CA1242207A - Substituted 5-aminopyrazoles - Google Patents

Abstract

ABSTRACT

A 5-aminopyrazole of the formula (II-I)

Description

~4~
- 1 - 23189-5~33D

This application has been divided out of parent application No. 465,253, filed on October 12th, 1984 relating to new substituted 5-acylamino-1-phenylpyrazoles, a process for their preparation and their use as herbicides.
This divisional application relates to 5-aminopyrazoles and to a process for their preparation. A second divisional application directed to phenylhydrazine derivatives and to a process for their preparation has also been filed.
It has already been disclosed that certain substituted 5-acylamino-1-phenylpyrazoles, such as, for example, 4-cyano-5-propionamido-1-(2,4,6-trichlorophenyl)-pyrazole, have herbicidal properties (compare, for example, DE-OS (German Publ:ished Specification) 3,226,513).
EIowever, the herbicidal action of these known compounds against weeds and their tolerance towards important crop plants is not always com~letely satisfactory in all cases.
The parent application relates to new substituted 5-acylamino-1-phenylpyrazoles of the general formula (I) Rl -1'' ~

~ \ ~H-CO-R2 (I) R ~ ~ ~ 3 R

in which Rl represents cyano, alkoxycarbonyl, alkenyloxycarbonyl, ; alkinyloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, alkenylamino-carbonyl or alkinylaminocarbonyl, ~

~29;~
- la - 23189-5833D
R2 represents hydrogen, alkyl, alkenyl, alkinyl, cycloalkyl optionally substituted by halogen, alkoxyalkyl, alkylthioalkyl, halogenoalkyl or aryl optionally substituted by at least one substituent selected from halogen~ cyano, nitro and alkyl, alkoxy, alkylthio and alkoxycarbonyl with in each case up to 4 carbon atoms in the individual alkyl parts and R3, R4, R5, R6 and R7, which are identical or different, represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylsulphonyl, alkoxycarbon yl or a radical -(X)n-R8, wherein X represents oxygen, sulphur, sulphinyl or sul-phonyl~
n represents 0 or 1 and R8 represents halogenoalkyl, ~;th the proviso that at least one of the radicals R3 R~, R5, R6 or R7 represents a radical -~X)n-R8, but R1 does not represent cyano iF R5 represents tri-fluoromethyL~
have been found.
It has furthermore been found that the new sub-stituted 5-acylatnino-1-phenylpyrazoles of the general formula (I~ are obta;ned when S-amino-pyrazoles of the formula (Il) N~ tII) ~N ~IH2 R7~ R3 in which R1, R3, R4, R5, R6 and R7 have the above-mentioned meaning, are reacted with acylating agents of the formula (III) R2 - CO - A (III) in which R2 has the abovementioned meaning and A represents an activating leaving group, if appropriate ;n the presence of a diluent and if approp-riate in the presence of an acid-binding agent.
Finally, it has been found that the ne~ substitu-Le A 22 664 .

ted S-acylamino-1-phenylpyrazoles of the formula (I) have herbic;dal properties, ;n particular also selective herbi-cidal properties.
Surprisingly, the new substituted 5-arylamino-1 phenylpyrazoLes o~ the formula ~I) have a betteF herbi-c;dal activ;ty against harmful plants, coupled with a better tolerance towards important useful plants~ than, ~or example, 4-cyano-5-propionamido-1-(~,~,6-trichloro-phenyl)-pyrazole, ~hich is known ~rom the prior art and is a closeLy related compound chemically and ~rom the point of view of its action.
Formula tI) provides a general definition of the ne~ substituted 5-acylamino-1-phenylpyrazoles. Preferred compounds of the formula ~I) are those 15 ;n which R1 represents cyano or aminocarbonyl, or repres-ents in each case stra;ght-chain or branched alkoxycarbonyl, alkenyloxycarbonyl, alkinyloxy-carbonyl, alkylaminocarbonyl, alkenylaminocarbonyl or alkinylam;nocarbonyl with in each case up to 4 carbon atoms in the ind;vidual alkyl parts, R2 represents hydrogen, or represents in each case straight-chain or branched alkyl, alkenyl or alkinyl with up to 6 carbon atoms, or represents cycloalkyl uhich has 3 to 7 carbon atoms and is optionally monosubstituted or polysubstituted by identical or d;fferent halogen atoms, or repres-ents ;n each case straight-chain or branched alkoxyalkyL or alkylthioalkyl ~;th in each case up to 4 carbon atoms in the individual alkyl parts, or represents straight-chain or branched halogeno-alkyl ~ith up to 6 carbon atoms and up to 9 iden-t;cal or d;f~erent halogen atoms, or represents phenyl which is optionally monosubstituted or polysubstituted by identical or different sub-stituents, possible substituents being: halogen, Le A 22 664 ,~
cyano, nitro and in each case straight-chain or branched alkyl, alkoxy, aLkylth;o and alkoxy-carbonyl with in each case up to 4 carbon atoms in the individuaL alkyi parts, and S R3, R4, RS, R6 and R7 independently o~ one another represent hydro~en, fLuorine, chlorine, bromine~ ;odine, cyanor nitro, in each case straight-chain or branched alkyl, alkoxy, alkyl-~ sulphonyl or alkoxycarbonyl with up to 4 carbon; 10 atoms in the particular alkyl parts, or a radicaL
-~X)n~R8, wherein X represents oxygen, sulphur, sulphinyl or sul phonyl, n represents 0 or 1 and R8 represents straight-chain or branched halo genoalkyl with up to 4 carbon atoms and up to 9 identical or di~ferent halogen atoms, w;th the proviso that at least one of the radicals R3, R4, RS, R6 or R7 represents a radical ~tX)n-R8, and R1 does not represent cyano if R5 represents trifluoromethyl~
Particularly preferred compounds of the formula tI) are those ; 25 in which R1 represents cyano, methoxycarbonyl, ethoxy-carbonyl, allyloxycarbonyl, propargyloxycarbonyl, aminocarbonyl, methylaminocarbonyl, dimethylamino-carbonyl, ethylaminocarbonyl, diethylaminocarbon-3n yl~ diallyl.aminocarbonyl or dipropargylamino-carbonyl, R2 represents hydrogen, methyl, ethyl, n- or i-propyl, n~ , s- or t-butyl, cyclopropyl, 2,2-dichlorocycLopropyl, 2,2-dichloro-1-methylcyclo-propyl, methylthiomethyl, cyclopentyl, cyclohexyl, ethoxymethyl, methoxymethyl, methoxyethyl, ethoxy-Le A 22 66~ .

_ 5 _ ethyl, chloromethyl, dichloromethyl, trichloro-methyl, trifluoromethyl, dichlorofluoromethyl, difluorochloromethyl or pentafluoroethyl, or rep-resents phenyl which is mono-, di- or tri-sub-stituted by identical or different radicals from the group comprising fluorine, chlorine, bromine, N0z, methyl and methoxy, and R3, R4, R5, R6 and R7 independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, methylsulphonyl, methoxy-carbonyl or ethoxycarbonyl, or a radical (X)n-R8, wherein X represents oxygen, sulphur, sulphinyl or sul-15 . phonyl, - -n represents 0 or 1 and R8 represents trifluoromethyl, trichloromethyl, dichlorofluoromethyl, difluorochloromethyl, di-chloromethyl, chloromethyl, difluoromethyl, penta-fluoroethyl, tetrafluoroethyl, trifluorochloro-ethyl, trifluoroethyl, difluorodichloroethyl, tri-fluorodichloroethyl or pentachloroethyl, with the proviso that at least one of the radicals R3, R4, R5, R6 or R7 represents a radical Z5 -(X)n-R8, and R1 does not represent cyano if R5 represents trifluoromethyl~
The following compounds of the general formula (I) may be mentioned specifically, in addition to the compounds mentioned in the preparation examples:
~ R 1 N~N ~ NH - C0 - R
R7 ~ - R3 (I) R6 ~5 ~ R4 Le A 22 664 Table 1:
R1 R2 R3 R~RS R6 R7 CN H F H~CF3 H F-CN H Cl HOCF3 H H
CN H Cl HOCF3 H Cl CN H Cl Cl OCF3 H
CN H Cl HOCF3 H F
CN H Lr HOCF3 H H
CN H ~r HOCF3 H ~r CN CH3 f HOCF3 H F

CN CH3 Cl HOCF3 H Cl CN CH3 Cl Cl OCF3 H H
CN CH3 Cl HOCF3 H F
CN CH3 8r HOCF3 H H
CN CH3 8r HOCF3 H 9r CN C2H5 Cl HOCF3 H H
CN C2H5 Cl HOCF3 H Cl CN C2H5 Cl Cl OCF3 H H
CN C2H5 Cl HOCF3 H F
CN C2H5 ar HOCF3 H H
CN C2H5 Br HOCF3 H Br CN ~ F HOCF3 H H
CN ~ H F HOCF3 H F

CN ~ F FOCF3 F F
CN ~H Cl HOCF3 H
Le A 22 664 Table 1 (Continuation):
R1 ~2 R3 Rb IR5 R6 R7 .. . . _ _ `~ CN D< CL H-OCF3 H Cl CN D<~i C l C l -~C F 3 H H
CN D~H Cl H-OCF3 H F
CN D~H 8r H-OCF3 H H
CN D~H ~r HOCF3 H Br CN ~H3 Cl H-S-CH2CF3 H H
CN CH3 Cl H-S-CH2CF3 H Cl CN CH3 Br H-S-CH2CF3 H H
CN CH3 Br H-S-CH2CF3 H Br CN CH3 Cl Cl-S-CH~CF3 H H
l:N C2~5 CL H-S-CH2CF.3 H H
CN C2H5 Cl H-S-CH2CF3 H Cl CN C2H5 ar H-S-CH2CF3 H
CN C2~5 Br H-S-CH2CF3 H ~r CN C2H5 Cl Cl-S-CH2CF3 H H
CN D~H CL H-S-CH2CF3 H H
CN D~H Cl H-S-CH2CF3 tl CL
CN D~ Br H-S-CH2CF3 H H
CN D~H Br H-S-CH2CF3 H Br CN D~H Cl Cl-S-CH2CF3 H H
CN CH30CH2- Cl H-S CH~CF3 H H
~ CH30cH2 Cl HS-CH2CF3 H Cl CN CH30CHz- E~t ~~S-CH2CF3 . H H
CN CH30CH2 ~r H-5CH2CF3 H ~r CN CH30CH2 Cl Cl-5-CH2CF3 H H
CN C~3 ~l H-O-CH2CF3 H H
CN ~H3 Cl H-O-CH2CF3 H Cl CN ~H3 Br H~o-GH2cf 3 H H
Le A 22 664 Table 1 (Continuat;on):
R~ ~2 ~3 ~4 RS R6 R7 = . , . . _ . . , CN CH3 Br H -O-CH2CF3 H ar CN C2H5 Cl H -O-CH2CF3 H - H
CN C2H5 Cl H -O~CH2CF3 H Cl CN C2H5 Br H -O CH2CF3 H H
tN C2H5 Br H -O-CH2CF3 H Br CN ~ H Cl H ~-O-CH2CF3 H H
CN ~ Cl H -O-CHzCF3 H Cl CN ~ H Br H -O-CH2CF3 H H
~ ~ Br H -O-CH2CF3 H Br CN CH30CHz- Cl H -O-CHzCF3 H H
CN CH30CH2- Cl H .-O-CH2CF3 H Cl CN CH30C~12- Or H -O-CH2CF3 H H
CN CH30CH2- Br H -O-CH2CF3 H Br CN CH3 SCF3 H Cl H H
CN CZH5 SCF3 H Cl H H
CN CH3 SCF3 H Cl H Cl CN C2HS SCF3 H Cl H Cl CN H Cl H SCF3 H
CN H Cl H SCF3 H Cl CN H Cl Cl SCF3 H H
GN H Cl H SCF3 H F
CN H Br H SCF3 H H
CN H Br H SCF3 H Br Le A 22 o64

2~

Table 1 (Continuat;on):
R 9 R2 R3 ~ R5 R6 R7 CNtH3 F F5CF3 F F
CN~H3 Cl HSCF3 ~ H
CN~H3 CL HSCF3 H Cl CN CH3 CL ClSCF3 H H

CN CH3 Hr HSCF3 H H
Ch CH3 ~r HSC F3 H Hr CNC2~5 F HSC F3 H F

CNC2H5 Cl HSCF3 H H
CNC2H5 Cl HSCF3 H Cl CNC2H5 Cl HSCF3 H F
CN~:2H5 Hr HSC F3 H H
CNC`~H F HSCF3 H M
CN D~H F HSCF3 H F
CN D<H F FSCF3 F F
CN D~ Cl HSCF3 H H
CND'~H CL HSCF3 H Cl CN D~ Cl CLSCF3 H H
D~ C ~ HS C F 3 H F
CN D~ ~r 11SCF3 H H
CN D~ ~r HSCF3 H 3r L e A 22 664 2~

TabLe 1 ~Continuat;on) CN H CF3 H -S02cH3 H H

CN H OC~3 H t~3 H H

CN CH3 CF3 ~ -S02CH3 ~ H

C~ CH3 CF3 ~ -SCF3 H H

CN ~ H CF3 H -S02CH3 H H
CN ~ H CF3 H ~SCF3 H
CN ~ H OCF3 H -OCF3 H H
CN ~ OCF3 H -CF3 H H
~ CN H Cl H -SCHF2 H H
: CN H Cl H -SCHF2 H Cl CN H ~r H -SCHF2 H H
CN H l~r H -SCHF2 H Br Le A 22 664 Table 1 ~Cont;nuat;on3:
R~ R~ ~3 ~4 R5 1~ ~7 CN l:H3 CL 11 -SCHF2 11 H
tN CH3 CL H -SCHF2 H CL
CN CH3 Br H ~SCHF2 - H H
CN CH3 Br H -SCHF2 H Br tN C2115 cl H -SCHF2 H H
CN ~2H5 CL H ~SCHF2 H Cl SN C2H5 Br H -SCHF2 H H
CN C2H5 Br H -SCHF2 H Br CN D< Cl H -SCHF~ H 11 CN D~:~H Cl H -SCHF2 H Cl CN D~H Br H -SCHF2 H H
CN ~ Br H -SCHF2 H er CN H Cl H -SCF2CHF2 H H
CN H Cl H -SCF2SHF2 H Cl CN H Br H -SCF2CHF2 H H
CN H 13r H -S-CF2CHF2 11 Br CN CH3 CL H -SCF2CHF2 H . H
CN CH3 Cl H ~5CF2CHF2 H Cl CN CH3 Br H -SCF2CHF2 H H
CN CH3 Br H -SCFzCHF2 H i3r tN ~2Hs Cl H -SCF2CHF~ H H
CN C2~5 Cl H -S-CF2CHF2 H Cl CN C2H5 Br H -SCF2CHF2 H H
CN C;!H5 3r H -SCF2C-1F2 H Br Le A 22 664 ~2'~

Table 1 (Continuat;on):
Rl R2 R3R4 R5 ~6 ~7 CN D~ Cl H SCF2CHF2 H H
CN ~ CL H -5CF2CHF2 H Cl CN D~H Br H -SCF2cHF2 H H
CN D~ Br H -SCF2cHF2 H ~r CN H CL H~SCF2CHFCl H H
CN H Cl H-SCF2CHFCl H Cl CN H Br H-SCF2CHFCl H H
tN H Hr H-SCF2CHFC l H Br CN CH3 Cl H-SCF2C11FCl H H
CN CH3 Cl H-SCF2CHFCl H CL
CN CH3 ~r H-SCF2CHFC l H H
CN CH3 Br H-SCF2CHFCL H Br CN C2H5 Cl H-SCF2CHFCl H H
CN C2H5 Cl H-SCF2CHFCl H Cl CN C2H5 ~r H-SCF2CHFCl H H
CN C2H5 Br H-SCF2CHFC l H Br CN D<H Cl H~SCF2CHFCL H H
CN D~ Cl 11-SCF2CHFCl H Cl CN D~H E~r H-SCFzCUFCl H H
CN C~, Br H-SCF2C11FCl H ~r CN ClCH2- Cl H-SCF3 H H
CN CLCH2- Cl ~--OCF3 H Cl CN ClCH2- ûr H-OCF3 H H
CN CLCH2- Br ~O~F3 H Br CN C~30C~2 CL H~OCF3 H H

L e A 22 6_ ~2~1~2~
~ 13 -TabLe 1 (Continuation):
. ..
CN CH30CH2 Cl H -OCF3 ~ CL
CN ClCHz- Cl H -SCF3 W H
CN ClCH2- CL H -SCF3 ~ - Cl CN ClCH2- Br H -SCF3 H H
tN H Cl H -SOCF3 H H
CH H Cl H -SOCF3 H Cl CN H ~r H -SOCF3 H ~Br CN H Br H -SOCF3 H H
CN H CF3 H -SûCF3 H H
CH H tF3 H -SOCF3 H Cl CN CH3 Cl H -SOCF3 H
CN CH3 CL H -SOCF3 H Cl CN CH3 Br H -SOCF3 H Br CN CH3 Br H -SOCF3 H H

CN CH3 CF3 H -SOCF3 H Cl CN CzH5 Cl H -SOCF3 H H
CN C2H5 Cl H -SOCF3 H Cl CN C2Hs ~r H -SOCF3 H ~r CN C2H5 Br H -SOCF3 H H

CN C2H5 CF3 H -SOCF3 H Cl CN ~ H Cl. H -SOCF3 H . H
CN ~ H CL H -SOCF3 H Cl CN ~ H ~r H -SOCF3 H Br CN ~ H Br H -SOCF3 . H H
CH ~ H CF3 H -SOCF3 H H

Le A 22 664 Table 1 (Continuation)~
___ _ _ _ CN D~H ~F3 H-SOCF3 H Cl CN H Cl H-OCF2CHFCl H Cl CN H Br H-OCF2CHFCl H
CN H Cl H-OCt~CHFCl H ~r CN CH3 Cl H-OCFzCHFCl H 11 CN ~H3 Cl H~OCF2CHFCl H Cl tN CH3 Br H~OCF2CHFCl H H
CN CH3 ar H-OCF2CHFCl H ~r CN C2H5 Cl H-OCF2CHFCl H H
CN C2H5 Cl H-OCF2CHFCl H Cl CN C2H5 Br H -OCF~CHFCl H H
CN C2H5 Br H-ûCF2CHFCl H ~r CN D~ Cl H-OCF2CHfCl H H
CN D~H Cl ~~OCf2CHfCl H CL
CN D~ 3r H-OCF2CHFCl H H
CN D~ Br H-OCF2CHFCl H ~r CN 1~ Cl H-OCF2CHCl2 H H
SN H Cl H-OCF2CHCl2 H Cl tN H ~r H-OCF2CHCl2 H H
CN H Br H-OCf2CHCl2 H Hr tN CH3 Cl H-OCF2CHCl2 H H
tN CH3 Cl H-OCF2CHCl2 H Cl C~ CH3 Br H-OCF2CHCl2 H H
tN tH3 E~r H-OCF2CHCl2 tl Br Le A 22 664 Table 1 tContinuation):
Rl~2 R3 R~ RS R6 R7 CN~2~5 - -OCF2CHC l ~ H H
CNC2H5 Cl H-OCF2CHC l,2 H CL
CNC2H5 ~r H-OCF2CHC l ;2 H H
CNC2H5 Br H-OCF2CHCl2 11 Br CND~H Cl H-OCF2CHCl2 H H
CND<H Cl H-OCF2CHCl2 H Sl CND<H Br H-OCF2CHCL2 H 11 CN~<~H E3r H-OCF2CHCl2 H ~r CN H Cl H. -OCFzCHF2 H H
CN H Cl H-OCF2CHF2 H Cl CN H 8r H-OCF2CHFz H H
CN H 8r H-OCF2CHF2 H Br CNCH3 Cl H-OCF2CHF2 H H
CNCH3 Cl H-OCF2c~F2 H Cl CNCH3 ~r HOC~2cHF2 H H
CNCH3 ~r H-OCFzCHf2 H ~r CNC2H5 Cl H-OCF2cHF2 i1 H
CNC2H5 Cl H-OCF2cHF2 H l~l CN~2H5 Br H-OCF2CHF2 H H
CNC2H5 Br H-OCF2CHF2 1! Br CND~ CL H-OCF2CHF2 H H
CN~>~H Cl H-OCF2cHF2 H Cl CNC~H Br H-OCF2CHF2 H H
CND<~ Br H-OCF2CHF~ H ~r L e A ?2 664 ~ 16 -Table 1 (Cont;nuat;on) RlR2 R3 R4 R5 R6 R7 CN H Cl H502CF3 H H

CN H 13r H -SD2CF3 H H
CN H Br H502CF3 ~ E3r CN H CF3 H -S02cF3 H H

CNCH3 CF3 H -S02cH3 H tl CNC2~l5 Cl H-502CF3 H CL
CNC2H5 Br HS02CF3 H H
CNC2H5 5r H-SOzC F3 H Br .:ND~ CL H-SO~CF3 11 H
CN D<H Cl H-S02CF3 ~ Cl ~N D<H E3r H-S02cF3 H H
~N D~H ~r H-S02CF3 H Br CN D<H CF3 H-502CF3 H tl CN H F HSCC l 2F H F
CN H F F~SCC l 2F F F
Cll H Cl H-SCCl2F H H
CN H Cl H-SCCl2F H Cl CN H C l H~SCC l 2F H F

Le A 22 664 2~7 Table 1 (Con~;nuat;on3:
. _ Rl R2 R3 R4 R5 S~6 R7 CN H ~r H -SCC L 2F H H
CN H ~r H -SCC l 2F H - ~r CN CH3 F H -SCCl2F H H
CN CH3 F H -SCCl2F H F
CN CH3 F F ~SCC l 2F F F
CN CH3 C L H -SCC l 2F - H H
CN CH3 Cl H -SCCl2F H Cl CN CH3 Cl H -SCCl2F H F
CN CH3 Br H -SCC l 2F H H
CN CH3 Br H -SCCl2F H Br CN C2Hs F H -SCC l 2F H H
CH C2H5 F H . -SCCl2f H F
CN C2H5 F H -SCC l 2F F F
CN C2H5 Cl H -SCCl2F H H
CN C2H5 Cl H ~SCCl2F H Cl CN C2H5 Cl H -SCClzf H F
CN C2~5 Br H -SCCl2F H H
CN Cz115 ar H -SCCl2F H Br C~ H F H -SCCl2F H
CN D~H F H -SCC l2F H F
CN D<~H F F SCCl2F F F
CN ~ Cl H -5CCl2F H H
CN D~H Cl H ~SCCl2F H Cl CN D<~H Cl H -SCCl2F H F
SN D~H Hr H -SCCl2F H H
CN Ds~ Br H -SCCLzF ~t Br Le A 22 664 :

~2~

Table 1 (Continuat;on)_ R1 R2 R~ R5 R6 R7 CN H F H~OCHFz tl H
CN H F H-OCHFz }I F

CN H Cl H-OCHF2 H M

CN H Cl H-OCHF2 H F
CN H Br H-OCHF2 H H
CN H Br H-OCHF2 H E3r CN CH3 F H- OCHFz H H

CN ~H3 F F-OCHF2 F F
CN CH3 Cl H-OCHF2 H H
CN CH3 Cl H-OCHF2 H Cl CN CH3 CL H-OCHf2 H F
CW CH3 E3r H-OCHF~ H H
CN CH3 Br H-OCHF2 H Br CN ~2H5 F H-OCHF2 H H

CN C2H5 Cl H-OCHF2 H H

CN C2H5 CL H-OCHF~ H F
CN C2H5 Hr H-OCIIF2 H H
CN C2H5 Br H-OCHF2 H 8r C~J D<H F H-OCHF2 H H
C N D~ O C H F 2 H F

Le A 22 664 ~2~ 7 Table 1 (Continuation):
~1 R2 R3 R4 ~5 ~6 R7 CN ~H f F -OCHF2 F F
~N D<~ CL H -OCHF2 H H
CN ~ C l H -OCHF2 H C L
CN Cx~H C l H -OCH2F H F
CN D<H ~r H -OCHF2 H H
CN iXH Br H -OCHF2 H ar C l~ _C L
CN L~CH3 Cl H -OCF3 H H
l:N 2~CH3 CL H -OCF3 H CL
Cl C~
CN E~CH3 CL H -SCF3 H H
C l'~c'C~
CN ~CH3 Cl H -SCF3 H Cl Cl Cl CN 2S CH3 Cl H -SO2cF3 H H
c l~,_C~L
CN ~cCH3 Cl H -S02CF3 H Cl CN ~- C l H ~OC F3 H Ç l CN ~)~ Cl H -SCF3 H Cl CN Cl~W Cl H -OCF3 H Cl CN Cl~ Cl H -SCF.3 H Cl CN CH3~- Cl H -OCF3 H Cl CN CH3-~)- Cl H -SCF3 H Cl CN 02N-~- Cl H -OCF3 H Cl CN 02N-~- Cl H -SCF3 H Cl Le A 22 S64 Generically a compound forming the subject of one of the divisional applications can be defined as a 5-aminopyrazole of the formula (II-I) N ~ NH (II-I) R6 ~ R

in which R a represents cyano, alkoxycarbonyl, alkenyloxycarbonyl, alkinyloxycarbonyl, alkylaminocarbonyl, alkenylaminocarbonyl or a].kinylaminocarbonyl and R3, R4, R5, R6 and R7 which are identical or d.if.Ecrent, represent hydroyen, halogen, cyano, nitro, alkyl, alkoxy, alkyl-sulphonyl, alkoxycarbonyl or a radical -(X)n-R8 wherein X represents oxygen, sulphur, sulphinyl or sulphonyl, n represent 0 or 1, R8 represents halogenoalkyl with the proviso that at least one of the radicals R3, R4, R5, R6, or R7 represents a radical - (X~n-R8, but Rla does not represent cyano if R5 represents trifluoromethyl, with the proviso that if Rla represents cyano or alkylaminocarbonyl at least one of the radicals R, R, R, R, R represents -X-R , and X does not rep-res~nt oxygen if R represents trifluoromethyl, or with the proviso that if Rla is methoxycarbonyl and if R3 or R7 are trifluoromethyl then R does not represent chlorine.

- l9a -. . ~ ,. . .
;1*~

Such compcunds can be produced by a process which comprises cyclizing a compound of formula (VI-I) R5--~' NH -NH - CH= C

R ~ R

at a temperature between +50C and +150C
A compound forming the subject of the other divisional application can generally be defined as a phenylhydrazine of the formula (VI-I) ~4 : R3 ~ CN
R ~ N~ NH-CH=C

in which R1a represents cyano, alkoxycarbonyl r alkenyloxycar-bonyl, alkinyloxycarbonyl, alkylaminocarbonyl, alkenylaminocar-bonyl or alkinylaminocarbonyl and R , R , R , R and R which are identical or differ-ent, represent hydrogen, halogen, cyano, nitro, al]cyl, alkoxy, alkylsulphonyl, alkoxycarbonyl or a :radical -(X)n-R8 wherein X represents oxygen, sulphur, sulphinyl or sulphon n-represent 0 or 1, R8 represent halogenoalkyl.
with the proviso that at least one of the radicals R , R , R5, R or R7 represents a radical -(X1n-R8, but R does not represent - l9b -2~7 cyano if R5 represents trifluoro~ethyl or with the provlso that if R1a represents cyano or alkylaminocarbonyl a~ least one of the radicals R , R , R , R6, R7 represents -X-R8 and X does not represent oxygen ~f R8 representstrifluoromethyl.
Such a compound can be prepared by a process which comprises reacting an acrylonitrile derivative of the formula (IVa) / CN
C2H5-CH=C la in which - I
Rla has the abovementioned meaning, with a phenyl-hydrazine o e the formula (V) H2N-NH ~ R5 (V) at a temperature between -20C and +20~C

-- l9c --2~

If, for example, 5-am;no-4-cyano-1-(2',6'-di-chloro-4'-trifluoromethylthio-phenyl)-pyrazole and pro-ionyl chloride are used as starting substances, the course of the reaction in the process according to the invention can be represented by the ~o(~o~ing equation:
CN

~;~NH2 Cl ~ ~ Cl - CO - C;~5 CN
S~F3 (Base) I
- > N ll -HCl ~N'~NH-CO-C2Hs Cl~Cl Formula tII) provides a general definition of the 5-aminopyrazoles requ;red as start;ng substances for carry;ng out the process according to the invention. In th;s formula (II)~ R1, R3, R4 R5 R6 a d R7 ably have that meaningswhich have already been mentioned as preferred for these substituents in the descr;ption of the substances of the formula (I) accord;ng to the inven-tion.
Some of the 5-aminopyrazoles of the formula (II) are known ~compare, for example, European 34,945; DE-OS
(German Publ;shed Spec;ficat;on) 3,226,496 and DE-OS
(German Publ;shed Specification) 3,129,429).
205-Aminopyrazoles of the formula (IIa) R1' ~ NH2 R7 - ~ ~3 (IIa) ~5 R4 Le A 22 664 ~2.,~

in which R represents alkoxycarbonyl, alkenyloxycarbonyl, alkinyloxycarbonyl, alkenylaminocarbonyl or alkinylaminocarhonyl and R , R , R , R and R have the abovementioned meaning, are not yet known and are part of the subject of this divisional application.
However, these compounds are obtained by processes which are known in principle, in which acrylonitrile derivatives of the formula (IVa) ,, CN
C2H50 - C~l - C (IVa) in which R has the abovementioned meaning~ are.reacted with phenylhydrazines of the formula (V) H2N - NH ~ - R5 (V) in which R , R4, R5, R6 and R7 have the abovementioned meaning, either initially in a first stage, if apPropriate ln the presence of a diluent, such.as, for example, glacial acetic acid or ethanol, and iE appropriate in the presence of a reaction assistant, such ~2~
- 21a - 23189-5833D
as, for example, glacial acetic acid or ethanol, and if appropriate in the presence of a reaction assistant, such as, for example, sodium acetate, at temperatures between -20C
and +20C, to give the phenylhydrazine derivatives of the formula (VIal \ ~ CN
R5_ ~ _ NH - CH = C (VIa) R R

in which Rl , R3, R4, R , R6 and R7 have the above-~2~ 2~

mentioned meaning ~these drawings axe part of the subject of the other divisional a~plicat-on),and these are cyclised in a second stage, if appropriate in the presence o:E a diluen-t, such as, for example, ethylene glycol monoethyl ethex, at temperatures between +50C and ~150C, or the compounds of the formulae (VIa) are directly cyclised in one reaction step, without isolation of the intermediate stage of the (VIal, if appropriate in the presence of a diluent, such as, for example, ethylene glycol monoethyl ether or ethanol, at temperatures between +50C and +150C.
5-Aminopyrazoles o~ the ~ormula (IIb) ~Rl ~ ~

~ NH2 (IIb) R~ ~ 4, in which R represents cyano or alkylaminocarbonyl and R3 , R4 , R5 , R6 and R7 , which are identical or different, represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylsulphonyl, alkoxycarbonyl or the radical -X-R8, wherein X represents oxygen, sulphur, sulphinyl or sulphonyl and R8 represents halogenoalkyl, with the proviso that at least one or the radicals R3 , R4 , R5 , R6 or R7 represents a radical -X-R3, and X does not xepxesent oxygen if R8 represents ~Z~ 137 ~ 22a - 23189-5833E
trifluoromethyl, are also not yet known and are also par-t of the subject of this divisional application.
They are likewise obta.ined in an analo~ous manner to the 5-aminopyrazoles of the formula (IIa) by processes which are known in principle, in which acrylonitrile derivatives of the formula (IVb) CN
C2H5O-cH = C \ l (IVb) R '' in which Rl has the abovementioned meaning, are reacted with phenylhydrazines of the formula (Va) R ' R4i H2N - NEI ~ ~ ~ R5' (Va) R7~ \ R6' in which R3 , R , R , R6 and R7 have the abovemen-tioned meaning, either initially in a first stage, if appropriate in the presence of a diluent, such as, for example, glacial acetic acid or ethanol, and i~ appropriate in the presence of a reaction assistant, such as, for example, sodium acetate, at temperatures between -20C and ~20C, to give the phenylhydrazine derivatives of the formula (VIb) R4~ R3~
\~-~/ CN
R ' - ~O ~ _ NH - NH - CH = C \
R6 R7' R

(VIb) 2~7 ~hich are known in princ;ple, in ~hich acrylonitrile derivatives of the formula (IVb) ~2~5~ ~ CH = C (IVb) in ~hich S R1 has the abovementioned meaning, are reacted ~ith pheny~hydrazines of the.formula (Va) R3' R4' H2N - ~H- ~ -R5' (Va) R7~ R6' ;n wh;ch R3 , R4 , R5 , R6 and R7 have the above-mentioned meaning, either init;ally ;n a f;rst sta~e, if appropriate ;n the presence of a d;luent, such as, for example, glacial acet;c acid or ethanol, and if appropr;ate in the Rresence of a reaction assistant, such as, for example, sodium acetate, at temperatures between -20C and +20C, to give the phenylhydrazine der;vat;ves of the formula (VIb) R5~ NH ~ NH - CH = C~ ~VIb) R~' R7' in which R , R , R , R , R and R7 have the above-mentioned meaning (these derivatives are part of the subject of the other divisional applicationl, and these are cyclised in a 2nd stage, if appropriate in the presence of a diluent, such as, for example, ethylene glycol monoethyl ether, at temperatures between +50C and +150~C, or the compounds of the formulae (IVb) and (~al are directly cyclised in one reaction step, without isolation of the intermediate stage of the formula (VIb), if appropriate ;n the presence of a diluent, such as, for example, ethylene glycol monomethyl ether or ethanol, at temperatures between ~5ûC and ~150C.
The acrylon;tr;le der;vatives of ~he formulae (Iva) and (Ivb) are known 5compare, for exa~ple, European 34,945 or DE-OS tGerman Publ;shed Specification) 3,129,429).
The phenylhydra~ines of the t'ormuLae (Y) and (Va) are known in most cases, or they can be prepared in a simple manner by processes analogous to known processes 1û (compare, for example, Houben-Weyl, "Methoden der organis-chen Chemie" ("Methods of Organ;c Chemistry"), Volume X/2, page 203, Thieme Verlag Stuttgart 1967), for example by reacting the known anilines of the formula (VII) R4 - R3 tVII) R5~ N112 in which R3, R4, R5, R6 or R7 have the abovementioned meaning, with sodium nitrite in the presence of an acid, such as, for example, sulphuric acid, and then with tin-II
chloride, like7ise in the presence of an ac;d, such as, for example~ hydrochloric acid, at temperatures between -20C and ~80C.
Formula tIII) provides a general definition of the acylating agents also re~uired as starting substances for carrying out the process according to the invention. In this formula (III), R2 preferably has those meanings which have already been mentioned as preferred for these radicals in the description of the substances of the formula (I) accordins to the invention. A preferably represents halogen~ in particular chlorine or bromine, or

3 radical R2-CO-O-, R2 having the abovementioned meaning.
The acylating agents of the formula (III) are generally known compounds of organ;c chem;stry.
Le A 22 b6~

~ 25 -Possible diluents for carrying out the process according to the ;nvention are inert organic solvents.
Preferred solYen~s ~hich are used are aLiphatic or aromatic~ optionally halogenated hydrocarbons~ such as benzine, benzene, toluene, xylene, pentane, hexane, hep-taneV cyclohexane, petroleum ether, ligroin, methylene chlor;de, ethyLene chloride, chloroform, carbon tetra-chloride, chLorobenzene or dichlorobenzene, e~hers, such as diethyl ether or di;sopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, ketones, such as acetone or butanone, methyl isopropyl ketone or methyl ;sobutyl ketone, esters, such as ethyl acetate, nitriles, such as acetonitrile or propion;trile, or amides, such as dimethylformamide, dimethylacetamide, N-methylpyrroLidone or hexamethylphosphoric acid triamide.
If acylating agents of the formula (III) are used in liquid form, it is also possible to employ these in an appropriate excess as the diluent.
Possible acid binding agents for the process accordin~ to the invention are all the inorganic and organic bases ~hich can usually be employed~ Bases which are preferably used are alkali metal hydroxides or car~
bonates, such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, or tertiary amines, such as, for example, triethylamine, N,N-d;methylan;l;ne~ pyridine, 4-(N,N-dimethylamino)-pyridine, diazabicyclooctane (DABC0), diazabicyclononene (DBN) or diazabicycloundecene (DBU~.
The reaction temperatures can be varied within a substantial range in the process according to the inven-tion~ In general, the reaction ;s carr;ed out between -~0C and +150C, preferably between 0C and ~100C.
For carry;ng out the process accord;ng to the invention, ;n general 1 to 20 moles~ preferably 1 to 15 moles, of acyLating agent of the formula (III) and in general 1 to 3 moles, preferably 1 to 2 moles, of acid-Le A 22 664 b;nding agent are employed per mole of 5-aminopyrazole of the formula (II). The reaction procedure, ~orking up and ïsolation of the end products of the ~ormula (I~ are effected in the customary manner.
The active compounds according to the ;nvention can be used as defoliants, desiccants, agents for destroy-ing broad-Leaved plants and, especially, 3s weedkillers.
8y weeds, in the broadest sense, there are to be under-stood all plants which grow in locations ~here they are 13 undesired. Whether the substances according to the inven-tion act as total or selec~ive herbicides depends essen-tially on the amount used.
The active compounds according to the inven~ion can be used~ for example, in connection ~ith the ~ollowing plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Gal-ium, Stellaria, Matricaria, Anthemis, Gal;nsoga, Chenopo-d;um, Urt~ca, Senec;o, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cir-sium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Linder-nia, Lamium, Veronica, Abutilon, Emex, Datura, ~iola, Galeopsis, Papaver and Centaurea.
Dicotyledon cultures of the genera: Gossypium, Glycine, ~eta, Daucus, Phaseolus, Pisum, Solanum, L;num, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, E~rass;ca~ Lac-tuca, Cucumis and Cucurb;ta.
Monocotyledon weeds of the genera- Echinochloa, SetariaO
Panicum, D;g;tar;a, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agro-pyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleo-charis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyl-octenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures o~ the ~enera: Oryza, ~ea, Triti-cum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
Houever, the use o~ the active compounds according Le A 2? 66~

~24~2~

to the invention is in no ~ay restricted to these genera, but also extends ;n the same manner to other plants.
The compounds are suitable, depending on the con-centration, for the total comoating of ~eeds, for example on industrial terrain and rail tracks, and on paths and squares w;th or without tree plantings. Equally, the com-pounds can be employed for combating weeds in perennial cultures, for examp~e afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orch-ards, banana pLantationsr coffee plantations, tea planta-t;ons, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.
Besides a particularly good general herb;cidal activity, the active co-mpounds of the formula ~I) thereby also show a considerably improved crop plant select;v;ty in important crops.
The ;ntermed;ates of the formula (II) and the ;ntermediates of the formulae tVIa) and (VIb) likew;se have herbic;dal actions and a pronounced selectivi-ty to-wards important crop plants.
~ hen applied in appropriate amounts, the active compounds of the formula ~I) according to the invent;on and their intermediates of the formula (II) also have a fungicidal action, for example against the rice disease pathogen Pyricularia oryzae.
The active compounds can be converted to the cus-tomary formulations, such as solutions, emulsions, wett-able powders, suspensions, powders, dusting agents, pastes~ soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very f;ne capsules ;n polymeric substances.
These formulat;ons are produced in known manner, for example by mixing the açtive compounds uith extenders, that is, liquid solvents and/or solid carriers, optionally _e A 22 664 ~;th the use of surface-active agents, that is, emulsify-ing agents and/or dispersing agents, and/or foam-forming agents.
In the case of the use of ~ater as an extender, organ;c solvents can, for example, also be used as auxi-liary solvents. As liquid solYents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated ali-phat;c hrdrocarbons, such as chlorobenzenes, chloroethyl-enes or methylene chloride, aliphatic hydrocarbons, suchas cyclohexane or paraffins, for example petroleum frac-tions, mineral and vegetable o;ls, alcohols, such as butanol or glycol as ~ell as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl ;so-butyl ketone or cyclohexanone, strongly polar solvents,such as dimethylformam;de and dimethylsulphoxide, as well as water.
As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kao-lins, clays, talc, chalk, quartz, attapulgite~ montmorillo-nite or d;atomaceous earth, and ground synthet;c minerals, such as highly dispersed s;lic;c ac;d, alum;na and sili-cates; as sol;d carr;ers for granules there are su;table:
for example crushed and fract;onated natural rocks such as calc;te, marble, pumice, sepiolite and dolomite, as well as synthet;c granules of ;norgan;c and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/
or foam-forming agents there are suitable: for example 3û non-;on;c ~nd anionic emulsifiers, such as polyoxyethyl-ene-fatty acid esters~ poLyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl-sulphonates, alkylsulphates, arylsulphonates as ~ell as albumin hydrolysation products; as dispersing agents there are su;table: for example lignin-sulph;te uaste l;quors and methylcellulose.
Le A 22 6~4 ~2~

Adhesives such as carboxymethylcellulose and natural and synthet;c polymers ;n the form of po~ders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as naturally occurring phospholipids, such as cephal;ns and lec;th;ns, and syn-thetic phospholip;ds, can be used in the formulations.
Further additives can be m;neraL and vegetable oils.
It is possible to use colorants such as ;norgan;c p;gments, for example ;ron ox;de, titanium oxide and Prus-ln sian Blue, and organic dyestuffs, such as alizarin dye-; stuf~s, azo dyestuffs and metal phthaLocyanine dyestuffs, and ~race nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and ~inc.
The formulations in general contain bet~een û.1 and 95 per cent by weight of active compound, preferablybetween 0.5 and 90%.
The active compounds according to the ;nvention, as such or in the form of their formulations, can also be used, for combating ~eeds, as mixtures with known herb;-cides, f;nished formulations or tank mixes being possible.
Possible components of the m;xtures are knownherbicides, for example diphenyl ether, pyridoxy-phenoxy-propion;c acids, phenoxyalkanecarboxylic acids, ureas, triazinones or triazindiones, such as, for example, 2-benzyloxyethyl, 2,2-diethoxyethyl or trimethylsilylmethyl a-C4-(3,5-d;chloro 2-pyridoxy)-phenoxy]-propionate, 2,4-dichlorophenoxyacetic acid, a-(2,4-dichlorophenoxy)-pro-pionic acid, 4-chioro-2-methylphenoxy-acetic ac;d, a-(4-chloro-2-methylphenoxy)-propionic acid, 1-amino-6-ethyl-th;o-3-(2,2-d;methylpropyl~-1,3,5-triaz;ne-2,4~1H~3H)-dione or N-(2-benzothiazolyl)-N,N'-dimethyl-urea, for ccmbating ~eeds ;n cereals; 4-amino-3-methyl-6-phenyl-~,2,4-tr;azin-5(4H) one, for combating ~eeds in sugar beet; and 4-amino-6-(1,1-dimethylethyl)-3-methylthio- or =~3-ethylthio-1,2,4-tr;az;n-5(4H)-one, ~or combat;ng ~eeds in soya bean. Surpris;ngly, some mixtures also exhibit a Le A 22 ~64 2~

synergistic action.
Mixtures w;th other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents ~hich improve soil structure, are also possible.
The activè cornpounds can be used as such~ in the forrn of their formulat;ons or in the use forms prepared therefrom by fur~her dilution~ such as ready-to-use solu-tions, suspensions, emulsions, po~ders, pastes and gran-ules. They are used in the customary manner, for exampleby water;ng, spray;ng, atomising or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants.
They can also be incorporated into the soil before so~;ng.
The amount of active compound used can vary w;thin a substantial range. It depends essent;ally on the nature of the des;red effect. In general, the amounts used are 2û bet~een 0.01 and 15 kg of act;ve coropound per hectare of soil surface, preferably bet~een 0.05 and 10 kg per ha.
The preparat;on and the use of the active com-pounds accord;ng to the ;nvention of the parent applicatio can be seen from the following examples.
Preparation Examples Example 1 CN

N~NH-CO-C2H5 CL ~ Cl (1 First 10 ml (D.11 mole) of propionyl chloride and then 1.8 ml (0.02 mole) of pyridine in 15 ml of chloroform are added to a suspens;on of 3.5 9 (0.01 mole) of S-amino-Le A 22 664 ~L2~22~7

4-cyano-1-(2,6-dichloro~4-trifluoromethylthio-ohenyl)-pyrazole in 30 ml of chloroform at 0C, with s~irring.
A clear soLution is obtained, and, when the addition has ended, stirring is cont;nued at room temperature for 2û
hours. The solution thus obtained is evaporated to dry-ness. For working up, the residue is taken up in 50 ml of ethanol, aqueous ammonia is added until the reaction is alkaline, the mixture is heated under reflux for 10 min-utes, the volatile constituents are removed in vacuo, the lC residue is taken up in 100 ml of chloroform, the mixture is ~ashed with water, then with 2 N aqueous hydrochloric acid and again with water and dried over sodium sulphate and the solvent is removed in vacuo. 3.4 9 (~3% of theory) of 5-propionylamino-4-cyano-1-(2,6-dichloro-4-trifluoromethylthio-phenyl)-pyrazole of melt;ng point 153C to 156C are obtained~

CN

NH-co-c2H5 Cl ~
Cf3 - 10 ml (0.11 mole) of propionyl chloride are added 2n to 2.9 9 (0.01 mole) of 5-amino-4-cyano-1-(2-chloro-4-trifluoromethoxy-phenyl)-pyrazole in 30 ml of chloroform at ûC, w;th stirring, and a solution of 1.ô ml (0~02 mole) of pyridine in 15 ml of chloroform is then added, also at 0C. When the addition has ended, stirring is continued at rooM temperature for 20 hours, the solvent is stripped off, the residue is taken up in 50 ml of ethanol, aqueous ammonia is added until the reaction is alkaline, the volatile constituents are removed in vacuo, the res;due is taken up in 100 mL of chloroform, the mix-ture ;s ~ashed ~;th ~ater, then ~ith 2 N aqueous hydro-Le A 22 664 .

~51 ;;~ 2d;~

chloric acid and again with water and dried over sodium sulphate and the solvent ;s removed in vacuo. 2.7 g ~75.3% of theory) of 4-cyano-1-(2-chloro-4-trifluorometh-oxy-phenyl)-5-propionylamino-pyrazole of melting point 127C are obtained.
The following compounds of the general formula (I~
are obtained in a corresponding manner~ according to the general preparation disolosure:

NH~CO-R2 (I) R7 ~ R 3 R6 ~ R4 Le A 22 664 ~2~

Table 2 Ex--NamoPle Rl R2 R3 R4 RS ~6 R7 point ~C) 3 C2~50C- C2H5 Cl H CF3 H Cl 63-67 : 4 C2HsOCO- C2~s Cl H CF3 H H 87-89 CN C2H5 H Cl OCF3 H H 1~2 143 7 C2H5~- C2H5 Cl H OCF3 H Cl &4-85 8 C2H53CO- C2H5 Cl H OCF3 H H oil nD~=1,507 CN C2H5 H Cl SCF3 H H 143 11 CN C2H5 Cl H SCF3 H H 161-163 12 CN CH3 Cl H SCF3 H Cl 173-175 13 C2H50CO- C2H5 H Cl SCF3 H H 136-137 14 CN C2H5 CF3 H Cr3 H H 150-154 CN C2~l5 CF3 H F3C_502_ H H 188-l90 16 CN C2H5 Cl H F3C-so2. H H 160 17 CN C2H5 H CF3 Cl H H 186 18 CN C2H5 CF3 H3 snz ~I H l48 l9 CN C2H5 CF3 H CH3-52- H Cl 198 CN C2H5 Cl H F3C-502_ H Cl 197 21 CN Cl-CH2 Cl H F3CS~ H Cl 79 22 CN C2H5 H ClF2C_502_ H Cl 213-214 Le A 22 664 .

Table 2 (continued) Exa~ple ~2 R3 R4 R5 R6 R7 MOlting Point 23 H2N-C- C2H5 Cl H F3C-S~ H Cl 170-171 CN ~ H Cl H F3C-S- H Cl 209 26 CN Cl-CH2- Cl H F3C-0- H H 125-128 27 CN ~ H Cl H F3C-0- H H 116 28 CN n-c3H7 Cl H F3C-0- H H 111 29 CN (CH2)2CH-CH2- Cl H F3C-0- H H 95-98 CN Cl CH2 CH2Cl H F3C-0- H H 109 31 CN Br-C-- Cl H F3C-0- H H 120 32 CNtCH3)3C- Cl H F3C-0- H H 159 33 CNCH3 (CH2)10 Cl H F3C-0- H H 7û-72 34 CNCH3-(CH2)3- Cl H F3C-0- H H 84-87 Le A 22 664 31 ;24~2~7 Table 2 (continued) E 1 Melting Point No. R R2 R3 R4 R5 R6 -~7 (C) .
CN CH3 Cl H F3C-0- H H 145-1~6 - 36 CN C2H5 fH Ci H F3C-0- H H lû7-109 37 CN CH3 Cl H F3C-0- H Cl 181-182 38 CN C2H5 Cl H F3C-0- H Cl 39 CN (CH3)2CH- Cl H F3C-0- H H 125-129 CN CH30-CH2- Cl H F3C-0- H H 102 41 CN C~l3S-C~I2- Cl ~I F3C-S- ~I Cl 132-135 42 CN CH30-CH2- Cl H F3C-S- H Cl 158-160 43 CN CH S-CH - Cl H F3C-0- ~I H 115 Le A 22 664 ~2~
- 36 ~ 23189-5833D

Preparation of the starting substances (some of which are the , subject of each of the divisional applications) CN

N ~
` N NH2 (II-l) Cl-- ~ Cl 14.1 g (0.04 mole) of 1-(2,2-dicyanethen-1-yl)-2-~2,6-dichloro-4-trifluoromethylthio~-phenyl)-hydrazine in 30 ml of ethylene glycol monoethyl ether are heated under reflux Eor 2 hours. Active charcoal is added to the hot solution, the mixture is filtered and the filtrate is diluted with 60 ml of water. The precipitate which has separated out is filtered off with suction and dried. 9.8 g (70% of theory) of 5-amino-4-cyano-1-(2,6-dichloro-4-trifluoromethylthio-phenyl)-pyrazole oE melting point 185C to 187C are obtained.

CN

(II-2) `N NH2 ~Cl ~z~

- 36a -3.08 g (0.025 mole) of ethoxymethylenemalonic acid dinitrile and 5.7 g (0.025 mole) of 2-chloro-4-trifluoromethoxy-phenylhydrazine in 50 ml of ethylene glycol monoethyl ether are heated under reflux for 3 hours and, after the mixture has been cooled, it is poured onto water, the crystalline precipi-tate is fil~ered off with suction and sti.rred with petroleum ether, the mixture is cooled and the precipitate is filtered off again with suction. 5.3 g (73. 6~o of theory) of 5-amino-4-cyano-1-(2-chloro-4 -trifluoromethoxyphenyl)-pyrazole of melting point 115C are ~2~

obta;ned.
The following ne~ 5-am;n~pyrazoLes of the formula ~ are obtained in a correspond;ng manner according to the general preparation statements:

b~
N~N - NH2 R7 ~ R3 tII) -Table 3:
ample R1 R3 R4 R5 R6R7 Me~tin~O
No.

II-3 C2HsOCO- CL H CF3 H Cl 134-35 II-4 C2HsOCO- Cl H CF3 H H 112-114 II-5 C2HsOCO~ Cl H OCF3 H H 115-11B
$I-6 C2HsOCO- Cl H OCF3 H Cl 153-154 II-7 CN Cl H SCF3 H H 159 II-8 C~ H Cl SCF3 H H 126-128 lI-9 CN H H SCF3 H H 122 II-10 C2HsQCO- H Cl SCF3 H H 12~122 II-11 C2HsOCO- Cl ~ SCF3 H H 129-130 Le A 22 664 ~2~2~7 Table 3 (continued) Example R3 R4 R5 R6 R7 (C) II-15 CN H CF3 Cl H H 118 II~16 CN Cl H F3C-S02- ~l H 187-1~9 II-17 CN ~F3 H C~13-S02- ~I Cl 181 II-lC CN Cl H F3C-502- H Cl 254 II-19 CN Cl H ClF2C-502- H Cl 211 II-2û CN ~F3 H H H CF~ 200-203 II-21 CN Cl H F3C-0- H Cl 171 F3C-S- ~ -NH - NH - CH - C ~ (YI-1) 6.1 g (0.05 mole) of ethoxymet~ylenemalonic ac;d din;tr;le are added to a suspension of 13.9 9 (0.05 mole) of (2,6-dichloro-4-trifluoromethylthio)-phenylhydrazine and 2.1 9 (0.025 mole) of sodium acetate in 25 ml of glacial acetic acid, w;th stirring. When the addition has ended, stirring is continued at room temperature for one Le A 22 664 -~2~

hour and the solid thus obta;ned is filtered off, ~ashed successively ~ith water, aqueous sodium bicarbonate solu-tion and aga;n ~ith water and then driedu 15.8 9 (89X of theory) of 1-(2,2-dicyanethen-1-yl)-2-(2~6-di~hLoro~4-trifluoromethylthiophenyl)-hydrazine of meltiny point 160C are obtained.
~JH-NH2 C~ ~ Cl ( V - 1 ) 16.6 g (û.24 mole) of sodium nitrite in 150 ml of concentrated sulphuric acid are first added to 50 9 (0.2 mole) of 2,6-dichloro-4-trifluoromethylthio-aniline in 435 ml of glacial acetic acid at 55C to 60C, and 18û~5 g (0.8 mole) of tin-II chlor;de dihydrate in 188 ml of concentrated hydrochloric acid are then added at 5C
to 10C. The prec;p;tate thus obtained is filtered off ~;th suct;on, stirred in 650 ml of a mixture of ice and aqueous ammonia solution, filtered off with suction, dried and bo;led up t~ice with in each case one litre of chloro-form, the mixture is filtered and the filtrate is freed from the solvent in vacuo~ 33 9 (62.4X of theory) of ~2,6-dichloro-4-trifluoromethylthio)-phenyLhydrazine of melting point 58C are obtained.
The following new ;ntermed;ates of the formula ~V) are obtained in a corresponding manner accord;ng to the general preparat;on statements:

25RS- ~ - NU - NH2 (V) .~

Le A 22 66~

~2~

Table 4:
Ex-ample R3 R4 R5 R6 R7 Melting point (C) ~.
V-2 Cl H OCF3 H il 35 V 3 tl H OCF3 H tl 61 V-5 H ~ OtF3 H H Oel, nD=1,~799 Y-6 H ff SCF3 H H 55 V-7 H Cl StF3 H 11 72 V-8 Cl H SCF3 tl H 83 Le A 22 664 ~2~

Use ExampLes_ The compound shown beLo~ is used as the comparison substance in the use examples wh;ch follow:

~ CN
I I

N~N~ NH-CO-c2lH5 (A) ~l~Cl 4-Cyano-5-propionylamino-1-(2,4,6-trichlorophenyl)-pyra-zole (known from DE-OS (German Published Specification) 3,226,513)~

Le A 2? 664 - 42 _ Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part ~y ~e;ght of alkylaryl poly~lycol ether To produce ~ su~tab(e preparation of a~tive com-pound, 1 part by ueight of active compound is mixed with the stated amount of solvent, the stated amount of emul-sifier ;s added and the concentrate is d;Luted w;th water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours~ ~atered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in X damage in comparison to the development of the untreated control. The fi~ures denot e:
OX = no action (like untreated control) 10û% = total destruction In this example, for example, the compound according to preparation example (1) exhib;ts a clear superiority in herbicidal activity and also in selectivity in useful plants compared ~ith the prior art; th;s particularly appl;es to wheat.

Le A 22 664 Example s ~ 43 ~
Post-emergence test Solvent: ~ parts by we;ght of acetone EmuLs;f;er: 1 part by weight of aLkylaryL polyglycol ether To produce a suitable preparation of active com-pound, 1 par~ by weight of active compound is mixed with the stated anount of so~vent, the stated amount of emulsi-fier is added and the concentrate is diluted ~ith ~ater to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation of the active compound in such a ~ay as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of act;ve compound desired are applied in 2,000 l of water/ha. After three ~eeks, the degree of damage to the plants is rated in X damage in comparison to the development of the untreated control. The figures denote:
0% = no action (l;ke untreated control) 100% = total destruction In this example, for example, the compound according to preparation example ~1~ exhibits a clear superiority in herbicidal activity and also in selectivity in useful plants compared with the prior art. This particularly applies to wheat.

Le A 22 664

Claims (30)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A 5-aminopyrazole of the formula (II-I) (II-I) in which R1a represents cyano, alkoxycarbonyl, alkenyloxycarbonyl, alkinyloxycarbonyl, alkylaminocarbonyl, alkenylaminocarbonyl or alkinylaminocarbonyl and R3, R4, R5 R6 and R7 which are identical or different, represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkyl-sulphonyl, alkoxycarbonyl or a radical -(X)n-R8 wherein X represents oxygen, sulphur, sulphinyl or sulphonyl, n represents 0 or 1, R8 represents halogenoalkyl with the proviso that at least one of the radicals R3, R4, R5, R6 or R7 represents a radical -(X)n-R8, but R1a does not re-present cyano if R5 represents trifluoromethyl, with the proviso that if R1a represents cyano or alkylaminocarbonyl at least one of the radicals R3, R4, R5, R6, R7 represents -X-R8, and X does not represent oxygen if R8 represents trifluoromethyl, or with the proviso that if R1a is methoxycarbonyl and if R3 or R7 are trif-luoromethyl then R5 does not represent chlorine.

2. A 5-aminopyrazole of the formula in which R1' represents alkoxycarbonyl, alkenyloxycarbonyl, alk-inyloxycarbonyl, alkenylaminocarbonyl or alkinylaminocarbonyl and R3, R4, R5, R6 and R7, which are identical or different, represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkyl-sulphonyl, alkoxycarbonyl, or a radical -(X)n-R8, wherein X represents oxygen, sulphur, sulphinyl or sulphonyl, n represents 0 or 1 and R8 represents halogenoalkyl, with the proviso that at least one of the radicals R3, R4, R5, R6 or R7 represents a radical -(X)n-R8, but R1' does not represent cyano if R5 represents trifluoromethyl.

3. A 5-aminopyrazole of the formula in which R1" represents cyano or alkylaminocarbonyl and R3', R4', R5', R6' and R7', which are identical or different, represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkyl-sulphonyl, alkoxycarbonyl or the radical -X-R8, wherein X represents oxygen, sulphur, sulphinyl or sulphonyl and R8 represents halogenoalkyl, with the proviso that at least one of the radicals R3', R4', R5', R6', R7' represents a radical -X-R8, and X does not represent oxygen if R8 represents trifluoro-methyl.

4. 5-Amino-1-(2,6-dichloro-4-trifluoromethoxy-phenyl) -4-cyano-pyrazole of the formula

5. 5-Amino-1-(2-chloro-4-trifluoromethoxyphenyl)-4-cyano-pyrazole of the formula .

6. 5-Amino-1-(2,6-dichloro-4-trifluoromethylsulphonyl phenyl)-4-cyano-pyrazole of the formula .

7. 5-Amino-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-cyano-pyrazole of the formula .

8. A process for preparing a compound of formula (II-I) as defined in claim 1 which process comprises cyclising a compound of formula (VI-I) (VI-I) at a temperature between +50°C and +150°C.

9. A method of combating weeds which comprises applying to the weeds or to their habitat a herbicidally effective amount of a compound according to claim 1.

10. A method according to claim 9 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable carrier or diluent.

11. A method according to claim 10 wherein the active ingredient concentration in said composition is between 0.1 and 95% by weight.

12. A method according to claim 10 wherein the active ingredient concentration in said composition is between 0.5 and 90% by weight.

13. A method according to claim 9, 10 or 12 wherein the compound is applied as a pre-emergence herbicide.

14. A method according to claim 9, 10 or 12 wherein the compound is applied as a post-emergence herbicide.

15. A method according to claim 9, 10 or 12 wherein the compound is applied to an area of cultivation at a rate of between 0.01 and 15 kg/ha.

16. A method according to claim 9, 10 or 12 wherein the compound is applied to the area of cultivation at a rate of between 0.05 and 10 kg/ha.

17. A method according to claim 9 or 10 wherein such compound is according to claim 2.

18. A method according to claim 9 or 10 wherein such compound is according to claim 3.

19. A method according to claim 9, 10 or 12 wherein such compound is 5-amino-1(2,6-dichloro-4-trifluoromethoxy-phenyl) -4-cyano-pyrazole.

20. A method according to claim 9, 10 or 12 wherein such compound is 5-amino-1-(2-chloro-4-trifluoromethoxyphenyl)-4-cyano -pyrazole.

21. A method according to claim 9, 10 or 12 wherein such compound is 5-amino-1(2,6-dichloro-4-trifluoromethylsulphonyl-phenyl)-4-cyano-pyrazole.

22. A method according to claim 9, 10 or 12 wherein such compound is 5-amino-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-cyano-pyrazole.

23. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim 1 as an active ingredient in admixture with a diluent or carrier.

24. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim 1 as an active ingredient in admixture with a solid diluent or carrier, a liquefied normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.

25. A composition according to claim 23 or 24 wherein such compound is according to claim 2.

26. A composition according to claim 23 or 24 wherein such compound is according to claim 3.

27. A composition according to claim 23 or 24 wherein such compound is 5-amino-1(2,6-dichloro-4-trifluoromethoxy-phenyl) -4-cyano-pyrazole.

28. A composition according to claim 23 or 24 wherein such compound is 5-amino-1(2-chloro-4-trifluoromethoxyphenyl)-4-cyano-pyrazole.

29. A composition according to claim 23 or 24 wherein such compound is 5-amino-1-(2,6-dichloro-4-trifluoromethylsulphonyl-phenyl)-4-cyano-pyrazole.

30. A composition according to claim 23 or 24 wherein such compound is 5-amino-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-cyano-pyrazole.