula (Im) .

(In the)

2-2

in which R ³ , R ² " ² , X and Py have the abovementioned meaning,

deacylated with acids or bases, if appropriate in the presence of a diluent, or (f) the B-amino-cyano-i-pyridyl-pyrazole derivatives of the formula (If) according to the invention are obtained,

(If)

Py

in which η is 2,3 or 4 and Py has the meaning given above,

if

B-haloacylamino-cyano-pyrazoles of the formula (In)

¹ (in)

Py

in which

Hai ^{1 is} halogen, η is 2,3 or 4 and Py has the meaning given above,

if appropriate, intramolecularly cyclized in the presence of a diluent and if appropriate in the presence of a basic reaction auxiliary, or (g) the 5-amino-4-cyano-1-pyridylpyrazole derivatives of the formula (Ig) according to the invention are

dg) Py "*" *

in which

R ³ " ^{2 is} alkyl or optionally substituted aryl,

X is oxygen or sulfur and R ¹ and Py are as defined above when

5-amino-4-cyano-pyridyl-pyrazoles of the formula (Ik),

(Ik)

in which

R ¹ and Py have the abovementioned meaning,

with iso (thio) cyanates of the formula (IX),

R ³ - ² - N = C = X (IX)

in which

R ³ " ² and X have the abovementioned meaning,

if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

Finally, it has been found that the new 5-amino-4-cyano-1-pyridyl-pyrazoles of the formula (I) have herbicidal properties, in particular also selective herbicidal properties.

Surprisingly, the 5-amino-4-cyano-1-pyridyl-pyrazoles of the general formula (I) according to the invention show a better herbicidal activity against harmful plants, while at the same time being more compatible with important crops than, for example, the compounds known from the prior art. Cyano-5-propionamido-1- (2,4,6-trichlorophenyl) - or - (2,3,4-trichlorophenyl) -pyrazole, which are chemically and operatively obvious compounds. The 5-amino-4-cyano-1-pyridyl-pyrazoles according to the invention are generally defined by the formula (I). Preference is given to compounds of the formula (I) in which

R ^{1 is} hydrogen, in each case optionally monosubstituted or polysubstituted, identically or differently substituted alkyl having 1 to 8 carbon atoms, alkenyl or alkynyl having in each case 2 to 8 carbon atoms, suitable substituents being in each case:

Halogen, cyano, nitro, hydroxy, carboxy, in each case straight-chain or branched alkoxy or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl moiety, aminocarbonyl which may be optionally substituted by alkyl, alkoxy, alkylsulfonyl, alkenyl or alkynyl and wherein the nitrogen atom of the aminocarbonyl also part of a saturated 3- to 7-membered heterocycle having 1 or 2 further heteroatoms, in particular nitrogen, oxygen or sulfur, may be: for optionally mono- or polysubstituted by identical or different halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted cycloalkyl with 3 to 7 carbon atoms or is a radical _ _C _ _R 3,

is hydrogen, in each case optionally monosubstituted or polysubstituted, identically or differently substituted alkyl having 1 to 8 carbon atoms, alkenyl or alkynyl having in each case 2 to 8 carbon atoms, suitable substituents being in each case:

Halogen, cyano, nitro, hydroxy, carboxy, in each case straight-chain or branched alkoxy or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl moiety, aminocarbonyl which may optionally be substituted by alkyl, alkoxy, alkylsulfonyl, alkenyl or alkynyl and wherein the nitrogen atom of the aminocarbonyl radical also May be part of a saturated 3- to 7-membered heterocycle having 1 or 2 further heteroatoms, in particular nitrogen, oxygen or sulfur: for optionally mono- or polysubstituted by identical or different halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted cycloalkyl having 3 to 7 Carbon atoms or represents a radical _Q_p3,

X stands for oxygen or sulfur,

R ^{3 is} hydrogen, in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl, alkylthio or alkylthioalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties, for straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, for in each case straight-chain or branched alkenyl or alkynyl having in each case 2 to 4 carbon atoms, optionally monosubstituted or polysubstituted, identically or differently, substituted cycloalkyl having 3 to 7 carbon atoms, where as substituents halogen, C ₁ -C ₄ -alkyl or halogeno-C-rd In each case optionally mono- or polysubstituted, identically or differently substituted phenyl, phenoxy, phenylthio or phenylamino, where as the phenyl substituent halogen, in each case straight-chain or branched alkyl or alkoxy each having 1 to 4 carbon atoms or straight-chain or branched halogen 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms in question, or for each straight-chain or branched alkylamino or dialkylamino having in each case 1 to 4 carbon atoms in the individual alkyl moieties or

R ¹ and R ² together with the nitrogen atom to which they are attached, for each optionally optionally mono- or polysubstituted, identically or differently by straight-chain or branched alkyl having 1 to 4 carbon atoms, heterocycle of the formula

stand and

Py is in each case monosubstituted or polysubstituted, identically or differently substituted 2-pyridyl, 3-pyridyl or 4-pyridyl, suitable substituents being considered in each case

Cyano, nitro, halogen, in each case straight-chain or branched alkyl, alkoxy or alkoxycarbonyl having in each case up to 4 carbon atoms in the alkyl moiety, in each case straight-chain or branched halogenoalkyl or haloalkoxy having in each case 1 to 4 carbon atoms and in each case 1 to 9 identical or different halogen atoms or a residual S (O ) _m -R ⁴ , where

R ^{4 is} amino, each straight-chain or branched alkyl, alkylamino, dialkylamino having in each case 1 to 4 carbon atoms in the individual alkyl moieties or represents straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and having 1 to 9 identical or different halogen atoms, and

m stands for a numberO, 1 or 2,

But Py is not the 5-nitro-2-pyridyl radical or the 3-chloro-5-trifluoromethyl-2-pyridyl radical.

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

R ^{1 is} hydrogen, each optionally mono- to trisubstituted, identically or differently substituted methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, allyl, propenyl, butenyl, propargyl or butynyl , in each case possible substituents: fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, carboxy, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i-, s-or-tert-butoxycarbony ^ aminocarbonyl, N-methylaminocarbony, N-ethylaminocarbonyl, N, N-dimethylaminocarbonyl, N-diethylaminocarbonyl,

N-methyl-N-ethylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N-methylaminocarbonyl, N-methylsulfonylaminocarbonyl, N-ethylsulfonylaminocarbonyl, N, N'-diallylaminocarbonyl, N-methyl-N-propargylaminocarbony, pyrrolidin-1-ylcarbony-1-piperidine -i-ylcarbony ^ morpholine ^ -ylcarbonyloder or perhydroazepin-1-ylcarbonyl:

represents cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl which is optionally mono- to pentane, identical or different or denoted by chlorine, methyl or ethyl, or represents a radical -C-R * ^,

R ^{2 is} hydrogen, in each case optionally mono- to trisubstituted by identical or different substituents, methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, allyl, propenyl, butenyl, propargyl or butynyl where suitable substituents are each: fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, carboxy, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i-, s-tert-butoxycarbonyl, aminocarbonyl, N-methylaminocarbonyl, N-ethylaminocarbonyl, N, N-dimethylaminocarbonyl, N, N -diethylaminocarbonyl, N -methyl-N-ethylaminocarbonyl, N -methyl-N-propylaminocarbonyl, N -methyl N-methoxyaminocarbonyl, N-methylsulfonylaminocarbonyl, N-ethylsulfonylaminocarbonyl, N, N-diallylaminocarbonyl, N-methyl-N-propargylaminocarbonyl, pyrrolidin-1-ylcarbonyl, piperidin-1-ylcarbonyI, morpholin-4-ylcarbonyl or perhydroazepine-1 ylcarbonyl:

represents cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl, each of which is optionally monosubstituted to pentavalent, identically or differently, or is a radical _p_p3,

I! x

X is oxygen or sulfur and

R ^{3 represents} hydrogen, methyl, ethyl, η- and i-propyl, methoxy, ethoxy, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthio, ethylthio, methylthiomethyl, trifluoromethyl, trichloroethyldichlorofluoroethyl difluorochloroethyl, chloromethyl, iodomethyl, bromomethyl, dichloromethyl, 1-chloroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoro-n-propyl, allyl, propenyl, butenyl, propargyl, in each case optionally mono- to disubstituted by identical or different fluorine, bromine, methyl or trifluoromethyl-substituted cyclopropyl, cyclopentyl or Cyclohexyl, in each case optionally mono- to trisubstituted by identical or different methyl, methoxy, chlorine or trifluoromethyl-substituted phenyl, phenoxy, phenylthio or phenylamino, or

R ¹ and R ² together with the nitrogen atom to which they are bonded, for each optionally optionally one to four times, identically or differently by methyl, ethyl, η- or i-propyl substituted heterocycle of the formula

or

stand and

Py is in each case one to four times, identically or differently substituted 2-pyridyl, 3-pyridyl or 4-pyridyl, suitable substituents being in each case: cyano, nitro, fluorine, chlorine, bromine, iodine, methyl, ethyl, η and i-propyl, n-, i-, s- and t-butyl, methyl, ethoxy, methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trichloromethyldichlorofluoromethyl, difluorochloromethyl, chloromethyl, dichloromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl difluorodichloroethyl, trifluorodichloroethyl Pentachloroethyltrifluoromethoxy, richloromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy, dichloromethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluorochloroethoxy, trifluoroethoxy, difluorodichloroethoxy, trifluorodichloroethoxy, pentachloroethoxy or a residue S (0) _m -R ⁴ , where

R ^{4 is} methyl, ethyl, amino, methylamino, ethylamino, dimethylamino, diethylamino, fluorodichloromethyl, difluoromethyl, tetrafluoroethyl, trifluorochloroethyl, trichloromethyl or trifluoromethyl and

m stands for a numberO, 1 or 2,

But Py is not the 5-nitro-2-pyridyl radical or the 3-chloro-5-trifluoromethyl-2-pyridyl radical.

Specifically, in addition to the compounds mentioned in the preparation examples, the following 5-amino-4-cyano-1

pyridyl-pyrazoles of the general formula (I) mentioned:.

Py

Table 1:

R ¹ P ²

Py

- Ν.

Cl

Cl

Cl

Cl

H -CH ₂ -COOCH ₃

-S

egg

Cl

Cl

H -C-SCH

Cl

Cl

H-CH-COOC ₂ H ₅

CH,

Cl

Cl

If, for example, 5-bromo-4-cyano-1- (3,5-dichloro-4-pyridyl) -pyrazole and diethylamine are used as starting materials, the course of the reaction of process (a) according to the invention can be represented by the following formula scheme:

CN

CN

U-

+ HN

-HBr

^C 2 ^H 5

^C 2 ^H 5

If, for example, 3,5-dichloro-2-pyridylhydrazine and ethoxymethylenemalononitrile are used as starting materials, the course of the reaction of process (b) according to the invention can be represented by the following formula scheme:

NH-NH ₂ 1

C ₂ H ₅ -O-CH =

1st stage

, -C ₂ H ₅ OH

Cl

CN

NH-NH-CH = C Cl

CN

2nd stage

If, for example, 5-amino-4-cyano-1- (3,5-dichloro-2-pyridyl) -pyrazole and propionyl chloride are used as starting materials, the course of the reaction of process (c) according to the invention can be represented by the following formula scheme:

+ C ₂ H ₅ -CO-Cl

-HCl

If, for example, 5- [N, N-bis (phenoxycarbonyl) amino] -4-cyano-1- (3-chloro-5-trifluoromethoxy-2-pyridyl) pyrazole and methanol are used as starting materials, the course of the reaction of process (d) according to the invention by the following formula scheme:

CN

/ 'COO-C ₆ H ₅

+ 2 CH ₃ OH XCOO-C ₆ H ₅

Cl -C ₆ H ₅ OH

-CH ₃ O-CO-OC ₆ H ₅

OCF

OCF.

If, for example, 5- (N-butyl-N-propionamido) -4-cyano-1- (3-chloro-5-trifluoromethylthio-2-pyridyl) -pyrazole is used as the starting material, the course of the reaction of the process (e) according to the invention can be determined. represented by the following formula scheme:

CN

NH- <CH ₂ > ₃ -CH ₃

H ₂ O / base

-C ₂ H ₅ -COOH

XT

SCF

SCF

If, for example, B-icij-chlorobutyramidoM-cyano-i-iS-dibromo-pyridyl-pyrazole is used as starting material, the course of the reaction of process (f) according to the invention can be represented by the following formula scheme:

-C- (CH ₂ > 3-Cl

base

-HCl

br

If, for example, 5-amino-4-cyano-1- (3,5-dichloro-2-pyridyl) -pyrazole and methyl isocyanate are used as starting materials, the course of the reaction of process (g) according to the invention can be represented by the following formula scheme:

CN

V ^s -

+ CH ₃ -N = C = O

NH-C-NH-CH ₃

For carrying out the process (a) required as starting materials ö-halo ^ cyano-i-pyridylpyrazolesind generally defined by the formula (II). In this formula (II), Py preferably represents those radicals which, in connection with the description of the substances of the formula (I) according to the invention, are preferred for this substituent

Hai is preferably chlorine or bromine.

The S-halo-i-cyano-i-pyridyl-pyrazoles of the formula (II) are not yet known. However, they are the subject of their own

simultaneously filed patent application (DE-P 3520329 of June 7, 1985).

They are obtained, for example, when pyridylhydrazines of the formula (IV), Py-NH-NH ₂

in which

Py has the meaning given above,

with diethyl ethoxymethylenemalonate of the formula (X) C ₂ Hc-O-CH = C

COOC ₂ H ₅

COOC ₂ H ₅

optionally in the presence of a diluent, such as ethanol, at temperatures between 50 ° C and

200 ° C, and the thus available ^ ethoxycarbonyl-i-pyridyl-δ-pyrazolones of the formula (XI),

COOC ₂ H ₅

in which he

pv

Py has the meaning given above,

in a second stage with ammonia, if appropriate in the presence of a diluent, such as, for example, ethanol, at temperatures between 20 ^° C. and 100 ^° C., and the pyrazole ammonium salts of the formula (XII) obtainable in this way,

COOC ₂ H ₅

0 © NH ₄ ® Py

in which

Py has the meaning given above,

in a 3rd stage with a phosphoroxyhalide of the formula (XIII),

/ Shark ²

O = P Hal ² (XIII)

^^ Hai ²

in which

Hal ^{2 is} halogen,

at temperatures between 100 and 200 ⁰ C converts.

The compounds of formulas (X) and (XIII) are well known organic chemical substances.

For carrying out the process (a) further required as starting materials amino compounds are generally defined by the formula (111). In this formula (III) R ¹ and R ² preferably represent those radicals which were not already in connection with the description of the substances of the formula (I) as being preferred for these substituents, in particular R ¹ and R ² is hydrogen, Alkyl, alkenyl, alkynyl or cycloalkyl.

The amino compounds of the formula (III) are generally known compounds of organic chemistry.

The pyridylhydrazines required as starting materials for carrying out the process (b) according to the invention are generally defined by the formula (IV).

In this formula (IV), Py preferably represents those radicals which are already mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this substituent.

The pyridylhydrazines of the formula (IV) are known (compare US Pat. No. 4,125,575, US Pat. No. 3,609,158, DE-OS No. 2,558,399, J. Chem. Soc. C, 167-174 (1971)) or can be prepared by methods which are known in principle in US Pat produce a simple analogous manner, if, for example, halopyridines of the formula (XIV),

Pyhal ³ _# (XIV)

in which

Py has the meaning given above and

Hal ^{3 is} halogen, in particular fluorine, chlorine or bromine,

With hydrazine hydrate optionally in the presence of a diluent such as pyridine or dioxane at temperatures between 0 ⁰ C and 15O ⁰ C reacts, or when aminopyridines of the formula (XV),

Py- NH ₂ , (XV)

in which Py has the meaning given above,

in a known manner, for. B. with sodium nitrite, diazotized in the presence of an acid such as sulfuric acid and then also in a known manner, the diazonium salts thus obtainable, for example with tin-II chloride in the presence of an acid such as hydrochloric acid, at temperatures between -20 ⁰ C and + 8O ⁰ C reduced.

The halopyridines of the formula (XIV) and the aminopyridines of the formula (XV) are generally known compounds of organic chemistry.

The acrylonitrile derivatives further required as starting materials for carrying out the process (b) according to the invention are generally defined by the formula (V). In this formula (V), A is preferably chlorine, bromine, hydroxy, methoxy, ethoxy or dimethylamines.

The acrylonitrile derivatives of the formula (V) are known (cf., for example: DE-OS 31 29429, DE-OS 3206878, EP 34945, J. Chem. Soc. D, 1255 [1970], Can. J. Chem. 48, 210-2109 [1970], J. Heterocyclic Chem. 19, 1279-1273 [1982], Can. J. Chem. 51, 123, 1244 [1973]) or can be obtained in a simple analogous manner by known methods.

For carrying out the process (c) required as starting materials ö-amino ^ cyano-i-pyridylpyrazole are generally defined by the formula (I k).

In this formula (I k), Py and R ^{1 are} preferably those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention; Py and R ¹ are particularly preferably those radicals , which are also already mentioned in the description of the compounds of the formula (I) according to the invention as being particularly preferred for these substituents.

The 5-amino-4-cyano-1-pyridyl-pyrazoles of the formula (I k) are compounds according to the invention. The B-AmincM-cyano-i-pyridylpyrazoles of the formula (I k) in which R ^{1 is} hydrogen can be obtained by means of the processes (a) and (b) according to the invention. The 5-amino-4-cyano-1-pyridyl-pyrazoles of the formula (Ik) in which R ^{1 is} different from hydrogen are obtainable by means of the processes (a), (d) and (g) according to the invention.

In addition, the 5-amino-4-cyano-1-pyridyl-pyrazoles of the formula (Ic) obtained according to the preparation process (c), in which R ^{1 is} hydrogen, can be used again as starting materials. In this way, for example, mixed alkyl-acyl-substituted compounds can be prepared.

The compounds further required as starting materials for carrying out the process (c) according to the invention are generally defined by the formula (VII). In this formula (VII), A ¹ preferably represents chlorine, bromine, iodine, p-toluenesulfonyloxy, alkoxysulfonyloxy or acyloxy, R ² " ¹ preferably represents in each case optionally monosubstituted or polysubstituted, identical or differently substituted alkyl having 1 to 8 carbon atoms, Alkenyl or alkynyl having in each case 2 to 8 carbon atoms, suitable substituents being in each case:

Halogen, cyano, nitro, hydroxy, carboxy, in each case straight-chain or branched alkoxy or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl moiety, aminocarbonyl which may optionally be substituted by alkyl, alkoxy, alkylsulfonyl, alkenyl or alkynyl and wherein the nitrogen atom of the aminocarbonyl radical also Part of a saturated 3- to 7-membered heterocycle having 1 or 2 further heteroatoms, in particular nitrogen, oxygen or sulfur, for optionally mono- or polysubstituted by identical or different halogen or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted cycloalkyl with third to 7 carbon atoms or for a residue - £ _] ρ3

Il

where X and R ^{3 are} preferably those substituents which are already mentioned in the description of the compounds of the formula (I) according to the invention as being preferred for X and R ³ . In the formula (VII), R ² " ¹ particularly preferably represents in each case optionally monosubstituted to trisubstituted by identical or different substituents, methyl, ethyl, η- or i-propyl, n-, i-, s-tert-butyl, allyl, Propenyl, butenyl, propargyl or butynyl, suitable substituents being: fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, carboxy, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i -Propoxycarbonyl, n-, i-, s- or

t-butoxycarbonyl, aminocarbonyl, N-methylaminocarbonyl, N-ethylaminocarbonyl, Ν, Ν-dimethylaminocarbonyl, N, N-dieththylaminocarbonyl, N-methyl-N-ethylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N- methoxyaminocarbonyl, N-methylsulfonylaminocarbonyl, N-ethylsulfonylaminocarbonyl, Ν, Ν -diallylaminocarbonyl, N-methyl-N-propargylaminocarbonyl, pyrrolidin-1-ylcarbonyl, piperidin-1-ylcarbonyl, morpholin ^ 4-ylcarbonyl or perhydroazepin-1-ylcarbonyl,

in each case optionally monosubstituted to pentavalent, identically or differently, cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl substituted by chlorine, methyl or ethyl, a radical £ _ p3

where X and R ^{3 are} particularly preferably those substituents which are already mentioned in the description of the compounds of the formula (I) according to the invention as being particularly preferred for X and R ³ .

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

For carrying out the process (d) required as starting materials 5- [N, N-bis (phenoxycarbonyl) -aminol] -1-pyridyl-pyrazoles are generally defined by the formula (II).

In this formula (II), Py preferably represents those radicals which are already mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.

The 5- [N, N-bis (phenoxycarbonyl) -aminol] -1-pyridyl-pyrazoles of the formula (II) are compounds according to the invention and can be obtained by means of process (c) according to the invention. The compounds which are furthermore required as starting materials for carrying out the process (d) according to the invention are generally defined by the formula (VIII).

In this formula (VIII) R ^{3 "1} preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms or represents optionally monosubstituted or polysubstituted by identical or different substituents, which are suitable as substituents: halogen, in each case straight-chain or branched alkyl, Alkoxy having in each case 1 to 4 carbon atoms, for straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms.

R ³ " ¹ is in particular methyl, ethyl or optionally mono- to trisubstituted by identical or different phenyl, fluorine, chlorine, methyl, methoxy or trifluoromethyl. Y is preferably oxygen, sulfur, an -NH-, -N-methyl - or -N-ethyl group.

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

For carrying out the process (e) required as starting materials 5- (N-acylamino) -4-cyano-1-pyridyl-pyrazoles are generally defined by the formula (Im).

In this formula (Im), R ³ , X and Py are preferably those radicals which are already mentioned in connection with the description _{y of} the substances of the formula (I) according to the invention as being preferred for these substituents.

R ² " ² is preferably in each case optionally monosubstituted or polysubstituted, identically or differently, substituted alkyl having 1 to 8 carbon atoms, alkenyl or alkynyl having in each case 2 to 8 carbon atoms, suitable substituents being in each case: halogen, cyano, nitro, hydroxy, carboxy , in each case straight-chain or branched alkoxy or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl moiety; also optionally mono- or polysubstituted by identical or different substituents comprising halogen or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted cycloalkyl having 3 to 7 carbon atoms, in particular, R ² " ² for each optionally mono- to trisubstituted by identical or different substituents methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, allyl, propenyl, butenyl, propargyl or butynyl, where as substituents respectively in question: fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, carboxy, methoxy, ethoxy, 'n-ori-propoxy; orfor each optionally mono- to fivefold, identically or differently substituted by chlorine, methyl or ethyl substituted cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl.

The 5- (N-acylamino) -4-cyano-1-pyrazoles of the formula (Im) are compounds according to the invention and can be obtained by means of process (c) according to the invention.

The 5-haloacylamino-4-cyanopyrazoles required as starting materials for carrying out the process (f) according to the invention are generally defined by the formula (In).

In this formula (In), Py preferably represents those radicals which are already mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this substituent. Hal ¹ is preferably chlorine or bromine and η is preferably a number 2, 3 or 4.

The ö-haloacylamino ^ -cyano-pyrazoles of the formula (I n) are compounds according to the invention and can be obtained by means of process (c) according to the invention.

For carrying out the process (g) required as starting materials S-amino-cyano-i-pyridylpyrazole are defined by the formula (I k). In this formula (I k), Py and R ^{1 are} preferably those substituents which are already mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these radicals.

The iso (thio) cyanates which are furthermore required as starting materials for carrying out the process (g) according to the invention are generally defined by the formula (IX).

In this formula (IX), X preferably represents oxygen or sulfur, R ³ " ² preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, or optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents : Halogen, in each case straight-chain or branched alkyl, alkoxy each having 1 to 4 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms.

R ³ ' ² is in particular methyl, ethyl and optionally mono- to trisubstituted by identical or different phenyl, substituted by fluorine, chlorine, methyl, methoxy or trifluoromethyl.

The iso (thio) cyanates of formula (IX) are well known compounds of organic chemistry.

For carrying out the process (a) according to the invention, suitable diluents are inert organic solvents. Preferably used aliphatic, cyclic or aromatic, optionally halogenated hydrocarbons, such as gasoline, benzene, toluene, xylene, pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene or dichlorobenzene, ethers such as diethyl ether, diisopropyl ether , Dioxane, tetrahydrofuran or ethylene glycol diethyl ether or dimethyl ether, ketones such as acetone, butanone, methyl isopropyl ketone or methyl isobutyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide. However, it is also possible to use a corresponding excess of the amino compound used as reactants of the formula (III) as a diluent.

The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, one works at temperatures between - 10 ° C and +120 ⁰ C, preferably at temperatures between ^{0 0} C and 8O ⁰ C.

For carrying out process (a), in general from 1.0 to 100.0 mol, preferably from 1.0 to 50.0 mol, are employed per mole of 5-halo-4-cyano-1-pyridyl-pyrazole of the formula (II) an amino compound of the formula (II)

To carry out the reaction, the reactants, which are optionally dissolved in a suitable diluent, are stirred for several hours at the required reaction temperature until no more starting material can be detected in the thin-layer chromatogram. The work-up is carried out by removing the volatile constituents of the reaction mixture in vacuo, taking up the residue in a water-immiscible organic solvent, washing with water, drying and removal of the organic solvent in vacuo. Suitable diluents for carrying out the preparation process (b) are inert organic solvents for both the 1st and the 2nd reaction stage. It is preferable to use alcohols, such as methanol, ethanol, propanol, butanol, ethylene glycol or ethylene glycol monomethyl or ethyl ether.

Suitable reaction auxiliaries for carrying out the 1st stage of the preparation process (b) are organic or inorganic acids. Sulfuric acid or acetic acid is preferably used, if appropriate also in the presence of a buffer substance, for example sodium acetate.

The preparation process (b) can also be carried out in a reaction step without isolation of the intermediates of the formula (VI) in the presence of a diluent.

The reaction temperatures can be varied in certain ranges when carrying out the 1st stage of the preparation process (b). In general, one works between -3O ⁰ C and + 50 ⁰ C, preferably between -20 ⁰ C and + 20 ⁰ C. As a reaction aid for carrying out the second stage of the preparation process (b) ko'mmen all commonly used acids, such as Sulfuric acid or phosphoric acid, in question.

The reaction temperatures can be varied within a wider range when carrying out the 2nd stage of the production process (b) as well as in the one-stage reaction regime. In general, one works between O ⁰ C and +200 ⁰ C, preferably between + 5O ⁰ C and -150 ° C.

In order to carry out the preparation process (fa), 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol, of acrylonitrile are generally employed per mole of pyridylhydrazine of the formula (IV) both in the single-stage and in the two-stage reaction regime. Derivative of the formula (V) and in the case of the two-stage process optionally in the I.Stufe 1.0 to 10.0 moles of reaction auxiliary and optionally in the second stage also 1.0 to 10.0 moles of reaction auxiliary.

The workup and isolation of the reaction products by conventional methods, for example by removing the organic diluent, precipitation of the reaction product in water, suction and drying of the product thus obtained.

For carrying out the preparation process (c) suitable diluents are also inert organic solvents. Preferably, the solvents mentioned in process (a) are used.

However, it is also possible to use the compounds of the formula (VII) used as reactants in appropriate excess as a diluent.

Suitable acid binders for carrying out the preparation process (c) are all commonly used inorganic and organic bases. Preference is given to using alkali metal hydrides, hydroxides, amides, carbonates or bicarbonates, for example sodium hydride, sodium amide, sodium hydroxide, sodium carbonate or sodium bicarbonate or else tertiary amides, for example triethylamine, N, N-dimethylaniline, pyridine, 4- (N, N-dimethylamino) -pyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out the production process (c). In general, one works between -20 ° C and + 15O ⁰ C, preferably between O ⁰ C and + 100 ° C.

In order to carry out the preparation process (c), in general 1.0 to 20.0 mol, preferably 1.0 to 15.0 mol, of compound of the formula (I) are employed per mole of 5-amino-1-pyridyl-pyrazole of the formula (Ic). VII) and optionally 1.0 to 3.0 moles, preferably 1.0 to 2.0 moles of acid binder. The reaction is carried out, working up and isolation of the reaction products of the formula (Ic) in a generally conventional manner.

Suitable diluents for carrying out process (d) according to the invention are likewise inert organic solvents. Preference is given to using the organic solvents or alcohols mentioned in process (a), such as methanol, ethanol or isopropanol.

However, it is also possible to use the alcohols, amines or thiols of the formula (VIII) used as reaction components in a corresponding excess simultaneously as a diluent.

The reaction temperatures can also be varied within a substantial range in the process (d) according to the invention. In general, one works between 0 ⁰ C and +200 ⁰ C, preferably between +20 ⁰ C and + 15O ⁰ C.

If appropriate, the process (d) according to the invention can be carried out in the presence of a basic reaction auxiliary. As such, all commonly used bases, such as those mentioned in process (c), are suitable.

For carrying out the process (d) according to the invention, in general from 1 to 20 mol, preferably from 1 to 10 mol, of the compound of the formula are employed per mole of 5- [N, N-bis (phenoxycarbonyl) amino-1-pyridylpyrazole of the formula (II) (VIII) and optionally 1 to 10 moles of base and heated for several hours to the required temperature. The workup and isolation of the reaction products of formula (Id) is carried out by conventional methods.

Suitable diluents for carrying out the process (e) according to the invention are inert organic or inorganic solvents.

In particular, mention may be made of the organic solvents listed in process (d). Particularly preferred are alcohols such as methanol or ethanol or mixtures thereof with water.

The process (e) is carried out either in the presence of a strong acid such as hydrochloric acid, trifluoroacetic acid or hydrobromic acid, in glacial acetic acid or in the presence of a base. As bases, aqueous solutions of sodium hydroxide or potassium hydroxide are preferred.

The reaction temperatures can be varied within a substantial range when carrying out the process (e) according to the invention. In general, one works at temperatures between -20 ⁰ C and +150 ⁰ C, preferably at temperatures between ^{0 0} C and +120 ⁰ C.

For carrying out the process (e) according to the invention is used per mole of 5- (N-acylamino) -4-cyano-1-pyridyl-pyrazole of the formula (Im) generally 1 to 30 mol, preferably 1 to 15 mol, of acid or Base one. The reaction is carried out, working up and isolation of the reaction products of the formula (I in a generally conventional manner.

Suitable diluents for carrying out the process (f) according to the invention are also inert organic solvents, preferably the solvents listed in process (d).

Suitable basic reaction auxiliaries when carrying out the process (f) according to the invention are all customary inorganic or organic bases. Preference is given to using alkali metal carbonates, such as potassium carbonate or potassium bicarbonate, alkali metal hydroxides or hydrides, such as sodium hydroxide or sodium hydride, or alkoxides, such as sodium methylate or ethylate.

The reaction temperatures can be varied within a substantial range when carrying out the process (f) according to the invention. In general, one works at temperatures between ^{0 0} C and 130 ⁰ C, preferably at temperatures between 2O ⁰ C and 100 ° C.

To carry out the process (f) according to the invention, 1.0 to 3.0 mol, in particular 1.0 to 2.0 mol, of basic reaction auxiliary are generally employed per mole of δ-haloacylamino-cyano-pyrazole of the formula (In) , The reaction procedure, workup and isolation of the reaction products of the formula (If) are carried out in analogy to known methods (cf., for example, DE-OS 3325488).

For carrying out the preparation process (g) suitable diluents are also inert organic solvents. Preference is given to using aliphatic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene or dichlorobenzene, ethers, such as diethyl ether, diisopropyl ether, dioxane , Tetrahydrofuran or ethylene glycol diethyl ether or dimethyl ether, ketones such as acetone, butanone, methyl isopropyl ketone or methyl isobutyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide. Is lso- (thio) -cyanates of the formula (IX) in liquid form, it is also possible to use these in a corresponding excess as a diluent.

Suitable reaction auxiliaries for carrying out the preparation process (g) are all commonly used inorganic and organic bases. Preference is given to using alkali metal carbonates or bicarbonates, for example sodium carbonate or sodium bicarbonate, or else tertiary amines, for example triethylamine, Ν, Ν-dimethylaniline, pyridine, 4- (N, N-dimethylamino) -pyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or Diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out the preparation process (g). In general, it is carried out between -2O ⁰ C and +150 ⁰ C, preferably between 0 ⁰ C and + 100 ⁰ C.

In order to carry out the preparation process (g), 1.0 to 20.0 mol, preferably 1.0 to 15.0 mol, are generally employed per mole of 5-amino-4-cyano-1-pyridyl-pyrazole of the formula (Ik) Compound of formula (IX) and optionally 1.0 to 3.0 mol, preferably 1.0 to 2.0 moles of reaction auxiliary. The reaction is carried out, working up and isolation of the reaction products of the formula (Ig) in a generally conventional manner.

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and especially as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides essentially depends on the amount used.

The active compounds of the invention may e.g. used in the following plants:

Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xa nthium, Convolvulus, lpomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocotyledonous cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

The compounds are suitable depending on the concentration for total weed control z. B. on industrial and railway tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, z. As forestry, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops become.

In this case, the active compounds of the formula (I) according to the invention can be used with particularly good success for the selective control of broadleaf weeds in monocotyledonous and dicotyledonous crops such as cotton, wheat or maize.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, active-ingredient-impregnated natural and synthetic substances and superfine encapsulations in polymeric substances.

These formulations are prepared in a known manner, for. B. by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally using. surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents.

In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for. As petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol 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.

Suitable solid carriers are: z. As ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as finely divided silica, alumina and silicates, as solid carriers for granules are: z. As broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of organic material such as sawdust, coconut shells, corncobs and tobacco stalks: as emulsifying and / or foam-forming agents are: z. B.

nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethyl fatty alcohol ethers, e.g. B. Alkylarylpolyglykolether, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; as dispersants come into question:

z. As lignin-sulphite liquors and methylcellulose.

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

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

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

The active compounds according to the invention can be used as such or in their formulations also in admixture with known herbicides for weed control, ready-to-use formulations or tank mixtures being possible.

For the mixtures are known herbicides, such as ζ. Β. 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,45 (1H, 3H) -dione or N- (2-benzthiazolyl) -N, N ' -dimethyl-urea for weed control in cereals: 4-amino-3-methyl-6-phenyl-1,2,4-triazine-5 (4H) -one for weed control in sugar beets and 4-amino-6- (1,1 -dimethylethyl) -3-methylthio-1,2,4-triazine-5 (4H) -one for weed control in soybeans.

Also, mixtures with N, N-dimethyl-N '- (3-chloro-4-methyl-phenyl) -urea, N, N-dimethyl-N' - (4-isopropylphenyl) -urea, 4-amino-6-t -butyl-3-ethylthio-1,2,4-triazine-5 (4H) -one, 2,4-dichlorophenoxyacetic acid, 2,4-dichlorophenoxypragionic acid, (2-methyl-4-chlorophenoxy) -acetic acid, (4-chloro 2-methylphenoxy) propionic acid, N-methoxymethyl (chloroacetic acid) -2,6-diethylanilide, ethyl e-methyl-Nd-methyl, -methoxyethyl-chloroacetanilide, dinitro-trifluoromethyl-N, -dipropylaniline, 2- [4- (3,5-dichloropyrid-2-yloxy) -phenoxy] -propionic acid (2-benzyloxyethyl ester), - (trimethylsilylmethyl ester) or - (2,2-diethoxyethyl ester), N, N-diisopropyl-S- (2,3,3-trichloroallyl) thiolcarbamate, [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl) oxy] -acetic acid or -1-methylheptyl ester, 3,5-dibromo 4-hydroxybenzonitrile, methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate, 3,5-diiodo-4-hydroxybenzonitrile, 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2- dioxide, 2-chloro-N - {[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl} benzenesulfonam id, N, N-dimethyl-N '- (3-trifluoromethylphenyl) urea, N-methyl-2- (1,3-benzthiazol-2-yloxy) -acetanilide, 2-chloro-4-ethylamino-6-isopropylamino -1,3,5-triazine, exo-1-methyl-4- (1-methylethyl) -2- (2-methylphenylmethoxy) -7-oxabicyclo [2.2.1! -Heptane, 2- {4 - [[ Ethyl 3-chloro-5- (trifluoromethyl) -2-pyridinyl] oxy] phenoxy} propanoate or propanoate, N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline or S-chloro -S-phenyl-pyridazine ^ -yl-S-octylthiocarbonate are advantageous. Surprisingly, some mixtures also show a synergistic effect.

Also, a mixture with other known Wirkstoffen.wie fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil conditioners is possible.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is done in the usual way, for. B. by pouring, spraying, spraying, spreading.

The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.

The amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.

embodiment

The preparation and the use of the active compounds according to the invention are evident from the following examples.

Preparation Examples: Example 1:

"" Cn

NH- (CH ₂ ) ₂ -CH ₃

Cl

[Method (a)]

3.2 g (0.01 mol) of 5-bromo-4-cyano-1- (3,5-dichloropyrid-2-yl) -pyrazole and 30 ml (0.36 mol) of n-propylamine are stirred for 15 hours at room temperature, concentrated in vacuo, the residue taken up in chloroform, washed twice with water, dried over sodium sulfate and freed from the solvent in vacuo.

This gives 2.2 g (75% of theory) of 4-cyano-5-n-propyl-amino * 1- (3,5-dichloropyrid-2-yl) -pyrazole of melting point 90 ⁰ C.

Preparation of the starting compound CN

To 12.7 g (0.05 mol) of 5-amino-4-cyano-1- (3,5-dichloropyrid-2-yl) -pyrazole in 100 ml of hydrobromic acid are added at -5 ° C to 0 ⁰ C 6g (0.087 Mol) sodium nitrite in 15 ml of water and stirred for 5 hours at room temperature. The deposited precipitate is filtered off with suction, slurried in water, made weakly alkaline with sodium bicarbonate, again filtered off with suction and dried.

This gives 11 g (70% of theory) of S-bromo ^ -cyano-HS ^ -dichloropyridyl-pyrazole of melting point 142 ° C (decomposition).

Example 2:

[Method (b)]

24.2 g (0.136 mol) of N- (3,5-dichloropyrid-2-yl) -hydrazine and 16.6 g (0.136 mol) of ethoxymethylenemalononitrile in 200 ml of ethanol are heated at reflux for 15 hours. The precipitated from the cooled reaction mixture precipitate is filtered off with suction and dried.

One obtains 28,8g (83% of theory) of 5-amino-4-cyano-1- (3,5-dichloro-2-pyridyl) -pyrazole of melting point 213 ° C-215 ⁰ C.

Preparation of the starting compound:

34.0 g (0.186 mol) of 2,3,5-trichloropyridine and 51 g (1.0 mol) of hydrazine hydrate in 400 ml of dioxane are refluxed for 3 hours and the precipitate precipitated from the cooled reaction mixture is filtered off with suction and dried. This gives 24.2 g (73% of theory) of N- (3,5-dichloropyrid-2-yl) -hydrazine of melting point 179 ° C-182 ° C.

Example 3:

[Method (c)]

To 2.5 g (0.01 mol of 5-amino-4-cyano-1- (5-trifluoromethyl-pyrid-2-yl) -pyrazole in 30 ml of chloroform are added dropwise at 0 ° C to 5 ⁰ C with stirring, first 10th ml (10.6 g / 0.11 mol) of propionyl chloride and then 1.8 ml (1.8 g / 0.02 mol) of pyridine in 15 ml of chloroform and, after completion of the addition, stirred at room temperature for 16 hours .. For working up, 50 ml of ethanol are added and Concentrated aqueous ammonia solution, the reaction mixture is alkaline, concentrated in vacuo, the residue is taken up in 100 ml of chloroform, washed with water, 2 normal hydrochloric acid and again with water, dried over sodium sulfate and the solvent is removed in vacuo g (84% of theory) of 4-cyano-5-propionamido-1- (5-trifluoromethylpyrid-2-yl) -pyrazole of melting point 130 ° C-132 ° C.

Example 4:

Cl

[Method (c)]

To 7.6 g (0.03 mol) of ö-amino ^ -cyano-i- ^ S-dichloro-pyridyl-pyrazole in 60 ml of chloroform are first added between O ⁰ C and 5 ° C first 15.7 g (0.09 mol Chloroformic acid phenyl ester and then 7.1 g (0.09 mol) of pyridine, stirred for 15 hours at room temperature, concentrated in vacuo, the residue is stirred with ether, the resulting crystalline solid is filtered off with suction, washed with ether and water, dried at 100 ° C and crystallized from toluene. This gives 9.8 g (66.1% of theory) of 4-cyano-5- [N, N-bis (phenoxycarbonyl) amino] -1- (3,5-dichloro-2-pyridyl) pyrazole of melting point 173 ° C-175 ° C.

Example 5:

[Method (c)]

To 12.7 g (0.05 mol) of S-amino-cyano-i-fS-dichloro-pyridyl-pyrazole in 100 ml of pyridine, 0.6 g (0.005 mol) of 4- (4) are initially added with stirring and ice-cooling. N, N-dimethylamino) -pyridine and then dropwise 81 g (0.5 mol) of diethyl pyrocarbonate and heated until the end of the evolution of carbon dioxide to 7O ⁰ C until the end of the evolution of carbon dioxide. For workup, concentrated in vacuo, the residue is boiled in 30ml Ethanol, filtered hot and the filtrate is cooled to 0 ° Cab. The crystals thus obtained can be recrystallized from ethanol / petroleum ether (1: 1). This gives 11 g (67.5% of theory) of 4-cyano-5-ethoxycarbonyiamino-i-IS ^ -dichlor ^ -pyridyO-pyrazole of melting point 131 ° C-132 ° C.

In a corresponding manner and according to the general preparation information, the following 5-amino-4-cyano-1-pyridyl-pyrazoles of the general formula (I) are obtained:

CN

Py

Table 2:

Ex. P ^] No.

6 H

7 C ₂ H ₅ -CO-

Py enamel point / * C Cl 195-200 S Cl Cl 165-168

8 H

N- ^ - ^ y> ~ ^CF 3 197-203

10 (CH ₃ ) ₂ CH-

1

1 oil

Cl

CH,

11 (CH ₃ O) ₂ CH-CH- H

12 C ₂ H ₅ -CO- C ₂ H ₅ -CO-

118-128

Cl

1 oil

Cl

13 C ₂ H ₅ -CO-

164-165

Cl

Table 2 (cont

Ex. R ^J No,

Py

Melting point / ° C

14 CH ₃ -CO-

1 189-190

Cl

15 C ₂ H ₅ O-CO- C ₂ H ₅ O-CO-

1 106-109

Cl

16 CH ₃ O-CO-CH ₃ O-CO-

1 130-132

Cl

17 CHOO-CO- H

18 (CH ₃ ) ₂ CH-CO- H

Cl

148-153 oil

Cl

19 CH ₃ O-CO-CH- H CH-,

101

Cl

applications

In the following application examples, the following compound was used as reference substance:

CN

Cl

Cl

4-cyano-5-propionamido-1- (2,3,4-trichlorophenyl) pyrazole (known from DE-OS 3226513).

Example A '

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired one

Concentration. '

Seeds of the test plants are sown in normal soil and watered after 24 hours with the preparation of active ingredient

 It is advisable to keep the amount of water per unit area reasonably constant. The concentration of active ingredient in the preparation does not matter, only the application rate of the active ingredient per unit area is decisive. After three weeks, the degree of damage of the plants is rated in% damage in comparison to the development of the untreated control. It means:

0% = no effect (as urT treated control) 100% = total destruction

A clear superiority in the effectiveness as well as in the crop selectivity compared to the comparison substance (A) show in this test, e.g. the compounds according to Preparation Examples 5, 9, 11, 12 and 15.

Step Example! B

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired level

Concentration.

With the preparation of active compound is injected test plants, which have a height of 5-15cm, so that the particular desired amounts of active ingredient per unit area are applied. The concentration of the spray mixture is chosen so that in 2000I

Water / ha the respective desired amounts of active ingredient are applied. After three weeks, the degree of damage of the plants is rated in% damage in comparison to the development of the untreated control.

It means:

0% = no effect (as untreated control) 100% = total destruction

A clear superiority in the crop selectivity compared to the reference substance (A) show in this test z. B. the compounds according to Preparation Examples 5,13,14,15 and 17.

Claims (1)

Invention claim: R ^{2 is} hydrogen for each substituted alkyl-alkenyl-L-AIk-yl or cycloalkyi or a radical "" wherein X stands for oxygen or sulfur and R ^{3 represents} hydrogen, alkyl, alkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl, haloalkyl, alkenyl, alkynyl, in each case optionally substituted cycloalkyl, aryl, aryloxy, arylthio or arylamino, for alkylamino or for dialkylamino stands or
R ¹ and R ² together with the nitrogen atom to which they are attached, represent an optionally substituted Heterocycle of the formula -M \ or '-N S O' stand and Py represents substituted pyridyl, but does not represent the 5-nitro-2-pyridyl or the S-chloro-6-trifluoromethyl-pyridyl radical, in addition to extenders and / or surfactants.
2. Composition according to item 1, characterized by a content of 5-amino-4-cyano-1-pyridyl-pyrazoles of the formula (I), (D, Py in which R ^{1 is} hydrogen, each optionally mono- or polysubstituted, identically or differently substituted alkyl rniti to 8 carbon atoms, alkenyl or alkynyl having in each case 2 to 8 carbon atoms, where as substituents in question: halogen, cyano, nitro, hydroxy, carboxy, in each case straight-chain or branched alkoxy or alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl moiety, aminocarbonyl which may be optionally substituted by alkyl, alkylsulfonyl, alkenyl or alkynyl and wherein the nitrogen atom of the aminocarbonyl radical is also part of a saturated 3- to 7-membered heterocycle having 1 or 2 other heteroatoms, in particular nitrogen, oxygen or sulfur, may be: represents optionally mono- or polysubstituted by identical or different halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted cycloalkyl having 3 to 7 carbon atoms or rw - -- - - ......... -C-R " a remainder ^w "stands is hydrogen, in each case optionally mono- or polysubstituted, identically or differently substituted alkyl having 1 to 8 carbon atoms, alkenyl or alkynyl having in each case 2 to 8 carbon atoms, where as substituents in each case eligible: Halogen, cyano, nitro, hydroxy, carboxy, in each case straight-chain or branched alkoxy or alkoxycarbonyl having 1 to 6 carbon atoms in the alkyl moiety, aminocarbonyl, which may optionally be substituted by alkyl, alkoxy, alkylsulfonyl, alkenyl or alkynyl and wherein the nitrogen atom of the aminocarbonyl also Part of a saturated 3-to 7-membered heterocycle having 1 or 2 further heteroatoms, in particular nitrogen, oxygen or sulfur can: represents optionally mono- or polysubstituted by identical or different halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted cycloalkyl having 3 to 7 carbon atoms or for a rest "" 3, X is oxygen or sulfur, R ^{3 is} hydrogen, in each case straight-chain or branched alkyl, alkoxy, alkoxyalkyl, alkylthio or alkylthioalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties, for straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, for in each case straight-chain or branched alkenyl or alkynyl having in each case 2 to 4 carbon atoms, optionally monosubstituted or polysubstituted by identical or different cycloalkyl having 3 to 7 carbon atoms, where as substituents halogen, Ci-C ₄ alkyl or halogen-C 1 -C ₄ -alkyl, in question phenyl, phenoxy, phenylthio or phenylamino, each being optionally monosubstituted or polysubstituted by identical or different substituents, where the phenyl substituent is halogen, in each case straight-chain or branched alkyl or alkoxy each having 1 to 4 carbon atoms or straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms in question, orfür each represents straight-chain or branched alkylamino or dialkylamino having in each case 1 to 4 carbon atoms in the individual alkyl moieties,
or R ¹ and R ² together with the nitrogen atom to which they are bonded, for each optionally mono- or polysubstituted, identically or differently by straight-chain or branched alkyl having 1 to 4 carbon atoms heterocycle of the formula * "% / '" ^N \ ^or if stand and
Py is in each case monosubstituted or polysubstituted by identical or different substituents 2-pyridyl, 3-pyridyl or 4-pyridyl, suitable substituents being in each case: cyano, nitro, halogen, in each case straight-chain or branched alkyl, alkoxy or alkoxycarbonyl having 1 to 4 carbon atoms in the alkyl moiety, in each case straight-chain or branched haloalkyl or halogenoalkoxy having in each case 1 to 4 carbon atoms and in each case 1 to 9 identical or different halogen atoms or a residue S (O) _m -R ⁴ , where
R ^{4 is} amino, in each case straight-chain or branched alkyl, alkylamino or dialkylamino having in each case 1 to 4 carbon atoms in the individual alkyl moieties or for straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, and m stands for numbersO, 1 or 2, But Py is not the 5-nitro-2-pyridyl radical or the 3-chloro-5-trifluoromethyl-2-pyridyl radical. 3. Composition according to item 1, characterized by a content of B-amino-cyano-i-pyridyl-pyrazoles of the formula (I) in which R ^{1 represents} hydrogen, in each case optionally mono- to trisubstituted by identical or different substituents, methyl, ethyl, n- or i-propyl, n-, i-, s- or tert-butyl, allyl, propenyl, butenyl, propargyl or butynyl , where suitable substituents are each: fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, carboxy, methoxy, ethoxy, n-ori-propoxy, Methoxycarbonyl, ethoxycarbonyl, η- or i-propoxycarbonyl, η-, i-, s- or tert-butoxycarbonyl, aminocarbonyl, N-methylaminocarbonyl-ethylaminocarbonyl-N-dimethylaminocarbonyl, N-methyl-N-ethylaminocarbonyl, N, -diethylaminocarbonyl, N Methyl N-propylaminocarbonyl, N-methyl-N-methoxyaminocarbonyl, N-methylsulfonylaminocarbonyl, N-ethylsulfonylaminocarbonyl, N-diallylaminocarbonyl, N-methyl-N-propargylaminocarbonyl, pyrrolidin-1-ylcarbonyl, piperidin-1-ylcarbonyl, morpholine. ylcarbonyloderPerhydroazepin-i-ylcarbonyl; represents cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl which are each optionally monosubstituted to pentavalent, identically or differently, by chlorine, methyl or ethyl or represents a radical -p_p3, Il χ R ^{2 is} hydrogen, in each case optionally mono- to trisubstituted by identical or different substituents, methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, allyl, propenyl, butenyl, propargyl or butynyl , where as substituents in question are: Flour, chlorine, bromine, iodine, cyano, nitro, hydroxy, carboxy, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i -, tert-Butoxycarbonyl, aminocarbonyl, N-methylaminocarbonyl, N-ethylaminocarbonyl, N-dimethylaminocarbonyl, N-diethylaminocarbonyl, N-methyl-N-ethylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N-methoxyaminocarbonyl, N -methylsulfonylaminocarbonyl; N-ethylsulfonylaminocarbonyl; N-diallylnaminocinolyl; N -methyl-N-propargylaminocarbonyl, pyrrolidin-1-ylcarbonyl, piperidin-1-ylcarbonyl, morpholino-4-ylcarbonyl or perhydroazepin-1-ylcarbonyl; is in each case optionally mono- to quintuply, identically or differently by chlorine, methyl or ethyl substituted cyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl or is a radical - p_r3, where Il χ X stands for oxygen or sulfur and R ^{3 is} hydrogen, methyl, ethyl, η- and i-propyl, methoxy, ethoxy, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthio, ethylthio, methylthiomethyl, trifluoromethyl, trichloroethyl, dichlorofluoroethyl, difluorochloroethyl, chloromethyl, iodomethyl, bromomethyl, dichloromethyl, 1-chloroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoro-n-propyl, allyl, propenyl, butenyl, propargyl, in each case optionally mono- to disubstituted by identical or different fluorine, chlorine, bromine, methyl or trifluoromethyl-substituted cyclopropyl, Cyclopentyl or cyclohexyl, in each case optionally mono- to trisubstituted by identical or different methyl, methoxy, chlorine or trifluoromethyl-substituted phenyl, phenoxy, phenylthio or phenylamino,