CA1291152C - Phenylhydrazine derivatives useful as intermediates in preparation of 5-amino-1-phenylpyrazoles - Google Patents

Abstract

ABSTRACT
A phenylhydrazine derivative of the formula (IV) in which R4 and R6 independently of one another represent cyano, nitro, halogen, alkyl, alkoxy, alkoxycarbonyl, halogenoalkyl, halogenoalkoxy or a radical -S(O)n-R13, and R5, R7 and R8 independently of one another and of R4 and R6 represent the same radicals as R4 and R6 and additionally represent hydrogen, R13 represents alkyl, halogenoalkyl, amino, alkylamino or dialkylamino, and n represents an integer of 0, 1 or 2, and Z represents one of the radicals , and wherein R1 represents hydrogen, nitroso, nitro, halogen, alkyl, halogenoalkyl, aryl (optionally substituted by halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-halogenoalkyl), or one of the radicals -S(O)n-R9; -?-R10; or -?(OR11)2 and R9 represents hydrogen, hydroxyl, halogen, alkylamino, dialkylamino, alkyl, halogenoalkyl or aryl optionally substituted by halogen C1-C4-alkyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy, R10 represents hydrogen, alkyl or aryl optionally substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-halogenoalkyl, R11 represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkynyl or aralkyl, and n is as defined above, and Hal and Hal' represents identical or different halogen atoms.
These compounds are useful as intermediates in the preparation of herbicidal 5 amino-1-phenyl-pyrazoles.

Description

This application is a divisional of application No.
472,597 ~iled on 22 January 1985. It relates to novel phenylhydrazine derivatives useful as intermediates in the preparation of herbicidal5-amino-1-phenylpyrazoles. It also relates to a process for preparing such phenylhydrazine derivat-ives.
The parent invention relates to the use of 5-amino-1-phenyl-pyrazoles, some of which are known, as herbicides.
It is known that certain 5-amino-1-phenyl-pyrazoles which are substituted in the 4-position by a cyano group, such as, for example, 4-cyano-5-propionylamino-1-(2,4,6-trichlorophenyl)-pyrazol~, possess herbicidal properties (see, for example, DE-053,226,513).
However, their herbicidal activity against some problem weeds, like their compatibility with important crop plants, is not always completely satisfactory in all fields of use.
5-Amino-l-phenylpyrazoles which are unsubstituted in the 4-position or substituted in the 4-position by methyl or phenyl, such as, for example 5-amino-1-(2,4-dinitrophenyl)-4-methylpyrazole, 5-amino-1-(2,4-dinitrophenyl)-4-phenylpyrazole, 5-amino-4-(4-chlorophenyl)-1-(2,4-dinitrophenyl)-pyrazole, 5-amino-l-(2,4-dinitrophenyl)-4-(4-methoxyphenyl)-pyrazole or 5-acetamido-l-(2,4,6-trinitrophenyl)-pyrazole, are also known (see J.Org.Chemistry 36, 2972-2974 [1971]; J.~eterocycl. Chem. 71 -la- 23189-5903D

345-349 [1970] and C.A. 62, 13137c). However, nothing is known about their activity as herbicides.
It has been found that the substituted 5-amino-1-phenyl-pyrazoles, some of which are known, of the general formula (I) N `N
R8 ~ 4~ R3 (I) R7 / ~ R5 in which R1 represents hydrogen, nitroso, nitro, halogen, alkyl, halogenoalkyl, aryl optionally substituted by halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-halogenoalkyl or one of the radicals ~S(O)n~R9; -C-Rl0; -C=N-OR11 or -~-(ORl1)2 R2 represents hydrogen or a radical -C-R12, R3 independently of R2 represents the same radicals as R2 and additionally represents alkyl, R4 and R6 independently of one another represent cyano, nitro, halogen, alkyl, alkoxy, alkoxy carbonyl, halogenoalkyl, halogenoalkoxy or a radical ~sto)n-Rl3~ and R5, R7 and R8 independently of one another and of R4 and R6 represent the same radicals as R4 and R6 and additionally represent hydrogen, and R9 represents hydrogen, hydroxyl, halogen, amino, alkylamino, dialkylamino, alkyl, halogenoalkyl or aryl, optionally substituted by halogen, C1-C4-alkoxy or Cl-C4-halogenoalkyl, s~
-2a- 23189-5903D

R10 representshydrogen, alkyl or aryl optionally substituted by halogen, Cl-C4-alkyl, c1-C~-alkoXy or C1-C4-halogenoal]cyl, Rll represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkinyl or aralkyl, R12 represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl optionally substituted by halogen, lower alkyl or lower halogenoalkyl, alkoxy, alkylthio, alkylamino, dialkylamino, aryl, aryloxy, arylthio or arylamino, each of the last four being optionally substituted by halogen, Cl-C~-alkyl, Cl-C4-alkoxy or Cl-C4-halogenoalkyl, R13 representsalkyl, halogenoalkyl, amino, alkylamino or dialkylamino, X representsoxygen or sulphur, and n represents the numbers 0, 1 or 2, -3- ~ 23189-590~D

possess herbicidal properties, in particular selective herbicidal properties.
Surprisingly, the substituted 5-amino-1-phenyl-pyrazoles of the formula (I) exhibit, in addition to an improv-ed herbicidal action against certain weeds, substantially improved compatibility with important crop plants compared with the 4-cyano-5-amino-1-phenylpyrazoles known from the prior art, such as, for example, 4-cyano-5-propionylamino-1-(2,4,6-tri-chlorophenyl)-pyrazole, which is a similar compound chemically and in terms of its action.
The substituted 5-amino-1-phenyl-pyrazoles thus represent an enrichment of the art.
Formula (I) gives a general definition of the substituted 5-amlno-l-phenyl-pyrazoles. Preferred compounds of the formula (I) are those in which R represents hydrogen, nitroso, nitro, halogen, alkyl or halogenoalkyl, each of which is straight-chain or branched and each of which has up to 6 car~on atoms and, in the case of halogenoalkyl, up to 9 identical or different halogen atoms, or represents phenyl which is optionally monosubsti-:
tuted or polysubstituted by identical or different substituents from amongst halogen, nitro, alkyl, alkoxy or~halogenoalkyl, each having up to 4 car-` bon atoms, or represents one of the radicals `'``'~``"'`' ~: ~

-3a- 23189-5903D

5~

-S(O)n-R ; -C-R ; -P(ORll)2 or -C-N-OR

R represents hydrogen or a radical -C-R12, R independently o~ R2 represents the same radicals as R2, and additionally represents straight-chain or branched alkyl having up to 4 :, : : :: :

: `~ ":: : :~
:~

- 4 ~ $~
carbon atoms, R4 and R6 independently of one another represent cyano9 nitro, halogen, or alkyl, alkoxy or alkoxy-carbonyl~ each of ~h;ch is s~raight-chain or branched and each of which has up to 4 carbon atoms, and furthermore represents halogenoalkyl or halogenoalkoxy, each of ~hich is straight-cha;n or branched and each of ~hich has up to 4 carbon atoms and up to 9 ;dentical or different halogen atoms, or represents a radical -S(o)n-R13O and RS, R7 and R8 independently of one another and of R4 and R6 represent the same radicals as R4 and R6 and additionally represent hydrogen and R9 represents hydrogen~ hydroxyl, fluorine, chlorine, bromine, am;no or alkylamino, dialkyl-am;no, alkyl or halogenoaLkyl, each of ~hich is straight-cha;n or branched and each of ~hich has up to 4 carbon atoms in the indiv;dual alkyl parts, and, ;n the case of halogenoalkyl, up to 9 ident;-cal or d;fferent halogen atoms, and represents phenyl ~hich ;s opt;onally monosubst;tuted or polysubstituted by identical or different substi- !
tuents, the follo~ing being suitable substituents:
halogen~ alkyl, alkoxy or halogenoalkyl, each of ~h1ch ;s straight-cha;n or branched and each of ~hich has up to 4 carbon atoms and, in the case of halogenoalkyl, up to 9 identical or different halogen atoms, R10 represents hydrogen, stra;ght- hain or branched alkyl havlng up to 4 carbon atoms, or phenyl ~hich is optionally monosubst;tuted or poly~
substitu~ted by ;dent;cal or differ~nt substituents, ~;su;~table phenyl subst;tuents be;ng those men-tioned in the case of R9, ~R11 represents hydrogenO halogenoalkyl hav;ng Le A 2Z 853 - 5 ~
up to 4 carbon atoms and up to 6 identical or d;f-ferent halogen atoms,~ alkyl, alkenyl or alkinyl, each of ~hich is stra;ght~chain or branched and each of ~h;ch has up to 8 carbon atoms, and stra;ght-chain or branched phenylalkyl having up to 4 carbon atoms ;n the alkyl part, R12 represents hydrogen, or alkyl which is straight-chain or branched and which has 1 to 12 carbon atoms, or alkenyl, alkinyl, alkoxyalkyl, alkylthioalkyl, alkoxy, alkylth;o,~ alkylam;no~ d;alkylamino or halogeno-alkyl, each of ~h;ch is straight-chain or branched and each of which has up to 4 carbon atoms in the individual alkyl parts and,, in the case of halo-genoalkyl, up to 9 identical or different halogen atoms, and furthermore represents cycloalkyl which has 3 to 7 carbon atoms and is optionally mono-substituted or polysubstituted by identical or r d;fferent substituents from amongst ~ logen, lower alkyl or lo~er halogenoalky ~ and represents phenyl, phenoxy, phenylth;o or phenylamino, each of ~h;ch ;s optionally monosubst;tuted or polysub- \
stituted by identical or different subst;tuen~s, ,' suitable phenyl substituents be;ng those stated in th:e case of R9;
R13 represents amino, and alkyl, alkylamino, dialkylamino or halogenoalkyl, each of ~hich is stra;ght-chain or branched and each of ~hich has up to 4 carbon atoms in the ind;v;dual alkyl parts and, in the case of halogenoalkyl, up to 9 iden-t1cal~ or different halogen atoms, X represents oxygen or sulphur and n~ represents ~he nu~ber 0, 1 or 2.
Particu~larly~ preferred compounds of the formula (I)~:are those~ ;n ~h~ch:
R1 represents hydr~ogen, nitroso, nitro, fluorine, : chlorine, brom;ne, methyl, ethyl, n- and ;-propyl, n-, ~;, s nd ~-butyl, tr'ifluoromethyl, or phenyl Le A 22 853 : ~ ~ : : :
, which is optionally monosubstituted to trisubsti-tuted by identical or different substituents from amongst fluorine, chlorine, bromine, nitro, methyl, ethyl, methoxy and trifluoromethyl, or represents one of the rad;cals ~StO) oR9; I-R~O ; -p(OR11)2 -C=N OR

R2 represents hydrogen or a rad;cal -C-R12 R3 independently of R2 represents the same . rad;cals as R2 and additionally represents methyl, ethyl, n- and ;-propyl, n-, ;-, s- and t-butyl, R4 and R6 ;ndependently of one another represent cyano, nitro, fluor;ne, chlorine, bromine~ ;odine, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy~ ethoxy, me~hoxycarbonyl, ethoxy-carbonyl, trifluoromethyl, trichloromethyl, di-chlorofluoromethyl, d;fluorochloromethyl, chloro-methyl, d;chloromethyl, difluoromethyl, penta~
fluoroethyl, tetrafluoroethyl, tr;fluorochloro-ethyl, trifluoroethyl, d;fluorod;chloroethyl, tri-fluorod;chloroethyl, pentachloroethyl, tr;fluoro-methoxy, trichloromethoxy, d;chlorofluoromethoxy, d;fluorochloromethoxy, chloromethoxy, dichloro ~ethoxy, d;fluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, tr;fluorochloroethoxy, tri-fluoroethoxy, difluorod;chloroethoxy, trifluoro-dichloroethoxy, pentachloroethoxy or a rad;cal -S(O~n-R12, and R , R and RB ;ndependently of one another and of R4 and R6 represent tKe same radicals as R4 and ~:R6 and additionally represent hydrogen, and o R represents:hydrogen, hydroxyl, fluorine, chlorine, brom;ne, amino, methylam;no, d;methyl-Le A 22 853 ., . ~

- 7 _ amino, ethylamino, diethylamino, diisopropy1amino, di-n-butylamino, methyl, ethyl, dichlorofluoromethyl or tri-fluoromethyl, and repre3ents phenyl which is optionally mono-substituted to tr;substituted by identical or dif-ferent substituents from amongst me~hyl, methoxy~trifluoromethyl and chlorine, R10 represents hydrogen, methyl, ethyL~ n- and i-propyl, and represents phenyl which is optio-nally monosubstituted to trisubstituted by iden-. t;cal or different subst;tuents from amongstmethyl, methoxy, trifluoromethyl and chlorine, R11 represents hydrogen, methyl, ethyl~ n- and i-propyl, n-, i-, s- and t-butyl, alkyl, butenyl, propargyl, benzyl, chloroethyl or bromoethyl, R12 represents hydrogen, methyl, ethyl, n- and i-propyl, undecyl, vinyl, allyl, propargyl, butenyl,methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl~ methyl-thiomethyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylam;no, dimethylamino, diethyl-amino, trlfluoromethyl, trichloroethyl, dichloro-fluoroethyl, difluorochloroethyl, chloromethyl, iodo-methyl, bromomethyl, dichloromethyl, l-chloroethyl, 2-chloroethyl, 2-bromoethyl, chloroprqpyl or heptafluoro-n-propyl, or represent:s cyclopentyl, cyclohexyl or cyclopropyl ~hich is optionally monosubstituted to tetrasubstituted by identical or different substituents from amongst fluorine, chlorine, bro-mine~ methyl and trifluoromethyl, and represents phenyl, phenoxy, phenylthio or phenylam;no~ each of ~hich is optionally monosubstituted to trisub-stituted by identical or different substituents from amongst methyl, methoxy, chlorine and tri-f l U oromethyl, R13 represents amino, methylamino, ethylamino, dimethylamino, diethylamino~ fluorodichloromethyl, d;fluoromethyl, tetrafluoroethyl, trifluorochloro- :
Le A 72 853 ethyl, trifluoromethyl, methyl or ethyl, X represen~s oxygen or sulphur, and n represents the number 0, 1 or 2~
In addition to the compounds mentioned in the pre-paration examples, the following 5-amino-1-phenyl-pyr-azoles of the general formula (I) may be mentioned indi-vidually:

~;~ N~R
~ R3 R8~ R4 (1) Table 1 H CH3C0 H Cl H Cl H H
H CH3C0 ~H3C0 Cl H Cl H H
H CH3C0 H Cl H Cl H Cl H CH~C0 CH3 Cl H ~ Cl H Cl H CH3C0 H NOz H NOz H H
H H H Cl H CF3 H Cl H CH3C0 H Cl H OCt3 H H
H C2HsC0 H CF3 H :SCF3 H H
H C2HstO H Cl Cl Cl H
H H H Cl Cl Cl H H
H CH3C0 tH3C0 Cl tl Cl H H
H tH3C0 t2H5C tl tl Cl H H

Le A 22 853 ::

_ 9 _ Tab e 1 (continued) Rl R2 - R~R4 R5 ~6 R7 R~ .

H C2H5CO H CL H CF3 H tl H CH3CO H CL H CF3 H tl Cû
H ~ H Cl H CF3 H Cl H CH30CO H Cl H CF3 H Cl H n-C3H~CO H Cl H CF3 H Cl H CH3CO CH3COCl H CF3 H Cl H E2HsCO H Cl H OCF3 H H
CO
H ~ H Cl H OCF3 H H

H n-C4Hg-CO Htl H OCF3 H H
H C2H5CO HCl H SCF3 H Cl H n-C3H7CO ~Cl H SCF3 H Cl CO
H ~ HCl H SCF3 H Cl H CH3CO HCl H SCF3 H Cl H tH30CO HCl H SCF3 H Cl H CH30CO HCl H OCF3 H H
H C2HsCO HCl Cl Cl H tl H CH3CO HCl Cl Cl H Cl H CH3CO HCl Cl Cl H H
CO
H ~ HCl Cl Cl H Cl H CH30CO HCl Cl Cl H Cl H CH3CO HCl Cl Cf3 H Cl H C2H5CO ~Cl Cl CF3 H Cl H n-C3H7CO HCl Cl CF3 H tl H ~ H: Cl Cl CF3 H Cl H
H tH30CO HCl Cl CF3 H Cl Le A 22 853 ... ..
, Table 1 tcont;nued) R1 ~2 ~ ~ R6 X7 RB
H -CO-N~CH3 H Cl Cl CL H H
H -CO-NHCH3 H Cl H ~F3 H Cl H CH3~0 H Cl Cl SCF3 H H
H CH3CO H F F oc~3 H ~ .
H C2HsCO CH3CO F F oc~3 F F
Cl H H Cl Cl Cl H H
Cl H H Cl H Cl H H
Cl H H Cl H CF3 H CL
Cl H H Cl H SCF3 H Cl Cl CH3CO ' H Cl Cl Cl H H
Cl CH3CO H Cl Cl OCF3 H
Cl CH3CO CH3 Cl Cl SCF3 H H

CL C2HsCO H Er H SCF3 H H
Cl C2HsCO H Cl H SCF3 H Cl CL C2HsCO CH3CO CL CL SCF3 H H
Cl CH3CO CH3C~ Cl fl Cl H H
Cl CH3CO C2HsCO Cl Cl Cl H H
Cl ~CO-NHCH3 H Cl Cl OCF3 H H
Cl -co-o~2H5 H Br H OCF3 H Br Cl -co-c6Hs H N02 H N02 H N02 Cl -CO-CF3 H N02 H N02 H H
Br CH3CO H Cl Cl Cl H H
Br CH30CH2CO H Cl H Cl H Cl Br CH3SCH2-CO H No2 H N02 H H
Br CH3CO CH3CO Cl Cl CF3 H H
ar t2H5~ CH3CO Cl H CF3 H Cl Br CH3CO H Cl H OCF3 H Cl CH3~CH3 Br- CO- H F H OCF3 H F

H~_ BrCO- H F F OCF3 H F
Cl tl Br : ~ O- H f F SCF3 H F
Le A 22 853 Table 1 (continued?
~1 R2 R~ ~4 R5 R6 ~7 R8 Br H H F H ~CF3 ~ F
ar C2H5C H Cl H Cl H Cl Br Cl ~ CO- H Cl H Cl H H
Br CH30 ~ CO- H Cl Cl Cl H H
Br CH3CO CH3 Cl H S02CF3 H Cl Br F3CCO H Cl H SOCF3 U Cl Br CLCH~CO H CF3 H C~3 H C
Br Cl2CHCO H CF3 H S02CF3 H CF
I H H Cl Cl Cl H H
I H H Cl H Cl ~H Cl I H H Cl H CF3 H Cl I CH3CO H Cl Cl Cl H H
I CH3CO H CL H tF3 H Cl I CH3CO CH3CO Cl H OCF3 H Cl I CH3CO CH3CO ~F3 H SCF3 H CF
I C2HsCO H CF3 H SCF3 H H
I C2HsCO CH3CO ar H CF3 H Br I C2HsCO CH3 CL Cl .Cl H H
I C6HsCO H F F OCF3 F F
I Cl ~ CO- H Cl H OCF3 H Cl I F3C-CO H F H OCF3' H F
I ClCH2CO H Cl H SCF3 H Cl I Cl2CH-CO H Cl H S02CF3 H Cl I CH3-CH~CO H F F S02CF3 F F
Cl I K H ~ Cl Cl CL H H
CO-CF3 H H Cl H Cl H Cl CF3 H ~ H~ N02 H No2 H N0 Le A 22 853 ';

:

Table 1 (continued?
~1 ~2 ~3 ~ ~5 ~6 ~7 R8 CF CH~CO H Cl H Cf~ U Cl CF3 CH3CO H Cl H OCF3 H Cl CF3 CH3CO CH3~0 CL CL CL H
CF3 C2U5C H Cl H SCF3 H Cl CF3 C2H5C CH3CO F ~ OCF3 F F
CF3 H6H5C H CL CL SCF3 Cl Cl CF3 CH3NHGO H Cl H 502CH3 H Cl CF3 Cl ~ -CO- H Cl H 502CF3 H Cl CF3 CH30 ~ eo- H Cl Cl Cl H H
CF3 Cl ~ CO- H CL H CL H Cl Cl CF3 K H Cl Cl Cl H H
CO- .

CF3 C2H50C H tL H LF3 H CL
N02 H H CL Cl Cl H
N02 H H Cl F CL H Cl N02 H H . Cl H 9CF3 H Cl N02 H H CL H SCF3 H Cl N02 CH3CO H CL Cl CL H H

N02 CH3CO H CF3 H , CF3 H CF

N02 CH3CO ~H3CO CL Cl CL H H
N02 CH3CO CH3 CL H Cl H Cl N02 C2HsCO H Cl H Cl H Cl N02 C2HsCO ~ CH3CO Cl Cl Cl H H

N2 C3H5C H F : F F F

Le A 22 853 ~ 13 ~
T a i~ L æ ~ o n t i n u e ~ ?
R l ~ It It ~ , R 5 ~ 6 ~ 7 R ~
., . _ , . .... . . _ . . . _ _ _ . _ NO~ C2~5C~ H Cl Cl tl H H
N2 C6H5C H Cl H Cl H H
N02 CH3NHCO H C l C l C l H H
N02 CH3NHCO CH3 C l H C l H t l N2 C6H5~0 H Cl Cl Cl Cl Cl N2 t l~ CO H F F F F F
N02 Cl~}CO H F H CF3 H F
N02 CH30~CO H Cl H CF3 H Cl N02 C2H50-CO H Cl Cl CF3 H H
N02 C2H50-CO H Cl H OCF3 H Cl H02 C6H50-CO H Cl H OCF3 H H
N02 C6H50-CO H Cl Cl Cl H H
2 D~co H C l H 502CH3 H C l N2 y H Cl H - S02CF3 H Cl CO
N02 CH30CH2CO H Cl CL Cl H H
N02 C l EH2CO- H C l H C l H H
N2 Cl2CHCO H Cl H Cl H Cl H02C l 2CHCO H C l H CF3 H C l NO H H Cl Cl Cl H H
NO H H Cl H Cl H Cl NO H H Cl H CF3 H Cl NOCH3CO H CL Cl . Cl H H
NOCH3CO H Cl H Cl H Cl NOCH3CO H Cl H C~3 H Cl NOCH3CO CH3CO Cl H OCF3 H Cl NOCH3CO .CH3 Cl Cl CF3 Cl Cl NOC2H5CO H t F OCF3 F F

I~le L~Cc~nt~ny~d) ~ R5 ~6 ~ R~

NO ClCH2CO H Cl H 502CH3 H Cl NO Cl2CHCO H Cl H SO2CF3 H Cl HO CF3CO H Cl CL SO2CF3 H H
NO CH3NHC~ H Cl H Cl H
NO C2H50CO H Cl Cl Cl H H
NO Ct3CO H Cl Cl Cl H H
NO C6H5CO H Cl Cl Cl H H
H-C~- H H Cl Cl Cl H H
H~CO- H H Cl H Cl H Cl H-CO- H H Cl H CF3 H Cl H-CO- CH3CO H Cl H C~3 H Cl H-CO- CH3CO H Cl H OCF3 H Cl H-CO- CH3CO H Cl H SCF3 H Cl H-CO- CH3CO CH3 Cl Cl Cl H CL
H-CO- CH3CO CH3 Cl H CF3 H Cl H-CO- C2HsCO H Cl Cl Cl H H
H-CO- C2HsCO H Cl H Cl H Cl H-CO- C2HsCO CH3CO Cl Cl Cl H Cl H-CO- CH3CO CH3CO Cl H CF3 H Cl H-CO- C2HsO-CO H Cl H CF3 H H
H-CO- C2HsOCO H F H CF3 H F
H~
H-CO- ~ H Cl Cl Cl H H
CO
H-CO- C6HsCO H CL H Cl H Cl H-CO- C6H~OCO H F F F F F
CH3-CO H H NO2 H '~ NO2 H H

CH3-CO CH3CO H Cl CL Cl H H
CH3-CO CH3CO H Cl H Cl H Cl CH3-CO CH3CO CH3CO Cl H Cl H H
CH3-CO C2H5CO H Cl H ~ CF3 H H
CH3-CO C2HsCO H Cl H tF3 H Cl CH3-CO C2HsCO H CL Cl Cl H H
Le A 22 853 . .

Table 1 (continued) Ql R2 ~ ~4 ~5 RS ~7 R~

CH3-CO- CF3CO H Cl H Cl H tl CH3-CO- CF3tO H Cl H CF3 ~ ~
CH3-CO- ClCH2CO H Cl H OCF3 H Cl CH3-tC\- CH30CH2CO H Cl H OCF3 H CL
CH3-CO- CH35CH2CO H CL H SCF3 H tl CH3-CO- Cl2CHCO H F H SCF3 H F
CH3-CO- Cl2CHCO H F H S02CF3 H F

Cl CH3-CO- Br-CH2CO H F F F F F
HO-N=CH- H H Cl H Cl H H
HO-N=CH- H H Cl H CF3 H H
HO-N=CH- H H Cl Cl Cl H H
HO-N=CH- H H F F F F F
HO-N=CH- CH3CO H Cl Cl Cl H H
HO-N=CH- CH3CO H Cl H Cl H CL
HO-N=CH- C2HsCO H CL H CF3 H Cl HO-N-CH- C2HsCO H e l H Cl H H
HO-N=CH- C2HsCO C2HsCO Cl H OCF3 H Cl HO-N=CH~ CH3CO CH3CO Cl H OCF3 H Cl HO-N=CH- CF3CO CF3CO ~ Cl H SCF3 H Cl HO-N=CH- CF3CO H Cl H OCH3 H Cl HO-N=CH- CLCH2CO H Cl H SCH3 H Cl HO-N=CH- Cl2CHCO H Cl H 52CH3 H Cl HO-N=CH- CH30CH2CO H Cl H So2cH3 H CL
HO-N-CH- CH30CH2CO H CL H S02CF3 H Cl HO-N=CH- CH35CH2CO H Cl Cl Cl H H

CH30-N=CH- H H F H F H F
CH30-N=CH- H H F H F H F

CH30-CH-N- CH3CO H ~ F F F ~ F
CH30-N=CH- CH3CO H Cl H Cl H Cl tH30-N-CH- CH3CO H Cl H Cl H H
Le A 22 853 -.

Table 1 (continued) .
R1 ~ R3 R6 ~5 ~6 ~7 CH30-N=CH^ C2HsCO H Cl Cl Cl H H
CH30-N-CH- t2Hs H Cf3 H CF3 H H
CH30-N=CH- C2HsCO H CF3 H CF3 H CF
tH30-N=CH~ CF3CO H Cl H CF3 H H
CH30-N=CH- t6HsCO H Cl H CF3 H Cl CH30-N=CH- ClCH2CO H Cl H OCF3 H Cl CH30-N=CH- lCH2CO H Cl Cl Cl h H
CH30-N=CH- OrCH2CO H F F F F F
CH30-N=CH- C2HsOCO H Cl H OCF3 H H
CH3~-N=CH- CH3CO ~H3 Cl H SCF3 H Cl CH30-N=CH- CH3CO H Cl H CF3 H Cl CH30-N-CH- C2HsCO H Cl H CF3 H Cl H2NS02- H H Cl- H Cl H Cl H2NS02- H H Cl H Cl H H
H3NS2 ~ tH3CO H Cl Cl CL H Cl H2NS02- ~H3CO H F F F t F
H2NS02- C~3CO H F F CF3 F F

H2NS02- C2H5CO H Cl H OCF3 H Cl H2NS02- CH3CO CH3CO Cl H SCF3 H Cl H2NS02~ CH3CO CH3 Cl H SOCF3 H Cl H2NS02- ClCH2CO H Cl H So2cF3 H Cl H2NS02- BrCH2~ H Cl H S02CH3 H H
H2NS02- ICH2CO ; H .~ Cl: H S02CF3 H H
H2NS02- C6HsCO H Cl H CF3 H Cl H2NS02- C2H5CO H Cl H Cf3 H H
H2N502- tF3CO H Cl Cl Cl H H

Le A 22 853 .

.
, - ~7 Table 1 (continued) R5 ~6 ~7 R~

H C2H5CO H CL H ~CF3 H CL

H ~ CO H Cl H OCF3 H tL
H n-C3H7CO H Cl H OCF3 H CL
H CH30CO H Cl H OCF3 H CL
H CH3DCO H Cl H S02CH3 H tl H CH3CO H Cl H SOzCH3 H Cl H C2H5CO H. Cl H S02CF3 H tl ~ H H CL H SOz~H3 H CL
H n-C3H7CO H Cl H S02CF3 .H Cl H n-C3H~CO H CL H S02CClFz H Cl H CH3CO- H tL H SOzCClF2 H Cl H C2H5CO H tl H S02CClF2 H Cl H CH3CO H ~r H OCF3 H Br H C~HsCO H ar H OCF3 H ~ H
H n-C3H7CO H er H OCF3 H H
H ~ CO H ar H OCF3 H H
H CH30CO H r H OCF3 H H
H CH3CO H Br H SCF3 H Br H CH3CO H Br H StF3 H H
H C2HSCO H Br H SCF3 H H
H n-C3H7CO H 9r H SCF3 H H
H C2HsCO H Cl H H H Cl H C2HsCO H ~r H Br H ~r H CzH5CO ~H Cl H Cl H H
H C2HsCO H ~r H 8r H H
NO C2H5CO H Cl H tF3 H Cl NO CH3CO H Cl H CF3 H Cl ~0 ~ H Cl H CF3 H Cl Le A 22 853 le 1 ~ ) ~1 R2 ~ 5 R6 ~7 Q3 ....... _ _ _ . . _ .
NO C~30CO H Cl H CF3 H Cl NO n~C3H7CO H Cl H CF3 H CL
~0 C~3CO CH3CO Cl H CF3 H Cl NO C2HsCO H Cl H OCF3 U H
CO
NO ~ H Cl H OCF3 H H

NO n-C4H9CO H CL H OCF3 H H
NO C2H5CO H Cl H SCF3 H Cl NO n-C3H~CO H Cl H . SCF3 H Cl tO
NO K H CL H SCf3 H Cl H

NO CH3CO H Cl H SCF3 H Cl NO EH30~Q H Cl H SCF3 H Cl NO CH30C0 H Cl H OCF3 H H
NO C2HsCO H Cl Cl Cl H Cl NO CH3CO H Cl Cl Cl H Cl NO CH3CO H Cl Cl Cl H H

NO ~ H H Cl CL Cl H Cl NO CH30CO H Cl Cl Cl H Cl NO tH3CO H CL Cl tF3 H Cl NO C2H5C~ H Cl Cl CF3 H Cl NO n-C3H7CO H Cl Cl CF3 H Cl CO
NO~ ~ H Cl Cl CF3 H Cl H , NO tH30CO H Cl Cl CF3 ~ Cl NO C2HsCO H Cl H OCF3 H Cl NO CH3~0 H ~tl H OCF3 H Cl CO ' , ' ~
NO ~ H Cl H OCF3 H Cl H
UO n-C3~7CO H Cl H OCF3 H Cl Le A 22 853 ~ ~ 19 Table 1 (continued) ~l ~2 R3 R~ ~S ~6 ~7 ~0 CH30CO ~ Cl H OCF3 H Cl HO CH30CCI H Cl H 5~2CF3 H tL
NO CH3CO H Cl H 502CF3 H tl HO C2HsCO H tl H S02CF3 H Cl CO
NO H H Cl H S02CF3 H Cl NO n-C3H~CO H Cl H S02CF3 H Cl NO n-C3H7CO H Cl H S02CClF2 H tL
NO CH3CO H tl H S02CClF2 H Cl NO C2H5C H tL H S02CCLF2 H Cl HO CH3CO H ~r H OCF3 H ~r NO C2HsCO H Br H OCF3 H H
NO n-C3H7CO H Br H OCF3 H H
CO
NO ~ H Br H OCF3 H H
NO CH30CO H ~r H OCF3 H H
NO CH3CO H ar H SCF3 H Br NO CH3CO H Gr H SCF3 H Br NO C2H5C : H Br H SCF3 H H
NO n-C3H7CO H Br H SCF3 H H
NO t2H5C ~ Cl H H H Cl NO C2HsCO H ~r H ~r H ~r NO C2HsCO H Cl H tl H H
NO C2HsCO H Br H ar . H H
N02 t2HsCO H tl H OCF3 H Cl N02 CH3CO H ~ Cl H OCF3 H Cl N02 K H Cl H OCF3 H Cl N02 n-C3H7CO H Cl H OCF3 H Cl N02 CH30CO H Cl H OCF3 H Cl N92 CH30CO ~ H tl H S02CF3 H tl N2 ~ ~tH3tO H tl H 502CF3 H tl N02 C2HsCO H Cl H S02CF3 H Cl Le A 22 853 :

Table 1 (continued) ~1 ~t ~ S R6 7 5o N2 ~ H Cl H 52tF3 H Cl ~2 n-C3H7CO H Cl H S02CF3 H Cl N02 n-C3H7CO H Cl H S02CtlF2 H Cl N~2 CH3CO H Cl H S02CClF2 H Cl N02 C2HsCO H Cl H 502CClF2 H Cl N02 CH3CO H Br H OCF3 H Br ~2 C2H~CO H Br H OCF3 H H
N02 n~C3H7C H ~r H OCF3 H H
tO
N2 ~ H Br H OCF3 H H
N02 CH30CO H Br H OCF3 H H
N02 CH3CO H ~r H SCF3 H Br N02 tH3CO H 8r H SCF3 H H
N02 C2HsCO H ~r H SCF3 H H
N02 n-C3H7CO H ar H SCF3 H H
Ne2 C2HsCO H Cl H H H Cl ND2 C2HsCO H Br H 8r H ~r N02 t2H5C H Cl H Cl H H
N02 C2HsCO H Br H Br H H
N02 C2HsCO H Cl H CF3 H Cl N02 CH3CO H Cl H CF3 H Cl CO
N2 ~ H Cl H CF3 H Cl N02 CH30CO H Cl H CF3 H Cl N02 n-C3H7CO H ~l H CF3 H Cl N02 CH3COCH3CO Cl H ' CF3 H Cl N02 t2H5C H Cl H OCF3 H H
CO
N2 ~ H tl H OCF3 H H
H

N02 n-C~HgCO H Cl H OCF3 H H
~2 C2H5C H Cl H SCF3 H Cl N02 n-C3H~CO H Cl H SCF3 H Cl Le A ?2 853 , Table 1 tcontinued) @ ~ S 11~6 ~1~7 ~0 N2 D~ ~ Cl U SCF3 H Cl NO2 CH3CO H C~ H SC~3 ~1 tl NO2 CH30CO H Cl H SEF3 H Cl NO2 CH30CO H Cl H OCF3 H H
N~2 C2H5CO H Cl Cl CL H tL
NO2 CH3CO H CL Cl tl tl NO2 CH3CO H Cl Gl CL ~ H
~o NO2 D< ~ Cl Cl Cl H Cl NOj~ tH30CO H C L C l C l H C i HO2 CH3CO H Cl Cl CF3 H Cl NO2 t2~5CO ~ Cl tl CF3 H Cl NO2 n-C3H7CO ~ El Cl CF3 H Cl KC ~l CL ~F3 H Cl NO2 eH3~0 H Cl Cl C~3 H Cl PO(OC2H5)2 t2H5~0 ~ Cl H ~F3 H Cl POtOC2H5) 2 CH3CO H Cl H CF3 H Cl ~c~ .
POtOC2H5)2 ~H H Cl H CF3 H Cl POtOC2H5)2 CK3tO H Cl H C~3 H Cl POt OC2H5) 2 n~C3H~CO l1 C l H C~3 ~ C L
POtOC2M5)2 ~H3CO CH3CO CL H tf3 H Cl POtOC2H5)2 C2H5CO H CL H OCF3 H N
POtOC2M5)2 KH H tl H OCF3 H H
POtOC2H5)2 n~C$H9CO H Cl H OCf3 H H
Potoc2Hs)2 ~ C2H5C ~ tl ~ SCF3 H Cl POtOC2Hs)2 n-C3H7CO H Cl H SCF3 H Cl potoc2H5)2 K H Cl N SCF~ H Sl Le A 22 853 . .

s~

Table 1 tcon_inued) 4 ~ r PO(OC2Hs)2 CH~CO H CL H SCF3 H tL
POtOC2Hs)2 C~130C0 1~1 Cl t1 SCF~S H Cl ~O(OC2H5)2 CH30CO H OCF3 H H
p~(OC2tls)2 t7H5C H tl Cl tl H Cl PO(OC2Hs)2 tH3CO H Cl tl Cl H H
Potoc2Hs)2 Ch'3C ~ Cl CL Cl H tl CO
pO(OC2H5)2 D<H H Cl Cl Cl H Cl PO(OC2Hs)2 CH3CO H tl tl tl H Cl PO(OC2H5)2 CH3CO H Cl Cl CF3 H Cl Potoc2li5)2 C2H5C H Cl Cl ~F3 H Cl PO(OC2H5)2 -~3H7C H Cl Cl C~3 H Cl po(oc2Hs)2 K H Cl tl CF3 tl Cl po(oc2Hs)2 62H5C H Cl tl t~3 H tl t f'O(OC~Hs)2 C2HsCO H Cl H OCF3 H Cl PO(OC2Hs)~ CH3CO . Cl Cl H OCF3 H Cl po(OC2H5) 2 D'~ C H Cl H OCF3 H Cl po(oc2H5)2 n-C3H7CO ~ Cl H OCF3 H Cl pO(OC2Hs)2 C~sûCO H Cl H OCF~ H Cl PO(OC2Hs)2 CH30CO H Cl H S02CF3 H Cl POtOC2Hs) 2 tH3CO H Cl H S02CF3 H tl Potoc2H5) 2 C2H5Co H Cl H S2t~3 H Cl CO
po(oc2H5~2 D< H Cl H S03CF3 H Cl potoc2~5)2 n^C3H7C~ ~ H S02CF3 H Cl POtOC2Hs)2 n-C3H7CO H Cl H S02cclF2 H Cl POtOC2Hs)2 tH3Co H Cl H 502CCl~2 H Cl PO(OC2Hs)2 C2H5C H tl H S02CClF2 H Cl POtOC2Hs)2 CH~CO H ~r 11 OCFs H Br Le A 22 853 Table 1 (c~ntinued) ~1 R2 R~ R~ ~S ~6 ~7 a~
P0t0C2Hs)2 C2HS0 H 0r H C~3 H H
P0(0C2H5)~ n-C3H7C0 H 2r H OCF3 H H
CO
Po(oc2Hs)2 K H 0r ~ OCF3 ~ H
Potoc2Hs~2 CH3~C0 ~ ~r H OCF3 H H
P0t0C2Hs)2 CH3C0 H Bt H SCF3 H Br P0t0~2H5)2 CH3C0 H ar H SCF3 H H
P0t0C2Hs)2 t2H~CO H ~r H S~3 W H
POtOC2H5)2 n-C3H7C0 H Br H StF3 H H
Potoc2Hs)2 C2H5C H CL H H H tl p0~0C2H5)2 C~H~0 H ~r H a, H ar po(oc2H5)2 ~2Hs~o H tl H Cl H H
P0~0C2Hs)2 C~5C0 H ~r H Br H H
Cl C2H5e0 ~ Cl H tF3 H Cl Cl CH3~0 H Cl H CF3 H tl CO
CL ~ H Cl H CF3 H Cl Cl CH30C0 H Cl H EF3 H Cl Cl n-C~H7CO- H Cl H CF~ H Cl Cl ~H3C0~3C0 Cl H CF3 H Cl Cl C2H5C0 H CL H OCF3 H
CO
Cl ~ H Cl H ~CF3 H H
H
Cl n-C~9C0 H Cl H OCF3 H H
Cl C2HsC0 H tl H SCF3 H CL
Cl n-C~H7C0 H 6l H SCF3 H Cl ~O
Cl ~ H eL H SCF3 H Cl Cl CH3C0 H Cl H SCF3 H Cl tl CH30C0 H Cl H SCF3 h tl Cl CH30C0 H CL H OCF3 H H
Cl C2H5CO H Cl Cl Cl H CL

el CH3tO H Cl Cl Cl H Cl Le A 22 853 . .

Table 1 tcontinued) Rl ~2 ~ R6 ~ r R 8 Cl t~3eo H Cl Cl Cl H H
Cl ~ H tl Cl Cl H tl Cl CH3~CD H tl tl Cl ~ Cl C( CH3CO H Cl tl CF3 H Cl Cl C2HsCO H Cl Cl CF3 H Cl Cl n-C3H~CO H Cl Cl EF3 H Cl CO
Cl H H Cl Cl CF3 H Cl Cl CH30CO H Cl Cl CF3 H Cl Cl C2HsCO H Cl H OCF3 H CL
Cl CH3CO H Cl H OCF3 H Cl ~,CO
Cl H H Cl H OCF3 H Cl Cl n-C3H7CO H Cl H OCF3 H Cl Cl CH30CO . H tl H OCF3 H Cl Cl CH30CO H Cl H S02CF3 H Cl Cl CH3CO H Cl H S02CF3 H: Cl Cl C2Hsc H Cl H S02CF3 H Cl Cl ~ C H CL ~ H 502CF3 H Cl Cl n-C3H7CO H Cl H S02CF3 H Cl Cl n-C3H7CO H~ Cl H 502CClf2 H Cl Cl CH3CO H Cl H S02CClF2 H CL
Cl C2HsCO H Cl H S02CClF2 H tl Cl CH3tO H ~r H OCF3 H ar Cl C2~sCO H ~r H OCF3 H H
Cl n-C3H7CO H ;~r H OtF3 H H
Cl ~ ~ H 2r ~ H OCF3 H H
H

l CH39CO H ~r H OCF3 H H
Le A 22 853 :

:
:

~ ~:

,'39~
- ~5 -Table 1 tcontinued) 2 R !5 ~ 1 5 R 6 ~t 7 R
Cl CH3CO H Br H StF3 H Br Cl CH3CO H Br H SCF3 ~ U
CL C2HsCO H Br H StF3 H H
Cl n-C3H~CO H Br H SCF3 H H
Cl C2HsCO H Cl H H H Cl Cl C2H5CO H Br H ~r H 8r Cl C2HsCO H Cl H tl H H
Cl C2H5CO H ~r H Br H H
H H-CO- H Cl H Cl H Cl H H-CO- H Cl Cl Cl H H
H H-CO- H Cl H OCF3 H Cl H H-CO- H Cl H SCF3 H Cl -H H~CO- H Cl H OCF3 H H
H H~CO- H Cl H CF3 H Cl H H-CO- H Br H Br H Br H H-CO- H Cl H Br H Cl H H-CO- H Cl H 502CF3 H H
H H-CO- H Cl H SO2CF3 H Cl No2 H-eo- H Cl H Cl H Cl NO2 H-CO- ~ H Cl- Cl CL H H
NO2 H-CO- H Cl H OCF3 H - Cl NO2 H-CO^ H Cl H OCF3 H H
NO2 H-CO- H Cl H SCF3 H Cl NO2 H-CO- H Cl H SCF3 H H
NO2 H-CO- H Cl H SO2CF3 H
NO2 H-CO- H Cl H 502CF3 H Cl NO2. H-CO- H Br H ~r H ~ Br NO2 H-CO- H Cl H Br H Cl NO2 H^CO- H Cl H Br H ~r NO2 H-CO- H Br H OCF3 H Br NO2 ~-CO- : H ~r H OCF3 H H
NO2 ~ H-CO : H ~r H StF3 H ~r NOz ~ H-CO- H :I H OCF3 H H
Le A 22 853 ~;
, ~ ?

Table 1 tcontinued) ~1 ~2 R3 ~4 ~5 R6 ~7 n~
= . ; ~ ~ . .. . . . .
~2 CH3~0 H Cl H Cl H CL
N02 CH3CO H Cl Cl Cl H H
N02 CH3CO H Cl H OCF3 H Cl N02 CH3CO ~ Br H Br H Hr N02 CH3CO H Cl H Br H CL
N02 CH3CO H Cl H Br H 3r N02 CH3CO H ~r H Cl H Cl N02 CH3CO H Br H DtF3 H H
N02 CH3CO H Br H OCF3 H ~r ~2 CH3CO H ~r H SCF3 H H
N02 CH3CO H Br H SCF3 H ~r N02 CH3CO H ~r H 52CH3 H H
N02 CH3CO H Br H S02~F3 H er N02 CH3CO H Or H S02CF3Cl H H
N02 CH3CO ~ Br H S02CF2Cl H Br N02 CH3CO H Cl H OCF2rl H H
N02 CH3CO H Cl H OCF2CHF2 H Cl N02 CH3CO H Cl H OCHF2 H H
N02 CH3CO H Cl H OCHF2 H Cl N02 CH3CO H Cl H OCH2CF3 H H
N02 CH3CO H Cl H OCH2CF3 H Cl N02 CH3CO H 9r H OCH2CF3 H H
N02 CH3CO H 3r H Q~H2CF3 H ar N2 CH3CO H ~r H CF3 H H
~2 CH3CO H Hr H CF3 H Br N02 C2HsCO H Cl H OCHF2 H Cl N02 C2HsCO H Cl H OCHF2 H H
N02 C2HsCO H Cl H OCF2CHF2 H H
N02 C2HsCO H Cl H OCF2CHF2 H Cl N02 C2HsCO : H Cl H C~F2 H ~ H

N02 : C2HsCO H Cl H tHF2 H Cl ~N02 CzHsCO H Cl H OCF2CHFCl H H
No2 C2H5C H Cl H OCF2CHFCl H Cl N02 C2HsCO H Cl H Br H Cl Le A 22 853 :' Some of the subst;tuted 5-am;no-1-phenylpyrazoles of the formula (I) ~hich are to be used according to the invention are known tsee: J Org.Chem. 36~Z972-2974 C1971~;
J.Heterocycl.Chem. 7, 345-349 ~1970] and C~A~ 6Z: 13137c).
Subst;tuted 5-amino-1-phenyl-pyrazoles ~h;ch were h;therto unknown are those of the formuLa (I') ~N ~ R3 t~ ) R8 ~ R4 R7 ~ R5 in ~hich R1 R2 R3 R4 R5, R6, R7 and R8 have the mean;ng g;ven above, except that, when R1 represents hydrogen, methyl or opt;onally substi-tuted phenyl, R4 and R6 cannot s;multaneously represent the nitro group.
The h;therto-unknown substituted 5-amino-1-phenyl-pyrazoles of the formula tI') are obta;ned ;f a) phenylhydraz;nes of the formula tll) ~S ~4 R6 ~ -NH-NH2 (II) ;n ~hlch R4, R5, R6, R7 and R8 have ~he mean;ng g;ven ab~ve~
are reacted ~;th acrylon;tr;le der;vatives of the formula ~III) ~

~- CH= C~ ~ ~ I I I ) L e A 2 Z 8 5 3 ::

-28~ 2318g-5gO3D
~2~
in uhich R1 has the meanin~ ~iven ~bove and A represents halo~cn, hydroxyl or alkoxy, or, in the case in uh;cll R1 represents hydro~en, also uith 2-halo~enoacrylon~triles of the formula (IlIa) ~ CN
SH2~C~ ~ a~
HaL
in uhich llal represents halogen, in particular ch~orine or bromine, or uith Z,3-dihalo~enopropion~triles of the for~ula ~ b) ~ CN
Hal -CH2-CH Slllb) ~ HDl ln uhich Hal represents halo~en~ ~n particular chlorine or bromine:, the reaction either bein~ carried out to ~ive the phenyl-I-ydrazine der~vat~ves of th~ formula SlY) R5 ~ R4 R6~ ~ - NH - NH ~ lV) Sneu sub~tsnces which form an aspect of the divi~ional Application) ~n uh~ch R4, R5, ~R~, R7 and R8 h~Ye the meanin~ given under formula (I ' ) and : :
Z represent~s~:one oE ~the radicals ~CN . ~:~ CN
CH C~R1 ~ or -cH2-cH~
: wherein Hal: represents ::

~: : ~: ~ :
:
-: :

~;~9~

identical or different halogen atonls, in a first stage, if appropriate in the presence of a diluent and, if appropriate in the presence of a reaction auxiliary, and the product being subjected to a cyclisation reaction in a second stage, if apE)ropriate in the presence of a diluent and, if appropriate, in the presence of an acid~binding agent, or cyclisation being carried out directly in one reaction step without isolation of the intermediate of the formula (IV) (the above process giving inter-mediates the formula (IV) ~orms an aspect of the divisional appli-cation), if appropriate in the presence of a diluent, to give the 5-amino-pyrazoles of the formula (Ia) ll~JRl R8 ¦ 2 ~ R4 tIa) R7 ~ R5 in which Rl, R4, R5, R6, R7 and R8 have the meaning given above, or iE
(b) the 5-amino-pyrazoles of the formula (Ia~

Rl 1~
`~ ~ Nl~
R8 ~ ~R4 (Ia) ~ R5 -29a- 23189-5903D

in which R1, R4, RS, p~6, ~7 and ~8 have the above meaning, which are obtainable by process (a) are reacted in a generally customary manner with acylating agents or alkylating agents of the formula (~) : ~ ' ~ ~ ;
.
, :
:

- , R14 _ A~ ~V) in ~hich X
R14 represents alkyl or a radical -~-R12, ~herein X and R12 have the above meaning, and A' represents an electron-attract;ng leavlng group, or with iso(thio)cyanates of the formula ~VI) R15 _ N = C ~ X (YI) in ~hich R15 represents alkyl or optionally substituted aryl and X has the above meaning, ;f appropr;ate ;n the presence of a d;luent and, ;f app-ropriate in the presence of an acid-binding agent, to give the 5-am;no-pyrazoles alkylated or acylated at the n;tro-gen, of the formula (Ib) N _ R 3 ~

7 ~ 5 t Ib ) in ~h;ch R1, R2, R4, R5, R6, R7 and R8 have the above mean;ng and ~ R3 represents the same rad;cals as R3 given above, ~ith the exception of the hydrogen radical, or ~f tc~ the S-amino-pyrazoles of the formula tIc) 17~ N
2 8~L R 4 R 3 ~ I c ) Le A 22 853 . :
.

- 31 ~ 15~
in ~h;ch R2 R3 R4, ~5~ R6, R7 and R8 have the above mean;ng, wh;ch are unsubst;tuted ;n the 4-pos;tion and are obta;n-able by process ta~ or (b), are substituted in the 4-pos;-t;on, likew;se in a generally customary manner, us;ng electrophil;c agents of the formula (VII~
R1 - E tVII) ;n ~h;ch R1 represents halogen, nitroso~ nitro, alkyl, formyl~ alkanoyl, aroyl, hydroxysulphonyl or chlorosulphonyl and E represents an electron-attracting leaving group-ing, or using other customary electrophilic reagents, if app-ropriate in the presence of a diluen~ and, if appropriate, in the presence of a catalyst or a reaction auxiliary, or if td) the 4-chlorosulphonyl-5-amino-pyrazoles obtain-able by process ~c) of the formula tId) S02-Cl R8 _R 2 ~ R7 ~ R5 tld) ;n which R2 R3~ R4, R5, R6, R7 and R8~have the above meanin~, are subst;tuted a~ the chlorosul-phonyl group in the 4-position, us;ng amines of the formula (VIII) H - N~ 17 (VIII) R
L~ .

- ~?~
. , . .

in ~h;ch R16 and R17 ;ndependently of one another rep-rPsent hydrogen or alkyl,or us;ng an alkal; metal fluor;de of the formula ~IX) M ~ ~ t~X) in uhich Me~ represents an alkal; metal cat;on, if appropriate ;n the presence of a d;luent and, ;f app-ropr;ate~ ;n the presence of an ac;d-binding agent, or ;f te) the 4-acyl-5-amino-pyrazoles of the formula ~Ie) ~_ R 1 U

N
I ~ R3 R~ ~ R4 tIe) ;n wh;ch R2 R3 R4 RSo R6, R7, R8 and R10 have the above meaning, ~hich are obta;nable by the process (c) or ~f~, are re-acted ~ith hydroxylam;ne der;vat;ves of the formula ~X) ~2N - oR1 1 ~X) in ~h;ch ~:.
R11 has the mean;n)g g;ven above, or v;th the;r hydro-salts, if appropr;ate ;n the presence of a d;luent and, ;f appropr;ate, in the presence of an ac;d-b;nd;ng agent, or ;f ~f) 4-cyano-5-amino-pyrazoles of the formula ~XI) .. . . _ .. _ +3 "hydro-salts" refers to hydrogen halide addition nalt-~, ~uch as hydrochlorides (HCl 8alt8).

Le A 22 853 ::

r~ r~ CN
N~N ~ N~
a~ ~ ; 4 (XI) ;n which R2 R3 R4 R5 R6, R7 and R8 have the meaning g;ven above, are reacted w;th form;c ac;d and Raney n;ckel to give the corresponding 5-amino-4-formyl-pyrazoles of the formula tIf) o ~-H

: N ~ N . ~If) in ~hich R2 R3, R4, R5, R6, R7 and R8 have the mean;ng g~ven above.
I~, for example, 2-chloroacrylonitrile and 2,6-d;-chloro-4-~rifluoromethy:l-phenylhydraz;ne are used as start-ing:materials, the course of the react;on of preparation process ta) can be represented by the following equation:
~ : :

:tF3 ~ -NH-NHz ~ tH2-C~ HCI >
:~ ~ Cl ~ase) Le ~A 22 853 : ~
_ - 34 ~ 52 N~N~L~- NH2 C~ Cl c~3 If, for example, 5-amins-1-t2,4,6-tr;chlorophenyl~-pyrazole and prop;onyl chloride are used as starting materials, the course of the react;on of preparation pro-cess (b) can be represented by the following equation:

N ~
~N NH2 C L_~l C l ~ C 2H 5 -HCl N~N~ ~ NH-C0 C2H~-tO-Cl Cl~ Cl Cl tbdse) Cl lf, for example, 5-propionamido-1-t2,3,4-trichloro-phenyl)-pyrazo~le and nitric acid are used as start;ng mater;als, the course of the reaction of preparation pro-cess tc) can be represented by~the follo~;ng equation:

NH-Co-c2H5 C~ N03 HzO
: tCH3C0)20 C L~

N~ N H- ~ O - ~ 2 R 5 : L~e A 22~853~

:

If, for example, 5-acetoamido-4-chlorosulphonyl-1-t2,4,6-trichlorophenyl)-pyrazole and d;ethylamine are used as start;ng materials, the course of the reaction of preparation process Sd) can be represented by the fol-lo~ing equation:

502-Cl ~ NH-CO-CH3 Cl ~ Cl ~ HN(C2HS)2 - HCl ~ >
~ase) SO2-N(C2H5)2 N~N NH-CO CH3 Cl_~_Cl Cl If, for example, 5-acetoam;do-4-acetyl-1-(penta-fluorophenyl)-pyrazole and O-methyl-hydroxylamine hydro-chloride are used as starting:mater;als~ the course of the react;on of preparat;on process (e) can be represen-ted by the follo~;ng equat;on:

N`N~L--NH~CO-CH3 F _ ~ F ~ H2N - OCH3 x HCl F ~ ~ F CH3 F t-N-OCH3 . ~
-HCl~ -H~~ N~N~ ~ NH-CO-CH3 (~iS~) ,F ~ ~ F
F I F
F
Le A 22 853 _.

::
:: :

1S~

If~ for example, 5-am;no-4-cyano-1-~2,3,4-tri-chlorophenyl)-pyrazole and formic ac;d are used as start-ing material, and Raney nickel is used as a reducing agent, the course of the reaction of process ~f) accor-ding to the invention can be represented by the follo~;ngequation:

CN
N
~N NH2 H-COOH Raney nickel Cl ~ C-H
N`N~` NH2 ~,~ Cl Cl Formula (II) gives a general def;nition of the phenylhydrazines required as starting materials for carry-10 ing out preparation process ta) according to ~he ;nven-tion. In th;s formula (II), R4, R5, R6, R7 and R8 preferably represent those substituents ~hich have already been mentioned in the descript;on of the substances which can be used according to the ;nvent;on, of the formula tI~, as being preferred for these radicalsO
The major;ty of the phenylhydrazines of the for-mula ~II) are known or can be prepared by known processes in a simple, analogous manner (see: for example, Houben-Weyl "Methoden der organischen Chemie" ~Methods of organic 20 chemistry~, Volume X,2, page 203~ Thieme Verlag Stutt-gart 1967) by, for exa~ple, reacting the known anilines of the formula tXII) R6~ NH2 (XII) \

Le A 22 853 ~ R7 R8 ' ' .

;n which R4, R5, R6, R7 and ~8 have the mean;ng g;ven above~
w;th sod;um n;tr;te~ in the presence of an ac;d, such as, for example, sulphur;c ac;d, and then ~;th tin~II) chLor-;de, l;ke~;se ;n the presence of an ac;dO such as, for example, hydrochlor;c ac;d, at temperatures between -20C
and +80C.
Formula (III~ g;ves a general def;nit;on of the acrylonitr;le der;vat;ves furthermore requ;red as start-;ng materials for carrying out preparat;on process ta).
In th;s formula tIII), R1 preferably represents those rad;cals wh;ch have already been ment;oned ;n the descr;p-t;on of the substances ~h;ch can be used accord;ng ~o t5 the ;nvent;on, of the formula ~I), as being preferred for these subst;tuents. A preferably represents chlor;ne or brom;ne, hydroxyl, methoxy or ethoxy. The acryloni~rile der;vatives of the formula tIII) are known ~see: for ex-ample, DE-OS ~German Publ;shed Spec;f;cat;on) 3~129,429, European Patent 34,945; J.Chem.Soc D 1970, 1255; Can.J~
Chem. 48, 2104-2109 t1970); J.Heterocycl;c Chem. 19, 1267-1273 (1982~; and Can.J.Chem. 51, 1239-1244 C1973~), or can be obta;ned by processes known from the literature ;n a s;mple analogous manner. ~he 2 halogeno-acrylon;tr;les 25 of the formula (IlIa) and the 2,3-dihalogeno-propioni-tr;les of the formula tIIIb) are l;kew;se kno~n (see, for example, J.Prakt. Chem;e 321, 93 C1979~; J~ Heterocyclic Chem. 19, 1265 ~1982]; and J. Heterocycl;c Chem. 19~ 1267 C1982~).
Formula ~Ia) ~ives a general def;n;tion of the 5-amino-pyrazoles requ;red as start;ng materials for carry;ng out preparat;on process ~b). In th;s formula (Ia), R1, R4, R5, R6, R7 and R8 preferably rep-resent those rad;cals which have already been mentioned 35 in the description of the substances wh;ch can be used accord;ng to the invent;on, of the formula tI), as be;ng Le A 22 853 preferred for these radicals.
The 5-amino-pyrazoles of the formula (Ia) were hitherto unknown. They are obtained by preparation process ta).
Formula (V) gives a general definition of the alkylating and acylating agents furthermore required as starting materials for carrying out preparation process tb). In this formula (V), Rl4 preferably represents a straight-chain or branched alkyl having up to 4 carbon atoms, and furthermore represents a radical -C wherein X and R12 preferably represent O those radicals which have already been mentioned for these radical:, in the description of the substances of the formula (I). A' preferably represents chlorine, bromine or iodine, p-toluenesulphonyloxy, alkoxysulphonyloxy or acyloxy. The alkylating and acylating agents of the formula (V) are generally known compounds of organic chemistry.
Formula (VI) gives a general definition of the isotthio)cyanate: which can alternatively be ased as starting materials for carrying out preparation process tb). In this formula, X~pref:rably represents oxygen or sulphur, and Rl5 preferably represent: straight-chaln or branch:d alkyl having up to. 4 carbon atoms, or phenyl which is optionally monosub-stituted~to tri:ub:tituted by identical or different sub-:tituent:,~suitable :ub~:tituents being halogen, or alkyl, alkoxy or halogenoalkyl, each of which is straight-chain or branched :
:

- :
`: , :
' .

and each of which has up to 4 carbon atoms and, in the case of halogenoalkyl, up to 9 identical or different halogen atoms. R 5 represents, in particular, methyl or ethyl, or phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents from amongst fluorine, chlorine, methyl, methoxy and trifluoromethyl.
The iso(thio)cyanates of the formula (VI) are likewise generally known compounds of organic chemistry.
Formula (Ic) gives a general definition of the 5-amino-pyrazoles required as starting materials for carrying out preparation process (c). In this formula (Ic), R , R , R , R , R , R7 and R8 preferably represent those radicals which have already been mentioned in the description of the substances of the formula (I), as being preferred for these substituents. The 5-amino-pyrazoles of the formuIa (Ic) were hitherto unknown. They are obtained by preparation process (a) or (b).
Formula (VII) gives a general definition of the electrophilic~agents furthermore required as starting materials for carrying out preparation process (c). In this formula (VII), R preferably represents chlorine, bromine, nitroso, nitro, hydroxysulphonyl or chlorosulphonyl,~formyl, and straight-chain or branched alkyl or alkanoyl, each having~up to 6 carbon atoms, or represents benzoyl~whlch is optionally monosubstituted or polysub-~stituted~by i^dentical or different substituents, suitable sub-stituents~belng halogen,~ in~partlcular fluorine, chlorine or ~, ~

.

~9~52 bromine, and alkyl, alkoxy or halogenoalkyl, each of which is straight-chain or branched and each of which has up to 4 carbon atoms and, in the case of halogenoalkyl, up to 9 identical or different halogen atoms, in particular methyl, methoxy or tri-fluoromethyl. E preferably represents halogen, in particular chlorine or bromine, hydroxyl, alkyl- or arylsulphonyloxy, alkanoyloxy or aroyloxy. Other electrophilic reagents which can be used are sulphuryl chloride, phosphorus oxychloride/dimethyl-formamide, nitrating acid and other substances customarily used for electrophilic substitutions. The electrophilic agents of the formula (VII), like the other customary electrophilic reagents, are generally known compounds. Formula (Id) gives a general definition of the 4-chlorosulphonyl-5-amino-pyrazoles required as starting materials for carrying out preparation process (d). In this formula (Id), R , R , R , R5, R , R and R preferably represent those radicals which have already been mentioned in the description of the substances of the formula (I), as being pre-ferred for these substituents. The 4-chlorosulphonyl-5-amino-pyrazoles were hitherto unknown. They are obtained by preparation process (c).
Formula (VIII) gives a general definition of the amines furthermore required as starting materials for carrying out prepar-ation pr~ocess (d). In this formula (VIII), R 6 and R17 independ-ently of one~another preferably represent hydrogen or straight-: ~ :

-41- 23l8g-59o3D

chain or branched alkyl having up to 4 carbon atoms.
Formula (IX) gives a general deinition of the alkali metal fluorides alternatively required as starting materials for carrying out preparation process (d). In this formula (IX~, preferably represents a sodium or potassium cation.
The amines of the formula (VIII), like the alkali metal fluorides of the formula (IX), are generally known compounds.
Formula (Ie) gives a general definition of khe 4-acyl-5-amino-pyrazoles required as starting materials or carrying out prepaxàtion process (e). In this~formula (Ie), R , R , R , R , R6, R7, R and R10 preferably represent those radlcals which have already been mentioned in the description of-the substances of the formula (I) as being preferred for these substituents. The 4-acyl-5-amino-pyrazoles of the formula (Ie) Were hitherto un-known. They are obtained by preparation;process (c) or (f).
~Formula~(X? qives a general deinition of the hydroxyl-amine derivatives~furthermore required as starting materials for carrying ~out~preparation process (e). In this formula (X), R
preferably represents those r~adicals which have already been mentioned ln the descriptlon of~the sùbstance~s of the formula (I), as: being~preferred~for these substituents. The hydroxylamine derivatives of~the~formula (X) and their hydro-salts are generally ~ :
known c~ompounds.

:

-41a- 23189-5903D

~9~5~

Formula (XI) gives a general definition of the 4-cyano-5-amino-pyrazoles required as starting materials for carrying out preparation process (f). In this formula (XI), R , R , R , R , R6, R7 and R8 preferably represent those radicals which have already been mentioned in the description of the substances of the formula ~I), as being preferred for these substituents. Some of the 4-cyano-5-amino-pyrazoles of the formula (XI) are known (see, for exampler European Patent 26,034; European Patent 34,945;
European Patent 53,687; DE-OS (German Published Specification) 3,226,496 and DE-OS (German Published Specification) 3,226,513) and some of them form the subject of a prior patent application of the applicant (German Patent 3,337,543 or 15.10.1983). They are obtained, for example, in a manner analogous to preparation process (a), if pheny}hydrazlnes of the formula ~II) R6 ~ NH - NH (II) ~/ R
in which R4, R5, R7 and R have the meaning given above, are reacted with the known ethoxymethylenemalodinitr]les of the formula (XII) ~ N

C2H50 - CH = C (XII) ~ ~ N

;f appropr;ate ;n the presence of a diluent, such as, for example~ ethanol~ and, if appropr;ate, in the presence of an ac;d-bind;ng agent, such as, for example, sod;um ace-tate~ at temperatures of between -20C and +150C.
Diluents ~hich can be used for carry;ng out pre-paration process (a) and are su;table for b~th the first and the second reaction stage are inert organic solvents.
Alcohols, such as methanol, ethanol, propanol~ butanol, ethylene glycol or ethylene glycol monome~hyl or ethyl 10 ether are preferably used.
Suitable reaction aux;l;ar;es for carrying out the first stage of preparation process (a) are organ;c or ;norganic acids. Sulphuric acid or acet;c acid, if app-ropriate also in the presence of a buffer substance, such 15 as, for example, sodium acetate, are preferably used.
In carrying out the first stage of preparation process (a), the react;on temperatures can be varied ~ith-in sertain rangesO In general, the reaction ;s carried out at bet~een -30 and ~50C, preferably between -20 2û and ~20C.
Suitable acid-b;nding agents for carrying out the second stage of preparation process (a) are all inorganic and organ;c bases which can customarily be used. Alkali metal carbonates or bicarbonates, such as sod;um carbonate, 25 potassium carbonate or potassium bicarbonate~ are pre-ferably used.
In carrying out the second stage of preparation process (a), the reaction tempe`ratures can, as in the single-stage reaction procedure, be varied ~ithin a ~ide range. In general the reaction is carr;ed out at between 0C and 200C, preferably between 50C and ~150C.
In carrying out preparation process ta~, in gene-ral 1.0 t~o 3.0 mol, preferably 1.0 to 1.5 mol, of the acrylonitrile derivative of the formula (III) or (IIIa) 35 or of 2,3-dichloropropionitrile of the formuLa SIIIb) are employed per~mol of phenylhydrazine of the formula (II) ~
Le A~2Z 8D ~ ~ ' both in the single-stage reaction procedure and ;n the t~o-stage reaction procedure, and, in the case of the two-stage process, ;f appropr;ate 1.0 to 10.0 mol of reaction auxil;ary are employed ;n the first stage, and, ;f appropriate, 1~0 to 10.0 mol of ac;d-b;nd;ng agent are employed ;n the second stage.
~ ork;ng-up and ;solation of the reaction products are carr;ed out by customary methods, for example by re-mov;ng the organ;c d;luent, prec;pitating the reaction product ;n ~ater, and filter;ng off the resulting product under suction and dry;ng it.
Suitable diluents ~or carry;ng out preparation process ~b) are l;ke~;se inert organ;c solvents. Pre-ferably used compounds are al;phat;c or aromat;c, opt;o-nally halogenated hydrocarbons, such as, for example,benzine, benzene, toluene, xylene~ pentane, hexaneO hep-tane, cyclohexane, petroleum ether, l;groin, methylene chloride, chloroform, carbon tetrachlor;de, chloroben~ene or d;chlorobenzene, ethers, such as diethyl ether, diiso-20 propyl ether, dioxane, tetrahydrofuran or ethylene glycold;ethyl ether or e~hylene glycol 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, 25 such as dimethylformaride, dimethylacetamide, N-methyl-pyrrolidone or hexamethylphosphoric acid triamideO If acylating or alkylating agents of the formula ~V) or (VI~
are used in liquid form, it is also possible to employ these in an appropriate excess, as a diluent.
Suitable acid-binding agents for carrying out pre-paration process ~b) are all inorganic and organic bases ~hich can customarily be used~ Preferably used compounds are alkali metal hydrides, hydroxides, amides, carbonates or b;carbonates, such as, for example, sodium hydride, 35 sodium amide, sodium hydrox;de, sod;um carbonate or so-dium b;carbonate, or tertiary amines, such as, for ex-Le A 2Z 853 ample, ~riethylamine, N,N-dimethylan;l;ne, pyr;d;ne, 4-tN,N-d;methylam;no)-pyr;d;ne, d;azab;cyclooctane ~DABC0), diazab;cyclononene ~D~N) or d;azabicycloundecene ~DBU).
In carrying out preparat;on process ~b), the re-action tenperatures can be varied ~ith;n a uide range.In general, the reaction is carried out at bet~een -20C
and +150C, preferably between 0C and +100C~
In carrying out preparation process ~b), in gene-ral 1.0 to 20.0 mol, preferably 1~0 to 15.0 mol, of acy-lating or alkylating agent of the formula (V) or ~VI) and,if appropriate, 1.0 to 3.0 molO preferably 1.0 to 2.0 mol, of acid-b;nd;ng agent are employed per mol of 5-amino-pyrazole of the formula (Ia). The react;on procedure and ~orking-up and isolat;on of the react;on products of the formula (Ib) are carried out in a generally customary manner.
Su;table d;luents for carry;ng out preparation process (c) are all solYents which can customar;ly be used for such electrophil;c subst;tutions. Preferably, the ac;ds or m;xtures wh;ch constitute suitable reagents, such as, for example, sulphur;c ac;d, chlorosulphon;c acid, n;tr;c ac;d, nitrat;ng acid, sulfuryl chlor;de, phosphorus oxychlor;de/d;methylformam;de or n;trat;ng ac;d, are simultaneously used as diluents. Inert organic sol-vents, such as, for example, glacial acet;c ac;d or chlo-rinated hydrocarbons, such as methylene chlor;de, chloro-form or carbon tetrachlor;de, can, ;f necessary, also be used as diluents.
Su;table catalysts or reaction aux;liar;es for carry;ng out preparat;on process ~c~ are l;kew;se the catalysts customar;ly used for such react;ons; ac;d;c catalysts~, such as, for example, sulphur;c acid, iron~III) chlor;de or o~ther Le~;s ac;ds or acet;c anhydr;de, are preferab~ly used.
In carry;ng out prep~arat;on process ~c), the reac-tion temperatures can be var;ed ~ithin a relatively ~ide Le A 22 853 ~ , :

.....
~ . -range~ In general, the reaction ;s carr;ed out at betueen -50C and ~200C, preferably between -20C and ~150C.
In carry;ng out preparat;on process ~c), ;n gene-ral 1.0 to 10.0 mol~ preferably 1.0 to 5~0 mol, of the electroph;l;c agent of the formula ~VII) and, ;f approp-r;ate, 0.1 to 10 mol of catalyst or react;on aux;l;ary are employed per mol of 5-am;no-pyrazole of the formula (Ic~.
The reaction procedure and ~ork;ng-up and ;solat;on of the react;on products of formula ~I) are carried out ;n a generally customary manner.
Suitable diluents for carry;ng out preparat;on process ~d) are l;ke~;se ;nert organ;c solvents. The solvents mentioned ;n the case of preparat;on process (b) are preferably used. For the reaction ~ith an alkali metal fluor;de of the formula tIX), ;t ;s also poss;ble to use water or aqueous m;xtures w;th one of the solvents ment;oned ;n the case of process (b).
Su;table acid-b;nd;ng agents for carry;ng out preparat;on process ~d) are l;kew;se all organic or inor-20 ganic bases ~hich can customarily be used~ Alkal; metal hydrox;des, carbonates or bicarbonates, such as, for ex-ample, potassium carbonate or sod;um bicarbonate, are preferably used. Tertiary organic bases, such as tr;-ethylam;ne or pyr;d;ne, are also su;table~
In preparat1On process (d), the react;on tempera-tures can likewise be varied ~;th;n a w;de range. In general, the react;on is carr;ed out at between -20C and +120C, preferably between 0C and ~90C.
In carry;ng out preparation process ~d)~ in gene~
ral 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of the am;ne of the formula tVIII) or the alkali metal fluoride of the formula (IX~ and, ;f appropriate, 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of ac;d-b;nd;ng agent are em-ployed per mol of 4-chlorosulphonyl-5-am;no-pyrazole of 35 the formula tId). The react;on procedure and ~ork;ng-up and ;s~olat;on of the react;on products of the formula (I) Le A 22 853 .

- ~6 -are carr;ed out ;n a customary manner~
Su;table d;luents for carry;ng out preparation process ~e) are Likew;se inert organic solvents. Alcohols, such as, for example, methanol, ethanol or propanol, are preferably used.
Suitable acid-b;nd;ng agents for carrying out pre-paration process (e) are likewise all organ;c and ;nor-gan;c bases which can customar;ly be used. The acid-b;nding agents ment;oned ;n the case of process tb) are preferably used.
In carry;ng out preparation process (e), the re-action temperature can likeuise be varied ~;th;n a wide range. In general~ the reaction is carried out at bet-ween +20C and +150C, preferably bet~een +20C and +120C.
In carrying out preparation process (e), in gene-ral 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of the hydroxyLamine derivatives of the formula ~X) and, if ap-propriate, 1.0 to 3.0 mol of acid-binding agent are em-ployed per mol of the 4-acyl-5-am;no-pyrazole of the for-mula tIe). The reaction procedure and working-up and iso-lation of the react;on products of the formula ~I) are carried out in a generally customary manner.
Suitable d;luents for carrying out preparation process ~f) are inert organic soLvents or aqueous systems.
25 The formic acid used as a reactant is preferably used as the diluent, in an appropriate excess and, if required, as a mixture ~ith ~ater.
In carrying out preparation process tf), the re-act;on temperatures can like~ise be var;ed within a wide range. In general, the reaction is carried out at bet~een 0C and i15DC, preferably between ~20C and 130C.
In c~arrying out preparation process ~f), in gene-ral 0.1 t~ 3 mol~ preferably O.S to 2 mol, of Raney nickel and in~ 0eneral 10 to 30 mol, preferably 1.0 to 15 mol, of 35 formic acid are employed per mol of 4-cyano-5-amino-pyr-azole of the formula (XI).
Le A 22 853 .:
,: .

-47~ 52 23l8g-5903D

The reaction procedure and working-up and isolation of the reaction products of the formula (I) are carried out in a customary manner analogous to known methods (see, or example, Chem. Pharm.Bull. _, 3120 [1976]).
The active compounds can be used as defoliants, desic-cants and agents for destroying broad-leaved plants, and especially as weedkillers. sy weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances act as total or selective herbicides depends esentially on the amount used.
The active compounds can be used, for example, in con-nection with the following plants:
Dicot ledon Weeds of the genera: Sinapis, Lepidium, Galium, Y
Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus,~Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanumr Rorippa,~ Rotala, Llndernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brasslca, Lactuca, Cucumis and Cucurbita.

`

.

: :
~ .

s~
4~- 23189-5903D

Monocotyledon weeds of the genera: Echlnochloa, 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 and Apera~
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, llordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
Tlowever, the use of the actlve compounds is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the con-centration, for the total combating of weeds, for example on industriàl terrain and rail tracks, and on paths and squares with or without tree plantinqs. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestatlons, decorative tree plantings, orchards, vineyards, citrus groves,~nut orchards, banana plantations, coffee plant-ations, tea plantations; rubber plantations, oil palm plantations,cocoa plantations,~ soft fruit plantings and hopfields, and for the selectlve combatlng of weeds in annual cultures.
In addition to exhibiting a particularly good general herbicidal activity, the active compounds of the formula ~I) also ;

,. , -48a- ~ ~ ~ 189-5903D

exhibit substantially improved selecti~ity with regard to crop plants in important cultures, and can be employed as agents for -selectively combating weeds both in dicotyledon cultures, such as, for example, cotton plantings, soya beans or groundnuts, and in monocotyledon cultures, in particular cereals, such as, for example, wheat.
The active compounds can be converted to the cus-tomary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is,:emulsify-' :

::

~: :
, :: ~: : : :

: : :

- : ~: : :

;ng agents andtor d;spers;ng agents, and/or foam-forming agents.
In the case of the use of ~ater as an extender, organic solvents can~ for example, also be used as auxi-l;ary solvents~ As l;qu;d solvents, there are su;table;n the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlor;nated aromatics or chlorinated ali-phat;c hydrocarbons, such as chlorobenzenes~ chloroethy-lene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins~ for example mineral o;l frac-t;ons, mineral and vegetable o;ls, alcohols, such as butanol or glycol as well as their ethers and esters, ~ketones, such as acetone, methyl ethyl ketone, methyl ;so-butyl ketone or cyclohexanone, strongly polar solvents, such as d;methylformam;de and dimethylsulphoxide, as well as water.
As solid carriers there are suitable: for ex-ample ammon;um salts and ground natural m;nerals, such as kaol;ns, clays, talc, chalk, quartz, attapulg;te, mont-mor;llon;te or d;atomaceous earth, and ground synthet;cm;nerals, such as h;ghly-d;spersed sil;c;c acid, alum;na and s;licates; as sol;d carriers for granules there are su;table: for examplè crushed and fract;onated natural rocks such as calc;te, marble, pum;ce~ sepiol;te and dolo-25 m;te, as well as synthet;c granules of ;norgan;c and or-gan;c meals, and granules of organic mater;al such as sa~-dust, coconut shells, ma;ze cobs and tobacco stalks; as emulsify;ng andlor foam~-form;ng agents there are su;table:
for example non-ion;c and an;on;c emuls;f;ers, such as polyoxyethylene-fatty ac;d esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as ~ell as album~n hydrolysation products; as d;spersing agents there are su;table: for example lign;nsulph;te waste l;quors and methylcellulose~ ~
Adhes;ves such as carboxymethylcellulose and Le A 22 853 ~:

; : :
~ ~ : : :
.
.

natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oil s .
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90~. -The active compounds can be employed as such or in the form of their formulations, can also be used, for combating weeds, as mlxtures with known herblcides, finished formulations or tank mixtures being posslble.
Suitable herbicides for the mixtures are known herbicides, such~as, for example, l-amlno-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(lH,3H)-dione or N-(2-benzothlazolyl)~-N,N'-dlmethylurea~ for combating weeds in ; ~ cereals, 4-amino-3-methyl-6-phenyl-1,2,4,-triazin-5(4H)-one for :
, :
: :

::: ::: ` :

~9~
-50a- 231g9-5903D
, combating weeds in sugarbeet and 4-amino-6-(1,,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one ~or combating weeds in soya beans. Mixtures with N,N-dimethyl-N'-(3-trifluoromethyl-phenyl)-urea, N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea, N,N-dimethyl-N'-(4~isopropylphenyl)-urea, 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one, 2,4-dichlorophenoxyacetic acid, 2,4-dichlorophenoxypropionic acid, (2-methyl-4-chlorophenoxy)-acetic acid, (4-chloro-2-methyl-phenoxy)-propionic acld, chloroacetic acid N-(methoxymethyl)-2,6-dimethylanilidej 2-ethyl-6-methyl-N-(l-methyl-2-methoxyethyl)-chloroacet- ~ ;

:

::
:

:: :, ~ , ~

-51- 2318g-5903D
5~:
an;l;de, 2~6-din;~ro-4-tr;fluoromethyl-N~N-dipropylan;line, and 2-benzyloxyethyl, tr;methyls;lylmethyl or 2,2-d;ethoxy-ethyl 2-C4-(3,5-d;chloropyr;d-2-yloxy)-phenoxy~-propion-ate are also poss;ble. Surpris;ngly, some m~xtures also exhibit a synerg;stic action.
M;xtures u;th other knoun act;ve compounds, such as fungic;des, ;nsectic;des, acaric;des, nematic;des, bird repellants, pLant nutrients and agents uhich improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution~ such as ready-to-use solu-t;ons, suspensions, emulsions, po~ders, pastes and gran-ules. They are used ;n the customary manner, for example by ~atering, spray~ng, atom;sing or scattering~
The active compounds can be applied either before or after emergence of the plants.
' They can also be incorporated ;nto the soil before sow;ng.
The amount of active compound used can varylu;th;n a substantial range. It depends essent;ally on the nature of the des;red effect. In general, the amounts used are betueen 0.001 and 10 kg of active compound per hectare of soll area, preferably bet~een 0.01 and 5 kg per ha.
The examples wh;ch follou illustrate the prepara-tion and the use of the active cGmpounds.

Preparat;on examples 30 Example 1 ~
~N NH2 ; "~1 Cf~
Le A 22 853 ;

::
.

~Process a) 20 mg of disodium ethylenediamine-tetraacetate t= T;triplex III) in 150 ml of methanol are added drop-wise to 24.5 9 (0.1 mol) of 2~6-dichloro-4-trifluoromethyl-phenylhydra~ine at the reflux temperature, and 25 ml(27.6 g/0.3 mol) of 2-chloroacrylonitrile are added. When the addit;on is complete, heating is continued for a fur-ther 8 hours at the reflux temperature, after Yhich 9 ml tO.16 mol~ of 96% strength sulphuric acid are added drop-10 ~;se and heating ;s cont;nued for a further 6 hours at thereflux temperature. 33.5 9 (0.3 mol) of anhydrous sodium carbonate are added to the cooled react;on mixture. After 4 hours, the solvent is removed in vacuo, the res;due is taken up ;n 500 ml of water, and the solut;on is stirred 15 for 10 hours at room temperature. The prec;p;tate ~hich separates out is filtered off, rinsed with water and dr;ed ;n vacuo at 500CA
28.5 9 t96X of theory~ of 5-amino-1-t2,6-dichloro-4-trifluoromethylphenyl)-pyrazole of melting po;nt 103-20 105C are obtained.Example 2:
b~
~ N~l-NH-CO-C2Hs tl- ~ tl Cl tProcess b) 5 ml tS.3 gl0.05 mol) of 98X strength prop;onyl 25 chloride and then 5 ml (5.û 910.063 mol) of anhydrous pyrid;ne are added in succession to 13.2 9 tO.05 mol) of S-amino-l-t2,4,6-trichlorophenyl)-pyrazole in 100 ml of dichloromethane at roo~ temperature, ~h;le stirring.
During the add;t;on, the temperature increases to 400CA
When the addition is complete, stirring is continued for a further 16 hours at room temperature, 50 ml of dichloro-: .

methane are added, ~he mixture ;s washed ~;th tw;ce 100 ml of ~ater, 100 ml of saturated sodium b;carbonate solut-tion and 100 ml of sod;um chloride solution znd ;s dried over magnesium sulphate, and the solvent ;s removed in vacuo~ The sol;d res;due ;s ~ashed ~;th a small amount of hexane and ;s dr;ed~
12.5 9 (81X of theory) of 5-propionamido-1-(2,4,6-trichlorophenyl)-pyra~ole of melt;ng po;nt 125C are obta;ned.
Example_3 ~r NH Co-C2Hs ~C C l ~l (Process c) 2 ml ~2.17 9/0.021 mol) of acet;c anhydride and then 0.9 ml (1.3 g/O.û2 mol) of 98X strength n;tric acid are added in success;on to 6.4 9 (0.02 mol) of 5-prop;on-15 amido-1-(2,3,4-tr;chlorophenyl~-pyrazole ;n 20 ml of gla-c;al acetic ac;d at 10C. When the addition ;s complete, the mixture ;s st;rred for 16 hours at 25C. To ~ork up the m;xture,-;~ is evapora:ted down in vacuo, ~he residue ;s taken up ;n 20 ml of diethyl ether, the solution is 20 washed three times with a total of 50 to 100 ml of concen-trated sodium bicarbonate solution and t~ice ~ith 50 ml of saturated sod;um chlor;de solut;on, the solvent ;s re~
moved ;n a vacuum from a water pump, and the solid res;-duè is washed u;th a small amount of uater and dr;ed in 25 a h;gh v:acuum at 30C to 40Ca 5~5 9 (76% of theory) of ~`-n;tro-5-prop;onamide-1-~2,3,4-trichlorophenyl)-pyra-zol~ o~f melt;ng polnt 79-81C are obta;ned.

Le A:22 853 ~
:

; ~

Example 4 H~N NH2 ~Cl C l tProcess c~
A solut;on of 1.6 g tO.02 mol) of bromine in 5 ml of glac;al acet;c ac;d ;s added drop~ise to 2.6 g tO.01 mol) of 5-amino-1-(2,3,4~trichlorophenyl)-pyrazole ;n 10 ml of glac~al acetic ac;d at 20C, wh;le stirr;ng~
When the add;t;on ;s complete, st;rring is continued for a further 3 hours at 20C, after ~h;ch 30 ml of ~ater and 3 9 tO.022 mol) of sod;um acetate trihydrate are added, st;rr;ng ;s continued for a further hour, and the crys-talline prec;p;tate 75 f;ltered off under suct;on, ~ashed ~;th ~ater and~dr;ed at 50C to 60C ;n vacuo~ 3.2 g t94X of theory) of 5-amino-4-bromo-1-t2,3,6-trichloro-15 phenyl)-pyrazole of:meLting po;nt 129C are obta;ned.
Example 5:
:

N ~ :
N ; N~-co-c2H5 c ~
~: ~ : C L
tProcess:c) ~ .Z~g ~(0.~0;09~mol) of sulfuryl chloride are added 20 dropw;~se~to:2D7:g ;t~0~085 mol) of 5-prop;onamide-1-t2,3,4-trichlorophenyl3-pyrazo:l~e ;n 20 ml of d;chloromethane at 0C to~5t~ ~When~the~addition is`complete, st;rring Le:A~22:853 ::

~ 9~

;s cont;nued for a further 16 hours at room temperature, the mixture ;s d;luted ~;th 30 ml of dichloromethane, uashed s~veral t;mes ~;th uater, saturated sod;um bicar-bonate solution and saturated sod;um chloride solut;on, 5 dr;ed over sod;um sulphate and evaporated do~n ;n vacuo, and the res;due ;s dr;ed at 50C in a h;gh vacuum. 2~5 9 ~83X of theory) of 4-chloro-5-prop;onam;do-1-(2,3,4-tri-chlorophenyl) pyrazole of melting po;nt 122C are ob-tained~
Example 6 ~0-~
~N~ N~2 ~Cl ~Process f) 12 9 (0O042 mol) of 5-am;no-4-cyano-1-(2-chloro-4-trifluoromethoxy-phenyl)-pyra~ole are boiled under reflux with 5 9 of Raney nickel ;n 50 ml of 75X str~ng~h aqueous form;c ac;d for 1 hour; ~he still ~arm solut;on is f;l-tered under suction, the res;due is r;nsed u;th water, the filtrate is extracted several t;mes with ether, and the combined ether phases are uashed ~;th saturated sodium 20 bicarbonate solution, dr;ed over sodium sulphate and evaporated down in vacuo~ 8.û 9 (6ZX of theory) of 5-amino-1-~2-chloro-4-trifluoromethoxy-phenyl)-4-formyl-pyrazole are obtained ;n the form of an oil~
1H-NMR ~ Cppm~ = 5~7 (s,2H) - singlet 7~3-7~6 (m,3H) - multiplet 7.85 (s,1H) - singlet 9.6 (s,1H) - singlet Le A 22 853 :

. , Example 7 ll~ OC2H5 ~3~ 0 C 2 H 5 ~N ~NHz ~CL
Cl Cl ~Process a) 6.3 9 (0.03 mol) of 2,3,4-trichlorophenyLhydrazine, 5.8 9 ~0.025 mol) of ethoxymethylene-diethylphosphonoaceto-nitrile and 1 9 of ~0.012 mol) of anhydrous sodium acetate are suspended in 10 ml of glac;al acetic acid, and the sus-pension is st;rred for 48 hours at room temperature. 50 ml of d;chloromethane and 100 mL of water are added ~o the reaction m;xture~ The organic phase is separated off and washed once in each case with 50 ml of saturated sod;um bicarbonate solution and 30 ml of saturated sodium chLo-ride solution. A~ter the solution has been dried over magnes;um sulphate, the solvent is d;st;lled off ;n vacuo, 15 the oily residue is dissolved in 15 ml of ethoxyethanol, and the solut;on is heated under reflux for 5 hours. It is then cooled to room temperature, 30 ml of uater are added to the solution and stirring ;s continued until the ;nitially oily precipitate crystall;ses. The sl;ghtly 20 yellow crystals are~f~iltered off under suct;on, washed ~;th water and dr~ied~;in vacuo at 50-60C.
5.6 9 (46;.8% of~theory) of~5-amino-4-d;ethylphos-phono-1-t2,3,4~-tr~;chlorophenyl)-pyrazole of melt;ng po;nt 114C~are obtained. ~
25~ Prep~;~ation~o~ ~he_starilog cor~pound:

; C2~HsO- CH ~ C ~ ~ OC2Hs : ~ L e A ~ 2 2_3 5 3 ~ o 0 ~ 2 H 5 35.4 9 tO.2 mol) of diethylphosphonoacetonitrile ~see Houben-~eyl "Methoden der organischen Chem;e" ~Me-thods of organic chem;stry), Volume E2, page 345, 4th Edi-tion, Thieme Verlag Stuttgart, 1982)~ 42 ml ~0~45 mol) of acetic anhydride and 56 ml ~0.34 mol) of ~r~ethyl o-for-mate are stirred for 2 hours at 110C~ Thereafter, the loY-boiling compounds are distilled off over a short column under atmospheric pressure, the bottom temperature increasing to 140C. This temperature is maintained 10 for a further 4 hours, and the unreacted starting com-pounds are then distilled off, first under a vacuum from a ~ater pump and then under a vacuum from an o;l pump.
2û.5 9 ~44% of theory) of ethoxymethylene-d;ethylphosphono-aceton;trile rema;n as an oil at the bottom~
1H-NMR tCDCL3) = ~ - 7.63 ppm ~d,1H) - doublet 4.3Z ppm tq,2H) - quartet 4.15 ppm ~m,4H) - multiplet 1.45 - 1.35 ppm tm,9H) - muLtiplet The follo~;ng compounds of the general formula ~I) 20 are obta;ned in a corresponding manner and in accordance ~;th the general preparation data.
Table 2 R1 R8 ~ R4 R7 ~ - R5 Examp~e R1 R2 R3 R6 5 6 R7 R~ Phys;cal No. propert;es ~ , . . . . ............ .
8 N2 C2H5C H Cl H Cl H Cl M.p.:54C
9 N02 C~5~0 H Cl H CF3 H Cl M.p.:48C
N0~ C2H5C H tl H CF3 H H M.p.:115~C
~decoposit;~n) Le A 22 853 ~ 58 --Tab le 2 (cont i nued) Examp~e ~l ~2 R~ 26 ~5 ~5 ~7 ~ Phys;caL
No. properties 11 ~2 C~HsCO H tl H SEF3 H Cl ~.p.:96-99C
12 N2 C2H5C H Cl H OCf3 H H M.p.:65C
13 N02 C2~5C H Cl Cl CF3 Cl Cl M.p.:54-60C
14 N2 ~2H5C H Cf3 H Cl H H Oil N2 H H Cl H Cl H Cl M.p.:218C
. 16 N02 CH3CO H Cl H CF3 H Cl M.p.:50C
17 N02 CH3CO H Cl H SCF3 H Cl M.p.:58-61C
18 N02 CH3(CH2)2CO H Cl H CF3 H Cl M.p.:44C
19 N02 CH30CO H Cl H CF3 H Cl M.p.:141-43C
N02 ClCH2CO H Cl ~ CF3 H Cl M.p.:130-33C
21 N2 C2~5C H Cl H Cl H H M.p.-63C
22 H H H Cl H Cl H Cl M.p.:113~C
23 H H H Cl H CF3 H H M.p.:88-92C
24 H H . H Cl H SCF3 H Cl M.p~:79C
H H H Cl Cl Cl H H M.p.:152~C
26 H H H Cl Cl CF3 Cl Cl M.p.:103-10C
27 H H H C~ H OCF3 H H M.p.:73-76C
28 H C2HsCO Cl Cl Cl H H M.p.:55C
29 ~ CaHsCO H Cl H CF3 H ~ M~p~:lo6-1o~c H C2HsCO H CL H SCf3 N Cl M.p.:136C
31 H C2HsC H Cl H CF3 H Cl M.p.:146C
32 H C2HsCO H Cl H OCF3 H ~ oiL
~3 H C2H5~0 : H Cl Cl CF3 Cl el M.p.:15~-58C
36 H C2HsCO N eF H tl H H il 35 ~ ; C2HSCO h~ Cl ; H Cl N H OiL
2H5C ~ Cl h S02CF2Cl ~ Cl M.p. 134C
` 37 : H tH~CO C2HsCO ~ ~l Cl Cl ~ ~ M.p.:142C
8 H~ :~CH~CO ~ ~tH3CO Cl tl Cl H H M~p~:142~C
39 H CH~OCO H CL H t~ H Cl M.p.:123-126C
H ¦ tH3CO H el H CF~ ~ Cl M.p.:173-76C
: ~1 H CH~O H Cl ~ SCF3 H Cl M.p.:131~C
~2 H ~cH3~cH2)2co H Cl N CF~ H Cl M.p.:128-31C
Le A 22 853 ~ ~ ' s;~
~ 59 --Tab le 2 ~ cont i nued) Exa~ple R1 / R~ ~3 R6 RS R~S ~ Physical No . ~ ~ . propert i es _ ~ . .......... . __ ___. _ _ .... . ...
63 H \C l CH2CO 11 I: l H C~3 t9 ~ l M.p. 1 49~50C
~4 ~r \ C2H5C H tl Cl Cl ~1 H M.p. :78C
I \H H tl Cl Cl H 11 M.p. 162C
46 eH3h \~ ~ t1 C l C ~ Cl H 11 M.p. :1 56-59C
~c~ ~
67 HON= C~l- H 11 e l H oc f 3 H ~1 M.p. ,180 C
~ 8 ~C~50) æe~¦ ~ U Cl Cl Cl H H Oi l -49 N0~ C2H5C0 H Cl H ~ CCl~ H CL M.p.:156-58C
50 N02 H H Cl ~ ~F3 H Cl M.p.:189-90C
51 ~2 ~ ~ 1 tl H SO~C~ H CL M.p.:208-09C
52 H C2H5 CH3 Cl ~ ~ Cl H Cl ~ .50-51 53 NO2 C2H5O~ CH3 C1 H Cl H Cl192-98 54 H C2H5CO H Cl H SOE 3 H HOil H C ~ H Cl H CF3 H Cl69-71 56 H CllH23t) H C1 H CF3 H Cl63-66 57 S~Cl2F H H Cl H Cl H Cl102 58 SCC12F C2H5~) H C1 H Cl H Cl128-29 59 NO2 H H Cl H OCF3 H H50 NO2 ~ H Cl H CF3 H Cl165-68 61 NO2 C11H23t~ H Cl H CF3 H Cl60-70 62 2~2 C2HSC H Cl H SCF3 H H90-93 63 Cl . C2H5~X) H Cl H CF3 H Cl63-65 64 C2H5C H Cl H OCF3 H C150-56 SOOC12F C2H5a H Cl H Cl H Cl143-46 66 ND2 ~ C2H5C() H Cl H S2CF3 H H60-64 67 902CC12F C2H5CO H Cl H ClH Cl 136-39 68 H~ C2H5CO H Cl Cl CF3H Cl 129-32 69 NO H H Cl H CF3H Cl 227 70; NO2 H Cl H S2CF3 H H 68-70 71 ~ 2 2H5C ~ H Cl H OCF3H Cl 130-35 72 ~ N~2 C2H5 H Cl H S2CF3 H Cl132-34 73 NO2 C2H5C~) H Cl Cl CF3 H Cl50-52 74 ~(C2H5O)2P(O) H : H Cl H CF3 H Cl Oil Le A_22 853 . . . :

s~
-- 60 _ l able 2 tcont~nued~
Example --Rl R2 R3 R4 R5 R6 R7 R8 Melting No. . ~DLnt (C) ._ ._ _ _ . . _ N~2 H H Cl H SCF3 H H 56-60 76 NO2. H H Cl H SCF3 H Cl 145-49 77 2 H H Cl H OCF3 H Cl 206-08 78 2 H H Cl H S2CF3 H Cl 249-53 79 2 H H Cl Cl CF3 H Cl 78-85 CH3NHOO H Cl H CF3 H Cl 178-82 81 H ~ H Cl H CF3 H Cl 65-67 82 ( 3)2N0 H Cl H CF3 H C1 137-38 83 H C2H5CO H Cl Cl C1 H Cl 62-67 84 ~ C2H5CO H Cl Cl C1 H Cl 60-67 CH2CH2-CD H Cl H CF3 H Cl 120-24 86 No2 CH3NH0O H Cl H CF3 H Cl 212-14 87 NO2 ~ H Cl H CF3 H Cl 48-52 88 NO2 H H Cl Cl Cl H Cl 83-89 89 N~2 H CH3 Cl H C1 H Cl167-75 H : H CH3 Cl H Cl H Cl186-88 91 H ClCH2-OoH Cl H CF3 H H103-05 92 H ClCH2-OoH Cl H OCF3 H H84-87 93 Nn2 H H C1 H CF3 H H55-58 ~4 N~2 ClCH2cH2-H Cl H CF3 H C1 135-40 2 ClCH2-CD H Cl H OCF3 H H Oil 96 N02. ClCH2-CO H C1 H CF3 H H 111-13 97 H C2H500 H Cl F CF3 F Cl 121-23 98 No2 C2H5O~ ,H Cl F CF3 F Cl 135-37 99 C2H5CO H C1 F Cl F Cl 190-93 100 No2 H CH3 Cl H CF3 H H 120-23 101 ~N~2 : C2H5~ CH3 C1 H CF3 H Cl 140-54 102 N~2 H H Cl F CF3 F Cl 158-65 103 N~2 C2H5oO H Cl F C1 F Cl 130-33 104 N32 CH2-CH-CO H Cl H C~3 H Cl 55~65 105 No2 H H Cl F Cl F C1 210-20 106 H HOO H C1 H CF3 H Cl 144~50 Le A 22 853 Table 2 ~contin~Jed) - 61 -Exa~ple Rl R~ R3 ~4 R5 R6 R7 R8 Melt mg No. poLnt (C) .. .. ~
107 No2 C2H5C H Cl H OCH3 H Cl 165-74 108 2 HCO H C1 H CF3 H Cl 144-50 109 No2 H CH3 Cl H CF3 H Cl 120-40 110 SCC12F H H Cl H CF3 H Cl 99-lOS
111 SOCC12~ H H C1 H CF3 H C1 55-62 112 ~ ~H3OO H Cl Cl CF3 H Cl 158-62 113 SO2CC12F H H Cl H CF3 H Cl 135-38 114 2 CH3CO H Cl Cl CF3 H Cl 124-33 115 CH3CO H Cl H CF3 H H ~ 50-52 116 No2 CH3CO H Cl H -CF3 H H 62-65 117 H H CH3 Cl H CF3 H Cl 135-37 118 H ~ H Cl H CF3 H Cl 62-64 119 No2 CH2cH2cH2co H Cl H CF3 H Cl 60-63 120 NO2 ~ H Cl H CF3 H Cl 157-65 121 H C2H500 H Cl H Br H H 86-88 122 H H H Br H Br H Br 141-43 123 H C2H5CO H Br H Br H Br 147-50 124 H R H Cl H Br H Cl 102 125 H H H Br H Cl H Br 98 126 NO2 H H Cl H Br H H 95-98 127 H ~ ` H H I H I H H 138-40 128 No2 C2H5Co H Br H Br H Br 92-94 129 H H Br 138-40 130 H C2H5OO H Cl H Br H C1 142-48 131 H H H Br ~H C1 H Cl 105-07 132 No2 C2H5C H Br H Cl H Br 146-48 133 H ClCH2CO H Br H Cl H Br 127-30 134 H H H Br H F H H 58-60 135 NO2 H 8 Br H C1 H 8r 230 136 ¦ H H H Br Cl Cl H Br 120-25 Le A 22 853 .

~ble ~ (con~inued) Exampl Rl R2 R3 R4 R5 R6 Ri R8 Melting No. point(C~
. . , ~,,. ._ _ . .
137 No2 C2H5CO H Cl H Br H Cl 94 138 NO2 H H Cl H Br H Cl 198 139 H . C2H5CO H Br H Br H Cl 114-18 140 N~2 ClCH200 H Br H Cl H Br 115-20 141 H C2H5CO H ~ H ~ H H Oil 142 H H H Br Cl Br H Cl 170 143 N~2 C2H5 H Br H Br H Cl 89-93 144 NO2 H H Br H Br H Cl 208-10 145 H C2H5CO H Br Cl Cl H Br 165 146 H C2H5CO H Br Cl ~r H Cl 140-50 147 No2 C2H5C H ~ H I H H 55-60 148 2 C2H5CO H Br Cl Cl H Br 130-40 149 N~2 C2H5CO H Br H F H H 72-74 150 NO2 C~H5CO H Br H OCF3 H ~ 83-85 151 Br H H Cl H Cl H Cl 119 !52 SCH3 H H Cl H Cl H Cl 114 153 Br H H OCH3H Cl H Cl 67-70 154 5CH3 C2H5 H Cl H Cl H Cl 92~95 155 SO2CH3 C2H5CO H Cl H Cl H Cl 146-50 156 -CHO H H Cl H OCF3 H H Oil 157 C2H5CO H Cl H OCF3 H ~ Oil 158 -CH=NCCH3 H . H~ Cl H OCF3 H H138-39 159 H ClCH2CH2CH2Co H Cl H CF3 Oil ` Le A 22 853 `

use examples The compound listed belo~ is used as a compara-tive substance in the use examples which follo~:

CM
~ NH - CO C2H5 Cl ~ Cl S 4-Cyano-S-propionam;do-1-(2,4,6-trichlorophenyl)-pyrazole ~disclosed ;n DE-OS 3,226,513).
Example A
Pre-emergence test Solvent: 5 parts by ueight of acetone Emulsifier: 1 part by ~eight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by ueight of active compound is mixed uith the stated amount of solvent, the stated amount of emul-s;fier is added and the concentrate is diluted uith uater to the desired concentration.
Seeds of the test plants are soun in normal soil and, after 24 hours, uatere~d uith the preparation of the actlve compound. It is expedient to keep constant the amount of ~ater per unit area. The concentration of the 2n active compound in the preparation is of no importance, only the~amount of active compound applied per unit area being decisive. After three ueeks, the degree of damage Le A 22 853 ~
~ ~ , ~: `
' ::;
~' ~
:: :

5~
- 64 _ to the plants is rated in X damage ;n comparison to the development of the untreated control. The f;~ures denote:
OX = no action (like untreated control) 100X = total destruction In this test, ~or example, the compound according to preparation example 3 is clearly superior to ~he prior art, both in herbicidal activity and in selec~ivity ~;th respect to crop plants.
Example ~
Post-emergence test Solvent: 5 parts by ueight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed withthe stated amoun~ of solvent, ~he s~ated amount of emulsi-fier is added and the concentrate is diluted ~ith water to the desired concentration.
Test plants uh;ch have a height of 5 - 15 cm are sprayed ~ith the preparation of the active compound in such a ~ay as to apply the particular amounts of active compound desired per unit area. The concentrat;on of the spray liquor ;s so chosen that the part;cular amounts of active compound desired are applied ;n 2,000 l of ~ater/ha. After three weeks, the degree of damage to the plants is rated in X damage ln comparison to the~development of the untreated control. The f;gures denote:
OX = no act;on ~l;ke untrea~ed control) ~ 100X = total destruction In this test, for exa-ple, the compound according to prep~a~ration example 3 is clearly superior to the prior art, both in herb;cidal activity and in selectivity w;th respect to crop plants.
Le A 22 853 `

Claims

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

1. A phenylhydrazine derivative of the formula (IV) in which R4 and R6 independently of one another represent cyano, nitro, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxycarbonyl, or C1-C4-halogenoalkyl or C1-C4-halogenoalkoxy each of which may have up to 9 halogen atoms, or a radical -S(O)n-R13, and R5, R7 and R8 independently of one another and of R4 and R6 represent the same radicals as R4 and R6 and additionally represent hydrogen, R13 represents C1-C4-alkyl, C1-C4-halogenoalkyl which may have up to 9 halogen atoms, amino, C1-C4-alkylamino or dialkyl-amino having 1-4 carbon atoms in each alkyl moiety, and n repre-sents an integer of 0, 1 or 2, and Z represents one of the radicals and wherein R1 represents hydrogen, nitroso, nitro, halogen, C1-C6-alkyl, C1-C6-halogenoalkyl which may have up to 9 halogen atoms, phenyl (optionally substituted by halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-halogenoalkyl), or one of the radicals -S(O)n-R9; -?-R10; or -?(OR11)2 and R9 represents hydrogen, hydroxyl, halogen, C1-C4-alkylamino, dialkylamino having 1-4 carbon atoms in each alkyl moiety, C1-C4-alkyl, C1-C4-halogenoalkyl which may have up to 9 halogen atoms or phenyl optionally substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy, R10 represents hydrogen, C1-C4-alkyl or phenyl optionally substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-halogenoalkyl, R11 represents hydrogen, C1-C8-alkyl, C1-C4-halogenoalkyl having up to 6 halogen atoms, C1-C8-alkenyl, C1-C8-alkynyl or phenalkyl having 1-4 carbon atoms in the alkyl part, and n is as defined above, and Hal and Hal' represents identical or different halogen atoms, with the proviso that when R1 represents hydrogen, methyl or optionally substituted phenyl, R4 and R6 cannot simultaneously represent nitro.

2. A compound according to claim 1 wherein R1 represents H, NO, NO2, Cl, Br, I, CHO, -P(O)(OC2H5)2, -CH=N-CH3, -CH=N-OH, -S-CCl2F, -SOCCl2F, -SO2CCl2F, -SCH3 or -SO2CH3, R4 represents Cl, -CF3, Br, I or -OCH3;
R5 represents H, Cl or F;
R6 representS -CF3, Cl, -OCF3, -SCF3, -SO2CF2Cl, -SO2CCl2F, -SO2CF3, Br, I or F;
R7 represents H, Cl or F; and R8 represents H, Cl or Br.

3. A compound according to claim 1 wherein R1 represents NO2;
R4 represents Cl;
R5 represents H or Cl;
R6 represents -CF3, Cl or -OCF3;
R7 represents H;
and R8 represents H or Cl.

4. A process for the preparation of the phenylhydrazine derivative of the formula (IV) as defined in claim 1, which process comprises reacting a phenylhydrazine of the formula (II):

(II) in which the symbols are as defined in claim 1, (i) with an acrylonitrile derivative of the formula (III):

(III) in which R1 is as defined in claim 1, and A represents halogen, hydroxy or alkoxy, (ii) when R1 represents hydrogen, with a 2-halogenoacrylonitrile of the formula (IIIa):

(IIIa) in which Hal represents halogen, or with a 2,3-dihalogenopropionitrile of the formula (IIIb):

(IIIb) in which Hal represents halogen.