Patent EA-002350-B1 (EA)
Title: Substituted pyrazole-3-yl benzazoles
Inventor: ZAGAR CYRILL
IPC: C07D413/04
Filed: 1997-12-01
Abstract: 1. A substituted pyrazol-3-ylbenzazole of the formula I   where the substituents have the following meanings: R<1> is hydrogen, C1-C4-alkyl or C1-C4-haloalkyl; R<2> is cyano, C1-C4-alkyl, C1-C4 haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsuffinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl or C1-C4-haloalkylsulfonyl; R<3> is hydrogen, halogen, cyano, nitro, C1-C4-alkyl or C1-C4-haloalkyl; R<4> is hydrogen or halogen; R<5> is hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy; Z is a group -N.dbd.C(XR<6>)-O- or -N.dbd.C(XR<6>)-S- which is bonded to a by the nitrogen, oxygen or sulfur; X is a chemical bond, oxygen, sulfur, -S(O)-, -SO2 -, -NH- or -N(R<7>)-; R<6> and R<7> independently of one another are each C1-C6-alkyl, C1-C6-haloalkyl, cyano-C1-C4-alkyl, hydroxy-C1-C4-alkyl, C3-C6-alkenyl, cyano-C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, cyano- C3-C6-alkynyl, C3-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-C4-alkenyloxy-C1-C4-alkyl, C3-C4-alkynyloxy-C1-C4-alkyl, C3-C6-cycloalkyloxy-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylaroino-C1-C4-alkyl, di (C1-C4-alkyl) amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkylthio-, C1-C4-alkyl, C3-C4-alkynylthio-C1-C4-alkyl, C1-C4-alkylsulfinyl-C1-C4-alkyl, C1-C4-haloalkylsulfinyl-C1-C4-alkyl, C3-C4-alkenylsulfinyl-C1-C4-alkyl, C3-C4-alkynylsulfinyl-C1-C4-alkyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-C4-alkyl which may carry a cyano or (C1-C4-alkoxy) carbonyl group, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, C1-C4-alkyllamino-carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl, (C1-C4-alkoxy)imino-C1-C4-alkyl, (C3-C4-alkenylloxy)imino-C1-C4-alkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl, 3- to 7-membered heterocyclyl or heterocyclyl-C1-C4-alkyl, where each cycloalkyl and each heterocyclyl ring may contain a carbonyl or thiocarbonyl ring member, and where each cycloalkyl, phenyl and heterocyclyl ring may be unsubstituted or carry one to four substituents selected in each case from the group consisting of cyano, nitro, amino, hydroxyl, carboxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyll, (C1-C4-alkoxy) carbonyl, (C1-C4-alkyl)carbonyl, (C1-C4-haloalkyl)carbonyl, (C1-C4-alkyl)carbonyloxy, (C1-C4-haloalkyl)carbonyloxy and di(C1-C4-alkyl)amino;| if X is a chemical bond, oxygen, sulfur, -NH- or -N(R<7>)-, R<6> may also be (C1-C4-alkyl)carbonyl, (C1-C4-haloallkyl)carbonyl, (C1-C4-alkoxy)carbonyl, C1-C4-alkylsulfonyl or C1-C4-haloalkylsulfonyl; if X is a cheroicar bond, R<6>| may furthermore be hydrogen, cyano, mercapto, amino, halogen, CH2-CH( halogen )-R<8>, -CH=CH-R<8> or -CH=(halogen)R<8>, where R<8> is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)phosphonyl; or R<6> and R<7> together are a 1,3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene chain which may in each case be unsubstituted or carry one to four C1-C4-alkyl groups or one or two (C1-C4-alkoxy)carbonyl groups, and the agriculturally useful salts of these compounds I. 2. The use of a substituted pyrazol-3-ylbenzazole and agriculturally useful salts thereof, as claimed in Claim 1, as herbicides or for the desiccation/defoliation of plants. 3. A herbicidal composition comprising a herbicidally active amount of at least one substituted pyrazol-3-ylbenzazole of the formula I or an agriculturally useful salt of I, as claimed in Claim 1, and at least one inert liquid and/or solid carrier and, if desired, at least one surfactant. 4. A composition for the desiccation and/or defoliation of plants, comprising an amount of at least one substituted pyrazol-3-ylbenzazole of the formula I or an agriculturally useful salt of I, as claimed in Claim 1, and at least one inert liquid and/or solid carrier and, if desired, at least one surfactant. 5. A proces for preparing herbicidally active compositions, which comprises mixing a herbicidally active amount of at least one substituted pyrazol-3-ylbenzazole of the formula I or an agriculturally useful salt of I, as claimed in Claim 1, with at least one inert liquid and/or solid carrier and, if desired, at least one surfactant. 6. A process for preparing compositions which act-as desiccants and/or defoliants, which comprises mixing an amount of at least one substituted pyrazol-3-ylbenzazole of the formula I or an agriculturally useful salt of I, as claimed in Claim 1, with at least one inert liquid and/or solid carrier and, if desired, at least one surfactant. 7. A method for controlling undesirable vegetation, which comprises allowing a herbicidally active amount of at least one substituted pyrazol-3-ylbenzazole of the formula I or of an agriculturally useful salt of I, as claimed in Claim 1, to act on plants, their habitat or on seeds. 8. A method for the desiccation and/or defoliation of plants, which comprises allowing an amount of at least one substituted pyrazol-3-ylbenzazole of the,formula I or of an agriculturally useful salt of I, as claimed in Claim 1, which acts as a desiccant and/or defoliant, to act on plants. 9. A method as claimed in Claim 8, wherein cotton is treated. 10. A process for preparing a substituted pyrazol-3-ylbenzazole of the formula I as claimed in Claim 1 where Z is -N=C(NH2)-S-, which comprises reacting an aminophenylpyrazole of the formula Ilia or Illb   either with a halogen and ammonium thiocyanate or an alkali metal thiocyanate or alkaline earth metal thiocyanate, or initially with ammonium thiocyanate or an alkali metal thiocyanate or alkaline earth metal thiocyanate and then with a halogen. 11. A process for preparing a substituted pyrazol-3-ylbenzazole of the formula I where XR<6> is halogen or cyano, which comprises diazotizing a substituted pyrazol-3-ylbenzazole I where XR<6> is amino and subsequently reacting the resulting diazonium salt with copper(I) halide or copper(I) cyanide. 12. A process for preparing a substituted, pyrazol-3-ylbenzazole of the formula I where X is sulfur, which comprises diazotizing a substituted pyrazol-3-ylbenzazole I where XR<6> is amino and subsequently reacting the resulting diazonium salt with a dialkyl disulfide of the formula R<6>S-SR<6>. 13. A process for preparing a substituted pyrazol-3-ylbenzazole of the formula I where XR<6> is -CH2-CH(C1)-R<8>, -CH2-CH(Br)-R<8>, -CH=CH-R<8>, -CH=C(C1)-R<8> or -CH=C(Br)-R<8>, which comprises diazotizing a substituted pyrazol-3-ylbenzazole I where XR<6> is amino and subsequently reacting the resulting diazonium salt with an alkene of the formula H2C=CH-R<8> or an alkyne of the formula HC=C-R<8> and copper(I) chloride, copper(I) bromide, copper(II) chloride or copper(II) bromide. 14. A process for preparing a substituted pyrazol-3-ylbenzazole of the formula I where X is oxygen, sulfur, -MH- or -N(R<7>)-or where XR<6> is CH(R<b>)R<c> where R<b> and R<c> independently of one another are each cyano or (C1-C4-alkoxy)carbonyl, which comprises reacting a substituted pyrazol-3-ylbenzazole I where XR<6> is chlorine, bromine, -SO2-alkyl or -SO2-haloalkyl in the presence of a base with a nucleophile HOR<6>, HSR<6>, H2NR<6> HN(R<6>)R<7> or H2C(R<b>)R<c>. 15. A process for preparing a substituted pyrazol-3-ylbenzazole of the formula I where XR<6> is C1-C6-alkyl, which comprises reacting a substituted pyrazol-3-ylbenzazole I where XR<6> is halogen, if appropriate in the presence of a catalyst, with a (C1-C6-alkyl)-Grignard reagent. 16. A process for preparing a substituted pyrazol-3-ylbenzazole of the formula I as claimed in Claim 1 where Z is -N=C(R<6>)-O-, which comprises diazatizing an aminophenylpyrazole of the formula Ilia or Illb   reacting the resulting diazonium .salt with an alkali metal azide to give an azidophenylpyrazole of the formula Va or Vb   and finally reacting this with a carboxylic acid of formula R<6>-COOH.