5-Acylamino-4-cyano-1-phenylpyrazole derivatives and use as herbicides

This invention relates to N-phenylpyrazole derivatives, compositions containing them and their use as herbicides.
In J. Org. Chem. Vol. 23, 191-200 (1958), C. C. Cheng and R. K. Robins have described experiments for the preparation of 6-alkyl-4-hydroxypyrazole[3,4-d]pyrimidines as analogues of degradation products of pseudovitamin B.sub.12. The authors report that these pyrazole[3,4-d]pyrimidine derivatives did not reveal any significant anti-tumour activity but affected the growth of bacteria. They employed, as starting materials, 1-phenyl-5-acetylamino-4-cyanopyrazoles of the general formula: ##STR2## wherein R represents phenyl, 2-chlorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-nitrophenyl or 4-methylphenyl. The compound of general formula I wherein R represents a phenyl group has also been described by T. Higashino, Y. Iwai and E. Hayashi, Chem. Pharm. Bull, 24 (12), 3120-3134 (1976), as an intermediate in the preparation of 1-phenyl-1H-pyrazolo[3,4-d]pyrimidine-5-oxide. Neither of these publications contains any suggestion that compounds of general formula I possess or would be expected to possess herbicidal activity.
It has now unexpectedly been found after extensive research and experimentation that certain acylamino-N-phenylpyrazole derivatives possess valuable herbicidal properties.
The present invention accordingly provides, as herbicides, new acylamino-N-phenylpyrazole derivatives of the general formula: ##STR3## wherein R.sup.1 represents an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 represents a hydrogen atom, a straight- or branched-chain alkyl group containing from 1 to 7 carbon atoms, a straight- or branched-chain alkoxy group containing from 1 to 4 carbon atoms or a straight- or branched-chain alkenyloxy group containing 3 or 4 carbon atoms, alkyl and alkoxy groups within the definition of R.sup.8 being unsubstituted or substituted by a straight- or branched-chain alkoxy group containing from 1 to 4 carbon atoms, an alkoxycarbonyl group containing from 2 to 5 carbon atoms, or one or more halogen, e.g. chlorine, atoms, or R.sup.8 represents a cycloalkyl group containing from 3 to 6 carbon atoms unsubstituted or substituted by a methyl or ethyl group, or R.sup.8 represents a phenoxy group, R.sup.2 represents a hydrogen atom or an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 is as hereinbefore defined, or R.sup.1 and R.sup.2 together represent --CO--(CR.sup.a R.sup.b).sub.m --CO--, R.sup.3 represents a fluorine, chlorine or bromine atom, a straight- or branched-chain alkyl group containing from 1 to 4 carbon atoms, unsubstituted or substituted by one or more halogen, e.g. fluorine, atoms, for example a trifluoromethyl group, or a straight- or branched-chain alkenyl group containing from 2 to 4 carbon atoms, R.sup.4 represents a fluorine, chlorine or bromine atom or a nitro, methyl or ethyl group, and R.sup.5, R.sup.6 and R.sup.7, which may be the same or different, each represent a hydrogen, fluorine, chlorine or bromine atom or a nitro, methyl or ethyl group, or R.sup.4 and R.sup.5 each represent a chlorine atom and R.sup.3, R.sup.6 and R.sup.7 each represent a hydrogen atom, R.sup.a and R.sup.b, which may be the same or different, each represent a hydrogen atom or a straight- or branched-chain alkyl group containing from 1 to 4 carbon atoms, and m represents 2 or 3.
It is to be understood that when R.sup.1 and R.sup.2 each represent a group R.sup.8 C(.dbd.O)--, wherein R.sup.8 is as hereinbefore defined, the aforesaid R.sup.8 C(.dbd.O)-- groups may be the same or different.
It is also to be understood that --(CR.sup.a R.sup.b).sub.m -- represents an unsubstituted ethylene or propylene group or an ethylene or propylene group in which one or more of the carbon atoms is substituted by one or two straight- or branched-chain alkyl groups containing from 1 to 4 carbon atoms.
It is also to be understood that, unless otherwise indicated, the term `halogen` means fluorine, chlorine, bromine or iodine.
Preferably, R.sup.1 represents an R.sup.8' C(.dbd.O)-- group and R.sup.8' represents an unsubstituted straight- or branched-chain alkyl group containing from 1 to 5 carbon atoms, e.g. methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, t-butyl, n-pentyl, 1-ethylpropyl or 1-methylbutyl, an unsubstituted methoxy group or an unsubstituted or methyl-substituted cyclopropyl group; preferably R.sup.2 represents a hydrogen atom or an R.sup.8" C(.dbd.O)-- group and R.sup.8" represents an unsubstituted straight- or branched-chain alkyl group containing from 1 to 5 carbon atoms, e.g. methyl, ethyl, n-propyl, iso-propyl, n-butyl or iso-butyl, an unsubstituted methoxy group or an unsubstituted or methyl-substituted cyclopropyl group, R.sup.8' and R.sup.8" being the same or different; preferably R.sup.3 represents R.sup.3' and R.sup.3' represents a chlorine atom or a trifluoromethyl or unsubstituted ethyl group or, when R.sup.4', R.sup.5', R.sup.6' and R.sup.7' are as hereinafter defined, each represents a fluorine atom, an unsubstituted methyl group; preferably R.sup.4 represents R.sup.4' and R.sup.4' represents a fluorine or chlorine atom; preferably R.sup.5 represents R.sup.5' and R.sup.5' represents a hydrogen, fluorine or chlorine atom; preferably R.sup.6 represents R.sup.6' and R.sup.6' represents a hydrogen or fluorine atom; preferably R.sup.7 represents R.sup.7' and R.sup.7' represents a hydrogen, fluorine or chlorine atom.
Particularly preferred compounds of general formula II as herbicides are those wherein R.sup.1 represents an R.sup.8' C(.dbd.O)-- group, wherein R.sup.8' is as hereinbefore defined, R.sup.2 represents a hydrogen atom or an R.sup.8" C(.dbd.O)-- group, wherein R.sup.8" is as hereinbefore defined, R.sup.8' and R.sup.8" being the same or different, and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 each represent, respectively, R.sup.3', R.sup.4', R.sup.5', R.sup.6' and R.sup.7', wherein R.sup.3', R.sup.4', R.sup.5', R.sup.6' and R.sup.7' are as hereinbefore defined.
The following compounds of general formula II are of particular interest as herbicides.
______________________________________No Compound______________________________________1 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole2 4-cyano-5-diacetylamino-1-(2,3,4-trichlorophenyl)pyrazole3 5-acetamido-4-cyano-1-(2,3,5,6-tetrafluoro-4-trifluoro- methylphenyl)pyrazole4 4-cyano-5-di(phenoxycarbonyl)amino-1-(2,3,4-trichloro- phenyl)pyrazole5 4-cyano-5-propionamido-1-(2,3,4-trichlorophenyl)pyrazole6 5-acetamido-4-cyano-1-(2,4,6-trichlorophenyl)pyrazole7 4-cyano-5-diacetylamino-1-(4-methyl-2,3,5,6-tetrafluoro- phenyl)pyrazole8 5-acetamido-4-cyano-1-(4-methyl-2,3,5,6-tetrafluoro- phenyl)pyrazole9 5-acetamido-4-cyano-1-(2,3,6-trichloro-4-trifluoromethyl- phenyl)pyrazole10 5-acetamido-4-cyano-1-(2,3,4,6-tetrachlorophenyl)pyrazole11 5-acetamido-1-(2-chloro-4-methylphenyl)-4-cyanopyrazole12 5-acetamido-1-(4-allyl-2,3,5,6-tetrafluorophenyl)-4- cyanopyrazole13 5-acetamido-1-(2-chloro-4-ethylphenyl)-4-cyanopyrazole14 4-cyano-5-dipropionylamino-1-(2,3,4-trichlorophenyl)- pyrazole15 5-n-butyramido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole16 4-cyano-5-isobutyramido-1-(2,3,4-trichlorophenyl)- pyrazole17 4-cyano-5-n-pentanamido-1-(2,3,4-trichlorophenyl)pyrazole18 4-cyano-5-(3-methylbutyramido)-1-(2,3,4-trichlorophenyl)- pyrazole19 4-cyano-5-n-heptanamido-1-(2,3,4-trichlorophenyl)pyrazole20 4-cyano-5-n-hexanamido-1-(2,3,4-trichlorophenyl)pyrazole21 4-cyano-5-n-octanamido-1-(2,3,4-trichlorophenyl)pyrazole22 5-acetamido-4-cyano-1-(2,3-dichlorophenyl)pyrazole23 5-acetamido-4-cyano-1-(2,4-dichlorophenyl)pyrazole24 4-cyano-5-(2-methylbutyramido)-1-(2,3,4-trichlorophenyl)- pyrazole25 4-cyano-5-(2-ethylbutyramido)-1-(2,3,4-trichlorophenyl)- pyrazole26 4-cyano-5-cyclopentylcarbonamido-1-(2,3,4-trichloro- phenyl)pyrazole27 4-cyano-5-cyclopropylcarbonamido-1-(2,3,4-trichloro- phenyl)pyrazole28 4-cyano-5-(2,2-dimethylpropionamido)-1-(2,3,4-trichloro- phenyl)pyrazole29 4-cyano-5-propionamido-1-(2,3,5,6-tetrafluoro-4-trifluoro- methylphenyl)pyrazole30 1-(2-chloro-4-ethylphenyl)-4-cyano-5-propionamidopyrazole31 4-cyano-5-propionamido-1-(2,3,4,6-tetrachlorophenyl)- pyrazole32 4-cyano-5-formamido-1-(2,3,4-trichlorophenyl)pyrazole33 4-cyano-5-(2-ethylhexanamido)-1-(2,3,4-trichlorophenyl)- pyrazole34 4-cyano-5-(2-ethyl-3-methylbutyramido)-1-(2,3,4-trichloro- phenyl)pyrazole35 5-acetamido-4-cyano-1-(4-methyl-2,3,6-trichlorophenyl)- pyrazole36 5-acetamido-4-cyano-1-(2,3-dichloro-4-ethylphenyl)- pyrazole37 5-acetamido-1-(2-chloro-4-isopropylphenyl)-4-cyano- pyrazole38 1-(2-chloro-4-methylphenyl)-4-cyano-5-propionamido- pyrazole39 1-(2-chloro-4-isopropylphenyl)-4-cyano-5-propionamido- pyrazole40 4-cyano-5-propionamido-1-(2,3,6-trichloro-4-trifluoro- methylphenyl)pyrazole41 5-n-butyramido-4-cyano-1-(2,3,5,6-tetrafluoro-4-tri- fluoromethylphenyl)pyrazole42 4-cyano-5-isobutyramido-1-(2,3,5,6-tetrafluoro-4-tri- fluoromethylphenyl)pyrazole43 4-cyano-5-cyclopropylcarbonamido-1-(2,3,5,6-tetrafluoro- 4-trifluoromethylphenyl)pyrazole44 4-cyano-5-(2-ethylbutyramido)-1-(2,3,5,6-tetrafluoro-4- trifluoromethylphenyl)pyrazole45 4-cyano-5-cyclohexylcarbonamido-1-(2,3,4-trichlorophenyl)- pyrazole46 4-cyano-5-[(2-ethoxy)ethoxy-carbonylamino]-1(2,3,4-tri- chlorophenyl)pyrazole47 4-cyano-5-methoxycarbonylamino-1-(2,3,4-trichlorophenyl)- pyrazole48 4-cyano-5-isopropoxycarbonylamino-1-(2,3,4-trichloro- phenyl)pyrazole49 5-n-butoxycarbonylamino-4-cyano-1-(2,3,4-trichlorophenyl)- pyrazole50 4-cyano-5-n-propoxycarbonylamino-1-(2,3,4-trichlorophenyl)- pyrazole51 4-cyano-5-ethoxycarbonylamino-1-(2,3,4-trichlorophenyl)- pyrazole52 5-t-butoxycarbonylamino-4-cyano-1-(2,3,4-trichloro- phenyl)pyrazole53 4-cyano-5-(2-propenyloxycarbonylamino)-1-(2,3,4-tri- chlorophenyl)pyrazole54 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-methoxy- carbonylaminopyrazole55 4-cyano-5-methoxycarbonylamino-1-(2,3,5,6-tetrafluoro- 4-trifluoromethylphenyl)pyrazole56 4-cyano-5-ethoxycarbonylamino-1-(2,3,5,6-tetrafluoro-4- trifluoromethylphenyl)pyrazole57 4-cyano-5-diacetylamino-1-(2,3,5,6-tetrafluoro-4-tri- fluoromethylphenyl)pyrazole58 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-diacetyl- aminopyrazole59 4-cyano-5-diacetylamino-1-(2,4,6-trichlorophenyl)pyrazole60 4-cyano-5-diacetylamino-1-(2,4-dichlorophenyl)pyrazole61 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-propion- amidopyrazole62 5-n-butyramido-1-(2-chloro-4-trifluoromethylphenyl)-4- cyanopyrazole63 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-(3-methyl- butyramido)pyrazole64 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-cyclopropyl- carbonamidopyrazole65 5-acetamido-1-(2-chloro-4-trifluoromethylphenyl)-4-cyano- pyrazole66 5-acetamido-1-(4-n-butyl-2,3,5,6-tetrafluorophenyl)-4- cyanopyrazole67 5-acetamido-4-cyano-1-(4-ethyl-2,3,5,6-tetrafluorophenyl)- pyrazole68 4-cyano-1-(4-methyl-2,3,5,6-tetrafluorophenyl)-5-propion- amidopyrazole69 4-cyano-5-diacetylamino-1-(4-ethyl-2,3,5,6-tetrafluoro- phenyl)pyrazole70 5-acetamido-1-(4-bromo-2,3-dichlorophenyl)-4-cyanopyrazole71 5-acetamido-4-cyano-1-(2-nitro-4-trifluoromethylphenyl)- pyrazole72 5-acetamido-4-cyano-1-(2,6-dichloro-4-trifluoromethyl- phenyl)pyrazole73 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-propion- amidopyrazole74 5-acetamido-4-cyano-1-(pentafluorophenyl)pyrazole75 4-cyano-5-propionamido-1-(2,4,6-trichlorophenyl)pyrazole76 4-cyano-1-(2,4-dichlorophenyl)-5-propionamidopyrazole77 5-isobutyramido-1-(2-chloro-4-trifluoromethylphenyl)-4- cyanopyrazole78 4-cyano-5-dichloroacetamido-1-(2,3,4-trichlorophenyl)- pyrazole79 4-cyano-5-cyclobutylcarbonamido-1-(2,3,4-trichlorophenyl)- pyrazole80 5-(4-chlorobutyramido)-4-cyano-1-(2,3,4-trichlorophenyl)- pyrazole81 4-cyano-1-(2,3-dichlorophenyl)-5-propionamidopyrazole82 4-cyano-5-di(phenoxycarbonyl)amino-1-(2,3,5,6-tetrafluoro- 4-trifluoromethylphenyl)pyrazole83 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-di(phenoxy- carbonyl)aminopyrazole84 1-(2-chloro-4-n-propylphenyl)-4-cyano-5-diacetylaminopyrazole85 4-cyano-5-diacetylamino-1-(2,6-dibromo-4-trifluoromethyl- phenyl)pyrazole86 5-acetamido-4-cyano-1-(2,6-dibromo-4-trifluoromethylphenyl)- pyrazole87 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-pentanamido- pyrazole88 5-acetamido-4-cyano-1-(2,3,4,6-tetrafluorophenyl)pyrazole89 4-cyano-5-(3-methylbutyramido)-1-(2,3,5,6-tetrafluoro-4- trifluoromethylphenyl)pyrazole90 5-isobutoxycarbonylamino-4-cyano-1-(2,3,4-trichlorophenyl)- pyrazole91 5-acetamido-1-(2-chloro-4-n-propylphenyl)-4-cyanopyrazole92 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-cyclohexyl- carbonamidopyrazole93 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-(2-methyl- butyramido)pyrazole94 5-(5-chloropentanamido)-4-cyano-1-(2,3,4-trichlorophenyl)- pyrazole95 4-cyano-5-cyclohexylcarbonamido-1-(2,6-dichloro-4-trifluoro- methylphenyl)pyrazole96 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-(2,2- dimethylpropionamido)pyrazole97 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(3- methylbutyramido)pyrazole98 5-n-butyramido-4-cyano-1-(2,6-dichloro-4-trifluoromethyl- phenyl)pyrazole99 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-(2-ethyl- butyramido)pyrazole100 4-cyano-1-(2,6-dibromo-4-trifluoromethylphenyl)-5-propion- amidopyrazole101 5-(3-chloro-2,2-dimethylpropionamido)-4-cyano-1-(2,3,4- trichlorophenyl)pyrazole102 4-cyano-5-dichloroacetamido-1-(2,6-dichloro-4-trifluoro- methylphenyl)pyrazole103 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-dichloro- acetamidopyrazole104 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5- isobutyramidopyrazole105 4-cyano-5-cyclopropylcarbonamido-1-(2,6-dichloro-4-tri- fluoromethylphenyl)pyrazole106 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-heptan- amidopyrazole107 4-cyano-5-cyclopentylcarbonamido-1-(2,6-dichloro-4-tri- fluoromethylphenyl)pyrazole108 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-hept- anamidopyrazole109 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5- methoxycarbonylaminopyrazole110 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5- pentanamidopyrazole111 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-cyclo- pentylcarbonamidopyrazole112 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(2- methylbutyramido)pyrazole113 4-cyano-5-(2-methylpentanamido)-1-(2,3,4-trichlorophenyl)- pyrazole114 5-acetamido-4-cyano-1-(2,4-dichloro-6-methylphenyl)pyrazole115 4-cyano-1-(2,4-dichloro-6-methylphenyl)-5-propionamido- pyrazole116 5-acetamido-1-(4-chloro-2,3,5,6-tetrafluorophenyl)-4- cyanopyrazole117 1-(4-chloro-2,3,5,6-tetrafluorophenyl)-4-cyano-5-propion- amidopyrazole118 4-cyano-5-propionamido-1-(2,3,4,6-tetrafluorophenyl)- pyrazole119 4-cyano-5-cyclobutylcarbonamido-1-(2,6-dichloro-4-tri- fluoromethylphenyl)pyrazole120 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(2,2- dimethylpropionamido)pyrazole121 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-cyclobutyl- carbonamidopyrazole122 4-cyano-1-(2-nitro-4-trifluoromethylphenyl)-5-propion- amidopyrazole123 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(2- ethylbutyramido)pyrazole124 4-cyano-5-isopropoxycarbonylamino-1-(2,3,5,6-tetrafluoro- 4-trifluoromethylphenyl)pyrazole125 5-(4-chloropentanamido)-4-cyano-1-(2,3,4-trichlorophenyl)- pyrazole126 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-(2-methyl- pentanamido)pyrazole127 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-(2-ethyl-3- methylbutyramido)pyrazole128 5-acetamido-4-cyano-1-(2,6-dichloro-4-ethylphenyl)pyrazole129 4-cyano-5-succinimido-1-(2,3,4-trichlorophenyl)pyrazole130 4-cyano-5-diacetylamino-1-(2,6-dichloro-4-trifluoromethyl- phenyl)pyrazole131 4-cyano-5-dibutyrylamino-1-(2,3,4-trichlorophenyl)pyrazole132 4-cyano-5-glutarimido-1-(2,3,4-trichlorophenyl)pyrazole133 4-cyano-5-dipentanoylamino-1-(2,3,4-trichlorophenyl)- pyrazole134 4-cyano-5-di(3-methylbutyryl)amino-1-(2,3,4-trichloro- phenyl)pyrazole135 5-(N--acetyl-N--propionyl)amino-4-cyano-1-(2,3,4-trichloro- phenyl)pyrazole136 4-cyano-5-diheptanoylamino-1-(2,3,4-trichlorophenyl)- pyrazole137 5-(N--acetyl-N--cyclopropylcarbonyl)amino-4-cyano-1-(2,3,4- trichlorophenyl)pyrazole138 5-(N--acetyl-N--2-ethylbutyryl)amino-4-cyano-1-(2,3,4-tri- chlorophenyl)pyrazole139 4-cyano-5-diisobutyrylamino-1-(2,3,4-trichlorophenyl)- pyrazole140 1-(2-chloro-4-isopropylphenyl)-4-cyano-5-diacetylamino- pyrazole141 5-(N--acetyl-N--heptanoyl)amino-4-cyano-1-(2,3,4-trichloro- phenyl)pyrazole142 5-(N--acetyl-N--isobutyryl)amino-1-(2,3,4-trichlorophenyl)- 4-cyanopyrazole143 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-dipropionyl- aminopyrazole144 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-diprop- ionylaminopyrazole145 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5- succinimidopyrazole146 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-succinimido- pyrazole147 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5- glutarimidopyrazole148 4-cyano-5-(N--isobutyryl-N--propionyl)amino-1-(2,3,4-tri- chlorophenyl)pyrazole149 5-(N--acetyl-N--propionyl)amino-1-(2-chloro-4-trifluorometh- ylphenyl)-4-cyanopyrazole150 4-cyano-5-diacetylamino-1-(2,4-dichloro-6-methylphenyl)- pyrazole151 5-(N--acetyl-N--pentanoyl)amino-4-cyano-1-(2,3,4-trichloro- phenyl)pyrazole152 1-(4-n-butyl-2,3,5,6-tetrafluorophenyl)-4-cyano-5-diacetyl- aminopyrazole153 4-cyano-5-diacetylamino-1-pentafluorophenylpyrazole154 4-cyano-5-diacetylamino-1-(2,3,4,6-tetrafluorophenyl)- pyrazole155 5-(N--acetyl-N--methoxycarbonyl)amino-4-cyano-1-(2,3,4-tri- chlorophenyl)pyrazole156 1-(2-chloro-4-methylphenyl)-4-cyano-5-diacetylaminopyrazole157 4-cyano-5-methylsuccinimido-1-(2,3,4-trichlorophenyl)- pyrazole158 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-glutarimido- pyrazole159 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-di- (phenoxycarbonyl)aminopyrazole160 5-acetamido-1-(2-bromo-4-trifluoromethylphenyl)-4-cyano- pyrazole161 1-(2-chloro-4-methylphenyl)-5-(3-chlorobutyramido)-4-cyano- pyrazole162 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(2- methylpentanamido)pyrazole163 1-(4-n-butyl-2,3,5,6-tetrafluorophenyl)-4-cyano-5-propion- amidopyrazole164 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(2- ethyl-3-methylbutyramido)pyrazole165 1-(2-bromo-4-trifluoromethylphenyl)-4-cyano-5-diacetyl- aminopyrazole166 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-di(3- methylbutyryl)aminopyrazole167 1-(4-chloro-2,3,5,6-tetrafluorophenyl)-4-cyano-5-diacetyl- aminopyrazole168 4-cyano-5-(N--isobutyryl-N--methoxycarbonyl)amino-1-(2,3,4- trichlorophenyl)pyrazole169 4-cyano-5-diacetylamino-1-(2-nitro-4-trifluoromethylphenyl)- pyrazole170 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(4- ethoxycarbonylbutyramido)pyrazole171 4-cyano-1-(4-methyl-2,3,6-trichlorophenyl)-5-propionamido- pyrazole172 5-acetamido-1-[4-sec-butyl-2,3,5,6-tetrafluorophenyl]-4- cyanopyrazole173 5-acetamido-4-cyano-1-(2,3,5,6-tetrafluoro-4-vinylphenyl)- pyrazole174 1-[4-sec-butyl-2,3,5,6-tetrafluorophenyl]-4-cyano-5- diacetylaminopyrazole175 1-(2-chloro-4-n-propylphenyl)-4-cyano-5-propionamido- pyrazole176 1-[4-sec-butyl-2,3,5,6-tetrafluorophenyl]-4-cyano-5-prop- ionamidopyrazole177 4-cyano-1-(2,3-dichloro-4-methylphenyl)-5-propionamido- pyrazole178 5-acetamido-4-cyano-1-(3,5-difluoro-2,4,6-trichlorophenyl)- pyrazole179 5-acetamido-1-(4-bromo-2,3,5,6-tetrafluorophenyl)-4- cyanopyrazole180 5-acetamido-4-cyano-1-(2,3-dichloro-4-methylphenyl)- pyrazole181 4-cyano-5-diacetylamino-1-(2,3,4,6-tetrachloro- phenyl)pyrazole182 4-cyano-5-diacetylamino-1-(2,3-dichloro-4-methyl- phenyl)pyrazole183 4-cyano-5-di(3-methylbutyryl)amino-1-(2,3,5,6- tetrafluoro-4-trifluoromethyl)pyrazole184 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5- (2-methylcyclopropylcarbonamido)pyrazole185 4-cyano-5-cyclopropylcarbonamido-1-(2,3,4,6- tetrachlorophenyl)pyrazole186 4-cyano-5-(2-methylcyclopropylcarbonamido)-1- (2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole187 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)- 5-(2-methylcyclopropylcarbonamido)pyrazole188 4-cyano-5-(2,2-dimethylsuccinimido)-1-(2,3,4- trichlorophenyl)pyrazole189 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5- di-(3-methylbutyryl)aminopyrazole______________________________________
The numbers 1 to 189 are assigned to the above compounds for identification and reference hereafter; compounds hereinafter identified by numbers are as indicated above.
Particularly preferred compounds according to the present invention are, referring to the identification by numbers hereinbefore indicated, Compounds Nos. 1, 2, 3, 5 to 10, 13 to 18, 20, 22 to 25, 27 to 31, 36, 40 to 44, 47, 54, 55, 57 to 65, 67, 68, 69, 72, 73, 75, 76, 77, 87, 89, 93, 96 to 99, 104, 105, 109, 110, 112, 113, 116, 117, 120, 123, 126, 128, 130, 131, 133, 134, 135, 137, 138, 139, 142, 143, 144, 148, 149, 151, 155, 162, 166, 167, 168, 178, 181, 183 to 187 and 189.
In experiments on herbicidal activity carried out on representative compounds of general formula II, the following results have been obtained:
EXPERIMENT 1
Test Methods
(a) Test Procedure (A)
The solutions of the test compounds were prepared by dissolving the test compounds in acetone. Application was from a standard laboratory herbicide sprayer using a flat fan jet travelling at 1.6 m.p.h. (2.6 km/hour) and delivering the equivalent of 530 liters of spray fluid per hectare, the spray pressure being 2.81 kg/cm.sup.2 (40 pounds/inch.sup.2). The solutions of the test compounds were prepared by dissolving 0.256 g of test compound in acetone and making up with more acetone to a volume of 34 ml, equivalent to an application rate of 4000 g of test compound per hectare. Solutions equivalent to application rates of 2000, 1000, 500, 250, 125, 63, 31, 16, 8 and 4 g/ha of test compound were then prepared by two-fold dilution with acetone.
Test Procedure (B)
The procedure described in Test Procedure (A) above was used except that a solution of test compound in acetone equivalent to an application rate of 2000 g/ha was prepared and solutions equivalent to application rates of 500, 125, 31 and 8 g/ha of test compounds were then prepared by four-fold serial dilution with acetone.
(b) Weed Control: Pre-emergence application
Weed seeds were sown on the surface of John Innes No. 1 potting compost (7 parts by volume of sterilized loam, 3 parts by volume of peat and 2 parts by volume of fine grit) in 9 cm diameter bitumenised paper pots. The quantities of seeds per pot were as follows:
______________________________________ Approximate numberWeed species seeds/pot______________________________________(i) Broad leafed weedsSinapis arvensis 30-40Polygonum lapathifolium 30-40Stellaria media 30-40(ii) Grass weedsAvena fatua 15-20Alopecurus myosuroides 30-40Echinochloa crus-galli 20-30______________________________________
The test compounds were applied to the uncovered seeds as described above in Procedures (A) or (B) and the seeds were covered with 25 ml of sharp sand after spraying. A single pot of each weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone. After treatment, the pots were kept in the greenhouse and were watered overhead.
Assessment Procedures
Assessment Procedure (i)
Visual assessment of weed control activity was made 19 to 28 days after spraying in comparison with unsprayed controls. The results were expressed as the minimum effective dose (MED) in kg/ha which gave 90% reduction in growth or kill of the weeds in comparison with plants in the control pots.
Assessment Procedure (ii)
Visual assessment of percentage weed destruction was made 19 to 28 days after spraying in comparison with unsprayed controls. The percentage weed destruction figures were then plotted against application rates on logarithmic-arithmetic paper to calculate the effective dose (ED.sub.90) in kg/ha which produced 90% destruction of weeds.
The results obtained are presented below in Tables I and II.
(c) Weed Control: Post-emergence application
Weed species were grown and then transplanted at the seedling stage into John Innes No. 1 potting compost in 9 cm diameter bitumenised paper pots, except for Avena fatua, which was sown directly in the test pot and not transplanted. The plants were then grown in the greenhouse until ready for spraying with the test compounds. The number of plants per pot and the growth stage of the plant at spraying were as follows:
______________________________________ Number of Growth stagesWeed species plants/pot at spraying______________________________________(i) Broad leafed weedsPolygonum lapathifolium 5 1-11/2 pairs of leavesStellaria media 5 4-6 leavesAbutilon theophrasti 3 2 pairs of leaves(ii) Grass weedsAvena fatua 10 1 leafAlopecurus myosuroides 5 11/2 leavesEchinochloa crus-galli 5 1-2 leaves______________________________________
The test compounds were applied to the plants as described above in Procedures (A) or (B). A single pot of each weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone. After spraying, the pots were kept in the greenhouse and watered overhead, commencing 24 hours after spraying. Assessment of the control of the growth of the weeds was made 19 to 28 days after spraying by Assessment Procedure (i) or (ii) described in (b) above. The results obtained are presented below in Tables III and IV.
EXPERIMENT 2
Test Method
Test Procedure
The solutions of the test compounds were prepared by dissolving the test compounds in acetone. Application was from a standard laboratory herbicide sprayer using a flat fan jet travelling at 1.6 m.p.h. (2.6 km/hour) and delivering the equivalent of 530 liters of spray fluid per hectare, the spray pressure being 2.81 kg/cm.sup.2 (40 pounds/inch.sup.2). The solutions of the test compounds were prepared by dissolving 0.0755 g of test compound in acetone (20 ml), equivalent to an application rate of 2000 g of test compound per hectare. Solutions equivalent to application rates of 500, 125, 32, 8 and 2 g/ha test compound were then prepared by four-fold serial dilution with acetone.
(b) Weed Control: Pre-emergence application
Weeds seeds were sown on the surface of John Innes No. 1 potting compost (7 parts by volume of sterilized loam, 3 parts by volume of peat and 2 parts by volume of fine grit) in 7 cm-square plastic pots. The quantities of seeds per pot were as follows:
______________________________________ Approximate numberWeed species of seeds/pot______________________________________(i) Broad leafed weedsChenopodium album 50Sinapis arvensis 30-40Abutilon theophrasti 15Ipomea purpurea 8(ii) Grass weeds and sedgesAvena fatua 15-20Echinochloa crus-galli 30Cyperus rotundus 3 nuts______________________________________
The test compounds were applied as described above and the seeds were covered with 25 ml of sharp sand after spraying. A single pot of each weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone. After treatment, the pots were kept in the greenhouse and watered overhead. Visual assessment of percentage weed destruction was made 21 days after spraying, in comparison with unsprayed controls. The percentage weed destruction figures were then plotted against application rates on logarithmic-arithmetic paper to calculate the effective dose (ED.sub.90) which produced 90% destruction of weeds. The results obtained are presented below in Table V.
(c) Weed Control: Post-emergence application
Weed species were grown and then transplanted at the seedling stage into John Innes No. 1 potting compost in 7 cm-square plastic pots, except for Avena fatua, which was sown directly in the test pot and not transplanted. The plants were then grown in the greenhouse until ready for spraying with the test compounds. The number of plants per pot and the growth stage of the plant at spraying were as follows:
______________________________________ Number of Growth stageWeed species plants/pot at spraying______________________________________(i) Broad leafed weedsChenopodium album 4 4 leavesSinapis arvensis 4 2 leavesAbutilon theophrasti 3 1-2 leavesIpomea purpurea 3 2 leaves(ii) Grass weeds and sedgesAvena fatua 10 1-2 leavesEchinochloa crus-galli 4 1-2 leavesCyperus rotundus 3 2-3 leaves______________________________________
The test compounds were applied as described above. A single pot of each weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone. After spraying, the pots were kept in the greenhouse and watered overhead, commencing 24 hours after spraying. Visual assessment of percentage weed destruction in comparison with unsprayed controls was made 14 days after spraying. The ED.sub.90 values were then calculated as described above. The results obtained are presented below in Table VI.
______________________________________KEY TO WEED SPECIES______________________________________(a) GRASS WEEDS AND SEDGES Af = Avena fatua Ec = Echinochloa crus-galli Am = Alopecurus myosuroides Cr = Cyperus rotundus(b) BROAD LEAF WEEDS Sm = Stellaria media Pl = Polygonum lapathifolium Sa = Sinapis arvensis At = Abutilon theophrasti Ca = Chenopodium album Ip = Ipomea purpurea______________________________________
TABLE I__________________________________________________________________________Test PRE-EMERGENCE MED (g/ha) [Assessment Procedure (i)]Compound Test Application ratesNo. Procedure Sm Pl Sa Af Ec Am applied (g/ha)__________________________________________________________________________1 A 250 63 63-125 125-250 125 250 16-10002 A 250 63-125 31-63 125-250 250 250 8-20003 A 500 31-63 125 125-250 125 125-250 4-20004 A NR 2000 500 4000 2000 >4000 500-40005 A 31 16 16-31 63 8-16 63 8-20006 A >2000 125 250 500-1000 125 500-1000 8-20007 A >>1000 125-250 125 >>1000 250-500 1000 4-10008 A 1000 125-250 125-250 >1000 250-500 1000 4-10009 A 16-31 31 8 63-125 31-63 63-125 4-100010 A 125-500 250 125 250-500 250-500 250-500 4-100011 A NR 250 1000-2000 >>2000 500-1000 >>2000 16-200012 B 2000 125-250 31 >2000 >>2000 500-2000 8-200013 B >>2000 125-500 125 >>2000 500-2000 >>2000 8-200014 A 31-63 63 31 63-125 63 63-125 31-100015 A 125-250 63-125 16-31 250 31-63 63 4-200016 A 125 63 31-63 125-250 31-63 63-125 4-100017 B 500-2000 125-500 125-500 >2000 500-2000 >2000 8-200018 B 500-2000 125-500 31-125 500 125 500 8-200019 B 2000 125-500 31 >2000 500-2000 >>2000 8-200020 B >2000 500-2000 125-500 500-2000 500-2000 2000 8-200021 A NR 500-1000 125-250 >1000 500-1000 >1000 4-100026 B 500 125- 500 31-125 500-2000 125-500 2000 8-200031 A 31-63 63-125 63 63-125 63-125 63-125 4-100032 B 1000-2000 500-1000 500-1000 1000-2000 500-1000 2000 8-4000__________________________________________________________________________
TABLE II__________________________________________________________________________ PRE-EMERGENCE ED90 (g/ha) [Assessment Procedure (ii)]Test Test Application ratesCompound No. Procedure Sm Pl Sa Af Ec Am applied (g/ha)__________________________________________________________________________22 B 1700 300 1000 >2000 1000 >>2000 8-200023 B 2000 125 1700 1900 1700 1900 8-200024 B 250 74 280 1400 125 380 8-200025 B 170 79 18 1500 250 500 8-200027 B 250 60 31 96 58 125 8-200028 B NR 2000 2000 NR 2000 NR 8-200029 B 330 18 300 90 80 350 8-200030 B >2000 380 380 2000 310 1700 8-200033 B 1800 500 250 >>2000 770 >2000 8-2000__________________________________________________________________________
TABLE III__________________________________________________________________________Test POST-EMERGENCE MED (g/ha) [Assessment Procedure (i)]Ccompound Test Application ratesNo. Procedure Sm Pl At Af Ec Am Cr applied__________________________________________________________________________ (g/ha)1 A 63-125 16 <16 >>1000 1000 >1000 >>1000 16-10002 A 31-63 8-16 8 2000 1000-2000 1000-2000 >>2000 8-20003 A 63-125 16 <4 1000 125-250 1000 >2000 4-20004 A NR <500 <500 NR NR >4000 NR 500-40005 A 63-125 16 <8 500 250-500 250-500 2000 8-20006 A NR 63 <8 >>2000 500-1000 2000 >>2000 8-20007 A >>1000 63-125 16 >>1000 500-1000 >>1000 -- 4-10008 A >>1000 63-125 16 >>1000 500-1000 NR -- 4-10009 A 8 4-8 <4 250 125-250 250 1000 4-100010 A 16 8-16 <4 1000 1000 1000 >1000 4-100011 A NR 63-125 <16 >>2000 >2000 >2000 NR 16-200012 B >>2000 31 <8 >>2000 500 >>2000 >>2000 8-200013 B >2000 125-500 8-31 NR 500 >>2000 NR 8-200014 A 31-63 <31 500 500 500 1000 >1000 31-100015 A 63-125 8-16 <4 2000 500-1000 500-1000 <2000 4-2000 (2000 only for Cr)16 A 63-125 16-31 <4 500-1000 500 500-1000 >1000 4-100017 B 125-500 8 <8 >2000 500-2000 >2000 >>2000 8-200018 B 125 8 <8 2000 125 2000 >2000 8-200019 B >2000 8-31 <8 2000 500 >2000 NR 8-200020 B >2000 31-125 <8 >2000 500 >>2000 >>2000 8-200021 A NR 125-250 8-16 >>1000 >>1000 >>1000 >>1000 4-100026 B 125-500 8-31 <8 >2000 500 2000 >>2000 8-200031 A 16 8-16 <4 1000 1000 1000 >1000 4-100032 B 2000 250 125 >>4000 >4000 NR >>4000 8-4000__________________________________________________________________________
TABLE IV__________________________________________________________________________ POST-EMERGENCE ED90 (g/ha) [Assessment Procedure (ii)]Test Test Application ratesCompound No. Procedure Sm Pl At Af Ec Am Cr applied (g/ha)__________________________________________________________________________22 B >>2000 58 31 >>2000 >2000 >>2000 NR 8-200023 B >>2000 25 20 >>2000 1600 >>2000 NR 8-200024 B 74 8 <8 >>2000 1200 1200 >>2000 8-200025 B 41 <8 <8 >2000 1700 2000 >>2000 8-200027 B 17 <8 <8 1100 200 500 2000 8-200028 B >>2000 16 <8 >>2000 >2000 >>2000 >>2000 8-200029 B 12 <8 <8 94 16 58 2000 8-200030 B 1400 31 <8 >>2000 400 500 2000 8-200033 B 500 125 14 >>2000 >>2000 >>2000 NR 8-2000__________________________________________________________________________
TABLE V__________________________________________________________________________ PRE-EMERGENCE ED90 (g/ha)Test Application ratesCompound No. Ca Sa At Ip Af Ec Cr applied (g/ha)__________________________________________________________________________34 8 70 18 1300 2000 125 >2000 8-200035 -- 60 60 500 >2000 500 >2000 8-200036 8 115 70 1100 >>2000 240 >>2000 8-200037 -- 72 22 500 >2000 460 NR 8-200038 -- 400 31 500 2000 180 2000 8-200039 -- 125 8 200 2000 125 1100 8-200040 -- 8 8 27 32 27 125 2-50041 -- 300 420 >2000 125 31 1250 8-200042 -- 31 94 2000 125 27 500 8-200043 -- 26 31 1100 105 20 125 8-200044 -- 125 125 2000 240 115 125 8-200045 -- 270 1050 NR >>2000 1100 NR 8-200046 -- 500 390 1900 1450 480 >>2000 8-200047 -- 31 31 250 500 31 500 8-200048 -- 74 60 >2000 2000 300 >>2000 8-200049 -- 180 1000 >2000 >>2000 500 >>2000 8-200050 -- 1100 660 >>2000 >>2000 1000 NR 8-200051 -- <8 31 500 220 125 260 8-200052 -- 1700 2000 >2000 >>2000 >2000 >2000 8-200053 -- 70 32 500 2000 500 >>2000 8-200054 -- 2 27 125 125 31 460 2-50055 -- 64 32 2000 160 125 500 8-200056 -- 31 64 2000 500 125 >2000 8-200057 -- 120 44 >500 125 66 500 2-50058 125 29 8 32 125 120 480 2-50059 125 240 31 1600 2000 500 >>2000 8-200060 125 430 125 50 >>2000 500 >>2000 8-200061 -- 27 8 27 125 29 125 2-50062 -- 17 8 56 125 31 125 2-50063 2 93 32 420 125 120 500 2-50064 <2 7 7 100 32 30 125 2-50065 -- 31 125 125 125 86 >125 2-12566 -- 110 125 >>2000 NR 1700 NR 8-200067 -- 120 120 1100 2000 220 500 8-200068 -- 31 31 450 >>2000 240 1200 8-200069 -- 8 8 780 2000 500 500 8-200070 -- <8 31 500 500 125 >2000 8-200071 -- 320 205 1600 2000 450 > >2000 8-200072 -- 32 29 110 125 120 430 8-200073 -- <8 <8 125 110 40 110 8-200074 -- 1500 270 >2000 860 320 500 8-200075 -- 110 100 720 840 180 840 8-200076 -- 100 31 500 500 160 500 8-200077 -- 6 6 82 94 31 107 2-50078 400 125 <8 500 >>2000 900 >2000 8-200079 -- 70 18 240 240 62 2000 8-200080 -- 400 180 1800 2000 1900 NR 8-200081 32 500 100 900 1700 480 2000 8-200082 -- 115 31 2000 2000 500 500 8-200083 -- 250 250 500 1800 500 500 8-200084 -- 210 32 >2000 >>2000 >2000 NR 8-200085 240 50 32 62 500 400 > 500 2-50086 <2 11 32 125 500 500 NR 2-50087 32 60 28 420 125 120 500 2-50088 -- 500 400 500 500 470 2000 8-200089 -- 120 260 >>500 125 125 >>500 2-50090 -- 1900 500 >>2000 >>2000 2000 >>2000 8-200091 -- 1000 32 >>2000 >>2000 1800 >>2000 8-200092 -- 120 110 >>500 >>500 >>500 >>500 2-50093 -- 8 7 66 100 31 125 2-50094 -- 430 220 2000 >2000 1800 1800 8-200095 -- 500 120 >>500 >>500 500 >>500 2-50096 -- 125 32 >500 >>500 >> 500 NR 2-50097 32 110 32 58 125 110 125 8-200098 -- 10 12 32 70 70 -- 2-50099 -- 8 8 125 110 50 -- 2-500100 16 8 31 125 125 240 >500 2-500101 <8 <8 <8 >2000 2000 >2000 NR 8-2000102 125 16 8 125 450 450 >500 2-500103 100 8 32 430 >>500 500 NR 2-500104 8 7 7 32 32 29 125 2-500105 13 8 7 55 31 31 32 2-500106 8 120 110 500 >500 190 -- 2-500107 31 120 29 125 125 125 -- 2-500108 8 58 31 390 500 500 -- 2-500109 58 12 5 58 125 110 -- 2-500110 31 54 15 100 125 240 -- 2-500111 47 32 27 125 125 120 500 2-500112 8 12 8 56 56 62 170 2-500113 <8 8 32 900 125 490 2000 8-2000114 <8 500 125 2000 2000 1100 >>2000 8-2000115 <8 32 32 2000 500 490 2000 8-2000116 <2 125 32 210 160 450 500 2-500117 <2 8 45 210 62 120 210 2-500118 8 500 2000 2000 125 500 800 8-2000119 2 30 8 62 32 32 120 2-500120 2 70 50 >500 >500 500 >>500 2-500121 2 8 8 70 68 32 125 2-500122 32 500 42 640 640 280 2000 8-2000123 <2 30 8 68 46 30 125 2-500129 -- 32 125 >>500 230 >>500 NR 2-500130 -- 32 14 18 125 125 500 2-500131 -- 31 32 500 470 120 2000 8-2000132 -- 115 >500 >500 NR 500 NR 2-500133 -- 430 120 2000 1900 490 >2000 8-2000134 <8 <8 <8 1800 500 440 2000 8-2000135 -- 31 8 110 110 110 -- 2-500136 -- 450 500 >>500 340 >500 -- 2-500137 <8 <8 30 110 120 170 >2000 8-2000138 <8 14 29 260 230 170 >2000 8-2000139 8 8 14 125 430 220 500 8-2000140 <8 <8 <8 500 >2000 160 NR 8-2000141 <8 32 58 270 1700 500 2000 8- 2000142 <8 <8 <8 125 490 125 1900 8-2000143 31 12 2 125 120 110 -- 2-500144 2 <2 5 125 120 110 >500 2-500145 2 8 125 125 110 >500 >>500 2-500146 8 32 500 160 500 >>500 >500 2-500147 8 220 1000 2000 125 >>2000 NR 8-2000148 <2 29 18 70 230 70 300 2-500149 <2 8 2 70 125 70 120 2-500150 8 500 120 500 500 1800 NR 8-2000151 <2 300 58 500 500 480 >500 2-500152 8 210 125 >>2000 >>2000 2000 >>2000 8-2000153 120 2000 280 >2000 2000 500 2000 8-2000154 8 840 490 640 640 490 2000 8-2000__________________________________________________________________________
TABLE VI__________________________________________________________________________ POST-EMERGENCE ED90 (g/ha)Test Application ratesCompound No. Ca Sa At Ip Af Ec Cr applied (g/ha)__________________________________________________________________________34 8 54 8 270 >2000 >2000 >2000 8-200035 <8 8 <8 300 >>2000 2000 >>2000 8-200036 <8 410 <8 27 >>2000 500 >>2000 8-200037 90 500 8 30 >>2000 1100 >>2000 8-200038 31 1200 <8 2000 >>2000 900 >2000 8-200039 15 270 <8 <8 >2000 470 2000 8-200040 2 8 <2 8 25 110 500 2-50041 16 330 <8 31 125 270 >2000 8-200042 89 115 22 1600 500 125 460 8-200043 80 76 <8 1500 125 76 1700 8-200044 <8 18 <8 18 240 80 2000 8-200045 500 2000 <8 1000 NR >>2000 NR 8-200046 31 410 18 125 >>2000 >>2000 >>2000 8-200047 <8 31 <8 31 1300 500 2000 8-200048 125 245 14 840 >>2000 >2000 NR 8-200049 70 500 23 500 >>2000 >2000 NR 8-200050 54 500 15 500 >>2000 >>2000 NR 8-200051 <8 125 <8 31 2000 500 >>2000 8-200052 8 460 <8 1700 >>2000 >2000 NR 8-200053 8 125 <8 110 NR >2000 NR 8-200054 2 95 6 15 500 125 >>500 2-50055 <8 60 <8 27 1600 125 2000 8-200056 32 310 32 24 500 125 2000 8-200057 8 260 7 110 >500 120 >500 2-50058 29 125 2 2 >500 230 >>500 2-50059 <8 2000 <8 32 >2000 2000 NR 8-200060 31 1700 28 31 2000 1600 NR 8-200061 <2 74 2 6 125 74 500 2-50062 2 110 <2 8 125 120 500 2-50063 2 125 6 3 500 450 >500 2-50064 <2 32 <2 7 125 60 500 2-50065 8 125 2 7 >>125 86 NR 2-12566 1650 1450 23 >2000 >>2000 >>2000 NR 8-200067 <8 125 <8 8 > 2000 500 2000 8-200068 31 300 <8 82 >>2000 1800 2000 8-200069 95 125 <8 27 >>2000 250 2000 8-200070 15 1600 <8 47 >2000 >2000 >>2000 8-200071 125 450 31 500 >2000 2000 >>2000 8-200072 20 64 8 27 500 125 900 8-200073 <8 32 <8 <8 125 125 500 8-200074 78 2000 125 1900 2000 1450 >2000 8-200075 31 460 <8 120 >>2000 480 >2000 8-200076 125 125 <8 400 1100 450 >>2000 8-200077 2 48 2 26 125 85 500 2-50078 125 90 68 125 >2000 2000 >>2000 8-200079 56 500 8 210 1200 500 >2000 8-200080 125 32 70 500 >>2000 >>2000 NR 8-200081 340 2000 8 125 >>2000 1800 >>2000 8-200082 31 2000 <8 500 >>2000 2000 NR 8-200083 31 500 125 125 >>2000 2000 NR 8-200084 125 1500 32 1400 >>2000 2000 NR 8-200085 14 100 8 17 >>500 500 >>500 2-50086 27 125 8 27 >500 500 >>500 2-50087 8 100 7 32 500 500 >>500 2-50088 <8 2000 <8 125 >2000 500 >>2000 8-200089 20 370 32 >500 500 125 >>500 2-50090 125 1600 32 1600 >>2000 >>2000 NR 8-200091 2000 >2000 8 >>2000 >>2000 2000 >>2000 8- 200092 92 32 32 500 >>500 >>500 NR 2-50093 2 12 <2 22 125 32 450 2-50094 460 190 25 420 >>2000 >2000 NR 8-200095 32 370 27 125 >>500 >>500 NR 2-50096 125 >500 32 500 NR NR NR 2-50097 125 380 <8 125 500 D 420 2000 8-200098 2 2 <2 2 230 110 230 2-50099 6 8 6 6 500 125 >500 2-500100 26 66 2 60 >500 450 >>500 2-500101 2000 170 <8 500 >>2000 >>2000 NR 8-2000102 8 8 6 8 500 125 >500 2-500103 27 8 32 32 >500 230 >>500 2-500104 7 13 <2 8 62 100 500 2-500105 8 8 2 <2 125 125 125 2-500106 8 60 8 32 >>500 >>500 >>500 2-500107 26 125 7 26 >500 >>500 >>500 2-500108 15 47 <2 8 >>500 >>500 >>500 2-500109 8 32 <2 <2 125 110 500 2-500110 12 125 6 <2 500 >500 >>500 2-500111 15 32 8 68 >500 >500 >>500 2-500112 8 15 2 8 500 230 >500 2-500113 60 125 70 100 >>2000 >2000 >>2000 8-2000114 900 2000 125 180 >>2000 >> 2000 >>2000 8-2000115 500 >2000 32 2000 >2000 2000 NR 8-2000116 125 125 32 160 >500 >500 >>500 2-500117 12 56 14 125 500 260 >500 2-500118 500 900 2000 110 500 500 1100 8-2000119 8 45 6 7 125 210 >500 2-500120 125 210 42 125 >>500 NR NR 2-500121 68 53 8 110 500 120 >500 2-500122 125 260 32 110 2000 2000 >>2000 8-2000123 8 17 2 8 500 440 >500 2-500129 125 2 8 125 >500 >>500 >500 2-500130 8 125 2 27 400 110 >500 2-500131 8 32 <8 32 750 125 >>2000 8-2000132 500 32 24 125 >>500 >>500 NR 2-500133 125 280 8 800 >>2000 1200 >>2000 8-2000134 <8 500 < <8 >2000 >>2000 NR 8-2000135 6 100 125 125 >500 380 >500 2-500136 125 32 8 500 >>500 >>500 NR 2-500137 8 30 <8 <8 500 110 >2000 8-2000138 <8 32 <8 40 2000 450 >2000 8-2000139 8 65 <8 25 500 240 >2000 8-2000140 125 240 14 32 >>2000 >2000 NR 8-2000141 8 240 32 30 >2000 >2000 >>2000 8-2000142 <8 70 <8 32 2000 740 >2000 8-2000143 7 50 7 12 300 125 500 2-500144 2 25 5 6 125 110 125 2-500145 125 8 12 7 >500 >500 >>500 2-500146 16 8 14 18 125 NR >>500 2-500147 500 32 30 500 2000 >>2000 NR 8-2000148 8 32 7 12 >500 330 >>500 2-500149 8 53 2 60 230 160 >500 2-500150 500 >2000 32 420 >>2000 >2000 NR 8-2000151 32 430 6 8 460 NR >>500 2-500152 125 840 500 >2000 >>2000 NR NR 8-2000153 280 >>2000 500 640 2000 1000 >>2000 8-2000154 500 >2000 240 110 1800 1800 NR 8-2000__________________________________________________________________________
The following symbols which appear in the above Tables have the following meanings:
">>" means much greater than
">" means greater than
"<" means less than
"NR" means no reduction at any dose rate applied
"-" means not tested
According to a feature of the present invention, there is provided a method for controlling the growth of weeds (i.e. undesired vegetation) at a locus which comprises applying to the locus a herbicidally effective amount of at least one N-phenylpyrazole derivative of general formula II. For this purpose, the N-phenylpyrazole derivatives are normally used in the form of herbicidal compositions (i.e. in association with compatible diluents or carriers suitable for use in herbicidal compositions), for example as hereinafter described.
The compounds of general formula II show herbicidal activity against dicotyledonous (i.e. broad-leafed) and monocotyledonous (e.g. grass) weeds by pre- and/or, post-emergence application.
By the term "pre-emergence application" is meant application to the soil in which the weed seeds or seedlings are present before emergence of the weeds above the surface of the soil. By the term "post-emergence application" is meant application to the aerial or exposed portions of the weeds which have emerged above the surface of the soil. For example, the compounds of general formula II may be used to control the growth of broad-leafed weeds, for example, Aethusa cynapium, Abutilon theophrasti, Amaranthus retroflexus, Amsinckia intermedia, Anagallis arvensis, Anthemis arvensis, Atriplex patula, Bidens pilosa, Brassica nigra, Capsella bursa-pastoris, Chenopodium album, Chrysanthemum segetum, Cirsium arvense, Datura stramonium, Desmodium tortuosum, Emex australis, Euphorbia helioscopia, Fumaria officinalis, Galeopsis tetrahit, galium aparine, Geranium dissectum, Ipomea purpurea, Lamium pupureum, lapsana communis, Matricaria inodora, Monochoria vaginalis, Papaver rhoeas, Physalis longifolia, Plantago lanceolata, Polygonum spp., (e.g. Polygonum lapathifolium, Polygonum aviculare, Polygonum convolvulus and Polygonum persicaria), Portulaca oleracea, Raphanus raphanistrum, Rotala indica, Rumex obtusifolius, Saponaria vaccaria, Scandix pectenveneris Senecio vulgaris, Sesbania florida, Sida spinosa, Silene alba, Sinapis arvensis, Solanum nigrum, Sonchus arvensis, Spergula arvensis, Stellaria media, Thlaspi arvense, Tribulus terrestria, Urtica urens, Veronica hederifolia, Veronica persica, Viola arvensis and Xanthium strumarium, and grass weeds, for example, Alopercurus myosuroides, Apera spica-venti, Agrostis stolonifera, Avena fatua, Avena ludoviciana, Brachiaria spp., Bromus sterilis, Bromus tectorum, Cenchrus spp., Cynodon dactylon, Digitaria sanquinalis, Echinochloa crus-galli, Eleusine indica, Setaria viridis and Sorghum halepense and sedges, for example Cyperus esculentus, Cyperus iria and Cyperus rotundus, and Eleocharis acicularis.
The amounts of compounds of general formula II applied vary with the nature of the weeds, the compositions used, the time of application, the climatic and edaphic conditions and (when used to control the growth of weeds in crop-growing areas) the nature of the crops. When applied to a crop-growing area, the rate of application should be sufficient to control the growth of weeds without causing substantial permanent damage to the crop. In general, taking these factors into account, application rates between 0.01 kg and 10 kg of active material per hectare give good results. However, it is to be understood that higher or lower application rates may be used, depending upon the particular problem of weed control encountered.
The compounds of general formula II may be used to control selectively the growth of weeds, for example to control the growth of those species hereinbefore mentioned, by pre- or post-emergence application in a directional or non-directional fashion, e.g. by directional or non-directional spraying, to a locus of weed infestation which is an area used, or to be used, for growing crops, for example cereals, e.g. wheat, barley, oats, maize and rice, soya beans, field and dwarf beans, peas, lucerne, cotton, peanuts, flax, onions, carrots, cabbage, oilseed rape, sunflower, sugar beet, and permanent or sown grassland before or after sowing of the crop or before or after emergence of the crop. For the selective control of weeds at a locus of weed infestation which is an area used, or to be used, for the growing of crops, e.g. the crops hereinbefore mentioned, application rates between 0.01 kg and 4.0 kg, and preferably between 0.01 kg and 2.0 kg, of active material per hectare are particularly suitable. More particularly, the compounds of general formula II may be used to control selectively the growth of broad leafed weeds, for example to control the growth of those broad leafed species hereinbefore mentioned, by pre, or more especially, post-emergence application in a non-directional fashion, e.g. by non-directional spraying, to an area used for growing cereal crops, e.g. wheat, barley, oats, maize and rice before or after emergence of both the crop and weeds and to control selectively the growth of broad-leafed and grass weeds, for example to control the growth of those broad-leafed weed species hereinbefore mentioned, by pre-emergence application in a non-directional fashion, e.g. by non-directional spraying, to an area to be used for growing soya beans or cotton before the emergence of both the crop and weeds.
For these purposes, i.e. the selective control of broad-leafed weeds by pre- or post-emergence application to an area used for growing cereal crops or by pre-emergence application to an area to be used for growing soya beans or cotton, application rates between 0.01 and 4.0 kg, and preferably between 0.01 kg and 2.0 kg, of active material per hectare are particularly suitable.
The compounds of general formula II may also be used to control the growth of weeds, especially those indicated above, by pre- or post-emergence application in established orchards and other tree-growing areas, for example forests, woods and parks, and plantations, e.g. sugar cane, oil palm and rubber plantations. For this purpose they may be applied in a directional or non-directional fashion (e.g. by directional or non-directional spraying) to the weeds or to the soil in which they are expected to appear, before or after planting of the trees or plantations at application rates between 0.25 kg and 10.0 kg, and preferably between 1.0 kg and 4.0 kg, of active material per hectare.
The compounds of general formula II may also be used to control the growth of weeds, especially those indicated above, at loci which are not crop-growing areas but in which the control of weeds is nevertheless desirable. Examples of such non-crop-growing areas include airfields, industrial sites, railways, roadside verges, the verges of rivers, irrigation and other waterways, scrublands and fallow or uncultivated land, in particular where it is desired to control the growth of weeds in order to reduce fire risks. When used for such purposes in which a total herbicidal effect is frequently desired, the active compounds are normally applied at dosage rates higher than those used in crop-growing areas as hereinbefore described. The precise dosage will depend upon the nature of the vegetation treated and the effect sought. Pre- or post-emergence application, and preferably pre-emergence application, in a directional or non-directional fashion (e.g. by directional or non-directional spraying) at application rates between 2.0 kg and 10.0 kg, and preferably between 4.0 and 10.0 kg, of active material per hectare are particularly suitable for this purpose.
When used to control the growth of weeds by pre-emergence application, the compounds of general formula II may be incorporated into the soil in which the weeds are expected to emerge. It will be appreciated that when the compounds of general formula II are used to control the growth of weeds by post-emergence application, i.e. by application to the aerial or exposed portions of emerged weeds, the compounds of general formula II will also normally come into contact with the soil and may also then exercise a pre-emergence control on later-germinating weeds in the soil.
Where especially prolonged weed control is required, the application of the compounds of general formula II may be repeated if required.
According to a further feature of the present invention, there are provided compositions suitable for herbicidal use comprising one or more of the N-phenylpyrazole derivatives of general formula II in association with, and preferably homogeneously dispersed in, one or more compatible herbicidally-acceptable diluents or carriers (i.e. diluents or carriers of the type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of general formula II). The term "homogeneously dispersed" is used to include compositions in which the compounds of general formula II are dissolved in the other components. The term "herbicidal compositions" is used in a broad sense to include not only compositions which are ready for use as herbicides but also concentrates which must be diluted before use. Preferably, the compositions contain from 0.05 to 90% by weight of one or more compounds of general formula II.
The herbicidal compositions may contain both a diluent or carrier and a surface-active (e.g. wetting, dispersing, or emulsifying) agent. Surface-active agents which may be present in herbicidal compositions of the present invention may be of the ionic or non-ionic types, for example sulphoricinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with nonyl- or octyl-phenols, or carboxylic acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxy groups by condensation with ethylene oxide, alkali and alkaline earth metal salts of sulphuric acid esters and sulphonic acids such as dinonyl- and dioctyl-sodium sulphonosuccinates and alkali and alkaline earth metal salts of high molecular weight sulphonic acid derivatives such as sodium and calcium lignosulphonates.
Suitably, herbicidal compositions according to the present invention may comprise from 0.05% to 10% of surface-active agent but, if desired, herbicidal compositions according to the present invention may comprise higher proportions of surface-active agent, for example up to 15% in liquid emulsifiable suspension concentrates and up to 25% in liquid water soluble concentrates.
Examples of suitable solid diluents or carriers are aluminium silicate, talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent carbon black and clays such as kaolin and bentonite. The solid compositions (which may take the form of dusts, granules or wettable powders) are preferably prepared by grinding the compounds of general formula II with solid diluents or by impregnating the solid diluents or carriers with solutions of the compounds of general formula II in volatile solvents, evaporating the solvents and, if necessary, grinding the products so as to obtain powders. Granular formulations may be prepared by absorbing the compounds of general formula II (dissolved in volatile solvents) onto the solid diluents or carriers in granular form and evaporating the solvents, or by granulating compositions in powder form obtained as described above. Solid herbicidal compositions, particularly wettable powders, may contain wetting or dispersing agent (for example of the types described above), which may also, when solid, serve as diluents or carriers.
Liquid compositions according to the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may incorporate a surface-active agent. Suitable liquid diluents for incorporation in the liquid compositions include water, acetophenone, cyclohexanone, isophorone, toluene, xylene and mineral, animal and vegetable oils (and mixtures of these diluents). Surface-active agents, which may be present in the liquid compositions, may be ionic or non-ionic (for example of the types described above) and may, when liquid, also serve as diluents or carriers.
Wettable powders and liquid compositions in the form of concentrates may be diluted with water or other suitable diluents, for example mineral or vegetable oils, particularly in the case of liquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use. When desired, liquid compositions of the compound of general formula II may be used in the form of self-emulsifying concentrates containing the active substances dissolved in the emulsifying agents or in solvents containing emulsifying agents compatible with the active substances, the simple addition of water to such concentrates producing compositions ready for use.
Liquid concentrates in which the diluent or carrier is an oil may be used without further dilution using the electrostatic spray technique.
Herbicidal compositions according to the present invention may also contain, if desired, conventional adjuvants such as adhesives, protective colloids, thickeners, penetrating agents, stabilisers, sequestering agents, anti-caking agents, colouring agents and corrosion inhibitors. These adjuvants may also serve as carriers or diluents.
Preferred herbicidal compositions according to the present invention are aqueous suspension concentrates which comprise from 10 to 70% w/v of one or more compounds of general formula II, from 2 to 10% w/v of surface-active agent, from 0.1 to 5% w/v of thickener and from 15 to 87.9% by volume of water; wettable powders which comprise from 10 to 90% w/w of one or more compounds of general formula II, from 2 to 10% w/w of surface-active agent and from 10 to 88% w/w of solid diluent or carrier; liquid water soluble concentrates which comprise from 10 to 30% w/v of one or more compounds of general formula II, from 5 to 25% w/v of surface-active agent and from 45 to 85% by volume of water-miscible solvent, e.g. dimethylformamide; liquid emulsifiable suspension concentrates which comprise from 10 to 70% w/v of one or more compounds of general formula II, from 5 to 15% w/v of surface-active agent, from 0.1 to 5% w/v of thickener and from 10 to 84.9% by volume of organic solvent; granules which comprise from 2 to 10% w/w of one or more compounds of general formula II, from 0.5 to 2% w/w of surface active agent and from 88 to 97.5% w/w of granular carrier, and emulsifiable concentrates which comprise from 0.05 to 90% w/v, and preferably from 1 to 60% w/v, of one or more compounds of general formula II, from 0.01 to 10% w/v, and preferably from 1 to 10% w/v, of surface-active agent and from 9.99 to 99.4%, and preferably from 39 to 98.99%, by volume of organic solvent.
Herbicidal compositions according to the present invention may also comprise the compounds of general formula II in association with, and preferably homogeneously dispersed in, one or more other pesticidally active compounds and, if desired, one or more compatible pesticidally acceptable diluents or carriers, surface-active agents and conventional adjuvants as hereinbefore described. Examples of other pesticidally active compounds which may be included in, or used in conjunction with, the herbicidal compositions of the present invention include herbicides, for example to increase the range of weed species controlled, for example alachlor[.alpha.-chloro-2,6-diethyl-N-(methoxymethyl)acetanilide], asulam[methyl(4-aminobenzenesulphonyl)-carbamate], alloxydim Na[sodium salt of 2-(1-allyloxyiminobutylidene)-5,5-dimethyl-4-methoxycarbonylcyclohexane-1,3-dione], atrazine[2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine], barban[4-chlorobut-2-ynyl N-(3-chlorophenyl)carbamate], benzoylprop-ethyl[ethyl N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate], bromoxynil[3,5-dibromo-4-hydroxybenzonitrile], butachlor[N-(butoxymethyl)-.alpha.-chloro-2,6-diethylacetanilide], butylate[S-ethyl N,N-diisobutyl(thiocarbamate)], carbetamide[D-N-ethyl-2-(phenylcarbamoyloxy)propionamide], chlorfenprop-methyl[methyl 2-chloro-3-(4-chlorophenyl)propionate], chloropropham[isopropyl N-(3-chlorophenyl)carbamate], chlortoluron[N'-(3-chloro-4-methylphenyl)-N,N-dimethylurea], cyanazine[2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-1,3,5-triazine], cycloate[N'-cyclohexyl-N-ethyl-S-ethyl(thiocarbamate)], 2,4-D[2,4-dichlorophenoxyacetic acid], dalapon[2,2-dichloropropionic acid], 2,4-DB[4-(2,4-dichlorophenoxy)butyric acid], desmedipham[3-(ethoxycarbonylamino)phenyl N-phenyl-carbamate], diallate[S-2,3-dichloroallyl-N,N-di-isopropyl(thiocarbamate)], dicamba[3,6-dichloro-2-methoxybenzoic acid], dichlorprop[(.+-.)-2-(2,4-dichlorophenoxy)propionic acid], difenzoquat[1,2-dimethyl-3,5-diphenyl-pyrazolium salts], dimefuron{4-[2-chloro-4-(3,3-dimethylureido)phenyl]-2-t-butyl-1,3,4-oxadiazolin-5-one}, dinitramine[N.sup.1,N.sup.1 -diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine], diuron[N'-(3,4-dichlorophenyl)-N,N-dimethylurea], EPTC[S-ethyl N,N-dipropyl(thiocarbamate)], ethofumesate[2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl methylsulphonate], flampropisopropyl[isopropyl(.+-.)-2-(N-benzoyl-3-chloro-4-fluoroanilino)propionate], flampropmethyl[methyl(.+-.)-2-N-benzoyl-3-chloro-4-fluoroanilino)-propionate], fluometuron[N'-(3-trifluoromethylphenyl)-N,N-dimethylurea], ioxynil[4-hydroxy-3,5-di-iodobenzonitrile], isoproturon[N'-(4-isopropylphenyl)-N,N-dimethylurea], linuron[N-(3,4-dichlorophenyl)-N-methoxy-N-methylurea], MCPA[4-chloro-2-methylphenoxyacetic acid], MCPB[4-(4-chloro-2-methylphenoxy)butyric acid], mecoprop[(.+-.)-2-(4-chloro-2-methylphenoxy)propionic acid], metamitron[4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one], methabenzthiazuron[N-(benzothiazol-2-yl)-N,N'-dimethylurea], metribuzin[4-amino-6-t-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one], molinate[S-ethyl N,N-hexamethylene(thiocarbamate)], oxadiazon[3-(2,4-dichloro-5-isopropoxyphenyl)-5-t-butyl-1,3,4-oxadiazolin-2-one], paraquat[1,1'-dimethyl-4,4'-bipyridylium salts], pebulate[S-propyl N-butyl-N-ethyl(thiocarbamate)], phenmedipham[3-(methoxycarbonylamino)phenyl N-(3-methylphenyl)carbamate], prometryne[4,6-bisisopropylamino-2-methylthio-1,3,5-triazine], propachlor[.alpha.-chloro-N-isopropylacetanilide], propanil[N-(3,4-dichlorophenyl)propionamide], propham[isopropyl N-phenylcarbamate], pyrazone[5-amino-4-chloro-2-phenylpyridazin-3(2H)-one], simazine[2-chloro-4,6-bisethylamino-1,3,5-triazine], TCA (trichloroacetic acid), thiobencarb[S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate], tri-allate[S-2,3,3-trichloroallyl N,N-di-isopropyl(thiocarbamate)] and trifluralin[2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline]; insecticides, e.g. carbaryl[naphth-1-yl N-methylcarbamate]; synthetic pyrethroids e.g. permethrin and cypermethrin; and fungicides, e.g. 2,6-dimethyl-4-tridecyl-morpholine, methyl N-(1-butyl-carbamoyl-benzimidazol-2-yl)carbamate, 1,2-bis-(3-methoxycarbonyl-2-thioureido)benzene, isopropyl 1-carbamoyl-3-(3,5-dichlorophenyl)hydantoin and 1-(4-chloro-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one. Other biologically active materials which may be included in, or used in conjunction with, the herbicidal compositions of the present invention are plant growth regulators, e.g. succinamic acid, (2-chloroethyl)trimethylammonium chloride and 2-chloroethane-phosphonic acid; or fertilizers, e.g. containing nitrogen, potassium and phosphorus and trace elements known to be essential to successful plant life, e.g. iron, magnesium, zinc, manganese, cobalt and copper.
Pesticidally active compounds and other biologically active materials which may be included in, or used in conjunction with, the herbicidal compositions of the present invention, for example those hereinbefore mentioned, and which are acids, may, if desired, be utilized in the form of conventional derivatives, for example alkali metal and amine salts and esters.
According to a further feature of the present invention there is provided an article of manufacture comprising at least one of the N-phenyl-pyrazole derivatives of general formula II or, as is preferred, a herbicidal composition as hereinbefore described, and preferably a herbicidal concentrate which must be diluted before use, comprising at least one of the N-phenylpyrazole derivatives of general formula II within a container for the aforesaid derivative or derivatives of general formula II, or a said herbicidal composition, and instructions physically associated with the aforesaid container setting out the manner in which the aforesaid derivative or derivatives of general formula II or herbicidal composition contained therein is to be used to control the growth of weeds. The containers will normally be of the types conventionally used for the storage of chemical substances which are solid at normal ambient temperatures and herbicidal compositions particularly in the form of concentrates, for example cans and drums of metal, which may be internally-lacquered, and plastics materials, bottles of glass and plastics materials and, when the contents of the container is a solid, for example granular, herbicidal compositions, boxes, for example of cardboard, plastics materials and metal, or sacks. The containers will normally be of sufficient capacity to contain amounts of the N-phenylpyrazole derivative or herbicidal compositions sufficient to treat at least one acre of ground to control the growth of weeds therein but will not exceed a size which is convenient for conventional methods of handling. The instructions will be physically associated with the container, for example by being printed directly thereon or on a label or tag affixed thereto. The directions will normally indicate that the contents of the container, after dilution if necessary, are to be applied to control the growth of weeds at rates of application between 0.01 kg and 10 kg of active material per hectare in the manner and for the purposes hereinbefore described.

The following Examples illustrate herbicidal compositions according to the present invention.
EXAMPLE 1
5-Acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole was formulated as a water soluble concentrate containing
______________________________________5-acetamido-4-cyano-1-(2,3,4- 10% w/v (weight/trichlorophenyl)-pyrazole volume)Ethylan KEO (nonylphenyl/ethylene 10% w/voxide condensate containing 9-10 moles ofethylene oxide per mol of phenol)Dimethylformamide to 100% by volume,______________________________________
by dissolving the Ethylan KEO in a portion of dimethylformamide and then adding the active ingredient with heating and stirring until dissolved. The resulting solution was then made up to 100% by volume by adding the rest of the dimethylformamide.
5 Liters of the above formulation may be dissolved in 200 liters of water and sprayed post-emergence onto 1 hectare of an emerged crop of spring-sown wheat to control Amaranthus retroflexus, Setaria viridis, Polygonum lapathifolium, Abutilon theophrasti and Solanum nigrum.
The 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole may, if desired, be replaced in the above water soluble concentrate by any other compound of general formula II.
EXAMPLE 2
A wettable powder was formed from:
______________________________________5-acetamido-4-cyano-1-(2,3,4-trichloro- 50% w/w (weight/phenyl)pyrazole weight)Ethylan BCP (a nonylphenol/ethylene 5% w/woxide condensate containing 9 molesof ethylene oxide per mol of phenol)Aerosil (silicon dioxide of microfine 5% w/wparticle size)Celite PF (synthetic magnesium 40% w/wsilicate carrier)______________________________________
by adsorbing the Ethylan BCP onto the Aerosil, mixing with the other ingredients and grinding the mixture in a hammer-mill to give a wettable powder which may be diluted with water and applied at an application rate of 2 kg of wettable powder in 300 liters of spray fluid per hectare to control the growth of Galium aparine, Veronica persica, Viola arvensis, Stellaria media and Galeopsis tetrahit by post-emergence application in an emerged crop of winter wheat.
Similar wettable powders may be prepared as described above by replacing the 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole by other compounds of general formula II.
EXAMPLE 3
An aqueous suspension concentrate was formed from:
______________________________________5-acetamido-4-cyano-1-(2,3,4-trichloro- 50% w/vphenyl)pyrazoleEthylan BCP 1.0% w/vSopropon T36 (sodium salt of 0.2% w/vpolycarboxylic acid)Ethylene glycol 5% w/vRhodigel 23 (polysaccharide xanthan 0.15% w/vgum thickener)distilled water to 100% by volume______________________________________
by intimately mixing the ingredients and grinding in a ball-mill for 24 hours. The concentrate thus obtained may be dispersed in water and applied at an application rate of 1 kg of aqueous suspension concentrate in 300 liters of spray fluid per hectare to control the growth of Galium aparine, Veronica persica, Viola arvensis, Stellaria media and Galeopsis tetrahit by post-emergence application in an emerged crop of winter barley.
Similar aqueous suspension concentrates may be prepared as described above by replacing the 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)-pyrazole by other compounds of general formula II.
EXAMPLE 4
An emulsifiable suspension concentrate was formed from:
______________________________________5-acetamido-4-cyano-1-(2,3,4-trichloro- 50% w/vphenyl)pyrazoleEthylan TU (a nonyl phenol/ethylene 10% w/voxide condensate containing 10 molesof ethylene oxide per mol of phenol)Bentone 38 (an organic derivative of 0.5% w/vspecial magnesium montmorillonitethickener)Aromasol H (an aromatic solvent to 100% by volumeconsisting predominantly of isomerictrimethylbenzenes)______________________________________
by intimately mixing the ingredients and grinding in a ball-mill for 24 hours. The emulsifiable suspension concentrate thus obtained may be diluted with water and applied at an application rate of 1.5 kg of emulsifiable suspension concentrate in 100 liters of spray fluid per hectare to control the growth of Setaria viridis, Polygonum convolvulus, and Chenopodium album by post-emergence application in an emerged crop of springsown wheat.
Similar emulsifiable suspension concentrates may be prepared as described above by replacing the 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole by other compounds of general formula II.
EXAMPLE 5
Granules were formed from:
______________________________________5-acetamido-4-cyano-1-(2,3,4-trichloro- 5% w/wphenyl)pyrazoleEthylan BCP 1% w/wOleic acid 1% w/wAromasol H 12% w/w30/60 Attapulgite granules (sorptive 81% w/wsilica clay)______________________________________
by mixing the phenylpyrazole, Ethylan BCP, oleic acid and Aromasol H and spraying the mixture onto the Attapulgite granules. The granules thus obtained may be applied at an application rate of 20 kg of granules per hectare to control the growth of Echinochloa crus-galli, Eleocharis acicularis and Monochoria vaginalis by pre-emergence application or application to seedling weeds in a crop of transplanted paddy rice.
Similar granules may be prepared as described above by replacing the 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole by other compounds of general formula II.
EXAMPLE 6
A water soluble concentrate was formed from:
______________________________________5-acetamido-4-cyano-1-(2,3,4-trichloro- 10% w/vphenyl)pyrazoleEthylan KEO 10% w/vDimethylformamide to 100% by volume______________________________________
by dissolving the Ethylan KEO in a portion of dimethylformamide and then adding the pyrazole derivative with heating and stirring until dissolved. The resulting solution was then made up to 100% by volume with dimethylformamide by adding the rest of the dimethylformamide. The water soluble concentrate thus obtained may be diluted with water and applied at an application rate of 10 liters of water soluble concentrate in 200 to 2000 liters of spray fluid per hectare to control the growth of Galium aparine, Veronica persica, Viola arvensis and Galeopsis tetrahit by post-emergence application in an emerged crop of winter wheat at the tillering growth stage.
EXAMPLE 7
A wettable powder was formed from:
______________________________________5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)- 90% w/wpyrazoleArylan S (sodium dodecyl benzene 2% w/wsulphonate)Darvan No. 2 (sodium lignosulphate) 5% w/wCelite PF 3% w/w______________________________________
by mixing the ingredients and grinding the mixture in a hammer-mill to give a wettable powder which may be diluted with water and applied at an application rate of 1 kg of wettable powder in 300 liters of spray fluid per hectare to control the growth of Galium aparine, Veronica persica, Viola arvensis and Galeopsis tetrahit by post-emergence application in an emerged crop of winter wheat.
Similar wettable powders may be prepared as described above by replacing the 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole by other compounds of general formula II.
EXAMPLE 8
A wettable powder containing 50% w/w of 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole, prepared as hereinbefore described in Example 2, may be diluted with water and applied at an application rate of 0.1 kg of wettable powder in 300 liters of spray fluid per hectare to control the growth of Abutilon theophrasti and Polygonum convolvulus by post-emergence application at the early seedling growth stage of these weeds in a crop of spring wheat.
EXAMPLE 9
A wettable powder containing 50% w/w of 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole, prepared as described in Example 2, may be diluted with water and applied at an application rate of 20 kg of wettable powder in 600 liters of spray fluid per hectare to produce a total herbicidal effect on vegetation at a locus which is not a crop-growing area.
EXAMPLE 10
A wettable powder containing 50% w/w of acylamino-N-phenylpyrazole derivative was prepared as hereinbefore described in Example 2 but replacing the 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole by 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-propionamidopyrazole. This wettable powder may be diluted with water and applied at an application rate of 0.02 kg of wettable powder in 300 liters of spray fluid per hectare to control the growth of Abutilon theophrasti and Polygonum convolvulus by post-emergence application at the early seedling stage of these weeds in an emerged crop of spring wheat.
EXAMPLE 11
An emulsifiable concentrate was formed from:
______________________________________5-acetamido-4-cyano-1-(2,3,5,6-tetrafluoro-4- 10% w/vtrifluoromethyl-phenyl)pyrazoleArylan CA (60% calcium dodecylbenzene 3% w/vsulphonate)Soprophor BSU (polyarylphenol ethoxylate) 7% w/vIsophorone 30% w/vSolvesso 150 (solvent mixture containing to 100% by volumepredominantly C.sub.10 -C.sub.13 aromatic isomers)______________________________________
by dissolving the Arylan CA and Soprophor BSU in the isophorone and then adding the phenylpyrazole with gentle heating and stirring. The Solvesso 150 was then added to the resulting solution to 100% by volume. The emulsifiable concentrate thus obtained may be diluted with water and applied at a rate of 2 liters of emulsifiable concentrate in 200 liters of spray fluid per hectare to control the growth of Digitaria sanguinalis, Chenopodium album, Abutilon theophrasti, Polygonum lapathifolium, Amaranthus retroflexus and Setaria viridis in a crop of soya beans by application before emergence of both the crop and weeds.
According to a further feature of the present invention, the compounds of general formula II wherein R.sup.1 represents an R.sup.9 C(.dbd.O)-- group, wherein R.sup.9 represents a straight- or branched-chain alkyl group containing from 1 to 7 carbon atoms, a straight- or branched-chain alkoxy group containing from 1 to 4 carbon atoms or a straight- or branched-chain alkenyloxy group containing 3 or 4 carbon atoms, alkyl and alkoxy groups within the definition of R.sup.9 being unsubstituted or substituted by a straight- or branched-chain alkoxy group containing from 1 to 4 carbon atoms, an alkoxycarbonyl group containing from 2 to 5 carbon atoms, or one or more halogen, e.g. chlorine, atoms, or R.sup.9 represents a cycloalkyl group containing from 3 to 6 carbon atoms, unsubstituted or substituted by a methyl or ethyl group or R.sup.9 represents a phenoxy group, R.sup.2 represents a hydrogen atom or an R.sup.9 C(.dbd.O)-- group, wherein R.sup.9 is as hereinbefore defined, which is identical to the group R.sup.9 C(.dbd.O) represented by R.sup.1, and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, i.e. compounds of the general formula: ##STR4## wherein R.sup.10 represents an R.sup.9 C(.dbd.O)-- group, wherein R.sup.9 is as hereinbefore defined, R.sup.11 represents a hydrogen atom or an R.sup.9 C(.dbd.O)-- group, wherein R.sup.9 is as hereinbefore defined and is identical to the group represented by the symbol R.sup.9 in the definition of the symbol R.sup.10, and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, are prepared by the reaction of a compound of the general formula: ##STR5## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, with a compound of the general formula:
R.sup.9 COX IV
wherein X represents a chlorine or bromine atom and R.sup.9 is as hereinbefore defined, or with a compound of the general formula:
(R.sup.9 CO).sub.2 O V
wherein R.sup.9 is as hereinbefore defined, in the absence or presence of a suitable inert organic solvent, for example a ketone, e.g. acetone, an aromatic hydrocarbon, e.g. benzene or toluene, chloroform, dichloromethane or dimethylformamide, and optionally in the presence of an acid-binding agent, for example pyridine, triethylamine or an alkali metal, e.g. sodium or potassium, carbonate or bicarbonate, at a temperature from 0.degree. C. to the reflux temperature of the reaction medium, to give a compound of general formula IIA wherein R.sup.10 is as hereinbefore defined and R.sup.11 represents either a hydrogen atom or an R.sup.9 C(.dbd.O)-- group, wherein R.sup.9 is as hereinbefore defined, depending upon the reaction conditions chosen and/or the use of an excess of the compound of general formula IV or V. If desired, an alkali metal derivative of the compound of general formula III may be used.
According to a further feature of the present invention, the compounds of general formula II wherein R.sup.1 represents an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 represents a hydrogen atom, R.sup.2 represents a hydrogen atom and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, i.e. compounds of the general formula: ##STR6## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, are prepared by reaction of a compound of general formula III, wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, with formic acid, in a suitable inert organic solvent, for example a ketone, e.g. methylisobutyl ketone, or an aromatic hydrocarbon, e.g. benzene or toluene, at the reflux temperature of the reaction mixture.
According to a further feature of the present invention, the compounds of general formula II wherein R.sup.1 represents an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 represents a hydrogen atom, R.sup.2 represents a hydrogen atom or an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 represents a hydrogen atom, and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, i.e. compounds of the general formula: ##STR7## wherein R.sup.12 represents a hydrogen atom or an HC(.dbd.O)-- group and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, are prepared by the reaction of a compound of general formula III, wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, with formylacetic anhydride (which may be prepared from formic acid and acetic anhydride), in the absence or presence of a suitable inert organic solvent, for example a ketone, e.g. acetone, or an aromatic hydrocarbon, e.g. benzene or toluene, and optionally in the presence of an acid-binding agent, for example pyridine, triethylamine or an alkali metal, e.g. sodium or potassium, carbonate or bicarbonate, at a temperature from 0.degree. C. to the reflux temperature of the reaction mixture, to give a compound of general formula II C wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined and R.sup.12 represents a hydrogen atom or an HC(.dbd.O)-- group, depending upon the reaction conditions chosen and/or the use of an excess of formylacetic anhydride.
According to a further feature of the present invention, the compounds of general formula II wherein R.sup.1 represents an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 is as hereinbefore defined, R.sup.2 represents a hydrogen atom and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, i.e. compounds of the general formula: ##STR8## wherein R.sup.13 represents an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 is as hereinbefore defined, and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, are prepared by the selective removal by hydrolysis of an R.sup.9 C(.dbd.O)-- group represented by the symbol R.sup.11 of a compound of general formula II A (wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.10 are as hereinbefore defined) or an HC(.dbd.O)-- group represented by the symbol R.sup.12 of a compound of general formula II C (wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined). Hydrolysis is effected under mild conditions, for example by treatment with an aqueous-ethanolic solution or suspension of an alkali metal, e.g. sodium or potassium, bicarbonate, or with aqueous ammonia.
According to a further feature of the present invention, the compounds of general formula II wherein R.sup.1 represents an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 represents a straight- or branched-chain alkoxy group containing from 1 to 4 carbon atoms unsubstituted or substituted by an alkoxy group containing from 1 to 4 carbon atoms, an alkoxycarbonyl group containing from 2 to 5 carbon atoms, or one or more halogen, e.g. chlorine, atoms, R.sup.2 represents a hydrogen atom and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, i.e. compounds of the general formula: ##STR9## wherein R.sup.14 represents an R.sup.15 C(.dbd.O)-- group, wherein R.sup.15 represents a straight- or branched-chain alkoxy group containing from 1 to 4 carbon atoms unsubstituted or substituted by an alkoxy group containing from 1 to 4 carbon atoms, an alkoxycarbonyl group containing from 2 to 5 carbon atoms, or one or more halogen, e.g. chlorine, atoms, and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, are prepared by the reaction of a compound of the general formula: ##STR10## wherein R.sup.16 represents a group R.sup.17 C(.dbd.O), wherein R.sup.17 represents a group within the definition of R.sup.15 as hereinbefore defined or a phenoxy group, and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, with a compound of the general formula:
R.sup.15 OH VI
wherein R.sup.15 is as hereinbefore defined, to replace one of the groups represented by the symbol R.sup.16 by a hydrogen atom, to replace the other group represented by the symbol R.sup.16 by a group within the definition of R.sup.14 when R.sup.16 represents a group R.sup.17 C(.dbd.O) wherein R.sup.17 represents a phenoxy group, and, if desired, to replace the other group represented by the symbol R.sup.16 by another group represented by the symbol R.sup.14 and R.sup.16 represents a group R.sup.17 C(.dbd.O), wherein R.sup.17 represents a group within the definition of R.sup.15. As will be apparent to those skilled in the art, the desired compound of general formula II E is obtained by selection of the appropriate compounds of general formulae II F and VI. The reaction may be effected in water or a suitable inert aqueous-organic or organic solvent, for example an alkanol containing 1 to 4 carbon atoms, e.g. ethanol, or an aromatic hydrocarbon, e.g. benzene or toluene, or which is preferably an excess of the compound of general formula VI, at a temperature from ambient temperature to the reflux temperature of the reaction mixture and, if necessary, at elevated pressure, and optionally in the presence of a base, for example an alkali metal alkoxide, e.g. of the compound of general formula VI.
According to a further feature of the present invention, the compounds of general formula II wherein R.sup.1 represents an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 is as hereinbefore defined, R.sup.2 represents an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 is as hereinbefore defined, which may be the same as, or different to, the R.sup.8 C(.dbd.O)-- group represented by the symbol R.sup.1 and R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, i.e. compounds of the general formula: ##STR11## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.13 are as hereinbefore defined and R.sup.18 represents an R.sup.8 C(.dbd.O)-- group, wherein R.sup.8 is as hereinbefore defined, which may be the same as, or different to, the R.sup.8 C(.dbd.O)-- group represented by the symbol R.sup.13, are prepared by the reaction of an alkali metal, e.g. sodium or potassium, derivative of a compound of general formula II A, wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.10 are as hereinbefore defined and R.sup.11 represents a hydrogen atom, or of a compound of general formula II B, wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, i.e. a compound of general formula II D wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.13 are as hereinbefore defined, with formic acid, formylacetic anhydride or a compound of general formula IV, wherein R.sup.9 and X are as hereinbefore defined. Reaction may be effected in a suitable aprotic solvent, e.g. dimethylformamide, at a temperature from laboratory temperature to the reflux temperature of the reaction mixture.
According to a further feature of the present invention, the compounds of general formula II wherein R.sup.1 and R.sup.2 together represent --OC--(CR.sup.a R.sup.b).sub.m --CO-- and R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.a, R.sup.b and m are as hereinbefore defined, are prepared by the reaction of a compound of general formula III, wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, with a compound of the general formula:
XOC--(CR.sup.a R.sup.b).sub.m --COX VII
wherein X, R.sup.a, R.sup.b and m are as hereinbefore defined, or with a compound of the general formula: ##STR12## wherein R.sup.a, R.sup.b and m are as hereinbefore defined, in the absence or presence of a suitable inert organic solvent, for example a ketone, e.g. acetone, an aromatic hydrocarbon, e.g. benzene or toluene, chloroform, dichloromethane or dimethylformamide, and optionally in the presence of an acid-binding agent, for example pyridine, triethylamine or an alkali metal, e.g. sodium or potassium, carbonate or bicarbonate, at a temperature from 0.degree. C. to the reflux temperature of the reaction medium. If desired, an alkali metal derivative of the compound of general formula III may be used.
Alkali metal derivatives of compounds of general formula III or II D may be prepared in situ by reaction of the compounds of general formula III or II D, wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.13 are as hereinbefore defined, with an alkali metal, e.g. sodium or potassium, hydride, in a suitable inert aprotic solvent, e.g. dimethylformamide, at a temperature from laboratory temperature to the reflux temperature of the reaction mixture.
The compounds of general formula III, wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, may be prepared by the process which comprises the cyclisation of a compound of the general formula: ##STR13## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined. Cyclisation may be effected in the presence of an inert organic solvent, for example an alcohol containing from 1 to 4 carbon atoms, e.g. ethanol, acetic acid or ethoxyethanol, at a temperature of from ambient temperature to the reflux temperature of the reaction mixture.
Compounds of general formula IX may be prepared by the reaction of a compound of the general formula: ##STR14## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as hereinbefore defined, or an acid addition salt thereof, e.g. the hydrochloride, with a compound of the general formula: ##STR15## wherein R.sup.19 represents a straight- or branched-chain alkyl group containing from 1 to 4 carbon atoms, preferably ethyl.
The reaction of a compound of general formula X with a compound of general formula XI may be effected in the presence of an inert organic solvent, for example an alkanol containing from 1 to 4 carbon atoms, e.g. ethanol, acetic acid or ethoxyethanol, and at a temperature from ambient temperature to the reflux temperature of the reaction mixture and optionally in the presence of an alkali metal, e.g. sodium or potassium, acetate, carbonate or bicarbonate. When an acid addition salt of the compound of general formula X is used, the reaction with the compound of general formula XI is effected in the presence of an alkali metal, e.g. sodium or potassium, acetate, carbonate or bicarbonate.
The compounds of general formula III may be prepared by reaction of a compound of general formula X with a compound of general formula XI without isolation of an intermediate compound of general formula IX from the reaction mixture. When the reaction of a compound of general formula X with a compound of general formula XI is effected in acetic acid, in the absence or presence of an alkali metal, e.g. sodium or potassium, acetate, the intermediate compound of general formula IX may separate from the reaction mixture, depending upon the solubility of the intermediate compound of general formula IX in the reaction medium, and may, if desired, be isolated before being cyclised as hereinbefore described to a compound of general formula III, preferably by heating in an inert organic solvent, e.g. ethoxyethanol, at the reflux temperature of the reaction mixture.
Compounds of general formulae X and XI may be prepared by methods known per se. (By the term `methods known per se` as used in the present specification is meant methods heretofore used or described in the chemical literature).
The following Examples and Reference Examples illustrate the preparation of compounds of general formula II.
EXAMPLE 12
Compounds 1 and 5
5-Amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (28.7 g) was heated at reflux in acetic anhydride (150 ml) for 8 hours. The reaction mixture was then evaporated to dryness and the solid residue was suspended in ethanol (250 ml). Saturated aqueous sodium bicarbonate solution was then added to give a pH of 8 and the suspension was then stirred magnetically for 16 hours. The solid obtained was separated by filtration, washed with water and dried, to give 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (23.7 g), m.p. 222.degree.-224.degree. C., in the form of an off-white powder.
By proceeding in a similar manner but replacing the acetic anhydride by propionic anhydride, there was prepared 4-cyano-5-propionamido-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 189.degree.-190.degree. C., after crystallisation from toluene.
EXAMPLE 13
Compound 2
5-Amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (2.9 g) was heated at reflux in acetic anhydride (30 ml) for 24 hours. The reaction mixture was then evaporated to dryness under reduced pressure (20 mmHg), to give a brown solid, which was then triturated with diethylether (20 ml) and boiled with ethanol (25 ml) for one hour. The insoluble material (1.5 g) was separated by filtration and crystallized from toluene (10 ml) to give 4-cyano-5-diacetylamino-1-(2,3,4-trichlorophenyl)pyrazole (1.2 g), m.p. 163.degree.-165.degree. C., in the form of a colourless crystalline solid.
EXAMPLE 14
Compound 1
4-Cyano-5-diacetylamino-1-(2,3,4-trichlorophenyl)pyrazole (0.2 g) in ethanol (5 ml) containing saturated aqueous sodium bicarbonate solution (4 drops), was heated at reflux for 20 minutes. The reaction mixture was then evaporated to dryness under reduced pressure (20 mmHg) to give a fawn coloured powder which was crystallized from ethanol (2 ml), to give 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (0.09 g), m.p. 222.degree.-224.degree. C., in the form of a colourless crystalline solid.
EXAMPLE 15
Compound 1
5-Amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (2.9 g) in acetylchloride (15 mg) was heated at reflux for 2 hours. The reaction mixture was then filtered and the solid residue was triturated with acetyl chloride (10 ml), to give 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (2.0 g), m.p. 220.degree.-223.degree. C., in the form of a colourless powder.
EXAMPLE 16
Compounds 3 and 6
5-Amino-4-cyano-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole (6.5 g) in acetic anhydride (30 ml) was heated at reflux for 3.5 hours. The reaction mixture was then evaporated to dryness and the solid residue was dissolved in ethanol (50 ml). Saturated aqueous sodium bicarbonate solution was then added to give a pH of 7-8 and the solution was then evaporated to dryness. The solid residue was triturated with hexane (20 ml) to give an off-white powder which was crystallized from toluene (50 ml) to give 5-acetamido-4-cyano-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole (1.4 g), m.p. 153.degree.-154.degree. C., in the form of colourless crystals.
By proceeding in a similar manner, but replacing the 5-amino-4-cyano-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole by 5-amino-4-cyano-1-(2,4,6-trichlorophenyl)pyrazole, there was prepared 5-acetamido-4-cyano-1-(2,4,6-trichlorophenyl)pyrazole, m.p. 163.degree.-164.degree. C., in the form of colourless crystals, after crystallisation from toluene.
EXAMPLE 17
Compound 4
Sodium hydride (0.5 g) was added to a solution of 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (5.8 g) in dimethylformamide (20 ml). After the initial exothermic reaction had subsided, the solution was heated on a steam-bath for 5 minutes and then cooled to 10.degree. C. Phenyl chloroformate (2.8 ml) was then added slowly in small portions with occasional cooling with water to keep the temperature below 50.degree. C. The mixture was then heated on a steam-bath for 10 minutes, cooled and evaporated to dryness. The solid residue was treated with diethyl ether (300 ml). The ethereal suspension was filtered and the filtrate was evaporated to dryness. The solid residue thus obtained was boiled in ethanol (200 ml) and separated by filtration, to give 4-cyano-5-di(phenoxycarbonyl)amino-1-(2,3,4-trichlorophenyl)pyrazole (1.7 g), m.p. 206.degree.-208.degree. C., in the form of colourless crystals.
EXAMPLE 18
Compound 6
5-Amino-4-cyano-1-(2,4,6-trichlorophenyl)pyrazole (10 g) in acetic anhydride (52 ml) was heated at reflux for 8 hours. The reaction mixture was then cooled and evaporated to dryness and the residue was crystallised from toluene to give a solid (7.0 g), m.p. 155.degree.-159.degree. C., which was recrystallised from toluene (50 ml) to give 5-acetamido-4-cyano-1-(2,4,6-trichlorophenyl)pyrazole (5.0 g), m.p. 163.degree.-164.degree. C., in the form of colourless crystals.
EXAMPLE 19
Compounds 7 and 8
5-Amino-4-cyano-1-(4-methyl-2,3,5,6-tetrafluorophenyl)pyrazole (5.4 g) in acetic anhydride (30 ml) was heated at reflux for 10 hours. The reaction mixture was evaporated to dryness and the residue was evaporated in the presence of toluene (4.times.20 ml) and xylene (50 ml) to give a white semi-solid, which was dissolved in toluene (20 ml). Insoluble material was removed by filtration and the filtrate was evaporated to dryness to give an orange semi-solid (4.2 g) which was triturated with diethyl ether. The suspension thus obtained was filtered and the precipitate was washed with diethyl ether to give 4-cyano-5-diacetylamino-1-(4-methyl-2,3,5,6-tetrafluorophenyl)pyrazole (1.8 g), m.p. 132.degree.-133.degree. C., in the form of a colourless solid.
The filtrate from the filtration of the suspension obtained by trituration of the orange semi-solid with diethyl ether, deposited a solid precipitate on standing. This precipitate was removed by filtration and the filtrate thus obtained was diluted with hexane to precipitate 5-acetamido-4-cyano-1-(4-methyl-2,3,5,6-tetrafluorophenyl)pyrazole (0.9 g), m.p. 161.degree.-163.degree. C., in the form of a colourless solid.
EXAMPLE 20
Compound 9
5-Amino-4-cyano-1-(2,3,6-trichloro-4-trifluoromethylphenyl)pyrazole (3.74 g) in acetic anhydride (20 ml) was heated at reflux for 6 hours. The reaction mixture was then evaporated under reduced pressure to remove unreacted acetic anhydride. The residual oil was dissolved in dichloromethane (50 ml) and filtered. The filtrate was evaporated to give a foam, which was then suspended in water (70 ml). The suspension was filtered and the filtrate deposited a solid on standing. The solid was collected by filtration and washed with water to give 5-acetamido-4-cyano-1-(2,3,6-trichloro-4-trifluoromethylphenyl)pyrazole (0.4 g), m.p. 177.degree.-178.degree. C., in the form of a fawn-coloured solid.
EXAMPLE 21
Compound 10
5-Amino-4-cyano-1-(2,3,4,6-tetrachlorophenyl)pyrazole (7.1 g) in acetic anhydride (40 ml) was heated at reflux for 17 hours. The reation mixture was then evaporated to dryness and the residue was evaporated in the presence of toluene (3.times.500 ml) to give a brown oil. The brown oil was triturated with diethyl ether. A solid precipitated and was collected and washed with diethyl ether to give a colourless solid (2.4 g), m.p. 110.degree. C. The solid thus obtained was crystallised from toluene (25 ml) to give 5-acetamido-4-cyano-1-(2,3,4,6-tetrachlorophenyl)pyrazole (1.3 g; containing 0.2M of toluene), m.p. 115.degree. C., in the form of colourless crystals. The diethyl ether filtrate and washings and the toluene filtrate were combined and evaporated to dryness. The residue thus obtained was triturated with diethyl ether (50 ml). The solid which precipitated was collected by filtration to give a second crop of 5-acetamido-4-cyano-1-(2,3,4,6-tetrachlorophenyl)-pyrazole (2.5 g; containing 0.2M of toluene), m.p. 115.degree. C. in the form of a colourless solid.
EXAMPLE 22
Compounds 11, 12, 13, 22, 23, 20 and 21
Acetyl chloride (34 ml) was added to a stirred suspension of 5-amino-1-(2-chloro-4-methylphenyl)-4-cyanopyrazole (8.0 g) in chloroform (34 ml) at 0.degree. C. A solution of pyridine (5.4 ml) in chloroform (34 ml) was then added to the suspension thus obtained over 10 minutes, with stirring at 0.degree. C. to 2.degree. C. maintained by external cooling. The reaction mixture was then stirred at laboratory temperature for 2.5 hours and the solution thus obtained was evaporated to dryness. The residue was dissolved in ethanol (100 ml) and basified with aqueous ammonia (d: 0.880). The basified solution was heated at reflux for 10 minutes and then evaporated to dryness. The residue was dissolved in dichloromethane (500 ml) and water (500 ml) and the organic layer was separated, washed successively once with water, twice with 2N hydrochloric acid and twice with water, dried over anhydrous magnesium sulphate and evaporated. The colourless solid thus obtained was crystallised from toluene (30 ml) to give 5-acetamido-1-(2-chloro-4-methylphenyl)-4-cyanopyrazole (6.54 g), m.p. 146.degree.-147.degree. C., in the form of colourless crystals.
By proceeding in a similar manner but replacing the 5-amino-1-(2-chloro-4-methylphenyl)-4-cyanopyrazole by the hereinafter indicated appropriately substituted phenylpyrazole, there were obtained: 5-Acetamido-1-(4-allyl-2,3,5,6-tetrafluorophenyl)-4-cyanopyrazole, m.p. 90.degree.-91.5.degree. C., in the form of colourless crystals, after crystallisation from aqueous ethanol, from 1-(4-allyl-2,3,5,6-tetrafluorophenyl)-5-amino-4-cyanopyrazole; 5-Acetamido-1-(2-chloro-4-ethylphenyl)-4-cyanopyrazole, m.p. 140.degree.-141.degree. C., in the form of buff-coloured crystals, after crystallisation from toluene, from 5-amino-1-(2-chloro-4-ethylphenyl)-4-cyanopyrazole; 5-Acetamido-4-cyano-1-(2,3-dichlorophenyl)pyrazole, m.p. 246.degree.-248.degree. C., in the form of colourless crystals, after crystallisation from a mixture of toluene and ethanol, from 5-amino-4-cyano-1-(2,3-dichlorophenyl)pyrazole; 5-Acetamido-4-cyano-1-(2,4-dichlorophenyl)pyrazole, m.p. 188.degree.-190.degree. C., in the form of colourless crystals, after crystallisation from a mixture of toluene and ethanol, from 5-amino-4-cyano-1-(2,4-dichlorophenyl)pyrazole [described by P. L. Southwick and B. Dhawan J. Heter. Chem. 12 1199-1205 (1975)].
By proceeding in a similar manner, but replacing the acetyl chloride by the hereinafter indicated acid chloride and the 5-amino-1-(2-chloro-4-methylphenyl)-4-cyanopyrazole by 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole, and carrying out the reaction at 20.degree. C. rather than 0.degree. C., there were prepared: 4-Cyano-5-n-hexanamido-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 114.degree.-114.5.degree. C., in the form of colourless crystals, after crystallisation from aqueous ethanol, from n-hexanoyl chloride; 4-Cyano-5-n-octanamido-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 134.degree.-136.degree. C., in the form of colourless crystals, after crystallisation from aqueous ethanol (50%), from n-octanoyl chloride.
EXAMPLE 23
Compound 14
5-Amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (172.5 g) in propionyl chloride (600 ml) was heated at reflux for 17 hours. The reaction mixture was evaporated to dryness and the residue was evaporated in the presence of toluene (3.times.500 ml) to give a dark gum. This gum was stirred with diethyl ether (1000 ml) and the solid which precipitated was collected by filtration and washed with diethyl ether to give a fawn-coloured solid (97 g), m.p. 127.degree.-129.degree. C. The solid thus obtained was crystallised from toluene (300 ml) to give a colourless solid (13.8 g), m.p. 250.degree.-251.degree. C. The toluene mother liquors were cooled and the solid which precipitated was collected by filtration and washed with diethyl ether to give 4-cyano-5-dipropionylamino-1-(2,3,4-trichlorophenyl)pyrazole (15.0 g), m.p. 133.degree.-134.degree. C., in the form of colourless crystals.
EXAMPLE 24
Compounds 15, 16, 17, 18, 24, 19, 25, 26, 27, 33, 28, 29 and 30
n-Butyryl chloride (4.7 ml) was added to a stirred suspension of 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (5.8 g) in chloroform (30 ml) at 0.degree. C. and a solution of pyridine (3.2 ml) in chloroform (30 ml) was then added over 10 minutes, with stirring at 0.degree.-5.degree. C. maintained by external cooling, to the suspension thus obtained. The reaction mixture was then stirred for 17 hours at laboratory temperature. Saturated aqueous potassium bicarbonate solution (100 ml) was added at 20.degree. C. to the clear solution thus obtained and the mixture was stirred vigorously for 1 hour. The chloroform layer was separated, washed with 2N hydrochloric acid and water, and evaporated to give an oil. This oil was dissolved in ethanol (150 ml) and saturated aqueous potassium bicarbonate solution (25 ml) was added. The solution thus obtained was heated at reflux for 1.5 hours and evaporated to dryness. The residue was dissolved in dichloromethane, washed with water, dried over anhydrous magnesium sulphate and evaporated to dryness, to give an oil (5.5 g) which was crystallised from toluene (25 ml) to give 5-n-butyramido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (1.7 g), m.p. 117.degree.-118.degree. C., in the form of colourless crystals.
By proceeding in a similar manner but replacing the n-butyryl chloride by the hereinafter indicated acid chloride, there were obtained:
4-Cyano-5-isobutyramido-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 159.degree.-160.degree. C., in the form of colourless crystals, after crystallisation from aqueous ethanol, from isobutyryl chloride.
4-Cyano-5-n-pentanamido-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 127.degree.-128.degree. C., in the form of colourless crystals, after crystallisation from toluene, from n-valeryl chloride;
4-Cyano-5-(3-methylbutyramido)-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 147.degree.-148.degree. C., in the form of colourless crystals, after crystallisation from toluene, from isovaleryl chloride; (.+-.)4-Cyano-5-(2-methylbutyramido)-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 186.degree.-187.degree. C., in the form of colourless crystals, after crystallisation from toluene, from (.+-.)2-methylbutyryl chloride;
4-Cyano-5-n-heptanamido-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 114.degree.-116.degree. C., in the form of colourless crystals, after crystallisation from toluene, from n-heptanoyl chloride.
By proceeding in a similar manner but replacing the n-butyryl chloride by the hereinafter indicated acid chloride and carrying out the addition of pyridine at 20.degree. C. rather than 0.degree. C., there were prepared:
4-Cyano-5-(2-ethylbutyramido)-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 182.degree.-183.degree. C., in the form of yellow crystals, after crystallisation from a mixture of ethyl acetate and hexane (1:6 by volume), from 2-ethylbutyryl chloride;
4-Cyano-5-cyclopentylcarbonamido-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 168.degree.-170.degree. C., in the form of colourless crystals, after crystallisation from toluene, from cyclopentylcarbonyl chloride;
4-Cyano-5-cyclopropylcarbonamido-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 219.degree.-221.degree. C., in the form of colourless crystals, after crystallisation from toluene, from cyclopropylcarbonyl chloride;
(.+-.)-4-Cyano-5-(2-ethylhexanamido)-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 128.5.degree. C., in the form of colourless crystals after crystallisation from a mixture of diethyl ether and hexane, from (.+-.)-2-ethylhexanoyl chloride.
By proceeding in a similar manner but replacing the n-butyryl chloride by the hereinafter indicated acid chloride and stirring the reaction mixture at its reflux temperature, there was prepared:
4-Cyano-5-(2,2-dimethylpropionamido)-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 210.degree.-211.degree. C., in the form of colourless crystals, after crystallisation from toluene, from trimethylacetyl chloride.
By proceeding in a similar manner but replacing the n-butyryl chloride with propionyl chloride and the 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole by the hereinafter indicated appropriately substituted phenyl pyrazole there were prepared:
4-Cyano-5-propionamido-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole, m.p. 114.degree.-116.degree. C., in the form of colourless crystals, from 5-amino-4-cyano-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole; 1-(2-Chloro-4-ethylphenyl)-4-cyano-5-propionamidopyrazole, m.p. 110.degree.-111.5.degree. C., in the form of colourless crystals, after crystallisation from toluene, from 5-amino-1-(2-chloro-4-ethylphenyl)-4-cyanopyrazole.
EXAMPLE 25
Compound 31
5-Amino-4-cyano-1-(2,3,4,6-tetrachlorophenyl)pyrazole (7.1 g) in propionyl chloride (40 ml) was heated at reflux for 16 hours. The reaction mixture was evaporated to dryness and the residue was dissolved in ethanol (250 ml), basified with saturated aqueous potassium bicarbonate solution (50 ml) and heated at reflux for 2 hours. The solution was evaporated to dryness and dissolved in a mixture of dichloromethane (250 ml) and water (250 ml). The organic layer was separated, washed once with water (250 ml), dried over anhydrous magnesium sulphate and evaporated to dryness to give a red gum (8.0 g), which was crystallised from toluene (25 ml) to give 4-cyano-5-propionamido-1-(2,3,4,6-tetrachlorophenyl)pyrazole (2.5 g), m.p. 203.degree.-204.degree. C., in the form of colourless crystals.
EXAMPLE 26
Compound 32
5-Amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (2.9 g) was added to a stirred solution of acetic anhydride (10 ml) and formic acid (10 ml) at laboratory temperature. The stirring was continued for 6 hours. The reaction mixture was then allowed to stand at room temperature for 64 hours and was then diluted with diethyl ether. The solution was filtered, washed once with water, dried over anhydrous sodium sulphate and evaporated to give a gum (1.0 g). The gum was chromatographed on a silica column (3.times.30 cm) eluated with a mixture of dichloromethane and gradually increasing amounts (from 0 to 100% by volume) of ethyl acetate.
Evaporation of first 1000 ml of eluate gave unreacted 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (0.13 g).
Evaporation of the next 500 ml of eluate gave a solid which was triturated with toluene to give 4-cyano-5-formamido-1-(2,3,4-trichlorophenyl)pyrazole (0.34 g), m.p. 190.degree.-192.degree. C., in the form of colourless crystals.
EXAMPLE 27
Compounds 4, 82, 83 and 159
Phenyl chloroformate (141 g) was added to a stirred suspension of 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (86.3 g) in chloroform (600 ml) at -5.degree. C. to -3.degree. C. A solution of pyridine (71 g) in chloroform (100 ml) was added with stirring at 0.degree. C. to 5.degree. C. maintained by external cooling. The reaction mixture was then stirred at laboratory temperature for 16 hours. The reaction mixture was then filtered and the solid product washed with chloroform to give 4-cyano-5-di(phenoxycarbonyl)amino-1-(2,3,4-trichlorophenyl)pyrazole (135.6 g), m.p. 205.5.degree.-206.5.degree. C., in the form of a colourless solid.
By proceeding in a similar manner but replacing the 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole by the hereinafter indicated appropriately substituted phenylpyrazole there were obtained: 4-Cyano-5-di(phenoxycarbonyl)amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole, m.p. 233.degree.-235.degree. C., after crystallization from a mixture of ethylacetate-acetonitrile, in the form of colourless crystals, from 5-amino-4-cyano-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole. 1-(2-Chloro-4-trifluoromethylphenyl)-4-cyano-5-di(phenoxycarbonyl)aminopyrazole, m.p. 156.degree.-158.degree. C., after crystallization from toluene, in the form of colourless crystals, from 5-amino-1-(2-chloro-4-trifluoromethylphenyl)-4-cyanopyrazole;
4-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-di(phenoxycarbonyl)aminopyrazole, 190.degree.-192.degree. C., after crystallisation from a mixture of ethyl acetate and hexane, in the form of colourless crystals, from 5-amino-4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole.
EXAMPLE 28
Compounds 84, 91, 85, 86, 69, 140, 165, 160, 102, 103, 129, 145, 146, 157, 132, 147, 170, 158, 131, 133, 134, 139, 136, 166, 172, 174, 182, 180, 183, 188 and 189
Acetyl chloride (11.5 ml) was added to a stirred suspension of 5-amino-1-(2-chloro-4-n-propylphenyl)-4-cyanopyrazole (3.02 g) in chloroform (25 ml) at 0.degree. C. A solution of pyridine (1.85 ml) in cloroform (5 ml) was then added to the reaction mixture at 0.degree.-5.degree. C. The reaction mixture was then warmed to laboratory temperature and allowed to stand overnight. The solution was then diluted with dichloromethane (50 ml) and washed with hydrochloric acid (2N; 50 ml) and twice with water (2.times.50 ml) and dried over anhydrous magnesium sulphate and evaporated to give a solid. This solid was chromatographed on a silica (Merck, 230-400 mesh; pressure 25 lb in.sup.-2) eluted with dichloromethane and gradually increasing amounts of ethyl acetate (from 0 to 10% by volume). Evaporation of the eluate containing the faster moving component gave 1-(2-chloro-4-n-propylphenyl)-4-cyano-5-diacetylaminopyrazole (1.08 g), m.p. 110.degree.-112.degree. C., in the form of colourless crystals. Evaporation of the eluate containing the slower moving component gave 5-acetamido-1-(2-chloro-4-n-propylphenyl)-4-cyanopyrazole (0.86 g), m.p. 143.degree.-144.degree. C., after crystallisation from ethanol, in the form of a colourless solid.
By proceeding in a similar manner but replacing the 5-amino-1-(2-chloro-4-n-propylphenyl)-4-cyanopyrazole by the hereinafter appropriately substituted phenylpyrazole, there were obtained:
4-Cyano-5-diacetylamino-1-(2,6-dibromo-4-trifluoromethylphenyl)-pyrazole, m.p. 164.degree.-165.degree. C., in the form of colourless crystals, and 5-acetamido-4-cyano-1-(2,6-dibromo-4-trifluoromethylphenyl) pyrazole, m.p. 229.degree.-230.degree. C., in the form of colourless crystals, following chromatography using diethyl ether and hexane mixture (1:1 v/v) as eluant, from 5-amino-4-cyano-1-(2,6-dibromo-4-trifluoromethylphenyl)pyrazole.
4-Cyano-5-diacetylamino-1-(4-ethyl-2,3,5,6-tetrafluorophenyl)pyrazole m.p. 112.5.degree.-113.5.degree. C. in the form of a colourless solid, following chromatography using hexanediethyl ether (1:1) as eluent, from 5-amino-4-cyano-1-(4-ethyl-2,3,5,6-tetrafluorophenyl)pyrazole.
1-(2-Chloro-4-isopropylphenyl)-4-cyano-5-diacetylaminopyrazole, m.p. 99.degree.-101.degree. C., in the form of a colourless crystalline solid, following chromatography using dichloromethane as eluent, from 5-amino-1-(2-chloro-4-isopropylphenyl)-4-cyanopyrazole.
1-(2-Bromo-4-trifluoromethylphenyl)-4-cyano-5-diacetylamino-pyrazole, m.p. 127.degree.-128.degree. C., in the form of colourless crystals, and 5-acetamido-1-(2-bromo-4-trifluoromethylphenyl)-4-cyanopyrazole, m.p. 186.degree.-187.degree. C., after crystallisation from a mixture of diethyl ether and hexane (1:1), in the form of colourless crystals, following chromatography using dichloromethane containing gradually increasing amounts of diethyl ether (0-100%), from 5-amino-1-(2-bromo-4-trifluoromethylphenyl)-4-cyanopyrazole.
By processing in a similar manner but replacing the substituted phenylpyrazole and/or the acetyl chloride there were prepared the following:
__________________________________________________________________________ Substituted phenylpyrazoleCom- Acid halide in in place of 5-amino-1-pound place of acetyl (2-chloro-4-n-propylphenyl)-No. chloride 4-cyanopyrazole Form Observations__________________________________________________________________________102 dichloroacetyl 5-amino-4-cyano- Colourless solid Recrystallisation chloride 1-(2,6-dichloro-4- m.p. 171-172.degree. C. from ethyl acetate trifluoromethylphenyl)- hexane pyrazole103 dichloroacetyl 5-amino-1-(2-chloro-4- Colourless solid chloride trifluoromethylphenyl)- m.p. 176-177.degree. C. 4-cyanopyrazole129 succinyl chloride 5-amino-4-cyano-1-(2,3,4- Pale yellow crystals Chloroform trichlorophenyl)pyrazole m.p. 206-208.degree. C. Chromatography145 succinyl chloride 5-amino-4-cyano-1-(2,6- light brown crystals Recrystallisation dichloro-4-trifluoromethyl- m.p. 240-242.degree. C. from toluene phenyl)pyrazole146 succinyl chloride 5-amino-1-(2-chloro-4-trifluoro- Colourless crystals Dichloromethane methylphenyl)-4-cyanopyrazole m.p. 172-173.degree. C. Chromatography, recrystallisation from ethyl acetate - petroleum ether b.p. 60-80.degree. C.157 (.+-.)methylsuccinyl 5-amino-4-cyano-1-(2,3,4- Colourless crystals Recrystallisation chloride trichlorophenyl)pyrazole m.p. 176-177.degree. C. from toluene - petroleum ether (b.p. 60-80.degree. C.)132 glutaryl chloride 5-amino-4-cyano-1-(2,3,4- Colourless needles Recrystallisation trichlorophenyl)pyrazole m.p. 203-205.degree. C. from ethyl acetate - hexane147 glutaryl chloride 5-amino-4-cyano-1-(2,6- Fine white powder Chromatography dichloro-4-trifluoromethyl- m.p. 184-186.degree. C. using 99:1 phenyl)pyrazole dichloromethane -170 4-ethoxycarbonylbutyryl 5-amino-4-cyano-1-(2,6- Colourless powder ethyl acetate chloride dichloro-4-trifluoromethyl- m.p. 144-145.degree. C. as eluant phenyl)pyrazole158 glutaryl chloride 5-amino-1-(2-chloro- Colourless crystals Recrystallisation 4-trifluoromethylphenyl)- m.p. 155-156.degree. C. from toluene - 4-cyanopyrazole petroleum ether (b.p. 60-80.degree. C.) for `170` and `158`131 butyryl chloride 5-amino-4-cyano-1- Colourless crystals (2,3,4-trichlorophenyl)- m.p. 90-92.degree. C. pyrazole133 valeryl chloride 5-amino-4-cyano-1- Colourless crystals Chromatography (2,3,4-trichlorophenyl)- m.p. 97-99.degree. C. using pyrazole dichloromethane as eluant134 isovaleryl chloride 5-amino-4-cyano-1- Colourless solid Recrystallisation (2,3,4-trichlorophenyl)- m.p. 82-84.degree. C. from toluene - pyrazole petroleum ether (b.p. 60-80.degree. C.)139 isobutyryl chloride 5-amino-4-cyano-1- Colourless crystals Chromatography using (2,3,4-trichlorophenyl)- m.p. 98-100.degree. C. dichloromethane as pyrazole eluant136 heptanoyl chloride 5-amino-4-cyano-1- Colourless crystals Recrystallisation from (2,3,4-trichlorophenyl)- m.p. 43-44.degree. C. petroleum ether pyrazole (b.p. 60-80.degree. C.)166 isovaleryl chloride 5-amino-1-(2-chloro- off-white solid Dichloromethane 4-trifluoromethylphenyl)- m.p. 55-56.degree. C. chromatograph 4-cyanopyrazole Reaction at reflux temperature174 acetyl chloride 5-amino-1-(4-sec-butyl- Colourless solid Chromatography using 2,3,5,6-tetrafluoromethyl- m.p. 97-99.degree. C. 1:1 diethyl ether -172 phenyl)-4-cyanopyrazole Colourless solid hexane as eluant m.p. 101.5-103.5.degree. C.182 acetyl chloride 5-amino-4-cyano-1-(2,3- Colourless solid Crystallisation dichloro-4-methylphenyl)- m.p. 146-148.degree. C. from toluene180 pyrazole Colourless solid (described in m.p. 198-200.degree. C. GB 2,070,604 A)183 isovaleryl chloride 5-amino-4-cyano-1- Off-white solid Chromatography (2,3,5,6-tatrafluoro-4- m.p. 64-65.degree. C. using dichloro- trifluoromethylphenyl)- methane- pyrazole petroleum ether (b.p. 60-80.degree. C.) 1:1 as eluant188 2,2-dimethyl- 5-amino-4-cyano-1- Colourless Recrystallisation succinyl chloride (2,3,4-trichloro- crystals from ethyl phenyl)pyrazole m.p. 162-163.degree. C. acetate- petroleum ether (b.p. 60-80.degree. C.)189 isovaleryl chloride 5-amino-4-cyano- Colourless Chromatography 2,6-dichloro-4- crystals using dichloro- trifluoromethyl- m.p. 94-95.degree. C. methane as eluant. phenyl)pyrazole Recrystallisation from ethyl acetate- petroleum ether (60-80.degree. C.)__________________________________________________________________________
EXAMPLE 29
Compounds 46, 47, 48, 49, 50, 51, 90, 54, 55, 56, 109 and 124
A stirred mixture of 4-cyano-5-di(phenoxycarbonyl)amino-1-(2,3,4-trichlorophenyl)pyrazole (prepared as described in Example 27; 20 g) in 2-ethoxyethanol (400 ml) was heated at reflux for 4 hours. The reaction mixture was evaporated to dryness and the residue crystallized from ethyl acetate-n-hexane to give 4-cyano-5-[(2-ethoxy)ethoxycarbonylamino]-1-(2,3,4-trichlorophenyl)pyrazole (10 g), m.p. 122.degree.-124.degree. C., in the form of colourless crystals. The mother liquors were evaporated to dryness and the residue chromatographed on aluminium oxide (120 g; May & Baker grade) using dichloromethane as eluent. Evaporation of the eluate and crystallisation of the residue from ethyl acetate-n-hexane gave a further quantity of 4-cyano-[5-(2-ethoxy)ethoxycarbonylamino]-1-(2,3,4-trichlorophenyl)pyrazole (3 g).
By proceeding in a similar manner but replacing the 2-ethoxyethanol by the hereinafter indicated alcohol, there were prepared the following 4-cyano-5-alkoxycarbonylamino-1-(2,3,4-trichlorophenyl)pyrazoles identified by compound number:
______________________________________ Alcohol inCompound place ofNo. 2-ethoxyethanol Form______________________________________47 methanol Colourless crystals m.p. 205-206.degree. C.48 isopropanol Colourless crystals m.p. 132-133.degree. C.49 n-butanol Colourless crystals m.p. 125-127.degree. C.50 n-propanol Colourless crystals m.p. 122-123.degree. C.51 ethanol Colourless crystals m.p. 124-125.degree. C.90 isobutanol Colourless crystals m.p. 109-110.degree. C.______________________________________
By proceeding in a similar manner but replacing the 4-cyano-5-di(phenoxycarbonyl)amino-1-(2,3,4-trichlorophenyl) pyrazole by the appropriately substituted bis-phenylcarbamate, and replacing the 2-ethoxyethanol by the hereinafter indicated alcohol, there were prepared:
1-(2-Chloro-4-trifluoromethylphenyl)-4-cyano-5-methoxycarbonylaminopyrazole, m.p. 163.degree.-164.degree. C., after crystallisation from ethyl acetate-n-hexane, in the form of colourless crystals, from 1-(2-chloro-4-trifluoromethylphenyl)-4-cyano-5-di(phenoxycarbonyl)aminopyrazole (prepared as described in Example 27) and methanol.
4-Cyano-5-methoxycarbonylamino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole, m.p. 114.degree.-115.degree. C., after crystallisation from n-hexane-diethyl ether, in the form of colourless crystals, from 4-cyano-di(phenoxycarbonyl)amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole and methanol.
4-Cyano-5-ethoxycarbonylamino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole, m.p. 102.degree.-103.degree. C., after crystallisation from ethyl acetate-n-hexane, in the form of colourless crystals, from 4-cyano-5-di(phenoxycarbonyl)amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole and ethanol.
4-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-methoxycarbonylaminopyrazole, m.p. 149.degree.-150.degree. C., after crystallisation from a mixture of diethyl ether and hexane, in the form of colourless crystals, from methanol. 4-Cyano-5-isopropoxycarbonylamino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole, m.p. 106.degree.-107.degree. C., after crystallisation from a mixture of ethyl acetate and hexane in the form of colourless crystals, from isopropanol.
EXAMPLE 30
Compound 52
Sodium (0.5 g) was added to a stirred mixture of 4-cyano-5-di(phenoxycarbonyl)amino-1-(2,3,4-trichlorophenyl)pyrazole (prepared as described in Example 27; 25 g) in t-butanol (400 ml) and the mixture was heated at reflux for 15 minutes. Solid carbon dioxide pellets were then added to the cooled reaction mixture to adjust the pH to 7. The neutralized reaction mixture was filtered and the filtrate evaporated under reduced pressure to give an oil which was crystallised from ethyl acetate-n-hexane to give 5-t-butoxycarbonylamino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (11.0 g), m.p. 140.degree.-141.degree. C., in the form of colourless crystals.
EXAMPLE 31
Compound 53
A solution of sodium 2-propenyloxide in allyl alcohol [30 ml; prepared by dissolving sodium metal (1.0 g) in allyl alcohol (40 ml)] was added to a stirred solution of 4-cyano-5-di(phenoxycarbonyl)amino-1-(2,3,4-trichlorophenyl)pyrazole (15 g) in tetrahydrofuran (300 ml). The mixture was stirred for 15 minutes at laboratory temperature then solid carbon dioxide pellets added to adjust the pH of the solution to pH7. The neutralized solution was filtered through diatomaceous earth and then evaporated under reduced pressure and the residue crystallised from a mixture of ethyl acetate and hexane to give 4-cyano-5-(2-propenyloxycarbonylamino)-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 154.degree.-155.degree. C., in the form of colourless crystals.
EXAMPLE 32
Compound 47
A solution of methyl chloroformate (0.4 g) in acetonitrile (5 ml) was added to a stirred mixture of 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (1 g) and sodium carbonate (0.5 g) in acetonitrile (10 ml) at laboratory temperature. After 72 hours the reaction mixture was filtered and the filtrate evaporated to give a yellow solid. The solid was chromatographed on a silica column (Merck 230-400 mesh; pressure 25 lb in.sup.-2) eluted with dichloromethane-ethyl acetate (19:1). Evaporation of the eluate containing the faster moving component gave 4-cyano-5-methoxycarbonylamino-1-(2,3,4-trichlorophenyl)(0.12 g), m.p. 204.degree.-205.degree. C., after crystallisation from ethyl acetate-n-hexane, in the form of colourless crystals.
EXAMPLE 33
Compounds 57, 58, 59, 60, 130, 150, 153, 169, 167 and 181
By proceeding in a similar manner to that hereinbefore described in Example 13 but replacing the substituted phenylpyrazole by the hereinafter indicated appropriately substituted phenylpyrazoles and chromatography on silica column (Merck 230-400 mesh; pressure 25 lb in.sup.-2) using dichloromethane as eluent and with recrystallisation from toluene-petroleum ether (b.p. 60.degree.-80.degree. C.), there were prepared the following 4-cyano-5-diacetylamino-1-(sub.phenyl)pyrazoles identified by Compound number:
______________________________________ Substituted phenylpyrazole in place of 5-amino-4-cyano-1-Compound (2,3,4-trichlorophenyl)No pyrazole used in Example 13 Form______________________________________ 57 5-amino-4-cyano-1-(2,3,5,6- Colourless tetrafluoro-4-trifluoromethylphenyl) crystals pyrazole m.p. 133-135.degree. C. 58 5-amino-1-(2-chloro-4-trifluoromethyl- Colourless phenyl)-4-cyanopyrazole crystals m.p. 128-130.degree. C. 59 5-amino-4-cyano-1-(2,4,6- Colourless trichlorophenyl)pyrazole crystals m.p. 130-131.degree. C. 60 5-amino-4-cyano-1-(2,4-dichloro- Colourless phenyl)pyrazole m.p. 113-114.degree. C. [J. Hetero Chem 12, 1199-1205 (1975)]130 5-amino-4-cyano-1-(2,6-dichloro- Colourless 4-trifluoromethylphenyl)pyrazole crystals m.p. 103-105.degree. C.150 5-amino-4-cyano-1-(2,4-dichloro- Colourless 6-methylphenyl)pyrazole crystals m.p. 119-120.degree. C.153 5-amino-4-cyano-1-pentafluorophenyl- Colourless pyrazole crystals (described in British Published m.p. Patent Specification No 2070604 A) 122-123.degree. C.169 5-amino-4-cyano-1-(2-nitro-4- Pale trifluoromethylphenyl)pyrazole yellow (described in British Published crystals Patent Specification No 2070604 A) m.p. 182-183.degree. C. Recrystalli- sation from ethyl acetate- petroleum ether (b.p. 60-80.degree. C.)167 5-amino-1-(4-chloro-2,3,5,6- Colourless tetrafluorophenyl)pyrazole crystals m.p. 144-146.degree. C.181 5-amino-4-cyano-1-(2,3,4,6-tetrachloro- Colourless phenyl)pyrazole crystals m.p. 130-132.degree. C.______________________________________
EXAMPLE 34
Compounds 35, 37, 36, 66, 67, 70, 71, 72, 65, 88, 114, 128, 116, 173, 178 and 179
By proceeding in a similar manner to that hereinbefore described in Example 22 but replacing the substituted phenylpyrazole by the appropriate phenylpyrazole substituted as hereinafter indicated, there were prepared the following 5-acetamido-4-cyano-1-(Sub.phenyl)pyrazoles identified by Compound number:
__________________________________________________________________________ Phenyl substitution in place of 5-amino-1-(2-chloro-4-Compound methylphenyl)4-cyanopyrazole Observations onNo. used in Example 22 Form recrystallisation__________________________________________________________________________35 4-methyl-2,3,6-trichloro Fawn-coloured toluene crystals m.p. 171-173.degree. C.37 2-chloro-4-isopropyl Cream- -- coloured crystals m.p. 133-134.degree. C.36 2,3-dichloro-4-ethyl Cream- toluene coloured crystals m.p. 175-176.5.degree. C.66 4-n-butyl-2,3,5,6- Colourless -- tetrafluoro solid m.p. 128-129.degree. C.67 4-ethyl-2,3,5,6-tetrafluoro Colourless ethanol-water crystals m.p. 138.5- 140.degree. C.70 4-bromo-2,3-dichloro Off-white toluene [described in GB 2070604A] solid m.p. 225-228.degree. C.71 2-nitro-4-trifluoromethyl Pale yellow -- [described in GB 2070604A] solid m.p. 220-222.degree. C.72 2,6-dichloro-4- Colourless toluene trifluoromethyl crystals m.p. 207-208.5.degree. C.74 pentafluoro Off-white toluene [described in GB 2070604A] solid m.p. 201-203.degree. C.65 2-chloro-4-trifluoromethyl Colourless ethanol-water crystals m.p. 191-193.degree. C.88 2,3,4,6-tetrafluoro Pale green toluene [described in GB 2070604A] solid m.p. 215-217.degree. C.114 2,4-dichloro-6-methyl Colourless toluene- crystals m.p. hexane 168-170.degree. C.128 2,6-dichloro-4-ethyl Colourless toluene crystals m.p. 158-160.degree. C.116 4-chloro-2,3,5,6-tetrafluoro Colourless toluene- solid m.p. hexane 206-208.degree. C.173 2,3,5,6-tetrafluoro-4-vinyl Pale yellow aqueous solid m.p. ethanol 149.5-151.5.degree. C.178 3,5-difluoro-2,4,6-trichloro Colourless toluene crystals m.p. 226-228.degree. C.179 4-bromo-2,3,5,6-tetrafluoro Colourless toluene crystals m.p. 218-220.degree. C.__________________________________________________________________________
EXAMPLE 35
Compounds 68, 73, 38, 39, 40, 75, 76, 81, 115, 117, 118 163, 175, 176 and 171
By proceeding in a similar manner to that hereinbefore described in Example 22 but replacing the acetyl chloride by propionyl chloride and the substituted phenylpyrazole by the appropriate phenylpyrazole substituted as hereinafter indicated, there were prepared the following 5-propionamido-4-cyano-1-(sub.phenyl)pyrazoles identified by Compound number:
__________________________________________________________________________ Phenyl substitution in placeCom- of 5-amino-1-(2-chloro-4-pound methylphenyl)-4-cyanopyrazoleNo used in Example 22 Form Observations__________________________________________________________________________68 4-methyl-2,3,5,6-tetrafluoro Colourless ethanol-water crystals m.p. 148.5-150.degree. C.73 2,6-dichloro-4- Colourless toluene trifluoromethyl crystals m.p. 179-180.5.degree. C.38 -- Fawn- toluene coloured crystals m.p. 138-139.degree. C.39 2-chloro-4-isopropyl Cream- -- coloured solid m.p. 120-122.degree. C.40 2,3,6-trichloro-4- Colourless -- trifluoromethyl crystalline solid m.p. 181-182.degree. C.75 2,4,6-trichloro Colourless toluene-hexane crystals m.p. 161-163.degree. C.76 2,4-dichloro Colourless toluene [J. Heter. Chem. 12 crystals m.p. 1199-1205 (1975)] 156-158.degree. C.81 2,3-dichloro Colourless toluene solid m.p. 174-175.degree. C.115 2,4-dichloro-6-methyl Colourless toluene-hexane solid m.p. 163-165.degree. C.117 4-chloro-2,3,5,6-tetrafluoro Colourless toluene-hexane solid m.p. 158-160.degree. C.118 2,3,4,6-tetrafluoro Off-white toluene (described in GB 2070604 A) solid m.p. 193-195.degree. C.163 4-n-butyl-2,3,5,6-tetrafluoro Oil Chromatography on a silica column175 2-chloro-4-n-propyl Colourless (Merck 230-400 solid m.p. mesh; 10 lb in.sup.-2) 101-103.degree. C. using 1:1 diethyl ether-hexane as eluant.176 4-sec-butyl-2,3,5,6- Colourless tetrafluoro solid m.p. 96.5-98.5.degree. C.171 4-methyl-2,3,6-trichloro Colourless toluene crystals m.p. 150-151.degree. C.__________________________________________________________________________
EXAMPLE 36
By proceeding in a similar manner to that hereinbefore described in Example 22 but replacing the acetyl chloride by isobutyryl chloride and the substituted phenylpyrazole by 5-amino-1-(2-chloro-4-trifluoromethylphenyl)4-cyanopyrazole, there was prepared:
__________________________________________________________________________ Phenyl substitution in place of 5-amino-1-(2-chloro-4-Compound methylphenyl)-4-cyanopyrazoleNo. used in Example 22 Form Observations__________________________________________________________________________77 2-chloro-4-trifluoromethyl Colourless reaction at 20.degree. C. solid m.p. rather than 0.degree. C. 169-171.degree. C.__________________________________________________________________________
EXAMPLE 37
Compounds 78, 79, 45, 34 and 113
By proceeding in a similar manner to that hereinbefore described in Example 24 but replacing the n-butyryl chloride by the hereinafter indicated acid halide, there were prepared the following 4-cyano-5-(sub.carbonamido)-1-(2,3,4-trichlorophenyl)pyrazoles identified by Compound number:
______________________________________ Acid halide in placeCompound of n-butyryl chlorideNo. used in Example 24 Form Observations______________________________________78 dichloroacetyl Colourless Addition of chloride crystals pyridine at m.p. 20.degree. C. rather 159-160.degree. C. than 0.degree. C. Recrystallisation from toluene79 cyclobutylcarbonyl Colourless Addition of chloride crystals pyridine at m.p. 20.degree. C. rather 3/4-186.degree. C. than 0.degree. C. Recrystallisation from ethyl acetate45 cyclohexylcarbonyl Colourless Addition of chloride crystals pyridine at m.p. 20.degree. C. rather 149-151.degree. C. than 0.degree. C. Recrystallisation from toluene - petroleum ether (b.p. 80-100.degree. C.)34 (.+-.)-2-ethyl-3- Colourless Stirring at methyl-butyryl crystals reflux. chloride m.p. Recrystallisation 155-156.degree. C. from toluene113 (.+-.)-2-methyl- Orange Stirring at pentanoyl chloride powder reflux. m.p. Recrystallisation 134-136.degree. C. from toluene- hexane______________________________________
EXAMPLE 38
Compounds 41, 42, 43, 44, 89 and 186
By proceeding in a similar manner to that hereinbefore described in Example 24 but replacing the n-butyryl chloride by the hereinafter indicated acid halide and the substituted phenylpyrazole by 5-amino-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-4-cyano-pyrazole, there were prepared the following 4-cyano-5-(sub. carbonamido)-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-pyrazoles identified by Compound number:
______________________________________ Acid halide inCom- place of n-butyrylpound chloride usedNo. in Example 24 Form Observations______________________________________41 -- Colourless Addition of crystals m.p. pyridine at 99-101.degree. C. 20.degree. C. rather than 0.degree. C. Recrystallisation from cyclohexane42 isobutyryl Colourless chloride crystals m.p. 149-151.degree. C.43 cyclopropyl- Colourless Addition of carbonyl crystals m.p. pyridine at chloride 148-149.degree. C. 20.degree. C. rather than 0.degree. C. Recrystallisation from toluene44 2-ethylbutyryl Colourless chloride crystals m.p. 138-139.degree. C.89 isovaleryl Colourless Stirring at reflux. chloride crystals m.p. Recrystallisation 148-150.degree. C. from toluene186 (.+-.)-cis,trans-2- Colourless Stirring at methylcyclo- crystals reflux propylcarbonyl m.p. 220-222.degree. Recrystallisation chloride C. from ethyl acetate- petroleum ether (b.p. 60-80.degree. C.)______________________________________
EXAMPLE 39
Compounds 92, 93, 96, 106, 111, 87, 99, 121, 61, 62, 63, 64, 126, 127 and 184
By proceeding in a similar manner to that hereinbefore described in Example 24 but replacing the n-butyryl chloride by the hereinafter indicated acid halide and the substituted phenylpyrazole by 5-amino-1-(2-chloro-4-trifluoromethylphenyl)-4-cyanopyrazole, there were prepared the following 4-cyano-5-(sub.carbonamido)-1-(2-chloro-4-trifluoromethylphenyl)pyrazoles identified by Compound number:
__________________________________________________________________________ Acid halide in place ofCompound n-butyryl chloride usedNo. in Example 24 Form Observations__________________________________________________________________________92 cyclohexycarbonyl chloride Colourless solid m.p. 160-161.degree. C.93 (.+-.)2-methylbutyryl chloride Colourless crystals m.p. 132-133.degree. C.96 pivaloyl chloride Colourless Addition of crystals m.p. pyridine at 190-192.degree. C. 20.degree. C. rather than 0.degree. C.106 heptanoyl chloride Colourless Recrystallisation crystals m.p. from ethyl 88-89.degree. C. acetate - petroleum ether111 cyclopentylcarbonyl Buff-coloured (b.p. 60-80.degree. C.) chloride crystals m.p. 119-120.degree. C.87 Valeryl chloride Colourless crystals m.p. 87-89.degree. C.99 2-ethylbutyryl chloride Colourless Reaction at crystals m.p. reflux 165-166.degree. C. temperature. Acetonitrile as solvent.121 cyclobutylcarbonyl chloride Colourless Recrystallisation crystals m.p. from ethyl 161-162.degree. C. acetate - petroleum ether (b.p. 60-80.degree. C.)61 propionyl chloride Colourless Addition of crystals m.p. pyridine at 20.degree. C. 154-156.degree. C. rather than 0.degree. C. Recrystallisation from toluene62 -- Colourless Addition of crystals m.p. pyridine at 20.degree. C. 135-137.degree. C. rather than 0.degree. C.63 isovaleryl chloride Colourless Recrystallisation crystals m.p. from ethyl 108-109.degree. C. acetate-petroleum ether (b.p. 60-80.degree. C.)64 cyclopropylcarbonyl Colourless Addition of chloride crystals m.p. pyridine at 20.degree. C. 156-158.degree. C. rather than 0.degree. C. Recrystallisation from toluene126 (.+-.)2-methylpentanoyl Colourless Reaction at chloride crystals m.p. reflux temperature 99-101.degree. C. Recrystallisation from toluene- hexane127 (.+-.)-2-ethyl-3-methylbutyryl Colourless Reaction at reflux chloride crystals m.p. temperature. 172-174.degree. C. Recrystallisation from ethyl acetate - petroleum ether (b.p. 60-80.degree. C.)184 (.+-.)-cis,trans-2- Colourless Reaction at methylcyclo- crystals reflux propylcarbonyl m.p. 130-132.degree. temperature. chloride C. Column chromatography ether-hexane (1:1) as eluent__________________________________________________________________________
EXAMPLE 40
Compounds 98, 112, 119, 104, 105, 110, 120, 123, 164, 162, 95, 97, 107, 108 and 187
By proceeding in a similar manner to that hereinbefore described in Example 24 but replacing the n-butyryl chloride by the hereinafter indicated acid halide and the substituted phenylpyrazole by 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-cyanopyrazole, there were prepared the following 4-cyano-5-(sub.carbonamido)-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazoles identified by Compound number:
__________________________________________________________________________ Acid halide in place ofCompound n-butyryl chloride usedNo. in Example 24 Form Observations__________________________________________________________________________98 -- Colourless powder Reaction at reflux m.p. 168-170.degree. C. temperature. Recrystallisation from toluene112 (.+-.)2-methylbutyryl chloride Colourless crystals Reaction at reflux m.p. 132-133.degree. C. temperature. Acetonitrile as solvent. Recrystallisation from ethyl acetate - petroleum ether (b.p. 60-80.degree. C.)119 cyclobutylcarbonyl chloride Colourless crystals m.p. 199-200.degree. C.104 isobutyryl chloride Colourless solid Reaction at reflux m.p. 172-173.degree. C. temperature105 cyclopropylcarbonyl chloride Colourless solid Recrystallisation m.p. 203-205.degree. C. from toluene110 valeryl chloride Colourless crystals m.p. 135-137.degree. C.120 pivaloyl chloride Colourless crystals Reaction at reflux m.p. 200-201.degree. C. temperature123 2-ethylbutyryl chloride Buff-coloured crystals Recrystallisation from m.p. 175-176.degree. C. ethyl acetate - petroleum ether164 (.+-.)2-ethyl-3-methylbutyryl chloride Buff-coloured crystals (b.p. 60-80.degree. C.) m.p. 195-196.degree. C.162 (.+-.)-2-methylpentanoyl chloride Pale yellow crystals Reaction at reflux m.p. 131-135.degree. C. temperature. Dichloromethane chromatography95 cyclohexylcarbonyl chloride Colourless crystals Addition of pyridine at m.p. 182-184.degree. C. 20.degree. C. rather than 0.degree. C.97 isovaleryl chloride Colourless solid Recrystallisation from m.p. 178-179.degree. C. ethyl acetate- petroleum ether (b.p. 60-80.degree. C.)107 cyclopentylcarbonyl chloride Colourless crystals m.p. 195-196.degree. C.108 heptanoyl chloride Colourless crystals m.p. 111-112.degree. C.187 (.+-.)-cis,trans-2- Colourless Reaction at reflux methylcyclopropyl- crystals temperature using carbonyl chloride m.p. 189-190.degree. C. acetonitrile as solvent. Recrystallisation from ethyl acetate- petroleum ether (b.p. 60-80.degree. C.)__________________________________________________________________________
EXAMPLE 41
Compounds 100, 122 and 177
By proceeding in a similar manner to that hereinbefore described in Example 24 but replacing the substituted phenyl pyrazole by the hereinafter indicated appropriate substituted phenylpyrazole, there were prepared the following compounds:
4-Cyano-1-(2,6-dibromo-4-trifluoromethylphenyl)-5-propionamidopyrazole, m.p. 160.degree.-161.degree. C., in the form of colourless crystals, from 5-amino-4-cyano-1-(2,6-dibromo-4-trifluoromethylphenyl)pyrazole.
4-Cyano-1-(2,nitro-4-trifluoromethylphenyl)-5-propionamidopyrazole, m.p. 162.degree.-163.degree. C., after crystallisation from a mixture of ethyl acetate and petroleum ether (bp 60.degree.-80.degree. C.), from 5-amino-4-cyano-1-(2-nitro-4-trifluoromethylphenyl)pyrazole (described in British Published Patent Specification No. 2,070,604A).
4-Cyano-1-(2,3-dichloro-4-methylphenyl)-5-propionamidopyrazole, m.p. 173.degree.-174.degree. C., after crystallisation from toluene, in the form of colourless crystals, from 5-amino-4-cyano-1-(2,3-dichloro-4-methylphenyl)pyrazole (described in Published British Patent Specification No. 2,070,604A).
EXAMPLE 42
Compounds 135, 137, 138, 141, 142, 151, 148, 149, 143, 144, 155, 168 and 156
Sodium hydride (480 mg; 50% dispersion in oil) was added in portions over 5 minutes to a stirred solution of 5-acetamido-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (3.3 g) in dry dimethylformamide (20 ml), under nitrogen, at a temperature of -10.degree. C. to 0.degree. C. The stirring was continued at 0.degree. C. for 1.5 hours after which time evolution of hydrogen had ceased. A solution of propionyl chloride (1.01 g) in dry dimethylformamide (10 ml) was added to the reaction mixture over 10 minutes at a temperature of 0.degree. C. The reaction mixture was stirred at 5.degree. C. overnight, then poured onto a mixture of ice and dilute hydrochloric acid, to precipitate a white solid. The solid was filtered off, washed with water and dissolved in dichloromethane, the dichloromethane solution was dried over anhydrous magnesium sulphate and evaporated to give an oil (3.7 g). The oil was chromatographed on a silica column (Merck 230-400 mesh; pressure 10 lb in.sup.-2) using dichloromethane as eluent. Evaporation of the eluate containing the major component gave a solid (2.7 g) which was crystallised from a mixture of toluene and petroleum ether (bp 60.degree.-80.degree. C.) to give 5-(N-acetyl-N-propionyl)amino-1-(2,3,4-trichlorophenyl)pyrazole (1.8 g), m.p. 114.degree.-115.degree. C. in the form of colourless crystals.
By proceeding in a similar manner, there were prepared the following:
______________________________________CompoundNo Chloride Reactant Pyrazole Reactant______________________________________137 cyclopropylcarbonyl chloride Compound 1 reacted with138 2-ethylbutyryl chloride Compound 1141 heptanoyl chloride Compound 1142 isobutyryl chloride Compound 1151 valeryl chloride Compound 1148 isobutyryl chloride Compound 5149 propionyl chloride Compound 65143 propionyl chloride Compound 61144 propionyl chloride Compound 73155 acetyl chloride Compound 47168 isobutyryl chloride Compound 47156 acetyl chloride Compound 11______________________________________
__________________________________________________________________________CompoundNo. Form Observations__________________________________________________________________________137 Colourless crystals Chromatography using dichloromethane as eluant m.p. 124-127.degree. C.138 Colourless crystals Chromatography using 1:1 dichloromethane - petroleum m.p. 129-130.degree. C. ether (b.p. 60-80.degree. C.) Recrystallisation from petroleum ether (b.p. 60-80.degree. C.)141 Colourless crystals Chromatography using dichloromethane as eluant m.p. 58-60.degree. C.142 Colourless solid m.p. 124-125.degree. C.151 Colourless solid Recrystallisation from petroleum ether (b.p. 60-80.degree. C.) m.p. 86-88.degree. C. Chromatography using 2:1 dichloromethane - petroleum ether148 Colourless crystals (b.p. 60-80.degree. C.) m.p. 102-103.degree. C. Recrystallisation from toluene and petroleum ether149 Colourless crystals Chromatography using dichloromethane as eluant m.p. 105-106.degree. C.143 Cream coloured solid m.p. 119-120.degree. C.144 Colourless crystals Ambient temperature. Tetrahydrofuran as solvent. m.p. 101-102.degree. C. Recrystallisation from toluene - hexane155 Colourless crystals m.p. 148-150.degree. C.168 Colourless crystals Tetrahydrafuran as solvent. Recrystallisation from m.p. 114-115.degree. C. ethyl acetate - hexane.156 Off white crystals Recrystallisation from aqueous ethanol m.p. 103-105.degree. C. after reaction in tetrahydrofuran__________________________________________________________________________
EXAMPLE 43
Compounds 154 and 152
A solution of 5-amino-4-cyano-1-(2,3,4,6-tetrafluorophenyl)pyrazole (2.6 g; described in British Published Patent Specification No. 2,070,604A.) in dry tetrahydrofuran (10 ml) was added dropwise to a stirred suspension of powdered sodium hydride (0.53 g) in dry tetrahydrofuran, under nitrogen, at a temperature not exceeding 30.degree. C. maintained by external cooling (ice). When the evolution of hydrogen had ceased a solution of acetyl chloride (1.5 ml) in tetrahydrofuran (15 ml) was added at a temperature not exceeding 30.degree. C. After stirring at laboratory temperature for 48 hours the reaction mixture was washed with saturated aqueous ammonium chloride and the organic layer separated and dried over anhydrous magnesium sulphate and evaporated to dryness. The residue was chromatographed on a silica column (Merck 230-400 mesh; 10 lb in.sup.-2) using dichloromethane as eluent. Evaporation of the eluate containing the major component gave a solid which was crystallised from a mixture of toluene and hexane to give 4-cyano-5-diacetylamino-1-(2,3,4,6-tetrafluorophenyl)-pyrazole (1.5 g), m.p. 132.degree.-134.degree. C., in the form of colourless crystals.
By proceeding in a similar manner but replacing the 5-amino-4-cyano-1-(2,3,4,6-tetrafluorophenyl)pyrazole with 5-amino-1-(4-n-butyl-2,3,5,6-tetrafluorophenyl)-4-cyanopyrazole, there was prepared:
1-(4-n-Butyl-2,3,5,6-tetrafluorophenyl)-4-cyano-5-diacetylaminopyrazole, m.p. 73.5.degree.-75.degree. C., in the form of a colourless solid, following chromatography using dichloromethane as eluent.
EXAMPLE 44
Compounds 125, 80, 94, 101 and 161
A mixture of 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (11.44 g) and (.+-.)-4-chloropentanoyl chloride (9.2 g) in dry acetonitrile (60 ml) was stirred and heated at reflux for 7 hours. The reaction mixture was evaporated under diminished pressure to give an oil. The oil was chromatographed on a silica column (Merck 230-400 mesh; pressure 25 lb in.sup.-2) using dichloromethane as eluent. Evaporation of the eluate containing the major component gave a light brown oil (14.3 g). This oil was crystallised from a mixture of diethyl ether and petroleum ether (bp 60.degree.-80.degree. C.) to give (.+-.)-5-(4-chloropentanamido)-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (9.0 g), m.p. 126.degree.-127.degree. C., in the form of colourless crystals.
By proceeding in a similar manner, but replacing the (.+-.)-4-chloropentanoyl chloride by the hereinafter indicated acid chloride, there were prepared: 5-(4-Chlorobutyramido)-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 173.degree.-174.degree. C. after crystallisation from toluene, in the form of pale yellow crystals, from 4-chlorobutyryl chloride.
5-(5-Chloropentanamido)-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 139.degree. C., after crystallisation from a mixture of ethyl acetate and hexane, in the form of colourless crystals, from 5-chloropentanoyl chloride. 5-(3-Chloro-2,2-dimethylpropionamido)-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole, m.p. 169.degree.-175.degree. C., in the form of colourless crystals, from .beta.-chloropivaloyl chloride.
By proceeding in a similar manner but replacing the 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole with 5-amino-1-(2-chloro-4-methylphenyl)-4-cyanopyrazole and the (.+-.)-4-chloropentanoyl chloride by (.+-.)-3-chlorobutyryl chloride there was prepared. (.+-.)-1-(2-chloro-4-methylphenyl)-5-(3-chlorobutyramido)-4-cyanopyrazole, m.p. 195.degree.-196.degree. C., after crystallisation from aqueous acetone, in the form of a colourless solid.
EXAMPLE 45
Compound 185
By proceeding in a similar manner to that hereinbefore described in Example 24 but replacing the n-butyryl chloride with cyclopropylcarbonyl chloride and replacing the substituted phenylpyrazole by 5-amino-4-cyano-1-(2,3,4,6-tetrachlorophenyl)pyrazole and carrying out the addition of pyridine at laboratory temperature rather than 0.degree. C. there was prepared.
4-Cyano-5-cyclopropylcarbonamido-1-(2,3,4,6-tetrachlorophenyl)pyrazole, m.p. 205.degree.-207.degree. C., after crystallisation from a mixture of ethyl acetate and petroleum ether (b.p. 60.degree.-80.degree. C.), in the form of buff-coloured crystals.
REFERENCE EXAMPLE 1
The hereinafter indicated N-phenylpyrazole derivatives used as starting materials in the foregoing Examples were prepared as follows:
2,3,4-Trichlorophenylhydrazine (106 g) was added at laboratory temperature to a stirred solution of anhydrous sodium acetate (20.5 g) in glacial acetic acid (250 ml). Ethoxymethylenemalononitrile (61 g) was then added with stirring to the suspension thus obtained. Partial solution occurred within 5 minutes, after which a fine precipitate was formed. The mixture was stirred for one hour and then filtered. The solid obtained was washed successively with water, aqueous sodium bicarbonate solution and water and dried to give 2,3,4-trichlorophenylhydrazinomethylenemalononitrile (118 g), m.p. 149.degree.-155.degree. C., in the form of a yellow powder.
The 2,3,4-trichlorophenylhydrazinomethylenemalononitrile thus obtained was then heated at reflux for one hour in ethoxyethanol (300 ml). The hot solution was treated with decolourising charcoal, filtered and diluted with water (100 ml). The pale yellow crystals which formed were separated, dried and recrystallised from toluene (400 ml) to give 5-amino-4-cyano-1-(2,3,4-trichlorophenyl)pyrazole (100 g), m.p. 159.degree.-160.degree. C., in the form of colourless crystals.
By proceeding in a similar manner, but replacing the 2,3,4-trichlorophenylhydrazine by the hereafter identified appropriately substituted phenylhydrazine, there was prepared:
5-Amino-4-cyano-1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)pyrazole, m.p. 122.degree.-122.5.degree. C., in the form of off-white crystals, after crystallisation from toluene, from 2,3,5,6-tetrafluoro-4-trifluoromethylphenylhydrazine (prepared as described by Alsop et al, J. Chem. Soc, 1962, 1801), via 2,3,5,6-tetrafluoro-4-trifluoromethylphenylhydrazinomethylenemalononitrile (isolated as a pale yellow solid, m.p. 90.degree.-93.degree. C.);
5-Amino-4-cyano-1-(2,4,6-trichlorophenyl)pyrazole, m.p. 213.degree.-214.degree. C., after crystallisation from a mixture of acetone and toluene, in the form of cream coloured crystals, from 2,4,6-trichlorophenylhydrazine (described by Chatterway and Irving, J. Chem. Soc, 1931, 1740), via 2,4,6-trichlorophenylhydrazinomethylenemalononitrile (isolated as a light fawn-coloured powder, m.p. 168.degree.-170.degree. C.).
REFERENCE EXAMPLE 2
2,3,4-Trichlorophenylhydrazine, used as a starting material in Reference Example 1 was prepared as follows:
2,3,4-Trichloroaniline (100 g) was dissolved with stirring in glacial acetic acid (875 ml) at 55.degree.-60.degree. C. A solution of sodium nitrite (39.5 g) in concentrated sulphuric acid (300 ml) was then added over 15 minutes at 55.degree.-60.degree. C. to the solution thus obtained. The viscous mixture obtained was cooled to 5.degree.-10.degree. C. and a solution of stannous chloride dihydrate (437 g) in concentrated hydrochloric acid (375 ml) was added at 5.degree.-10.degree. C. over 20 minutes. A fine, off-white solid precipitated. To aid filtration, the mixture was warmed to 60.degree. C., allowed to cool to laboratory temperature and then filtered. The precipitate was washed on the filter with saturated aqueous sodium chloride solution (100 ml). The damp powder thus obtained was added to a stirred mixture of aqueous ammonia (1.3 liters; S.G. 0.880) and ice. The fine slurry which formed was filtered and the precipitate obtained was dried at 80.degree. C., and boiled twice with chloroform (2.times.1.5 liters). The chloroform extracts were combined and evaporated to dryness to give 2,3,4-trichlorophenylhydrazine (86 g), m.p. 142.degree.-143.degree. C., in the form of a colourless powder.
2,3,4-Trichloroaniline is a known compound, which is readily available.
REFERENCE EXAMPLE 3
The hereinafter indicated N-phenylpyrazole derivatives used as starting materials in the foregoing Examples were prepared as follows:
2,3,6-Trichloro-4-trifluoromethylphenylhydrazine (10.1 g) was added in one portion to a solution of ethoxymethylenemalononitrile [4.40 g; described by Huber, J. Amer. Chem. Soc., 65, 2224 (1943)] and anhydrous sodium acetate (1.47 g) in glacial acetic acid (34 ml) stirred at laboratory temperature. After stirring at laboratory temperature for 5 minutes, a fine precipitate formed and stirring at laboratory temperature was continued for 2 hours. The reaction mixture was then allowed to stand overnight at laboratory temperature and filtered. The solid precipitate was washed successively with a small quantity of glacial acetic acid, saturated aqueous sodium bicarbonate solution and water, to give 2,3,6-trichloro-4-trifluoromethylphenylhydrazinomethylenemalononitrile (9.6 g), m.p. 169.degree.-170.degree. C. in the form of a fawn-coloured powder.
The 2,3,6-trichloro-4-trifluoromethylphenylhydrazinomethylenemalononitrile thus obtained was heated at reflux for 1 hour in ethoxyethanol (50 ml). The hot solution was filtered and the filtrate was cooled, diluted with water (70 ml) and the solid precipitate was filtered off to give 5-amino-4-cyano-1-(2,3,6-trichloro-4-trifluoromethylphenyl)pyrazole (6.36 g), m.p. 186.degree.-187.degree. C., after crystallisation from toluene (25 ml), in the form of a buff-coloured crystalline solid. By proceeding in a similar manner, but replacing the 2,3,6-trichloro-4-trifluoromethylphenylhydrazine by the hereinafter identified appropriately substituted phenyl hydrazine, there was prepared:
5-Amino-1-(2-chloro-4-ethylphenyl)-4-cyanopyrazole, m.p. 174.degree.-175.degree. C., after crystallisation from toluene, in the form of light orange crystals, from 2-chloro-4-ethylphenylhydrazine, via 2-chloro-4-ethylphenylhydrazinomethylenemalononitrile.
REFERENCE EXAMPLE 4
The hereinafter indicated N-phenylpyrazole derivatives used as starting materials in the foregoing Examples were prepared as follows:
4-Methyl-2,3,5,6-tetrafluorophenylhydrazine [29.8 g; described by Burdon et al, J. Chem. Soc., 5152 (1965)] was added in one portion to a solution of ethoxymethylenemalononitrile (19 g) and anhydrous sodium acetate (5.3 g) in glacial acetic acid (65 ml) stirred at laboratory temperature. After stirring at laboratory temperature for 1 minute, a fine precipitate formed and stirring at laboratory temperature was continued for 4 hours. The reaction mixture was then allowed to stand overnight at laboratory temperature, diluted with water (50 ml) and filtered. The solid precipitate was washed successively with glacial acetic acid, water, saturated aqueous sodium bicarbonate solution and water, to give 4-methyl-2,3,5,6-tetrafluorophenylhydrazinomethylenemalononitrile (37 g), m.p. 140.degree.-143.degree. C., in the form of a yellow solid. The 4-methyl-2,3,5,6-tetrafluorophenylhydrazinomethylenemalononitrile thus obtained was heated at reflux for 45 minutes in ethoxyethanol (50 ml). The hot solution was treated with charcoal and filtered. The filtrate was cooled, diluted with water (20 ml) and the solid precipitate was filtered off and washed with water to give 5-amino-4-cyano-1-(4-methyl-2,3,5,6-tetrafluorophenyl)-pyrazole (26 g) m.p. 169.degree.-170.degree. C., in the form of a yellow solid. By proceeding in a similar manner, but replacing the 4-methyl-2,3,5,6-tetrafluorophenylhydrazine by the hereinafter identified appropriately substituted phenylhydrazine, there were prepared:
1-(4-Allyl-2,3,5,6-tetrafluorophenyl)-5-amino-4-cyanopyrazole, m.p. 124.degree.-125.degree. C., after crystallisation from toluene, in the form of colourless crystals, from 4-allyl-2,3,5,6-tetrafluorophenylhydrazine, via 4-allyl-2,3,5,6-tetrafluorophenylhydrazinomethylenemalononitrile (isolated in the form of a brown solid, m.p. 121.degree.-123.degree. C.);
5-Amino-1-(2-chloro-4-methylphenyl)-4-cyanopyrazole, m.p. 143.degree.-144.degree. C., in the form of fawn-coloured crystals, from 2-chloro-4-methylphenylhydrazine, m.p. 70.degree.-72.degree. C. [described by Bulow and Engler, Ber. 52, 639 (1919)], via 2-chloro-4-methylphenylhydrazinomethylenemalononitrile (isolated in the form of a fawn-coloured solid, m.p. 133.degree.-134.degree. C.);
5-Amino-4-cyano-1-(2,3-dichlorophenyl)pyrazole, m.p. 148.degree.-150.degree. C., in the form of colourless crystals, after crystallisation from toluene, from 2,3-dichlorophenylhydrazine [described in U.S. Pat. No. 2,863,864 (1958)] via 2,3-dichlorophenylhydrazinomethylenemalononitrile (isolated in the form of a sandy-coloured solid, m.p. 145.degree.-146.degree. C.).
REFERENCE EXAMPLE 5
Phenylhydrazines used as starting materials in Reference Example 3 were prepared as follows:
2-Chloro-4-ethylaniline [14.5 g.; described by K. Altau, J. Chem. Eng. Data, 8, 122 (1963)] was dissolved, with stirring, in glacial acetic acid (113 ml). A solution of sodium nitrite (7.0 g) in concentrated sulphuric acid (55 ml) was then added at 55.degree.-60.degree. C. The solution thus obtained was cooled to 0.degree.-5.degree. C. and a solution of stannous chloride (70 g) in concentrated hydrochloric acid (80 ml) was added with vigorous stirring. A cream-coloured solid precipitated. The mixture was filtered and the solid obtained was added to a mixture of aqueous ammonia and ice. The mixture thus obtained was extracted with diethyl ether (4.times.300 ml) and the combined ethereal extracts were dried over sodium sulphate, filtered and evaporated to dryness, to give 2-chloro-4-ethylphenylhydrazine (9.6 g), m.p. 55.degree.-57.degree. C., in the form of a cream-coloured solid. By proceeding in a similar manner, but replacing the 2-chloro-4-ethylaniline by the hereinafter indicated appropriately substituted aniline, there was prepared:
2,3,6-Trichloro-4-trifluoromethylphenylhydrazine, m.p. 72.degree.-74.degree. C., in the form of a white solid, from 2,3,6-trichloro-4-trifluoromethylaniline.
REFERENCE EXAMPLE 6
4-Allyl-2,3,5,6-tetrafluorophenylhydrazine, used as a starting material in Reference Example 4 was prepared as follows:
Allylpentafluorobenzene [41.6 g; described by Harper et al, J. Org. Chem., 29, 2385 (1964)] was added to a solution of hydrazine hydrate (100 ml) in ethanol (150 ml) and the mixture was heated at reflux for 24 hours. The solid precipitate which formed was collected by filtration and washed with ethanol and hexane to give 4-allyl-2,3,5,6-tetrafluorophenylhydrazine (18.8 g), m.p. 82.degree.-84.degree. C., in the form of colourless crystals. The filtrate was evaporated to dryness and the yellow solid thus obtained was washed with ethanol and hexane to give a further quantity (22.0 g) of 4-allyl-2,3,5,6-tetrafluorophenylhydrazine, m.p. 79.degree.-81.degree. C., in the form of a cream-coloured solid.
REFERENCE EXAMPLE 7
2,3,6-Trichloro-4-trifluoromethylaniline, used as a starting material in Reference Example 5, was prepared as follows:
A mixture of 3-chloro-4-trifluoromethylaniline [20 g; described in British Patent Specification No. 459,890] and hydrochloric acid (d:1.18; 12 ml) was suspended in water (600 ml). Chlorine gas (from 13 ml of liquid chlorine) was then passed into the stirred suspension with heating at reflux. On completion of the addition of chlorine gas, stirring was continued for a further 15 minutes. After cooling, the solution thus obtained was extracted with dichloromethane (3.times.250 ml). The combined organic extracts were washed with water, saturated aqueous sodium bicarbonate solution and water, dried over anhydrous sodium sulphate and evaporated. The red oil thus obtained was distilled (bp 143.degree.-147.degree. C./20 mmHg) to give an orange oil which crystallized on standing to give 2,3,6-trichloro-4-trifluoromethylaniline (12.26 g), m.p. 37.degree.-39.degree. C., in the form of an orange solid.
REFERENCE EXAMPLE 8
Ethoxymethylenemalononitrile [1.84 g; described by Huber, J. Amer. Chem. Soc., 65, 2224 (1943)] and 2,6-dichloro-4-trifluoromethylphenylhydrazine (3.7 g) were added to a magnetically-stirred solution of sodium acetate (0.6 g) in glacial acetic acid (15 ml) at laboratory temperature. After stirring for 15 minutes, a colourless solid precipitated from the clear brown solution obtained and stirring was continued for a further 15 minutes. The mixture was then filtered. The solid obtained was washed successively with acetic acid, water, aqueous sodium bicarbonate solution and water, to give 2,6-dichloro-4-trifluoromethylphenylhydrazinomethylenemalononitrile (3.4 g), m.p. 153.degree.-154.degree. C., in the form of colourless crystals.
The 2,6-dichloro-4-trifluoromethylphenylhydrazinomethylenemalononitrile thus obtained was then heated at reflux for 45 minutes in ethoxyethanol (15 ml). The hot solution was filtered and the filtrate was cooled, diluted with water (5 ml), and filtered, to give 5-amino-4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (2.5 g), m.p. 165.degree.-167.degree. C., in the form of off-white crystals.
By proceeding in a similar manner, but replacing the 2,6-dichloro-4-trifluoromethylphenylhydrazine by the hereinafter indicated appropriately substituted phenylhydrazine, there were prepared:
5-Amino-1-(2-chloro-4-trifluoromethylphenyl)-4-cyanopyrazole, m.p. 185.degree.-187.degree. C., after crystallisation from toluene, in the form of fawn-coloured crystals, from 2-chloro-4-trifluoromethylphenylhydrazine, via 2-chloro-4-trifluoromethylphenylhydrazinomethylenemalononitrile, in the form of a brown powder, m.p. 138.degree.-143.degree. C.
REFERENCE EXAMPLE 9
Phenylhydrazines used as starting materials in Reference Example 8 were prepared as follows:
2,6-Dichloro-4-trifluoromethylphenylaniline (4.3 g) (described in U.S. Pat. No. 3,850,955) was dissolved, with stirring, in glacial acetic acid (23 ml). A solution of sodium nitrite (1.5 g) in concentrated sulphuric acid (11 ml) was then added at 55.degree.-60.degree. C. The solution thus obtained was cooled to 0.degree.-5.degree. C. and a solution of stannous chloride (16.4 g) in concentrated hydrochloric acid (14 ml) was added with vigorous stirring. A cream-coloured solid precipitated. The mixture was filtered and the solid obtained was added to a mixture of aqueous ammonium hydroxide solution and ice. The mixture thus obtained was extracted with diethyl ether (6.times.500 ml) and the combined ethereal extracts were dried over sodium sulphate, filtered and evaporated to dryness to give 2,6-dichloro-4-trifluoromethylphenylhydrazine (3.7 g), m.p. 54.degree.-56.degree. C., in the form of a colourless crystalline solid. By proceeding in a similar manner, but replacing the 2,6-dichloro-4-trifluoromethylaniline by 2-chloro-4-trifluoromethylaniline (described in U.S. Pat. No. 3,850,955), there was prepared:
2-Chloro-4-trifluoromethylphenylhydrazine, m.p. 38.degree.-39.degree. C., in the form of a colourless solid.
REFERENCE EXAMPLE 10
2,6-Dichloro-4-ethylphenylhydrazine (2.54 g) was added in one portion to a stirred solution of ethoxymethylenemalononitrile [1.55 g; described by Huber. J. Amer. Chem. Soc., 65, 2224 (1943)] and anhydrous sodium acetate (0.5 g) in glacial acetic acid (12 ml) at laboratory temperature. A fine precipitate formed after 5 minutes and stirring was continued for 2 hours. The reaction mixture was allowed to stand at laboratory temperature overnight then filtered. The solid product was washed successively with a small quantity of glacial acetic acid, saturated aqueous sodium bicarbonate solution and water, to give 2,6-dichloro-4-ethylphenylhydrazinomethylenemalononitrile (1.41 g), m.p. 137.degree.-138.degree. C., in the form of a fawn coloured solid.
The 2,6-dichloro-4-ethylphenylhydrazinomethylenemalononitrile thus obtained was heated at reflux for 1 hour in ethoxyethanol (15 ml). The hot solution was filtered and the filtrate diluted with water (15 ml) and the solid precipitate filtered off to give 5-amino-4-cyano-1-(2,6-dichloro-4-ethylphenyl)pyrazole (1.15 g), m.p. 189.degree.-190.degree. C., in the form of fawn-coloured crystals.
REFERENCE EXAMPLE 11
The phenylhydrazine used as starting material in Reference Example 10 was prepared by proceeding in a similar manner to that hereinbefore described in Reference Example 5 but replacing the 2-chloro-4-ethylaniline by 2,6-dichloro-4-ethylaniline. 2,6-Dichloro-4-ethylphenylhydrazine, m.p. 48.degree.-50.degree. C., was obtained in the form of a cream-coloured solid.
REFERENCE EXAMPLE 12
4-n-Butyl 2,3,5,6-tetrafluorophenylhydrazine, used as starting material in Reference Example 14 was prepared as follows:
n-Butylpentafluorobenzene [19.0 g; described by J. M. Birchall and R. N. Haszeldine J. Chem. Soc p 3719 (1961)] was added to a solution of hydrazine hydrate (50 ml; 99-100% w/w) in ethanol (100 ml) and the mixture heated at reflux for 72 hours. The reaction mixture was cooled, evaporated to dryness to give a solid which was filtered off and washed with ethanol and hexane to give 4-n-butyl-2,3,5,6-tetrafluorophenylhydrazine (20.5 g), m.p. 80.degree.-81.degree. C., in the form of colourless crystals.
REFERENCE EXAMPLE 13
2,6-Dichloro-4-ethylaniline used as a starting material in Reference Example 11 was prepared as follows:
A solution of 4-amino-3,5-dichloroacetophenone [15.8 g; described by Lutz et al, J. Org. Chem., 12, 617 (1947)] in glacial acetic acid (100 ml) and sulphuric acid (d:1.84; 8.2 g) was treated at 22.degree.-27.degree. C. for 22.5 hours with hydrogen in the presence of charcoal containing 5% palladium and filtered. The filtrate was evaporated to dryness and the yellow solid thus obtained was suspended in ice-water (150 ml). Aqueous sodium hydroxide solution (20% w/v) was added to pH10 and the mixture was then extracted with diethyl ether (3.times.150 ml). The ethereal extracts were combined, washed with water, dried over anhydrous sodium sulphate and evaporated to dryness. The yellow solid (11.75 g) thus obtained was chromatographed on a silica column (Merck, 250-400 mesh; pressure 25 lb in.sup.-2) eluated with hexane-toluene (5:1). Evaporation of the eluate containing the faster-moving component gave 2,6-dichloro-4-ethylaniline (4.59 g), m.p. 47.degree.-48.degree. C., in the form of colourless crystals.
REFERENCE EXAMPLE 14
By proceeding in a similar manner to that hereinbefore described in Reference Example 10 but replacing the 2,6-dichloro-4-ethyl-phenylhydrazine by the hereinafter identified appropriately substituted phenyl-hydrazine, there were prepared:
5-Amino-4-cyano-1-(4-methyl-2,3,6-trichlorophenyl)pyrazole, m.p. 187.5.degree.-189.5.degree. C., in the form of off-white crystals, from 4-methyl-2,3,6-trichlorophenylhydrazine, via 4-methyl-2,3,6-trichlorophenylhydrazinomethylenemalononitrile (isolated in the form of a cream-coloured solid, m.p. 145.degree.-147.degree. C.).
5-Amino-4-cyano-1-(2,3-dichloro-4-ethylphenyl)pyrazole, m.p. 152.degree.-154.degree. C., in the form of a colourless solid, from 2,3-dichloro-4-ethylphenylhydrazine, via 2,3-dichloro-4-ethylphenylhydrazinomethylenemalononitrile (isolated in the form of a cream-coloured solid, m.p. 138.degree.-140.degree. C.).
5-Amino-1-(2-chloro-4-n-propylphenyl)-4-cyanopyrazole, m.p. 117.degree.-118.degree. C., in the form of a fawn-coloured solid, from 2-chloro-4-n-propylphenylhydrazine via 2-chloro-4-n-propylphenylhydrazinomethylenemalononitrile (isolated in the form of a colourless solid, m.p. 136.degree.-137.degree. C.).
5-Amino-4-cyano-1-(2,6-dibromo-4-trifluoromethylphenyl)pyrazole, m.p. 187.degree.-188.degree. C., in the form of a colourless solid, from 2,6-dibromo-4-trifluoromethylphenylhydrazine, via 2,6-dibromo-4-trifluoromethylphenylhydrazinomethylenemalononitrile (isolated in the form of a cream-coloured solid, m.p. 174.degree.-175.degree. C.).
5-Amino-1-(2-chloro-4-isopropylphenyl)-4-cyanopyrazole, m.p. 180.5.degree.-182.degree. C., after crystallization from toluene, in the form of fawn-coloured crystals, from 2-chloro-4-isopropylphenylhydrazine, via 2-chloro-4-isopropylphenylhydrazinomethylenemalononitrile.
5-Amino-1-(4-n-butyl-2,3,5,6-tetrafluorophenyl)-4-cyanopyrazole, m.p. 123.degree.-124.degree. C., after crystallization from toluene, in the form of colourless crystals, from 4-n-butyl-2,3,5,6-tetrafluorophenylhydrazine, via 4-n-butyl-2,3,5,6-tetrafluorophenylhydrazinomethylenemalononitrile. 5-Amino-4-cyano-1-(4-ethyl-2,3,5,6-tetrafluorophenyl)pyrazole, m.p. 145.5.degree.-146.5.degree. C., after crystallization from toluene, in the form of colourless crystals, from 4-ethyl-2,3,5,6-tetrafluorophenylhydrazine, via 4-ethyl-2,3,5,6-tetrafluorophenylhydrazinomethylenemalononitrile.
5-Amino-4-cyano-1-(2,3,5,6-tetrafluoro-4-vinylphenyl)pyrazole, m.p. 157.degree.-159.degree. C., after crystallization from toluene, in the form of off-white crystals, from 2,3,5,6-tetrafluoro-4-vinylphenylhydrazine, via 2,3,5,6-tetrafluoro-4-vinylphenylhydrazinomethylenemalononitrile.
REFERENCE EXAMPLE 15
Phenylhydrazines used as starting materials in Reference Example 14 were prepared as follows:
By proceeding in a similar manner to that hereinbefore described in Reference Example 1 but replacing the 2-chloro-4-ethylaniline by the hereinafter indicated appropriately substituted aniline, there were prepared:
4-Methyl-2,3,6-trichlorophenylhydrazine, m.p. 131.degree.-133.degree. C., in the form of a white solid, from 4-methyl-2,3,6-trichloroaniline [described by F. Bell, J. Chem. Soc. p 2376, (1955)].
2,6-Dibromo-4-trifluoromethylphenylhydrazine, m.p. 65.degree.-67.degree. C., in the form of a fawn-coloured solid, from 2,6-dibromo-4-trifluoromethylaniline (prepared as described in Reference Example 20).
REFERENCE EXAMPLE 16
Phenylhydrazines used as starting materials in Reference Example 14, were prepared as follows:
By proceeding in a similar manner to that hereinbefore described in Reference Example 12 but replacing the n-butylpentafluorobenzene by the hereinafter indicated appropriately substituted benzene, there were prepared:
4-Ethyl-2,3,5,6-tetrafluorophenylhydrazine, m.p. 82.degree.-83.degree. C., in the form of colourless crystals, from ethylpentafluorobenzene [described by R. J. Harper et al. J. Org. Chem. 29, 2385 (1964)].
2,3,5,6-Tetrafluoro-4-vinylphenylhydrazine, m.p. 88.5.degree.-89.5.degree. C., after crystallization from aqueous ethanol, in the form of colourless crystals, from vinylpentafluorobenzene [described by J. C. Tatlow et al. J. Chem. Soc. pp 166-171 (1959)].
REFERENCE EXAMPLE 17
Phenylhydrazines used as starting materials in Reference Example 14 were prepared as follows:
A solution of 2-chloro-4-isopropylacetanilide (9.3 g) in a mixture of glacial acetic acid (66 ml) and hydrochloric acid (44 ml; density 1.19) was heated at reflux for 4 hours. After cooling, the reaction mixture was stirred and a solution of sodium nitrite (3.72 g) in concentrated sulphuric acid (27 ml) added at 15.degree.-20.degree. C. The solution thus obtained was cooled to 0.degree.-5.degree. C. and a solution of stannous chloride (40 g) in concentrated hydrochloric acid (35 ml) was added with vigorous stirring. A cream coloured precipitate formed. The mixture was filtered and the solid obtained basified with aqueous sodium hydroxide (2N, 350 ml). This was extracted with dichloromethane (3.times.200 ml) and the combined extracts washed with water (2.times.500 ml), dried over anhydrous magnesium sulphate and evaporated to dryness to give 2-chloro-4-isopropylphenylhydrazine (4.5 g), m.p. 64.degree.-66.degree. C., in the form of a colourless solid. The filtrate from the stannous-complex filtration was reduced under diminished pressure and the residue basified with aqueous sodium hydroxide (50% w/v), ice being added to maintain the temperature at 20.degree.-25.degree. C. The mixture was similarly extracted with dichloromethane to furnish a further quantity of 2-chloro-4-isopropylphenylhydrazine (3.03 g), m.p. 65.degree.-67.degree. C., in the form of a yellow solid.
By proceeding in a similar manner but replacing 2-chloro-4-isopropylacetanilide by the hereinafter appropriately substituted acetanilide, there was prepared:
2,3-Dichloro-4-ethylphenylhydrazine, m.p. 80.degree.-82.degree. C., in the form of a yellow solid, from 2,3-dichloro-4-ethylacetanilide.
2-Chloro-4-n-propylphenylhydrazine, in the form of an brown oil, from 2-chloro-4-n-propylacetanilide.
REFERENCE EXAMPLE 18
Sodium hypochlorite (60 ml; bleach grade 14-15% w/v available chlorine) was added to a solution of 3-chloro-4-ethylacetanilide [5 g; described by J. P. Hambooy J. Med. Chem. 16 765 (1973)] in a mixture of glacial acetic acid (10 ml), ethanol (10 ml) and water (10 ml). An exothermic reaction occurred resulting in the precipitation of an orange oil. The aqueous layer was decanted and the oil dissolved in diethyl ether and the ether was washed with water, aqueous sodium bicarbonate (sat.), water and then dried over anhydrous magnesium sulphate and was evaporated to dryness to give an oil which partially crystallized on standing. The orange semi-solid (4.27 g) thus obtained was chromatographed on a silica column (Merck, 250-400 mesh, pressure 25 lb in.sup.-2) eluted with dichloromethaneethyl acetate (19:1), fractions being taken every 25 ml. Evaporation of the eluate (fractions 12+13) containing the faster moving component gave 2,5-dichloro-4-ethylacetanilide (0.8 g), m.p. 113.degree.-114.degree. C., in the form of a colourless solid. Evaporation of the eluate (fractions 16-20) containing the slower moving component gave 2,3-dichloro-4-ethylacetanilide (1.39 g), m.p. 94.degree.-96.degree. C., in the form of a colourless solid. Evaporation of the remaining eluate (fractions 24-37) gave recovered 3-chloro-4-ethylacetanilide (1.0 g), m.p. 100.degree.-101.degree. C., in the form of a colourless solid.
By proceeding in a similar manner, but replacing the 3-chloro-4-ethylacetanilide by the hereinafter appropriately substituted acetanilide and chromatographing the crude product using the eluent hereinafter specified there was prepared:
2-Chloro-4-n-propylacetanilide, m.p. 78.degree.-79.degree. C., after crystallization from ethanol-water, in the form of colourless crystals, after chromatography of the crude product using dichloromethane as eluent, from p-n-propylacetanilide [described by Willgeralt Ann, 327, 307 (1903)].
REFERENCE EXAMPLE 19
Acetic anhydride (21 ml) was added to a solution of 4-isopropylaniline (27 g) in glacial acetic acid (62 ml) and the reaction mixture heated at reflux for 1.5 hours. The solution was then stirred and cooled to 10.degree. C. and concentrated hydrochloric acid (67 ml) added. The reaction mixture was then stirred vigorously while a solution of sodium chlorate (6.7 g) in water (18 ml) was added dropwise at 15.degree.-20.degree. C. and the stirring continued at laboratory temperature for 6 hours. After standing at room temperature overnight, the reaction mixture was poured onto ice-water (1.51) to precipitate a brown solid which was filtered off and washed with water. The solid was chromatographed on a silica column (Merck, 250-400 mesh; pressure 25 lb in.sup.-2) using dichloromethane-ethyl acetate (15:1) as eluent. Evaporation of the eluate containing the faster moving component gave 2-chloro-4-isopropylacetanilide (9.76 g), m.p. 115.degree.-116.degree. C., in the form of a fawn coloured solid.
REFERENCE EXAMPLE 20
Bromine (96 g) was added dropwise to a stirred mixture of 4-aminobenzotrifluoride (48.3 g) and reduced iron (3 g) in ethyl acetate (300 ml) at a temperature of 30.degree.-50.degree. C. The solution was then heated at reflux for 1 hour, after which evolution of hydrogen bromide ceased. The reaction mixture was evaporated to dryness and the residue dissolved in diethyl ether (1.51) and basified with aqueous sodium hydroxide (2N) to pH 14. The organic layer was removed and the aqueous layer extracted with diethyl ether (500 ml). The ether extracts were combined, washed with water (2.times.500 ml) and dried over anhydrous sodium sulphate, then evaporated to give a brown semi-solid (90.0 g). The semi-solid was treated with hexane (50 ml) and filtered, the filtrate was cooled to -30.degree. C. to precipitate a solid which was removed by filtration to give 2,6-dibromo-4-trifluoromethylaniline (65.4 g), m.p. 37.degree.-39.degree. C., in the form of fawn-coloured crystals.
REFERENCE EXAMPLE 21
By proceeding in a similar manner to that hereinbefore described in Reference Example 4 but replacing the 4-methyl-2,3,5,6-tetrafluorophenylhydrazine by the hereinafter identified appropriately substituted phenyl-hydrazine, there were prepared:
5-Amino-4-cyano-1-(3,5-difluoro-2,4,6-trichlorophenyl)pyrazole, m.p. 210.degree.-212.degree. C., after crystallisation from toluene, in the form of a colourless solid, from 3,5-difluoro-2,4,6-trichlorophenylhydrazine [described by N. Ishikawa, Nippon Kagaku Zasshi 86, 1202 (1965)] via 3,5-difluoro-2,4,6-trichlorophenylhydrazinomethylenemalononitrile.
5-Amino-4-cyano-1-(2,4-dichloro-6-methylphenyl)pyrazole, m.p. 199.degree.-202.degree. C., after crystallisation from toluene in the form of a colourless solid, from 2,4-dichloro-6-methylphenylhydrazine (described in British Pat. No. 904,852) via 2,4-dichloro-6-methylphenylhydrazinomethylenemalononitrile (isolated in the form of an off-white solid, m.p. 151.degree.-153.degree. C.).
5-Amino-1-(4-bromo-2,3,5,6-tetrafluorophenyl)-4-cyanopyrazole, m.p. 208.degree.-210.degree. C., after crystallisation from toluene, in the form of a colourless solid, from 4-bromo-2,3,5,6-tetrafluorophenylhydrazine [described by J. Burdon. Tet. Lett. 22, 1183 (1966)] via 4-bromo-2,3,5,6-tetrafluorophenylhydrazinomethylenemalononitrile.
5-Amino-1-(4-chloro-2,3,5,6-tetrafluorophenyl)-4-cyanopyrazole, m.p. 164.degree.-166.degree. C., after crystallisation from toluene, in the form of a colourless solid, from 4-chloro-2,3,5,6-tetrafluorophenylhydrazine [described by N. Ishikawa, Nippon Kagaku Zasshi 89, 321 (1968)] via 4-chloro-2,3,5,6-tetrafluorophenylhydrazinomethylenemalononitrile.
5-Amino-1-(2-bromo-4-trifluoromethylphenyl)-4-cyanopyrazole, m.p. 194.degree.-196.degree. C., after crystallisation from toluene in the form of colourless crystals, from 2-bromo-4-trifluoromethylphenylhydrazine, via 2-bromo-4-trifluoromethylphenylhydrazinomethylenemalononitrile. (.+-.)-5-Amino-1-(4-sec-butyl-2,3,5,6-tetrafluorophenyl)-4-cyanopyrazole, m.p. 125.5.degree.-127.degree. C., after crystallisation from toluene, in the form of colourless crystals, from (.+-.)-4-sec-butyl-2,3,5,6-tetrafluorophenylhydrazine via (.+-.)-4-sec-butyl-2,3,5,6-tetrafluorophenylhydrazinomethylenemalononitrile.
5-Amino-4-cyano-1-(2,3,4,6-tetrachlorophenyl)pyrazole, m.p. 193.degree.-194.degree. C., in the form of a colourless crystalline solid, from 2,3,4,6-tetrachlorophenylhydrazine [described by Chattaway J. Chem. Soc. p 1925 (1931)] via 2,3,4,6-tetrachlorophenylhydrazinomethylenemalononitrile (isolated in the form of a fawn coloured solid, m.p. 174.degree.-176.degree. C.).
REFERENCE EXAMPLE 22
2-Bromo-4-trifluoromethylphenylhydrazine, in the form of a red oil, used as a starting material in Reference Example 21, was prepared by proceeding in a similar manner to that hereinbefore described in Reference Example 5 but replacing the 2-chloro-4-ethylaniline by 2-bromo-4-trifluoromethylaniline (described in U.S. Pat. No. 3,995,042, Pharm Doc 94181X).
REFERENCE EXAMPLE 23
One of the phenylhydrazines used as a starting material in Reference Example 21 was prepared as follows:
By proceeding in a similar manner to that hereinbefore described in Reference Example 12 but replacing the n-butylpentafluorobenzene by the hereinafter appropriately substituted pentafluorobenzene, and adding sufficient dioxan to the reaction mixture to obtain a homogeneous solution, there was obtained:
4-sec-Butyl-2,3,5,6-tetrafluorophenylhydrazine, m.p. 23.degree.-29.degree. C., in the form of a yellow waxy solid, from sec-butylpentafluorobenzene.
REFERENCE EXAMPLE 24
sec-Butylpentafluorobenzene, used as a starting material in Reference Example 23, was prepared as follows:
A solution of sec-butyl lithium (350 ml; 12% in cyclohexane) was added over a period of 1 hour to a stirred mixture of hexafluorobenzene (80 g) in cyclohexane (750 ml) at a temperature of 0.degree. C. On warming the reaction mixture above 0.degree. C. a violently exothermic reaction took place which was brought under control by external cooling (Cardice-acetone). The reaction mixture was subsequently brought to room temperature (no further reaction occurred) and was quenched with water (600 ml). The organic layer was separated, washed with dilute hydrochloric acid (2N; 2.times.200 ml) and water (2.times.200 ml) and dried over anhydrous magnesium sulphate, and afterwards distilled through a 15 cm vigreux column. The fraction distilling at 160.degree.-170.degree. C. was collected to give sec-butylpentafluorobenzene (50.3 g), b.p. 162.degree.-164.degree. C. (760 mm), in the form of a colourless liquid.
Hexafluorobenzene is a known compound and is readily available.

Number	Date	Country	Kind
8122143	Jul 1981	GBX
8203371	Feb 1982	GBX

Number	Name	Date	Kind
3211731	Schmidt et al.	Oct 1965
4260775	Plath et al.	Apr 1981

5-Acylamino-4-cyano-1-phenylpyrazole derivatives and use as herbicides

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Cheng et al., J. Org. Chem., 1958, vol. 23, pp. 191-200.
Kreutzberger et al., Eur. J. Med. Chem.-Chim. Ther., 1979, vol. 14, pp. 539-541.