NZ221199A - Phenylhydrazine derivatives and their use in preparing 5-amino-1-phenylpyrazole derivatives - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £21199 Priority Date(s c ..2 Complete Specification Fited:^Zr.l7$.. Class: . C91WV.W, V.S 2 9 APR 1988 im::::::.

Publication Date: P.O. Journal. No: NO 0-Am5 MM vy »i\\ Under the provisions of RegtfS J latlon 23 (I) the C^Np'efe _ Specification has been ante-dated to ...Ocurv 19 221199 Divided out of N.Z. No. 210890 filed 22 Januaryl985 Initials NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION PHENYLHYDRAZINE DERIVATIVES o We, BAYER AKTIENGESELLSCHAFT, a company registered under the laws of the Federal Republic of Germany of Leverkusen, Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us , and the method by which it is to be performed, to be particularly described in and by the following statement:- - 1 - (Followed by 1A) < i i y 9 The present invention relates to Pheny1hydrazine derivatives, end in particular to phenylhydrazine derivatives useful in the preparation of certain 5-amino-l-phenyl-pyrazoles, such use is the subject of our related application No 210890. zoles which are substituted in the 4-position by a cyano group, such as, for example, 4-cyano-5-propionylBmino-l-(2 , 4 ,6-1rich1 oropheny1)-pyrazole, possess herbicidal properties (see, for example, NZ Patent No 196337). problem weeds, like their compatibility with Important crop plants, Is not always completely satisfactory 1n all fields of use. 1n the 4-pos1t1on or substituted 1n the 4-pos1t1on by •ethyl or phenyl, such as, for example 5-am1no-1-(2,4-di-n1trophenyl)-4-methylpyrazole, 5-am1no-1-(2,4-d1nitro-phenyl)-4-phenylpyrazole, 5-am1no-4-(4-chlorophenyl)-1-(2,4-d1n1tropher»yl)-pyrazole, 5-am1no-1-(2,4-d1n1tro-phenyl)-4-(4-methoxyphenyl)-pyrazole or 5-acetam1do-1-(2,4,6-tr1n1trophenyD-pyrazole, are also known (see J.Org.Chemlstry 36, 2972-2974 C19713; J.Heterocyc I. Chen. 7, 345-349 C19703 and C.A. 62, 13137c). However, nothing Is known about their activity as herbicides.

The present invention provides phenylhydrazine derivatives of the formula IV It is known that certain 5-amino-1-pheny1-pyra- However, their herbicidal activity against some -Am1no-1-phenyIpyrazoles which are unsubst1tuted NH - NH - Z (IV) 221199 in which R^ and independently of one another represent cyano, nitro, halogen, alkyl, alkoxy, alkoxy carbonyl, halogenoalkyl, halogenoalkoxy or a radical -S(O) -R^, and 7 8 R , R and R independently of one another and 4 6 of R and R represent the same radicals as R4 and R*5 and additionally represent hydrogen R^ represents alkyl, halogenoalkyl, amino, alkylamino or dialkylamino, n represents the number 0, 1 or 2, and Z represents one of the radicals CN yea -CH-C or -CH2-CH ' R1 Hal wherein R^ represents hydrogen, nitroso, nitro, halogen, alkyl, halogenoalkyl, optionally substituted aryl or one of the radicals 0 0 9 " 10 11 " 11 -S(0) -R ; -C-R ; -C=N-OR or -P(OR )_ n . z R10 in which 9 R represents hydrogen, hydroxyl, halogen, amino, alkylamino, dialkylamino, alkyl, halogenoalkyl or optionally substituted aryl, R*^ represents hydrogen, alkyl or optionally substituted aryl, R*1 represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkinyl or aralkyl, except that where R1 represents hydrogen, methyl or optionally 4 6 substituted phenyl, R and R do not simultaneously represent the nitro group; and Hal represents halogen r/V - f MAR f 988 221199 3 The invention results from the realisation, as described and claimed in our related Application No 210890, that the substituted 5-amino-1-pheny1-pyrazoles, some of which are known, of the general formula (I) O 1 which R1 represents hydrogen, nitroso, nitro, halogen, alkyl, halogenoalkyl, optionally substituted aryl or one of the radicals 0 0 -S(0) -R9; -C-R10; -C'N-OR11 or -P(OR")> n ■ i J1* X o |l , .

R represents hydrogen or a radical -C-R1* , R3 independently of R* represents the sane radicals as R* and additionally represents alkyl, L f.

R and R° independently of one another represent cyano, nitro, halogen, alkyl, alkoxy, alkoxy carbonyl, halogenoalkyl, halogenoalkoxy or a radical -S(0>n-R^', and c 7 <> R , R and R independently of one another and of R^ and R^ represent the same radicals as / d.

R and R and additionally represent hydrogen, and o R represents hydrogen, hydroxyl, halogen, amino, alkylamino, dialkylamino, alkyl, halogenoalkyl or optionally substituted aryl, R^® represents hydrogen, alkyl or optionally substituted aryl, 1 represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkinyl or aralkyl, represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, alkoxyalkyl, a Iky IthioaIky I, optionally substituted cycloalkyl, optionally substituted aryl, alkoxy, alkylthio, optionally substituted aryloxy, optionally substituted arylthio, alkylamino, dialkylamino or optionally substituted a ryI am 1 no, represents alkyl, halogenoalkyl, amino, alkylamino or dialkylamino, X represents oxygen or sulphur, and n represents the numbers 0, 1 or 2, if? 11 99 possess herbicidal properties, 1n particular selective herbicidal properties.

Surprisingly* the substituted 5-am 1no-1-phenyl-pyrazoles of the formula (I) which are to be used according to the invention exhibit, 1n addition to an improved herbicidal action against certain weeds, substantially Improved compatibility with Important crop plants compared with the 4-cyano-5-am 1 no-1-phenyIpyrazoles known from the prior art, such as, for example, 4-cyano-5-propionyI amino-1-(2,4,6-1richlorophenyl)-pyrazole, which Is a similar compound chemically and 1n terms of its action.

The substituted 5-amino-1-phenyl-pyrazoles to be used according to the invention thus represent an enrichment of the art.

Formula (I) gives a general definition of the substituted 5-amino-1-phenyl-pyrazoles to be used according to the invention. Preferred compounds of the formula (I) are those in which alkyl or halogenoalkyl, each of which is straight-chain or branched and each of which has up to 6 carbon atoms and, 1n 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 carbon atoms, or represents one of the radicals -S(0)n-R9; -tl-RlO. -$<0R11)2 2 "12 R represents hydrogen or a radical -C-R , r' independently of R2 represents the same 2 radicals as R , and additionally represents X II straight-chain or branched alkyl having up to 4 carbon atois, R* and R^ Independently of one another represent cyano, nitro, halogen, or alkyl, alkoxy or alkoxy-carbonyl, each of which 1s straight-chain or branched and each of which has up to 4 carbon atoms, and furthermore represents halogenoalkyl or halogenoa Ikoxy, each of which 1s stra1ght-cha1n or branched and each of which has up to 4 carbon atoms and up to 9 Identical or different halogen atoms, or represents a radical -S(0>n-R^, and t 7 a R , R and R° independently of one another and of and R^ represent the same radicals as R^ and and additionally represent hydrogen and 9 R represents hydrogen, hydroxyl, fluorine, chlorine, bromine, amino or alkylamino, dialkylamino, alkyl or halogenoalkyl, each of which is stra1ght-cha in or branched and each of which has up to 4 carbon atoms 1n the Individual alkyl parts and, in the case of halogenoalkyl, up to 9 identical or different halogen atoms, and represents phenyl which is optionally nonosubstituted or polysubst1 tuted by identical or different substi-tuents, the following being suitable subst1tuents: halogen, 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^ ® represents hydrogen, straight-chain or branched alkyl having up to 4 carbon atoms, or phenyl which Is optionally monosubst1tuted or poly substituted by identical or different substituents suitable phenyl substituents being those men- 9 tioned in the case of R , represents hydrogen, halogenoalkyl having ✓ 99 up to 4 carbon atoms and up to 6 Identical or different halogen atoms, alkyl, alkenyl or alkinyl, each of which is atra 1ght-cha1n or branched and each of which has up to 8 carbon atoms, and 5 straight-chain or branched phenylalkyl having up to 4 carbon atoms in the alkyl part, 1 2 R represents hydrogen, or alkyl which ie straight-chain or branched Bnd which has 1 to 12 carbon atoms, or alkenyl, alkinyl, alkoxyelkyl, alkylthioeJkyl, elkoxy, 10 alkylthio, alkylamino, dialkylamino or halogeno alkyl, each of which 1s straight-chain or branched and each of which has up to 4 carbon atoms in the Individual alkyl parts and, in the case of halogenoalkyl, up to 9 Identical or different halogen 15 atoms, and furthermore represents cycloalkyl which ^_) has 3 to 7 carbon atoms and is optionally mono- substituted or poIysubst1tuted by identical or different substituents from amongst halogen, lower alkyl or lower halogenoalkyl, and represents 20 phenyl, phenoxy, phenylthio or phenylamino, each of which 1s optionally monosubstituted or polysub-stituted by identical or different substituents, suitable phenyl substituents being those stated in the case of R^; R1* represents amino, and alkyl, alkylamino, dialkylamino or halogenoalkyl, each of which 1s straight-cha1n or branched and each of which has up to 4 carbon atoms in the individual alkyl parts and, in the case of halogenoalkyl, up to 9 iden-[ 'v_/ 30 tical or different halogen atoms, X represents oxygen or sulphur and n represents the number 0, 1 or 2.

Particularly preferred compounds of the formula (I) are those in which: W 35 R^ represents hydrogen, nitroso, nitro, fluorine, chlorine, bromine, aiethyl, ethyl, n- and i-propyl, n-, i, s- and t-butyl, tr1fIuoromethyI, or phenyl ^1199 which is optionally monosubst1tuted to trisubsti-tuted by Identical or different substituents from amongst fluorine, chlorine, bromine, nitro, methyl, ethyl, methoxy and t r 1 f luor one t hy I, or represents one of the radicals 0 0 R™ -S(0>n-R9 ; -C-R10 ; -PCOR11)* °r -C«N-0R11 X 7 I 4 R represents hydrogen or a radical -C-Rlc R Independently of Rfc represents the same radicals as R2 and additionally represents ■ethyl, ethyl, n- and 1-propyl, n-, 1-, s- and t-but yI, R* and independently of one another represent cyano, nitro, fluorine, chlorine, bromine, iodine, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methoxycarbonyI, ethoxy-carbonyl, tr1fIuoromethyI, trichloromethyl, di-ch lorof luoromethy I, difIuorochloromethyI, chloro-methyl, dichloromethyI, d1fIuoronethyI, penta-fluoroethyl, tetrafluoroethy I, tr1fluoroch loro-ethyl, tr1fIuoroethyI, difluorodichloroethyI, tri-f luorodichloroethyl, pentachloroethy I, trifluoro-■ethoxy, trichloromethoxy, dichlorof luoromethoxy, d1fLuorochloromethoxy, chloromethoxy, dichloro-methoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluorochloroethoxy, tri-fluoroethoxy, dif luorodichloroethoxy, trifluoro-dichloroethoxy, pentachloroethoxy or a radical -S(0>n-R12, and r^, r7 and R® independently of one another and of R* and R^ represent the same radicals as R* and R^ and additionally represent hydrogen, and A R represents hydrogen, hydroxyl, fluorine, chlorine, bromine, amino, methyI amino, dimethyl- 221199 amino, ethylamlno, diethylamino, diiaopropylamino, di-butylamino, methyl, ethyl, dichlorofluoromethyl or tri fJuoromethyl, and repreaenta phenyl which is optionally substituted to trisubstltuted by Identical or different substituents from amongst methyl, methoxy, tr1fluoromethyl and chlorine, R^® represents hydrogen, methyl, ethyl, n- and 1-propyl, and represents phenyl which 1s optionally monosubst1tuted to tr 1 subst11uted by Identical or different substituents from amongst methyl, methoxy, tr 1 f luoromethyI and chlorine, represents hydrogen, methyl, ethyl, n- and 1-propyl, n-, 1-, a- and t-butyl, alkyl, butenyl, propargyl, benzyl, chloroethyl or bromoethyl, R12 represents hydrogen, methyl, ethyl, n- and i-propyl, undecyl, vinyl, sllyl, propargyl, butenyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methyl-thlomethyl, methoxy, ethoxy, methylthlo, ethylthlo, methylamlno, ethylamlno, d1nethylam1no, diethyl-amino, trifluoromethyl, trich loroethyI, dichloro-fluoroethyl, difluorochloroethyl, chloromethyI, iodo-methyl, bromomethyl, dichloromethyl, 1-chloroethyl, 2-chloroethyl, 2-bromoethyl, chloropropyl or heptafluoro n-propyl, or represents cyclopentyl, cyclohexyl or cyclopropyl which is optionally monosubst1 tuted to tetrasubstituted by Identical or different substituents from amongst fluorine, chlorine, bromine, methyl and tr1fluoromethyI, and represents phenyl, phenoxy, phenylthio or phenylamino, each of which 15 optionally monosubstituted to trisub-stituted by identical or different substituents from amongst methyl, methoxy, chlorine and tri-fluoromethyI, R1' represents amino, methyI amino, ethylamino, dimethylamlno, diethylamino, fluorodichloromethyI, difluoromethyl, tetrafluoroethyl, tr1fluorochIoro- ■WH-. c^ ??1199 ethyl, tr1fluoromethyl, methyl or ethyl, X represents oxygen or sulphur, and n represents the number 0, 1 or 2.

In addition to the compounds mentioned 1n the pre* parttlon examples, the following 5-a»1no-1-phenyl-pyr-azoles of the general formula (I) may be «ent1oned 1ndi-vlduaIly : J Table 1 nC r' (2) r1 R* *3 R* r5 R6 r' r8 M ch3co h ci h ci h h h chjco ch3co ci h ci h h m ch3c0 h ci h ci h ci h ch3co chj ci h ' ci h ci H ch3co k mo2 H no2 h h H h h ci H "3 H ci H ch3co K ci H ocf3 H H h c;h5c0 h "3 h scfj h h H c2h5c0 H ci ci ci h H M h h ci ci ci H H H ch3co ch3co ci ci ci h h m ch3co c2h5co ci ci ci m h Table 1 (continued) i1 i* •v *5 ** «« H CjHjCO H CI H "3 H CI M CHjCO H CI H »3 H CI ..CO H IX M H CI H "3 H CI H CH3OCO H CI H "3 H CI H n-CjH7C0 H CI H "3 H CI H CH3CO CH3CO CI H "3 H CI M C2H5C0 H CI H OCf3 H H H \X H H CI H 0CF3 N H H n-C«H9-C0 H CI H OCF3 H H H C2H5CO H CI H scf3 H CI H n-CSH7CO M CI H scf, H CI . CO " Cx H H CI H SCF3 M CI H CH3CO H CI H scf3 H CI H CH3OCO H CL H scf3 N CI H CH3OCO H CI H OCF3 H H H C2H5CO H CI CI CI H CI H CH3CO H CI CI CI H CI H CH3CO H CI CI CI H H . CO H IX H H CI CI CI H CI H CK3OCO H CI CI CI H CI H CH3CO H CI CI cf3 H CI H C2H5CO H CI CI "3 H CI H n-C3H7C0 ^ CO H tx H H H CI CI CI CI "3 "3 H H CI CI M CHjOCO H CI CI "3 H CI n * -A CJ o Table 1 (continued) <! 119 9 ft' ft' ft} ft* ft* ft6 ft' h -co-nnchj N ci cl cl m n h -to-nhchj h ci h CFj n cl m ch jco h c i cl scf5 h h h chjco h r f ocf3 m f h c2h5c0 CH3CO f f OCF3 f f ci h h cl cl cl h h ci h h cl h cl h h ci h h cl h tr3 h cl cl h h cl h SCFj h cl ci chjco h cl cl cl h h ci chjco h cl cl OCF3 h h ci CHjCO chj cl cl SCF3 h h ci c2h5co h f f OCF3 f f ci c2h5c0 h Br h s c f 3 h h ci c2h5co h cl N SCF3 h cl ci c2hsco CH3CO cl cl sc f 3 h h ci CHjco CH3CO cl cl cl h h ci CH3CO c2h5c0 cl cl cl h h ci -co'nhchj h cl cl OCF3 h h ci -c0-0c2h5 N Br h OCF3 h Br ci -co-c4h5 h n02 h n02 h n02 ci -co-crs n ND2 h w02 h n Br ch3c0 h cl cl cl h h Br chsocm2co h c i h cl h cl Br ch35ch2- co h no2 h no2 N h Br CH3CO CH3CO cl cl Cf3 h h Br c2h5c0 CH3CO cl h CFS h cl Br CHjco h cl h OCF3 h cl Br a—co- h f h 0CF3 h f Br nyh ^ co- h f f 0CF3 h f ci ^cl Br -10 h f f scf3 w f rs o o -Ma,. able 1 (continued) < i i 5 9 ft* *« ft5 ft6 ft* ft* M H f H »CFS *4 f c2h5co N cl H cl H cl cl«®-co- H cl h cl M H chjo^^co- H cl cl cl H h chjco chj cl h so2cf3 H c i f jtco H cl H socf3 H c i cicn2co H "3 H C'3 H Cf3 cl2chco K "3 H S02CFj H ^3 N H cl cl cl H h N H cl h cl X cl H H CL H c fl H cl CHjCO h CL cl cl H h CHjCO h cl h C'3 h cl CHjCO chjco c i h ocf3 h cl ch3co CHjCO CF5 h s c f 3 h cfj c2h5co h CFS h s c f 3 h h c2h5co ch3co Br h cf3 h Br c2h5co chj cl cl cl h h C^HjCO h f f ocf3 f f cl-@»C0- h cl h ocf3 h cl f3c-co h f h ocf3 h f cich2co h cl h scf3 h cl ci2ch-co h cl h s02cf3 h cl CHJ-ch-cc 1 cl h tXc > h f f so2cf3 f f h cl cl cl h H H h cl h cl H cl J « h W02 h W02 H NO2 « • • « - • o ^1199 Table 1 (continued) 0 O u O «1 o ft« ft* ft* ft* ft* CFj CHjCO N Cl H CFj M Cl "3 CHjCO H Cl H OC f j H Cl CF3 CHjCO CHj Cl Cl CFj H H "3 CHjCO CHjCO Cl Cl Cl H H CFS C2H5C0 N Cl H SCFj M Cl "3 CjHJCO H F F SCFj H F «3 c2h5co 1 CHjCO F F OCFj F F "3 m6h5co H Cl Cl SCFj Cl Cl CFj CHJNHCO H Cl h S02CHJ H Cl CF3 ci«®-co- m Cl h so2cf3 H Cl CFj CHjD-^>-CO h Cl cl Cl h h CFj ci-^Vco- h Cl H Cl h Cl Cl h CFj [X H Cl Cl Cl CO- CF3 C5H5OCO H CF3 H cf3 H H cf3 C2H5OCO H Cl H CFj H Cl no2 N H Cl Cl Cl H H no2 H H Cl F Cl H Cl no2 N H CL H CF3 H Cl K02 H H CL « OCF3 H Cl NO2 N H Cl H SCF3 H Cl no2 CHjCO H Cl Cl Cl N H no2 CH2C0 H Cl H CF3 H Cl no2 CH3CO H cf3 H .

CF3 N CFj no2 CHjCO CH3CO CF3 H cf3 H H no2 CH3CO CH3CO Cl Cl Cl H H HO 2 CHjCO ch3 Cl H Cl H CL N02 CH3CO ch3 cf3 H CFj H H no2 C2HsCO H Cl H Cl H Cl no2 c2h5co CH3CO Cl Cl Cl H H NO 2 C3H5CO N F F F F F W02 C2HjCO H F F CFS F F mmttii. www' ^ J?"' - 2i: 1199 Table 1 (continued) T■ t* T> w> no; cjhjco N cl cl cl h h n02 C4H5CO h cl h cl n h no2 CHjNHCO h cl cl cl m m no 2 CHjNHCO ch3 cl h cl n cl no £ c6h5co h cl cl cl cl cl n0? cl«®-co N f f f f f no2 CI-0-co h f h cf3 h f no 2 chjo-0-co h cl h h cl no ^ c2h5o-co h cl cl cfj h h no 2 c2h50-c0 h cl h OCFj h cl no 2 C^hjo-co h cl h ocfj h h no 2 C6Hj0-c0 h cl cl cl N h no; h X co m cl h S02CHj h cl no2 h Ko h cl h S02CFj h cl no 2 ch3och2co h cl cl cl h h no2 cich2co- h Cl h cl h h no 2 ci2chco h Cl N cl h Cl no2 ci2chco N cl h cfj h cl MO h h cl cl cl h h no h N cl h cl w cl no h h Cl h cfj h Cl no CHjCO h Cl cl Cl h h no CHjCO h Cl h cl h Cl no CHjCO h Cl h cfj h cl no CHjCO CHjCO Cl h OCFj h cl no CHjCO chj cl Cl cf5 cl cl no CHjCO C2H5CO f h OCFj h f no c2h5co m f f OCFj f f MO c2h5co h f f f f f 221199 u J*1bL' 1 ttcpnt<nu*j^ NO ClCH2CO H Cl H S02CHj H Cl NO Cl2CHCO H Cl H S02CFj H Cl NO CFjCO H Cl Cl S02CFj H H NO CHjNHCO H Cl M Cl H H NO C2H5OCO H Cl Cl Cl H H NO CFjCO H Cl Cl Cl H H NO C5H5CO H Cl Cl Cl H H H-CO- H H Cl Cl Cl H H H-CO- H H Cl H Cl H Cl H-CO- H H CL H H Cl H-CO- CHjCO H Cl H "3 H Cl H-CO- CHjCO H Cl H OCFj H Cl H-CO- CHjCO H Cl H SCFj H Cl H-CO- CHjCO CHj Cl Cl Cl H Cl H-CO- CHjCO CHj Cl H cf3 H Cl H-CO- C2HSC0 H Cl Cl Cl H H H-CO- C2H5CO H Cl H Cl H Cl H-CO- C2H5C0 CHjCO Cl CL Cl H Cl H-CO- CHjCO CHjCO Cl H cf3 H Cl H-CO- C2H50-C0 H Cl H "J H H H-CO- C2H50C0 H r H cfj H F ^ H H-CO-[>^ H Cl Cl Cl H H h-CO- C6H5C0 H Cl H Cl H Cl h-CO- C6H50C0 H F f f F F CHj-CO H H no2 H ' no2 H H CHj-CO H H NO2 H "3 H H CHj-CO CHjCO H Cl CL CL H H CHj-CO CHjCO H Cl h Cl H Cl CHj-CO CHjCO CHjCO Cl h Cl H h CHj-CO C2H5C0 H Cl H "3 H H CHj-CO C2H5C0 H Cl h "3 h Cl CHj-CO C2H5C0 H Cl Cl Cl h H >21199 Teble 1 (continued) I' I' I SJ ch3-co- CF3CO h Cl h Cl h Cl CHj-CO- CF3CO M Cl h "3 h h chj-co- cichgco N Cl h OCF3 M Cl ch3-co- ch3och2co h Cl h ocfj H Cl CH3-CO- ch3scm?c0 h Cl h SCFj h Cl CH3-GO- ci2chco h f h SCF3 h f CH3-CO- ci2chco h f H 502CF5 h f CH3-CO- CH3-chc0 1 r 1 H f H 502cf3 H f CH3-CO- m I Br-CH2C0 h f f f f f MD-NeCM- h H Cl h Cl h h HO-mch- h N Cl h "3 h H MO-N=CH- h H Cl cl Cl M h HO-N=ch- h h f f f f f H0-N=ch- CH3CO h Cl Cl Cl H h HO-MCH- CH3CO h Cl h Cl H cl H0-N=CH- C2h5c0 h Cl h cf3 h Cl HO-N=ch- c2hsco h Cl H Cl h h w0-n=ch- c2h5co c2h5co Cl h OCF3 h cl H0-N=ch- CH3C0 CH3CO Cl h OCF3 h cl ho-n»ch- •CF3CO CF3CO Cl M SCF3 h Cl ho-n=ch- CF3CO H Cl H OCH3 h Cl h0-n=ch- cich2co H Cl H SCH3 h Cl ho-n=ch- ci2chco h Cl H soJchJ H cl «0-n=ch- ch30ch2c0 H cl H SO^CHj H cl m0-n=ch- ch3och2co h Cl H S02CF3 H Cl ho-n=ch- ch3sch2c0 H Cl Cl cl H h chjo-n=ch- - H H h "3 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 F ch3d-n=ch- - CH3CO h cl H Cl H Cl ch3o-k=ch- - ch3co H Cl H Cl H H •*WW!8P98^®^ 221199 Table 1 (continued) a1 0 o chjo-n=CH - c2h5co h cl cl cl h h chjo-n*ch - c2h50 h cfs h «3 w m ch3o-wch - c2h5co h "3 h "3 w ch3o-n=ch - CFjCO m cl h h h CHjo-n=ch- - c4h5C0 h cl H cf3 M cl chjo-n*ch - cich2co h cl h ocfj H cl chjo-n*ch- - 1CH2C0 h cl cl cl h h chjo-n=ch - BrCH2C0 h F F F F F CHjD-nbch" - c2H5OCO h cl h OCF3 h h chjo-n=ch- - CHjCO CH3 cl h SCF3 h cl c«jo-n*ch- - CHjCO h cl h «3 h cl ch3o-n=ch - c2h5co h cl h "j h cl h2ns02- h h «3 n "3 h h h2nso2- h m cl h cl h cl h2nso2- h h cl h cl h n hjns02 - CHjCO h cl cl cl h cl m2ns02- CHjCO h F F F F F h2nso2- CH3CO h F F "3 F F h2nso2- c2n5c0 h F F ocfj F F h2nso2- c2n5co h F F SCFj F F h2nso2- c2m5co h cl h OCFj H cl h2n502- CHjCO CHjCO cl h scf3 h cl h2nso2- ch3co CHj cl h SOCF3 h CL H2N502- clch2c0 h cl h so2cf3 h cl h2nso2- BrCH2C0 h cl h s02ch3 N h h2nso2- 2ch2co H cl h so2cf5 h H «2nso2- c6h5co N cl h "3 h cl h2nsd2- c2h5co N Cl h "3 H H «2nso2- CFjCO N cl cl cl h h o 221199 Table 1 (continued) ft) n H C2H5CO M Cl H ocf3 H Cl H CHjCO H Cl H OCFj H Cl H N Cl H ocf3 H H n-C3HrC0 H Cl N ocf3 N Cl H CHjOCO N Cl H ocf3 H Cl H CHjOCO H Cl H S02CH3 H Cl H ch3co H Cl H S02CHj H Cl H C2H5C0 m cl H so2cf3 H Cl H H cl H so2ch3 H Cl H n-CjHyCO H cl H S02CF3 H cl H rr-CjH/CO h cl H so2ccif2 H cl H ch3co h cl H so2ccif2 H Cl H c2h5co H cl H so2ccif2 H Cl H ch3co H Br H ocf3 H Br H c2H5C0 h Br h ocf3 h H H n^CsH/CO H Br h ocf3 H H H x° h Br H ocf3 h h H ch30c0 h Br H OCFs H H N ch3c0 H Br h scf3 H Br H ch3c0 h Br H scf3 H H H c2H5C0 H Br H scf3 H H m •l-CjHyCO h Br H 5cf3 H H w c2H5CO H Cl N H H Cl « c2h5co H Br h Br H Br w c2h$co h Cl H Cl H h m c2h5co H Br h Br h h no c2h5co h Cl h cfj h Cl no ch3co H Cl n cf5 h Cl no t>? h Cl h cfj h Cl "21199 Ttble 1 (continued) ft1 t* a .O w Q MO CHjOCO M NO n-CjHyCO H NO CHjCO CH3C NO C?HSC0 N NO V xAn o H NO n-C^^CO H NO C?HSC0 H NO n-CjHyCO H NO o Y H NO CHjCO H NO CHjOCC H NO CH3OCC H NO C2H5CO H NO CM3CO H NO CH3CO H NO 1^ C0 K H NO CH3OCO N NO CH3CO N NO c2hsco H NO n-C3H7C0 N NO . CO tx H H NO CH3OCO H NO c2H5C0 H NO CH3CO H NO . CO X M h NO rr-CsB/CO N H cfJ N Cl M "J H Cl H cf3 H Cl N OCFj H H H ocf3 H H H OCFj H H H SCFj H Cl H SCF3 H Cl N $CFS N Cl H SCFj H Cl H SCFj H Cl H ocf3 H Cl Cl H Cl Cl Cl H Cl Cl Cl H Cl Cl H Cl Cl Cl H Cl Cl cfJ H Cl Cl cfs N Cl Cl cf3 H Cl Cl t cf3 H Cl Cl "J H Cl H OCFj H Cl H OCFj H Cl H ocf3 H Cl H ocf3 H Cl Wiemvs :' n 1199 Table 1 (continued) • ' • * I 'c: vj O NO NO CHjOCO CHjOCO M H cl cl H H OCFj so2cf3 M N cl cl NO CHjCO H cl H *02CFj H cl NO C2HSCO H cl H S02CF3 N cl NO . co tx H H cl H S02CF3 H cl NO n-CjHyCO H cl H so2cf3 H cl NO n-CjH/CO H cl H so2ccif2 H cl NO CHjCO H cl H so2ccif2 H cl NO C2H5CO H cl H so2ccif2 H cl NO CHjCO H Br H OCFj H Br NO C2H5CO H Br H OCFj H H NO n-CjH7CO H Br H ocf5 H H NO ^ C0 H Br H OCFj H H NO CHjOCO H Br H OCFj H H NO CHjCO M Br N SCFj H Br NO CHjCO N Br H SCFj H Br NO C2H5CO H Br H scf3 H H NO n-C3H7C0 H Br H SCFj H M NO C2H5CO h cl *4 H H cl NO c2h5co H Br N Br H Br NO c2h5co h cl H cl H H NO C2HsC0 h Br H Br h H NO 2 c2h5co h cl H ocf3 H cl HO 2 HO 2 o o u o, ,x h h cl cl N H OCFj ocf3 H h cl cl NO; n-C3H7C0 H cl H ocf3 H cl N02 CHjOCO H cl H ocf3 H cl no2 CHjOCO h cl H so2cf3 H cl no2 CHjCO h cl H so2cf3 H cl no 2 c2h5co H cl H so2cf3 H cl _ A 21199 Table 1 (continued) O' o ftl ft' NO; **T H I H SO;CFj H Cl NO; n-C5H7C0 H I M SO;CFj N Cl NO; n-CjHyCO H I H SO;CClF; H Cl NO; CH3CO H I H SO;CCIF; H Cl NO; C;HjCO M I M SO;CClF; H Cl NO; CH3CO H r H OCF3 H Br C;H5CO H r H OCF3 H H NO; n-C5H7C0 h r N OCF3 H H NO; ^ C0 * M r H OCF3 H h NO; CH3OCO h r H OCF3 H H NO; C«3C0 h r H SCF3 H Br NO; CH3CO h r H SCF3 H H NO; C;HjCO h r H SCF3 H H NO; n-C3H7C0 H r H SCF3 H H NO; C;HjCO H I H H H Cl NO; C;H5CO H r H Br H Br NO; C;H5CO H I H Cl H H NO; C;H5CO H r H Br H H NO; C;HSCO H I H CFj H Cl NO; NO; CHjCO ^ C0 K H H I M I H CF3 CF3 H H CL Cl NO; CH3OCO H I H CF3 H cl NO; n-CsH7C0 H i h CFJ H cl NO; CH3CO CH3CO i h ' CFj H cl NO; C;HjCO H I H OCFj H H NO; . CO tx H H I H OCF3 H N NO; n-C^HjCO H I H OCFj H H NO; C;HjCO h I H SCF3 h Cl NO; n-C5H7C0 h I H SCFj h Cl o c o o * 1 1 o o o o o O O O O O © o o o o o o o © o O o o n o n n n o n n n n N w to to to to to to to to to X X X X X X X X X X X K* w w w ss \*0 w vifi v A ^ A i V) X OS o <o O n O o o o 3 rt n n » I ** Inn Z Id U r» v» r» X O r» o o n O © r» O n n I x N w tt X o O v» n r» O o O O O X X XXX w w O ci o n -n -»» -n W U M O o o r> r» r» n ■»» ■»» ■w -n U U U u u r» n o -»i U M ID XXX XX r» o x r» n r* (7 * zxzz * ******* O OOOO O OOOOOO o rj M N nt N N *» •» N M N *1 T7 j n n n \7 n n n o n n \ / Y 1 N I I x t I N III V A n x k u T xn w w z u w u x^ r§ C n Vi vi n O o n n w o O o o O I n O n o O o n n O n o O O o O X X XXX I* www rt O i* « r» n n n -n -n ^ W M M X X X X n r» n r» o n j n n J « n JJ i - fo u rv mmi mnwrTETT ■' © Table 1 (continued) 221199 o r0(0C2H5)2 CHjCO M CL H JCF, M Cl rO(OC2H5>2 CHjOCO M CL H SCF, •4 Cl r0(0C2M5)2 CHjOCO N Cl M OCFj •4 H rDC0C2h5>2 C2H5CO H Cl Cl Cl •4 Cl f0(0C2H5)2 CHjCO H Cl Cl Cl H H r0(0C2H5>2 CKjCO H Cl Cl Cl H H P0(0C2H5>2 XC° H H Cl Cl Cl H Cl PO(OC2H5)2 CHjCO H Cl Cl Cl M Cl P0(0C?HS)2 CHjCO H Cl Cl CFj H Cl p0(0c?h5)2 C2H5CO H Cl Cl cfj M Cl fo(OC?H5)2 •CjHyCO H Cl Cl CFj M CL P0(0C2H5)2 tx" H H Cl Cl CFj H Cl fococ2h5>2 c2H5co H Cl Cl CFj H Cl P0(0C2H5>2 c2hsco H Cl H OCFj H Cl P0(0c2h5)2 CHjCO Cl Cl H OCFj H Cl PO(OC2H5)2 txco ^ M M CL H OCFj H Cl r0(0C2H5)2 n-CjHyCO H Cl H OCFj H Cl rococ2H5)2 CHjOCO H Cl H OCFj H Cl r0(0C2H5)2 CHjOCO H Cl H SOJCFj H Cl P0(0C2H5)2 CHjCO H Cl H S02cfj M Cl F0(0C2H5>2 c2h5co H Cl H S02CFj H Cl poco:2h5)2 . co IX H H Cl H SOjCFj H Cl rO(OC2«5)2 ffCjHyCO H Cl H S02Cfj H Cl P0(0C2H5>2 fr-cjhyco H Cl H so2ccif2 H Cl PO(OC2«5>2 CHjCO H Cl H SO2CCIF2 H Cl PO(OC2H5>2 C2H5C0 H Cl H so2ccif2 H Cl P0(0c2hs)2 CHjCO H •r M OCFj 14 Br G O o €) o o o xzx 'V 1 1 * •» ■» ■» * o o o o o Q o o o o o o »-> *■> o o o o o O o o o o o o r» #— n n n r-* n n n n n r-t ry n N N N N 1S» ra M N IV M hi fa X X X X X X X X X X X X Ut V* \j* u» u> w w V* V* w w w w w w 3 1 n n M X n 7 r> w X n X w =? n n X u ,3? n X u o fv X f> n r> n 3 n « r» O 3 n M V* 'N V* r> M o X n n t* ** 1 M X X X v-j 1 A# X n X X r» o O X n o O n r X X X X u u w v n z O « a o -«* O O V V Vt v* W Vi n o o X u vt r» r» n n o O n X n O O n A X O O O 9 o O o o O i i n X o rt r» O O O X w X X X X X n o X X X X X X X X X X X X X X X X X XX X XXX X X X X X X X X X o o o www XXX •n ti-w-n -n -n W W W W WW W WWW W W «*•*«» O O O O -n ■« -»» ■»» W W W W W WW X XXX x x X o XXXXXXXXXXX X X X X T X er * o 3 J c <• a. w Si u> : . K>; <o o 1199 Table 1 (continued) : i U CJ CMjtO H Cl Cl Cl M H * H Cl Cl Cl H Cl CHjOCO H Cl Cl Cl M Cl CHjCO H Cl Cl "3 H Cl C2HsC0 H Cl Cl "3 H Cl n-CjH7C0 H Cl Cl "3 H Cl txT H H Cl Cl Cf3 H Cl CHjOCO H Cl cl «3 H cl c2h5co H cl H ocf3 H cl CHjCO H cl H OCFj H cl H H cl H ocf3 H cl n-C3H7C0 H cl H ocf3 H cl ch3oco H cl H ocf3 H cl CHjOCO H cl H S02CFj H cl ch3co H cl H s£>2cf3 H cl C2H5CO H cl H so2cf3 H cl - CO IX H H cl H S02CFj H cl n-CsH7CO H cl H so2cf3 H cl n-C3H7CO H cl H so2ccif2 H cl CHjCO H cl H so2ccif2 H cl C2H5CO H cl H so2ccif2 H cl CH3CO H Br H ocf3 H Br C2H5CO H Br H ocf3 H H n-C3H7C0 H Br H OCFj H H Kt0 H H Br > H ocf3 H H CHjOCO H Br H OCFj H H '21199 Table 1 (continued) n w It cl CHjCO M Br M «CFj M Br cl CHjCO M Br M SCFj M H cl C2H5CO M Br H SCFj H H cl n-C3H7CO H Br M SCFj M H cl c2H5C0 M cl M M M cl cl c2H5C0 M Br M Br M Br cl c2h5co H cl M cl H H cl c2h5co H Br H Br H M H M-co- H cl M cl M cl H M-CO- H cl cl cl H H H M-co- H cl H ocf3 M cl H M-CO- H cl M SCFj H cl H H-CO- H cl M OCFj H h H H-CO- H cl H "5 H cl H M-CO- H Br M Br H Br H M-CO- H cl H Br H cl H H-CO- H cl H S02CFj h h H M-CO- H cl H so2cf3 H cl no2 h-co- H cl N cl H cl no2 M-co- H cl cl cl H M no2 h-co- H cl H OCFj H cl NO 2 h-co- H cl H ocf3 H M n02 H-CO- n cl H SCFj H cl no2 H-CO- H cl H SCFj h M no2 h-co- H cl K so2cf3 M h no2 n-cd- n cl H so2cf3 M cl no2 m-co- h Br N Br H Br NO 2 h-co- M cl H Br H cl n02 H-CO- H cl H Br N Br no 2 H-CO- M Br H ocf3 n Br NO 2 H-CO- H Br H ocf3 H H no2 H-CO M Br H scf3 H Br NO 2 M-CO- H X H ocf3 M M r* o o 221199 Table 1 (continued) •* no2 CHjCO H Cl H Cl n Cl no2 CHjCO H Cl Cl Cl H H no2 CHjCO H Cl W ocf3 H Cl no2 CHjCO H Br H Br H Br no 2 CHjCO H Cl H Br H Cl no 2 CHjCO n Cl H Br M Br n02 CHjCO N Br H Cl H Cl no2 CHjCO H Br H ocf3 H M no2 CHjCO H Br H ocf3 n Br no2 CH3co H Br H SCFj H H no 2 CH3CO H Br H SCFj n Br n02 ch3co H Br H S02CHj H H no2 ch3co H Br H s02cfj H Br wo 2 ch3co N Br H 502cf3ci H H no2 ch3co H Br H S02CF2CI H Br no2 ch3co H Cl H OCF2CI H H no2 ch3co H Cl H OCF2CHF2 H Cl no2 ch3co H Cl H OCHF2 H H nd2 ch3co H Cl H OCHF2 H Cl no2 CHjCO H Cl H OCH2CF3 H H no2 ch3co H Cl H och2cf3 H Cl no2 CH3CO H Br H och2cfs H M no2 ch3co H Br H OCH2CFs H Br no2 ch3co H Br H CFj H H no2 ch3co H Br H "3 H Br no2 C2H5CO H Cl H OCHF2 H Cl no2 C2H5CO H Cl H ochf2 H N no2 c2h5co H Cl H ocf2chf2 H H no2 c2h5co H Cl H ocf2chf2 H Cl no2 c2h5co H Cl H chf2 H H no2 c2h5co h Cl H chf2 H Cl no2 c2h5co h Cl K ocf2chfci H H no2 c2h5co h Cl H ocf2chfci H Cl no2 c2h5co H Cl H Br H Cl 221199 Some of the substituted 5-am1no-1-phenyIpyrazo I es of the formula (I) which are to be used according to the Invention are known (see: J.Org.Chen. 3^,2972-2974 C19713; J.Heterocycl.Chem. 7, 345-349 M9703 and C.A. 62: 13137c).

Substituted 5-am1no-1-phenyl-pyrazoles which were hitherto unknown are those of the formula (I*> (i') 1n which R1, R2, R3, R4, R5, R6, R7 and R8 have 10 the meaning given above, except that, when R^ represents hydrogen, methyl or optionally substituted phenyl, R* and R^ cannot simultaneously represent the nitro group.

The hitherto unknown substituted 5-anil no-1 -pheny l-15 pyrazoles of the formula (I1) are obtained if a) phenylhydrazines of the formula (II) R* r6~"^^"NH"NH2 (11> 7 v .

R7 R® 1n which R4, R*, R^, R7 and R® have the meaning given 20 above, are reacted with aery lonitrile derivatives of the formula (III) ^CN A-CH*CV^ (111) ?s o In which A represent* halogen, hydroxyl or alkoxy, :he case In which R^ represents hydroge 5 2-halogenoacryloni tr11es of the formula (Ilia) 221199 R^ has the aieanlng given above and e or, 1n the case In which R^ represents hydrogen, also with CH2«C (Ilia) ^Hal 1n which Hal represents halogen, 1n particular chlorine or b rom ine, or with 2,3-dihalogenopropionitr11es of the fornula (Illb) ^ CN Ha I -CHj-CH CHIb) Hal • 1n which Hal' represents halogen, in particular chlorine or bromine, the reaction either being carried out to give the phenyl-hydrazine derivatives of the formula (IV) R 5 *4 \0/"* NH - NH - 2 (IV) (new substances) R« in which R*, R*, R^, R7 and R® have the neaning given under fornula (I*) and -CH*C"""""' , -CH>-CH"*^^N >Sv*1 ^ Ha I 2 represents one of the radicals or -CH^-CH wherein Hal and Hal1 represent ^ Hal • r* o 221199 Identical or different halogen atoms, In a first stage. If appropriate In the presence of a diluent and, If appropriate 1n the presence of a reaction auxiliary, and the product being subjected to a cycllsa-5 tion reaction 1n a second stage, 1f appropriate 1n the presence of a diluent and. If appropriate, 1n the presence of an acid-binding agent, or cyclisation being carried out directly 1n one reaction step without isolation of the Intermediate of the formula (IV), if appropriate 1n the 10 presence of a diluent, to give the 5-amino-pyrazoles of C" the formula (la) (la) In which R^ , R*, R^, R^, R7 and R® have the meaning 15 given above, or if (b) the 5-amino-pyrazoles of the formula (la) (la) R6 in which R1, R*, R*, R6, R7 and R® 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 (V) o - 32 -I14 - A• (V) 221199 1n which R^4 represent* alkyl or a radical -l!-R^, wherein 1 2 X and R have the above Meaning, and 5 A* represents an electron-attracting leaving group, or with 1so(th1o)cyanates of the formula (VI) r15 - N « C ■ X (VI) 1n wh i ch R^® represents alkyl or optionally substituted 10 aryl and X has the above meaning, 1f appropriate In the presence of a diluent and. If appropriate 1n the presence of an acid-binding agent, to give the 5-ai»1no-pyrazoles alkylated or acylated at the ritro- gen, of the fornula (Zb) 1 K jJ - N^r3, ! rb>^ R7 (lb) R6 In which R^, R^, R4, R^, R^, r7 #n(j p8 have the above neaning and 20 R3' represents the sane radicals as R3 given above, with the exception of the hydrogen radical, or 1 f (c) the 5-amino-pyrazoles of the formula (Ic) im (Ic) 221199 In which R*, R3, R*, R5, R6, R7 and R8 have the ■bove Meaning, which are unsubst1tuted 1n the ^-position and are obtain-5 able by process (a) or (b), are substituted 1n the 4-pos1 tlon, likewise 1n a generally customary Manner, using eIectroph1 11 c agents of the formula (VII) R1' - E (VII) In wh1ch R^ " represents halogen, nitroso, nitro, alkyl, formyl, alkanoyl, aroyl, hydroxysulphonyI or chlorosulphonyl and E represents an electron-attracting leaving group Ing, or using other customary electroph111c reagents, 1f appropriate in the presence of a diluent and, if appropriate in the presence of a catalyst or a reaction auxiliary, or if (d) the 4-chlorosu Iphonyl-5-amino-pyrazo I es obtain- able by process (c) of the formula (Id) (Id) in whi ch R^, r'/ r*, r5# r6^ r7 an£j r8 have the above meaning, are substituted at the chlorosul* 15 phonyl group in the 4-posit1on, using amines of the formula (VIII) R16 H - (VIII) * •© 221199 in which F^' and F^ 7 Independently of one another represent hydrogen or alkyl, or using an alkali netal fluoride of the fornula (IX) n& (z) (ix) 1n wh1ch represents an alkali Metal cation, 1f appropriate 1n the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, or if \L (e) the 4-acy l-5-amino-pyrazoles of the formula (le) (le) in which R2, R3, R*, R5, R6, R7, R8 and R10 have 15 the above Meaning, which are obtainable by the process (c) or (f), are reacted with hydroxylanlne derivatives of the fornula (X) H2N - OR11 (X) in which R^ has the Meaning given above, or with their hydro-salts, 1f appropriate in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, or if (f) 4-cyano-5-am1no-pyrazoles of the fornula (XI) +) "hydro-salts" refer6 to hydrogen hBlide addition salts, such bs hydrochlorides (HC1 salts). 221199 (XI) in which R2, R5, Vic"' Meaning given above, •re reacted with fornic acid and Raney nickel to give the 5 corresponding 5-amino-4-fornyl-pyrazoles of the formula (If) (If) in wh i ch R2, R3, R4, R^, R^, R7 and R® have the 10 Meaning given above.

If, for exawple, 2-chloroacrylonitrile and 2,6-di-chloro-4-trifluoromethy l-phenyIhydrazine are used as starting Materials, the course of the reaction of preparation process (a) can be represented by the following equation: <g- Cl / CN - HCl cfj-0»-nh-nn2 ♦ ch = c, Cl Cl (base) Vj 221199 CFS If, for example, 5-amino-1-(2,4,6-tr1chloropheny I) ■ pyrazole and proplonyl chloride are used as starting Materials, the course of the reaction of preparation process (b) can be represented by the following equation: If, for example, 5-prop i onari i do-1 - (2,3,4-1 r 1 c h I or o-phenyI)-pyrazo le and nitric acid are used as starting materials, the course of the reaction of preparation process (c) can be represented by the following equation: fi j] NH-CO-C2H5 (8C„ I Cl Cl 4 HNOj -"2° (CHjC0>20 221199 If, for example, 5-acetoamido-4-chlorosulphonyl-1-(2,4,6-tr1chlorophenyl)-pyrazole and dlethylamine are used as starting materials, the course of the reaction of preparation process (d) can be represented by the following equation: s02-Cl rr~iT Cl 4 mn(c2h$)2 Cl - HCl kH (base) ,$0^*N( NH-CO-CHx t^T" Cl If, for example, 5-acetoamido-4-acety1-1-(penta-fluorophenyl)-pyrazole and 0-methyl-hydroxylamine hydrochloride are used as starting materials, the course of the reaction of preparation process (e) can be represented by the following equation: ^C0-CH3 f~TT NH-CO-CHj H2N - OCH3 x HCl -HCl/ -Hpg (base) {H, NrlC :4r: - .. 221199 I If, for example, 5-am1no-4-cyano-1**(2,3,4-tr1-chloropheny l)-pyrazole and formic acid are used as starting Material, and Raney nickel 1s used as a reducing agent, the course of the reaction of process Cf) accor-5 ding to the Invention can be represented by the following equat1on: rr~^CH 3 VN' NH 2 Cl Cl H-COOH Raney nickel O Formula (II) gives a general definition of the phenylhydrazines required as starting materials for carry-10 ing out preparation process (a) according to the invention. In this formula (II), R4, R^, R^, R7 and R® preferably represent those substituents which have aLready been mentioned in the description of the substances which can be used according to the Invention, of the formula 15 (1), as being preferred for these radicals.

The majority of the phenylhydrazines of the formula (II) are known or can be prepared by known processes in a simple, analogous manner (see: for example, Houben-Weyl "Hethoden der organischen Chemie" (Methods of organic 20 chemistry). Volume X,2, page 203, Thieme Verlag Stuttgart 1967) by, for example, reacting the known anilines of the formula (XII) R5 R* (XII) \ R7 R ® 221199 In which R4, R^, R®, R7 and R® have the Meaning given above, with sodium nitrite, in the presence of an acid, such as, 5 for example, sulphuric add, and then with t1n(II) chloride, likewise 1n the presence of an acid, such as, for example, hydrochloric add, at temperatures between -20°C and ♦80°C.

Formula (III) gives a general definition of the 10 acrylonltr 1 le derivatives furthermore required as starting materials for carrying out preparation process (a). In this formula (III), preferably represents those radicals which have already been mentioned In the description of the substances which can be used according to 15 the invention, of the formula (I), as being preferred for these substituents. A preferably represents chlorine or bromine, hydroxyl, methoxy or ethoxy. The acrylonitri le derivatives of the formula (III) are known (see: for example, US Patent Specification No 4472192, NZ Patent no 15 b 3 3 7; J.Chem.Soc. D 1970, 1255; Can.J.

Chem. 48, 2104-2109 (1970); J.HeterocycIic Chem. 19, 1267-1273 (1982); and Can.J.Chem. 51,, 1239-1244 C19733), or can be obtained by processes known from the literature in a simple analogous manner. The 2-halogeno-acrylonitr1 les 25 of the formula (Ilia) and the 2,3-dihalogeno-propioni-triles of the formula (Illb) are likewise known (see, for example, J.Prakt. Chemie 321, 93 C1979J; J. Heterocyclic Chem. 1265 [19823; and J. Heterocyclic Chem. 1_9, 1267 C19823).

Formula (la) gives a general definition of the -am1no-pyrazoles required as starting materials for carrying out preparation process (b). In this formula (la), R^, R4, R^, R^, R7 and R® preferably represent those radicals which have already been mentioned 35 1n the description of the substances which can be used according to the invention, of the formula (I), as being 221199 preferred for these radicals.

The 5-amlno-pyrazoles of the foraula (la) were hitherto unknown. They are obtained by preparation process (a) .

Formula (V) gives a general definition of the alkylating and acylating agents furthermore required as starting materials for carrying out preparation process 1 L (b). In this formula (V), R preferably represents a straight-chain or branched alkyl having up to 4 carbon atoms, and furthermore represents a radical -C , 1 2 wherein X and R" preferably represent those radicals which have already been mentioned for these radicals, in the description of the substances which can be used according to the invention, of the formula (1). k* preferably 15 represents chlorine, bromine or iodine, p-toIuenesuIphonyl-oxy, a IkoxysuIphonyloxy 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 20 1so(thio)cyanates which can alternatively be used as starting materials for carrying out preparation process (b). In this formula, X preferably represents oxygen or sulphur, and R^ preferably represents straight-chain or branched alkyl having up to 4 carbon atoms, or phenyl which 25 is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents 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 30 9 Identical or different halogen atoms. R^ represents, in particular, methyl or ethyl, or phenyl which is optionally monosubstituted to trlsubstituted by Identical or different substituents from amongst fluorine, chlorine, methyl, methoxy and trifluoromethyI.

The 1 so(th1o)cyanates of the formula (VI) are likewise generally known compounds of organic chemistry. o 221199 Formula (Ic) gives a general definition of the 5-amino-pyraroles required as starting Materials for carrying out preparation process (c). In this formula (Ic), R2, R5, R4, R5, R^, R7 and R® preferably 5 represent those radicals which have already been Mentioned In the description of the substances which can be used according to the invention, of the forMula (I), as being preferred for these substituents. The 5-amino-pyrazoles of the formula (Ic) were hitherto unknown. They are obtained 10 by preparation process (a) or (b).

Formula (VII) gives a general definition of the e lectroph1 Iic agents furthermore required as starting Materials for carrying out preparation process (c). In this formula (VII), R" preferably represents chlorine, 15 bromine, nitroso, nitro, hydroxysulphonyI or chlorosul-phonyl, formyl, and straight-chain or branched alkyl or alkanoyl, each having up to 6 carbon atoms, or represents benzoyl which 1s optionally monosubstituted or polysub-stituted by identical or different substituents, suitable 20 substituents being halogen, in particular fluorine, chlorine or 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 25 particular methyl, Methoxy or trifIuoromethy I. E preferably represents halogen, 1n particular chlorine or bromine, hydroxyl, alkyl- or aryIsuIphonyIoxy, alkanoyloxy or aroyloxy. Other eIectrophi 11 c reagents which can be used are sulphuryl chloride, phosphorus oxychloride/di-30 methylformamide, nitrating acid and other substances customarily used for eIectrophi11c substitutions. The electrophi11c agents of the formula (VII), like the other customary electrophi11c reagents, are generally known compounds. Formula (Id) gives a general definition of the 35 4-chlorosulphonyl-5-amino-pyrazoles required as starting materials for carrying out preparation process (d). In ! - ^ • - 42 - o 221199 th11 formul a (Id), R2, R3, R4, r5, r6, R7 and R® preferably represent those radicals which have already been Mentioned 1n the description of the substances which can be used according to the invention, of the formula 5 (1), being preferred for these substituents. The 4-ch lorosulphonyl-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 10 carrying out preparation process (d). In this formula (VIII), R^ and R^7 independently of one another preferably represent hydrogen or straight-chain or branched alkyl having up to 4 carbon atoms.

Formula (IX) gives a general definition of the ^ 15 alkali metal fluorides alternatively required as starting materials for carrying out preparation process (d) . In this formula (IX), 1^ preferably represents a sodium or potassium cation.

The amines of the formula (VIII), like the alkali 20 metal fluorides of the formula (IX), are generally known compound s.

Formula (le) gives a general definition of the 4-acyl-5-am1no-pyrazoles required as starting materials for carrying out preparation process (e). In this 25 formula (le), R2, R3, R4, R*, R^, R7, R® and R^® preferably represent those radicals which have already been mentioned in the description of the substances which can be used according to the invention of the formula (I) s as being preferred for these substituents. The 4-acyl- 5-am1no-pyrazoles of the formula (le) were hitherto unknown. They are obtained by preparation process (c) or (f).

Formula (X) gives a general definition of the hydroxylamine derivatives furthermore required as start-35 ing materials for carrying out preparation process (e). In this formula (X), R^ preferably represents those 43 - 221199 radicals which have already been Mentioned 1n the description of the substances which can be used according to the Invention, of the fornula (I), as being preferred for these substituents. The hydroxylamine derivatives of the formula (X) and their hydro-salts are generally known compounds.

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 for-D mula (XI), R2, R3, R4, R^, R^, R7 and R® preferably represent those radicals which have already been mentioned in the description of the substances which can be used according to the Invention, of the fornula (I), as being preferred for these substituents. Some of the 15 4-cyano-5-amino-pyrazoles of the formula (XI) are known (see, for example, European Patent 26,034; NZ Patent No 196337 European Patent 53,687; NZ Patent No 201281 and NZ Patent i:o 2C12G2) .

They are obtained, for example, 1n a manner analogous to preparation process (a), if phenylhydrazines of the forMula (II) I4 r6 v^y nh ~wH2 * cii) R7R8 1n which L e f a R , R , R' and R have the meaning given above, are reacted with the known ethoxymethylenemalodinitriles of the formula (XII) CN C^HjO - CH « C CXII) CN " O - hh - 221199 If approprlate In the presence of • diluent, such at, for example, ethanol, and, if appropriate, in the presence of an acid-binding agent, such as, for example, sodium acetate, at temperatures of between -20°C and +150°C. 5 Diluents which can be used for carrying out pre paration process (a) and are suitable for both the first and the second reaction stage are Inert organic solvents. Alcohols, such as methanol, ethanol, propanol, butanol, ethylene glycol or ethylene glycol monomethyl or ethyl 10 ether are preferably used.

Suitable reaction auxiliaries for carrying out the first stage of preparation process (a) are organic or Inorganic acids. Sulphuric acid or acetic acid, if appropriate also 1n 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 reaction temperatures can be varied within certain ranges. In general, the reaction is carried out at between -30° and +50°C, preferably between -20° 20 and +20°C.

Suitable acid-binding agents for carrying out the second stage of preparation process (a) are all Inorganic and organic bases which can customarily be used. Alkali metal carbonates or bicarbonates, such as sodium carbonate, 25 potassium carbonate or potassium bicarbonate, are preferably used.

In carrying out the second stage of preparation process (a), the reaction temperatures can, as in the single-stage reaction procedure, be varied within a wide 30 range. In general the reaction 1s carried out at between 0°C and 200°C, preferably between 50°C and 4150°C.

In carrying out preparation process (a), in general 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol, of the acryI on 11r1le derivative of the formula (III) or (Ilia) 35 or of 2,3-dichloropropionitrile of the formula (111b) are employed per mol of phenylhydrazine of the formula (II), 221199 both 1n the single-stage reaction procedure and in the two-stage reaction procedure, and, 1n the case of the two-stage process, If appropriate 1.0 to 10.0 mol of reaction auxiliary are employed 1n the first stage, and, 5 1f appropriate, 1.0 to 10.0 mol of acid-binding agent are employed 1n the second stage.

Work1ng-up and Isolation of the reaction products are carried out by customary methods, for example by removing the organic diluent, precipitating the reaction 10 product in water, and filtering off the resulting product > under suction and drying it.

Suitable diluents for carrying out preparation process (b) are likewise Inert organic solvents. Preferably used compounds are aliphatic or aromatic, optio-15 nally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, methylene chloride, chloroform, carbon tetrach loride, chlorobenzene or dich lorobenzene, ethers, such as diethyl ether, diiso-20 propyl ether, dioxane, tetrahydrofuran or ethylene glycol diethyl ether or ethylene 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 propionitr1le, amides, 25 such as dimethylformamide, dimethylacetam1de, N-methyl-pyrrolldone or hexamethyIphosphoric acid triamide. If acylating or alkylating agents of the formula (V) or (VI) are used in liquid form, 1t 1s also possible to employ these in an appropriate excess, as a diluent. / 30 Suitable acid-binding agents for carrying out pre paration process (b) are all inorganic and organic bases which can customarily be used. Preferably used compounds are alkali metal hydrides, hydroxides, amides, carbonates or bicarbonates, such as, for example, sodium hydride, 35 sodium amide, sodium hydroxide, sodium carbonate or sodium bicarbonate, or tertiary amines, such as, for ex- 221199 ample, tr lethy lami ne, N,N-d 1met hy lanll 1 ne, pyridine, 4-(N,N-d1methyI ami no)-pyr1d1ne, dlazableyelooctane (DABCO), diazab1cyclononene (DBN) or d 1 a z ab1 cy c loundecene (DBU).

In carrying out preparation process (b), the r e-5 action temperatures can be varied within • wide range.

In general, the reaction 1s carried out at between -20°C and ♦150°C, preferably between 0°C and ♦100°C.

In carrying out preparation process (b), In general 1.0 to 20.0 mol, preferably 1.0 to 15.0 mol, of acy-10 latlng or alkylating agent of the formula (V) or (VI) and, 1f appropriate, 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of acid-binding agent are employed per mol of 5-amino-pyrazole of the formula (la). The reaction procedure and worklng-up and Isolation of the reaction products of 15 the formula (lb) are carried out In a generally customary manner.

Suitable diluents for carrying out preparation process (c) are all solvents which can customarily be used for such eIectrophiI1c substitutions. Preferably, 20 the acids or mixtures which constitute suitable reagents, such as, for example, sulphuric acid, chlorosulphonic acid, nitric acid, nitrating acid, sulfuryl chloride, phosphorus oxychI oride/dimethyIfornam1de or nitrating acid, are simultaneously used as diluents. Inert organic sol-25 vents, such as, for example, glacial acetic acid or chlorinated hydrocarbons, such as methylene chloride, chloroform or carbon tetrachloride, can, 1f necessary, also be used as diluents.

Suitable catalysts or reaction auxiliaries for 30 carrying out preparation process (c) are likewise the catalysts customarily used for such reactions; acidic catalysts, such as, for example, sulphuric acid, iron(III) chloride or other Lewis acids or acetic anhydride, are preferably used.

In carrying out preparation process (c), the reac tion temperatures can be varied within a relatively wide 221199 range. In general, the reaction 1t carried out at between -50°C and ♦200°C, preferably between -20°C and ♦150°C.

In carrying out preparation process (c), 1n general 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol, of the 5 electroph1 11c agent of the formula (VII) and, 1f appropriate, 0.1 to 10 mol of catalyst or reaction auxiliary are employed per mol of 5-am1no-pyrazo le of the formula (Ic). The reaction procedure and worklng-up and isolation of the reaction products of formula (1) are carried out In a 10 generally customary manner.

Suitable diluents for carrying out preparation process (d) are likewise Inert organic solvents. The solvents mentioned 1n the case of preparation process (b) are preferably used. For the reaction with an alkali 15 metal fluoride of the formula (IX), it is also possible to use water or aqueous mixtures with one of the solvents mentioned in the case of process (b).

Suitable acid-binding agents for carrying out preparation process (d) are likewise all organic or inor-20 ganic bases which can customarily be used. Alkali metal hydroxides, carbonates or bicarbonates, such as, for example, potassium carbonate or sodium bicarbonate, are preferably used. Tertiary organic bases, such as tri-ethylamine or pyridine, are also suitable. 25 In preparation process (d), the reaction tempera tures can likewise be varied within a wide range. In general, the reaction 1s carried out at between -20°C and +120°C, preferably between 0°C and +90°C.

In carrying out preparation process (d), In gene-30 ral 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of the amine of the formula (VIII) or the alkali metal fluoride of the formula (IX) and, 1f appropriate, 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of acid-binding agent are employed per mol of 4-chlorosulphonyl-5-amino-pyrazole of 35 the formula (Id). The reaction procedure and working-up and isolation of the reaction products of the formula (I) sswl" ■ *.-' 221199 are carried out 1n a customary Banner.

Suitable diluents for carrying out preparation process (e) are likewise Inert organic solvents. Alcohols, such as, for example, methanol, ethanol or propanol, are 5 preferably used.

Suitable acid-binding agents for carrying out preparation process (e) are likewise all organic and Inorganic bases which can customarily be used. The acid-binding agents Mentioned 1n the case of process (b) are 10 preferably used. w In carrying out preparation process (e), the re action temperature can likewise be varied within a wide range. In general, the reaction is carried out at between +20°C and +150°C, preferably between +20°C and +120°C. /*"■> 15 In carrying out preparation process (e), In gene- ra I 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of the hydroxyI amine derivatives of the formula (X) and, If appropriate, 1.0 to 3.0 mo I of acid-binding agent are employed per mol of the 4-acyl-5-amino-pyrazole of the for-20 Hula (le). The reaction procedure and working-up and Isolation of the reaction products of the formula (I) are carried out in a generally customary manner.

Suitable diluents 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, 1n an appropriate excess and, if required, as a mixture with water.

In carrying out preparation process (f), the re-action temperatures can likewise be varied within a wide 30 range. In general, the reaction is carried out at between 0°C and +150°C, preferably between +20°C and 130°C.

In carrying out preparation process (f), in general 0.1 to 3 mol, preferably 0.5 to 2 mol, of Raney nickel and in general 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).

■'TWHWWTOWP'W;**-* ■ •U 221199 The reaction procedure and working-up and Isolation of the reaction products of the formula (I) are carried out 1n a customary manner analogous to known methods (see, for example, Chem. Pharm.Bull. 24, 3120 C19763). 5 The active compounds which can be employed accor ding to the Invention can be used as defoliants, deslc-cants and agents for destroying broad-leaved plants, and especially as weedkillers. By weeds, 1n the broadest sense, there are to be understood all plants which grow 10 1n locations where they are undesired. Whether the substances which can be used according to the Invention act as total or selective herbicides depends essentially on the amount used.

The active compounds which can be employed accor-15 ding to the Invention can be used, for example, in connection with the following plants: Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, SteLlaria, Matricaria, Anthemis, Galinsoga, Cheno-podium, Urtlca, Senecio, Amaranthus, Portulaca, Xanthium, 20 Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cir-sium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lin-dernla, Lamium, Veronica, Abutllon, Emex, Datura, Viola, 6aleops1s, Papaver and Centaurea.

Dicotyledon cultures of the genera: 6ossypium, Glycine, 25 Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, V1c1a, Nicotlana, Lycoperslcon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitarla, Phleum, Poa, Festuca, Eleusine, 30 Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agro-pyron, Cynodon, Monochoria, F1mbristy11s, Sagittaria, Eleo-charls, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyl-octenium, Agrostls, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triti-35 cum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium. • /* 221199 However, the use of the active compounds which can be employed according to the Invention 1s 1n no way restricted to these genera, but also extends 1n the same manner to other plants.

The compounds are suitable, depending on the con centration, for the total combating of weeds, for example on Industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds 1n perennial r*\ 10 cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for 15 the selective combating of weeds 1n annual cultures.

In addition to exhibiting a particularly good general herbicidal activity, the active compounds of the formula (I) which can be used according to the Invention also exhibit substantially improved selectivity with 20 regard to crop plants in important cultures, and can be employed as agents for selectively combating weeds both 1n dicotyledon cultures, such as, for example, cotton plantings, soya beans or groundnuts, and 1n monocotyledon cultures, 1n particular cereals, such as, for example, 25 wheat.

The active compounds can be converted to the customary formulations, such as solutions, emulsions, wet-table powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion 30 concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.

These formulations are produced in known manner, O 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- J 221199 Ing agents and/or dispersing agents, and/or foam-forming agents.

In the case of the use of water as an extender, organic solvents can, for example, also be used as auxl-5 Hary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as ch lorobenzenes, chloroethy-lene or methylene chloride, aliphatic hydrocarbons, such 10 as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl iso-butyl ketone or eyelohexanone, strongly polar solvents, 15 such as dimethylformamlde and dimethylsulphoxlde, as well as water.

As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, mont-20 morillonite or dlatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiollte and dolo-25 mite, as well as synthetic granules of Inorganic 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 non-ionic and anionic emulsifiers, such as 30 polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, a Ikylsulphonates, a IkyIsulphates, aryIsulphonates as well as albumin hydrolysat 1 on products; as dispersing agents there are suitable: for example ligninsulphlte waste 35 liquors and methyIceIlulose.

Adhesives such as carboxymethyIcel lulose and t 221199 natural and synthetic polymers in the form of powders, granules or latlces, such as gum arable, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic 5 phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.

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 dye-10 stuffs, 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 15 between 0.5 and 90X.

The active compounds which can be employed according to the invention, as such or in the form of their formulations, can also be used, for combating weeds, as mixtures with known herbicides, finished formulations or 20 tank mixtures being possible.

Suitable herbicides for the mixtures are known herbicides, such as, for example, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4dH,3H)-dione or N-(2-benzothiazo ly I)-N,N*-dimethyI urea for combating 25 weeds 1n cereals, 4-am1no-3-nethyl-6-pheny1-1,2,4-triazin-5(4H)-one for combating weeds 1n sugarbeet and 4-amino-6-(1,,1-dimethylethyl)-3-methylthio-1,2,4-tri a zi n-5(4H)-one for combating weeds 1n soya beans. Mixtures with N,N-^ dimethyl-N'-(3-trifluoromethyIphenyI)-urea, N,N-dimethyl- N *-(3-ch loro-4-met hy Ipheny I )-urea, N,N-d i met hy l-N *-(4-i so-propylphenyl)-urea, 4-amino-6-t-butyl-3-ethylthi0-1,2,4-triazln-5(4H)-one, 2,4-d 1 ch lorophenoxyacet 1 c acid, 2,4-di-chlorophenoxyproplonic acid, (2-methyl-4-chlorophenoxy)-acetic acid, (4-chloro-2-methyl-phenoxy)-propionic acid, 35 chloroacetic acid N-(methoxymethyl)-2,6-dimethyIani I ide, 2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacet- Vj ?? 11 99 anilide, 2,6-din1tro-4-tr1fluoromethyl-N,N-d1propylan1line, and 2-benzyIoxyethyI, tr1«ethyIs1tyImethyI or 2,2-d1ethoxy-et hy I 2-C4-(3,5-dichloropyrid-2-yloxy)-phenoxyD-propion-ate ire alto possible. Surprisingly/ some mixtures also 5 exhibit a synergistic action. as fungicides, insecticides, acariddes, nematlcides, bird repellents, plant nutrients and agents which Improve soil structure, are also possible. form of their formulations or 1n the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example 15 by watering, spraying, atomising or scattering.

The active compounds which can be used according to the invention can be applied either before or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.001 and 10 kg of active compound per hectare of 25 soil area, preferably between 0.01 and 5 kg per ha.

The following example IV-I illustrates the preparation of a phenylhydrazine derivative in accordance with the invention: Example IV-1 Mixtures with other known active compounds, such The active compounds can be used as such, in the \ Cl .O g (0.095 mol) of 2-chloro-4-trifluoromethyl-phenylhydrazine are dissolved in 150 ml of methanol and 20 mg of ethylenediamine-tetraacetic acid disodium salt are added. '.21199 The solution is heated to boiling and 32 ml (0.38 mol) of 2-chloro-acrylonitrile are added dropwise. The reaction mixture is subsequently stirred for 10 hours at the boiling temperature, cooled and evaporated to dryness in vacuo at 0,1 mm Hg. The residue yields 27.9 g ( = 98.6 % of theory) of N■-(2■-chloro-2'-cyanoethyl)-2-chloro-4-trifluoromethyl-phenylhydrazine of a melting point of 56-57° C.

The examples which follow Illustrate the preparation and the use of the active compounds which can be used.

Preparation examples 30 Example 1 (Process a) mg of disodlum ethylenediamlnt-tetraacetate (* Tltr1pl/x 111) 1n 150 ml of methanol are added drop-wise to 24.5 g (0.1 mol) of 2,6-di c h loro-4-tr 1 f luoromethyl' 5 phenylhydrazine at the reflux temperature, and 25 ml (27.6 g/0.3 mol) of 2-chIoroacryIon11r11 e are added. When the addition 1s complete, heating 1s continued for a further 8 hours at the refLux temperature, after which 9 ml (0.16 mol) of 96* strength sulphuric acid are added drop-10 wise and heating 1s continued for a further 6 hours at the reflux temperature. 33.5 g (0.3 mol) of anhydrous sodium carbonate are added to the cooled reaction mixture. After 4 hours, the solvent is removed 1n vacuo, the residue is taken up 1n 500 ml of water, and the solution is stirred 15 for 10 hours at room temperature. The precipitate which separates out is filtered off, rinsed with water and dried in vacuo at 50°C. 28.5 g (96X of theory) of 5-amino-1-(2,6-dichloro-4-trifluoromethy lphenyl)-pyrazole of melting point 103-20 105°C are obtained.

O 221199 Example 2; © m ^{J^~NH-CO-C2H5 "t©T Cl Cl (Process b) ail (5.3 g/0.05 vol) of 98X strength proplonyl 25 chloride and then 5 ml (5.0 g/0.063 mol) of anhydrous pyridine are added 1n succession to 13.2 g (0.05 mol) of 5-are1no-1-(2,4,6-trlchlorophenyl)-pyrazole 1n 100 til of dlchloronethane at room temperature, while stirring.

During the addition, the temperature Increases to 40°C. 30 When the addition 1s complete, stirring 1s continued for a further 16 hours at room temperature, 50 ml of dlchloro- O 221199 •ethane are added, the Mixture 1s washed with twice 100 Ml of water, 100 ml of saturated sodium bicarbonate solut-tion and 100 ml of -sodium chloride solution and 1s dried over Magnesium sulphate, and the solvent 1s reaoved In vacuo. The solid residue is washed with a small amount of hexane and 1s dried. 12.5 g (81X of theory) of 5-prop1onam1do-1-(2,4,6-tr1chlorophenyI)-pyrazole of melting point 125°C are obta1ned.

Example 3 M02 nh-co-c2h5 (Process c) 2 ml (2.17 g/0.021 nol) of acetic anhydride and then 0.9 ml (1.3 g/0.02 aiol) of 98X strength nitric acid are added in succession to 6.4 g (0.02 mol) of S-propion-am1do-1-(2,3,4-1richlorophenyl)-pyrazo le in 20 ml of glacial acetic acid at 10°C. Uhen the addition is complete, the Mixture 1s stirred for 16 hours at 25°C. To work up the Mixture, it 1s evaporated down 1n vacuo, the residue Is taken up in 20 ml of diethyl ether, the solution is washed three times with a total of 50 to 100 ml of concentrated sodium bicarbonate solution and twice with 50 ml of saturated sodium chloride solution, the solvent 1s re-Moved in a vacuum from a water pump, and the solid residue 1s washed with a small amount of water and dried in a high vacuum at 30°C to 40°C. 5.5 g (76X of theory) of 4-n11 ro-5-prop1 onamide-1 - (2,3,4-t r i ch loropheny O-pyra-zole of melting point 79-81°C are obtained.

Example 4 Br I Cl Cl Cl (Process c) A solution o1 1.6 g (0.0? mol) of bromine in 5 ml of glacial acetic add is added dropwise to 2.6 g (0.01 mol) of 5-ainino-1-(2,3,4-tr 1 chlorophenyl)-pyrazole 1n 10 ml of glacial acetic acid at 20°C, while stirring.

When the addition is complete, stirring is continued for a further 3 hours at 20°C, after which 30 ml of water 10 and 3 g (0.022 mol) of sodium acetate trihydrate are added, stirring is continued for a further hour, and the crystalline precipitate is filtered off under suction, washed with water and dried at 50°C to 60°C in vacuo. 3.2 g (94% of theory) of 5-amino-4-bromo-1-(2,3,6-trieh Ioro-15 pheny l)-pyrazole of melting point 129°C are obtained. Example 5; dropwise to 2.7 g (0.0085 mol) of 5-prop1onamide-1-(2,3,4-trich lorophenyl)-pyrazole in 20 ml of dichIoromethane at 0°C to 5°C. When the addition is complete, stirring Cl Cl (Process c) 1.2 g (0.009 mol) of sulfuryl chloride are added 221199 Is continued for a further 16 hours at room temperature, the Mixture 1s diluted with 30 Ml of dichIoronethane, washed several tines with water, saturated sodium bicarbonate solution and saturated sodium chloride solution, dried over sodium sulphate and evaporated down in vacuo, and the residue Is dried at 50°C in a high vacuum. 2.5 g (83% of theory) of 4-chIoro-5-prop1 on am 1do-1-(2,3,4-1r1-chIorophenyI)-pyrazole of Melting point 122°C are obtained.

Example 6 CO-H (Process f) 12 g (0.042 nol) of 5-amino-4-cyano-1-(2-chloro-4-trif luoromethoxy-phenyl)-pyrazole are boiled under reflux 15 with 5 g of Raney nickel in 50 ml of 75* strength aqueous formic acid for 1 hour; the still warm solution is filtered under suction, the residue is rinsed with water, the filtrate 1s extracted several tines with ether, and the combined ether phases are washed with saturated sodium 20 bicarbonate solution, dried over sodium sulphate and evaporated down in vacuo. 8.0 g (623! of theory) of 5-amino-1-(2-chloro-4-t rifluoromethoxy-phenyl)-4-formyl-pyrazole are obtained in the form of an oil.

^ H-NMR € CppmD * 5.7 (s,2H) - singlet 25 7.3-7.6 (m,3H) - nultiplet 7.85 (s,1H) - singlet 9.6 (s,1H) - singlet •% Example 7 991199 h/OC2H5 / VOC2H5 (Process •) 6.3 g (0.03 no I) of 2,3,4-tr1chIorophenyIhydraz1ne, 5.8 g 5 (0.025 mol) of ethoxymethytene-d1ethyIphosphonoaceto- nitrile and 1 g of (0.012 mol) of anhydrous sodium acetate are suspended in 10 ml of glacial acetic acid, and the suspension is stirred for 48 hours at room temperature. 50 ml of dichI oromethane and 100 ml of water are added to the 10 reaction mixture. The organic phase is separated off and washed once in each case with 50 ml of saturated sodium bicarbonate solution and 30 ml of saturated sodium chloride solution. After the solution has been dried over magnesium sulphate, the solvent is distilled off in vacuo, 15 the oily residue is dissolved in 15 ml of ethoxyethano I, and the solution Is heated under reflux for 5 hours. It is then cooled to room temperature, 30 ml of water are added to the solution and stirring is continued until the initially oily precipitate crystallises. The slightly 20 yellow crystals are filtered off under suction, washed with water and dried in vacuo at 50-60°C. .6 g (46.8% of theory) of 5-amino-4-diethyIphos-phono-1-(2,3,4-trichlorophenyD-pyrazole of melting point 114°C are obtained. £.reP®.rA°H £f_t_he_s_ta_rt_i_n£ ^compound: CN CjHjO- CH = C ^ 0C jH 5 0 OC2H5 t ,199 .4 g (0.2 mol) of dlethyIphosphonoacetonltrl le (tee Mouben-Weyl "Methoden der organlschen Chemle" (Methods of organic chemistry)/ Volume E2/ page 345/ 4th Edition/ Thleme Verlag Stuttgart/ 19B2)/ 42 ail (0.45 mol) of 5 acetic anhydride and 56 ml (0.34 aol) of trlethyl o-for-mate are stirred for 2 hours at 110°C. Thereafter/ the low-boiling compounds are distilled off over a short column under atmospheric pressure, the bottom temperature Increasing to 140°C. This temperature 1s maintained 10 for a further 4 hours, and the unreected starting compounds are then distilled off/ first under a vacuum from a water pump and then under a vacuum from an oil pump. 20.5 g (44* of theory) of ethoxymethylene-diethyIphosphono-acetonltrile remain as an oil at the bottom. 1H-NHR (CDC Ij) * S * 7.63 ppm (d/lH) - doublet 4.32 ppm (q/2H) - quartet 4.15 ppm (m/4H) - multlplet 1.45 - 1.35 ppm («/9H) - multlplet The following compounds of the general formula (I) 20 are obtained in a corresponding manner and 1n accordance with the general preparation data.

Table 2 R? (I) Example R1 R* R^ R* r5 r& r7 rB Physical No. properties 8 no? c2h5co h Cl h Cl h cl k.p.:54®C 9 no 2 c2h5co h Cl h "3 h cl M.p. :48°C no2 c2h5co h Cl h "3 h h M.p.:115°C (deccnpositicn) Jtf ! •?' • • 1' - /~v 27 I( Table 2 (continued) Exaaple •* No.

Physical properties s "1 <t J V 2 6 AUG m 11 N02 CjHJCO h Cl h scfj M I H.p.: 96-99°c 12 NO 2 c2h5co h Cl h ocfj H *.p.:65°C 13 NO 2 c2h5co h Cl Cl "3 Cl I M.p.:54-60°C U NO; c2m5co h cf3 H Cl h Oil NO2 H h Cl H Cl h I R.p.:218°C 16 NO 2 CHjCO h Cl h "3 h I W.p.:50°C 17 NO 2 CHjCO h Cl H SCFj h I n-p-: 58-61 °C 18 no2 CHjCCH2)2CO n Cl H "3 H I H.p.:uec 19 no2 CHJOCO h Cl H "3 H I H.p.:U1-43°C NO 2 cich2co h Cl 1 h I *.p.:130-33°C 21 NO 2 c2h5co h Cl H Cl h N.p.:63°C 22 h h h Cl H Cl h I H.p.:113°C 23 h h h Cl H "3 H N.p.:88-92®C 2 i. h h h Cl h SCFj H I n.p.: 79 ®C h H h Cl Cl Cl h n-p.:152°C 26 h h h Cl Cl "3 Cl I h.p.: 103-10°C 27 h h H Cl h OCFj H n.p^73-76°C 28 h c2h5co H Cl Cl Cl h *.p.:55°C 29 H C|«jCO H Cl H CFj H ft.p. :106-10°C SO N C,WsCO H Cl H SCFj N i nj>. :136°c 31 H c,h5co H Cl H CFj n i h.p. :146°c 32 H cjhjco H Cl H OCFj H Oil 33 H C2HsC0 H Cl Cl CFj Cl I H.p. :154=58»C 34 H c2m5co H CFj M Cl N Oil H c2hsco H cl H cl N Oil 36 N c2h5co H cl H s02cf2c1 h I H.p. :134®C 37 N CHjCO C2H5C0 cl cl cl H «.p.:U2®C 38 N CHjCO CHjCO cl cl cl H H.p. :k2°c 39 n CHjOCO H cl H CFj h i M.p. :123-126#c 4° H CHjCO H cl H CFj n i «.p.:173-76®c " 'X 41 .<■ \« :^42 n CHjCO H Cl H SCFj H I H.p.:131®C N CHj(CH2)2CO H Cl H CFj H I *.p.:128-31 ®C b l< (Mp Ho, 43 44 45 46 47 42 49 5c 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 7-7.1 c J (continued) •'/ «* H \cICHjCO •r \ CJHJCO I \h j? V' chj0 v m MCH-\ M0N«CH-| h N h h h n no2 NO; no2 h no2 h h h e0c12f socl2f N02 N02 no2 nd2 Cl H soocljf no.

SO2oci2F h no n02 no2 no- no. cna CjHjCO H H (c^o^pfo) c2hsoo C^OO C^co C>io Cii^00 h C^OO h C>oo C^CO c2h5cx) c2H&CO C-j^CD c2H5CO c2h500 C^OO c2h500 h h c2h5°° c2h500 c2h5oo H Cl Cl Cl Cl Cl Cl Cl Cl Cl ch h h h h h h h h h h h h h h h h h h h H H Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl N Cl Cl Cl h Cl C'J Cl Cl Cl OCfj Cl h h h h h H h h h h h H H H h H Cl h R h K Cl h SOjCCljF CFj SOjCCljf N c3 Cl scf3 cf3 Cl Cl OCF3 cf3 ff3 scf3 gf3 OCFj Cl S02CF3 Cl ct3 cf. 3 V ocf, so2CF3 so2cf3 cf3 cf, >le mple 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 1199 (cont1nu#d) R2 R3 R4 R5 R6 R7 R8 Melting »int (°C) H H Cl H SCF3 H H 56-60 H H Cl H SCF- H Cl 145-49 H H Cl H «*3 H Cl 206-08 H H Cl H 602CF3 H Cl 249-53 H H Cl Cl CT3 H Cl 78-85 CH3NHOO H Cl H ^3 H Cl 178-82 Q-o-oo H Cl H -3 H Cl 65-67 (CH3)2NCD H Cl H H Cl 137-38 c2h5cd H Cl Cl Cl H Cl 62-67 c^oo H Cl Cl Cl H Cl 60-67 CIQ^O^-CO H Cl H <*3 H Cl 120-24 O^NHOO H Cl H ^3 H Cl 212-14 Qo-oo H Cl H -3 H Cl 48-52 H H Cl Cl Cl H Cl 83-89 h ®3 Cl H Cl H Cl 167-75 h Cl H Cl h Cl 186-88 C1CH2-00 H Cl h ff3 H H 103-05 C1CH2-C0 H Cl H OCF3 H H 84-87 H h Cl h <*3 H H 55-58 CICHjCHJ-CJO H Cl H <*3 h Cl 135-40 cichj-co H Cl H OCF3 h H Oil C1CH2-€D H Cl H ^3 h H 111-13 C2hgco H Cl F <*3 F Cl 121-23 C^CO .H Cl F ^3 F Cl 135-37 c2h500 H Cl F Cl F Cl 190-93 H Cl H <*3 H H 120-23 c^oo 0>3 Cl H <*3 H Cl 140-54 H H Cl F CT3 F Cl 158-65 W° H Cl F Cl F Cl 130-33 c5j2«ch-od h Cl h ^3 h Cl 55-65 h h Cl F Cl F Cl 210-20 BCD h Cl h h Cl 144-50 *>2 no2 »2 ">2 ^2 h h h h NO? h no2 no2 N02 no2 h h h no2 no2 no2 NO, h no2 h no2 N02 no2 no2 no2 no2 h bte anpl • 107 108 109 UO 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 2! (contInutd) r3 r4 rs r* r7r8 nd2 c2h5oo h cl h och3 h cl no2 hoo h cl h <*3 h 6l nd2 h ch3 cl h <*3 h cl s0c12f h h cl h ^3 h cl s0cc12f h h cl h ^3 h cl h ch3od h cl cl °3 h cl 8020c12f h h cl h <*3 h cl n02 ch300 h cl cl <*3 h cl h ch3od h cl h *3 h h no2 CH-jCO h cl h ^3 h h h h <*3 cl h <*3 h cl h qco h cl h <*3 h cl no2 cichjchjchjoo h cl h <*3 h cl h cl h <*3 h cl h c2 h5cr> h cl h br h h h h h br h br h br h c^oo h br k br h br h h h cl h br h cl h h h br k cl h br h h cl h br h h h h h j h j h h no2 c^oo h br h br h br h c^od h br h cl h br h c^oo h cl h br h cl h h h br h cl h cl k>2 cjhjoo h br h cl h br h cichjoo h br h cl h br h h h br h f h h no2 h h br h cl h br h h h br cl cl h br %' e, 22^199 T»blt 2 (continued? Exanple Ho.

R1 R2 R3 R4 R5 R6 t,1 R8 Melting point (*C 137 K>2 C^OO H Cl H Br H Cl 94 138 H H Cl H Br H Cl 198 139 H C2H5OD H Br H Br H Cl 114-18 140 *>2 ciaijoo H Br H C1 H Br 115-20 141 H C^OD H J H J H H Oil 142 H H H Br Cl Br H Cl 170 143 *>2 C2H5CO H Br H Br H Cl 89-93 144 H H Br H Br H Cl 208-10 145 H C2H5CO H Br Cl Cl H Br 165 146 H C2HsOO H Br Cl Br H Cl 140-50 147 no2 C^00 H J H J H H 55-60 148 ^2 C2H5<3> H Br Cl Cl H Br 130-40 149 ND2 C2HsCO H Br H F H H 72-74 150 *>2 C2H5G0 H Br H OCF3 H B 83-85 151 Br H H Cl H Cl H Cl 119 152 SCH3 H H Cl H Cl H Cl 114 153 Br H H OCH, H Cl H Cl 67-70 154 £0*3 C2H5CO H Cl H Cl H Cl 92-95 155 ^3 c^oo h Cl h Cl h Cl 146-50 156 -cho h h Cl h OCF3 h h Oil 157 -cho c2h5oo h Cl h OCF3 h h Oil 158 -ch=noch3 h h Cl h ocf3 H H 138-39 159 H C1CH2CH2CH2CX> H Cl h "3 h Cl Oil c*. -«- - - "t 19 9 Use m»ptet: The compound listed below 1* used as a comparative substance 1n the use examples which follow: Cl 4-Cyano-5-propionamido-1-(2,4,6-trichlorophenyl)-pyrazole (disclosed 1n NZ Patent No 196337) .

Example A Pre-emergence test Solvent: 5 parts by weight of acetone 10 Emulsifler: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound/ 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifler Is added and the concentrate 1s diluted with water 15 to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It Is expedient to keep constant the amount of water per unit area. The concentration of the 20 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

Claims (4)

1 : 5 10 S-\ 15 20 25 30 o 2? 119 9 to the plant* is rated 1n X damage In comparison to the development of the untreated control. The figures denote: OX * no action (like untreated control) 100X * total destruction In this test, for example, the compound according to preparation example 3 1s clearly superior to the prior art, both in herbicidal activity and in selectivity with respect to crop plants. Example B Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier 1s added and the concentrate 1s diluted with water 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 way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor 1s so chosen that the particular amounts of active compound desired are applied in 2,000 I of water/ha. 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 figures denote: OX * no action (like untreated control) 100X * total destruction In this test, for example, the compound according to preparation example 3 1s clearly superior to the prior art, both in herbicidal activity and in selectivity with respect to crop plants. - 68 - 221199 what we CLAIM IS:

1. Phenylhydrazine derivatives of the formula IV »5 \ / R6_/Q\ _ NH - NH - Z (IV) y x_8 in which R R R^ and independently of one another represent cyano, nitro, halogen, alkyl, alkoxy, alkoxy carbonyl, halogenoalkyl, halogenoalkoxy or a 13 radical -S(0) -R , and 5 7 8 R , R and R independently of one another and 4 6 of R and R represent the same radicals as and and additionally represent hydrogen 13 R represents alkyl, halogenoalkyl, amino, alkylamino or dialkylamino, and n represents the number 0, 1 or 2, and Z represents one of the radicals CN ^ CN -CH=C or -CH--CH wherein R1 ^ Hal R^" represents hydrogen, nitroso, nitro, halogen, alkyl, halogenoalkyl, optionally substituted aryl or one of the radicals o o 9 " 10 11 " 11 -S(0) -R ; -C-R ; -C=N-0R or -P(0R )„ n 2 - R10 in which 9 R represents hydrogen, hydroxyl, halogen, amino, alkylamino, dialkylamino, alkyl, halogenoalkyl or optionally substituted aryl, L.. - 69 - 221199 R10 represents hydrogen, alkyl or optionally substituted aryl, R11 represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkinyl or aralkyl, except that where R*" represents hydrogen, methyl or optionally substituted phenyl, R^ and R^ do not simultaneously represent the nitro group; and Hal represents halogen.

2. A compound according to claim 1 substantially as herein described or exemplified.

3. A process for forming a compound according to claim 1 or claim 2 substantially as herein described or exemplified.

4. The use of a compound according to claim 1 as an intermediate in the preparation of a 5-Amino-l-phenyl-pyrazole of the formula I' 11 1 n j wherein (!') R^", R^, R"*, R®, R7 and R®, are as defined in claim 1, X 2 "12 R represents hydrogen or a radical -C-R , in which X is halogen or sulphur, 3 2 R independently of R represents the same 2 radicals as R and additionally represents alkyl, and 12 R represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, alkoxyalkyl, alkylthioalkyl, optionally substituted cycloalkyl, optionally substituted aryl, alkoxy, alkylthio, optionally substituted aryloxy, optionally substituted arylthio, - 70 - "11 alkylamino, dialkylamino or optionally substituted arylamino. BAYER AKTIENGESELLSCHAFT By their Attorneys HENRY HUGHES LIMITED