Patent DE-19701032-A1 (DE)
Title: 2-(Hetero)aryl-1,2,4-triazolinone derivative preparation in high yield
Inventor: WECKBECKER CHRISTOPH DR
IPC: A01N43/90
Filed: 1997-01-15
Abstract: Preparation of 2-(phenyl or benzoheterocyclyl)-4,5-dialkyl-1,2,4-triazolin-3(2H)-(thi)one derivatives of formula (I) involves (i) reacting an amide of formula (IV) with phosgene or thiophosgene (or a substitute), optionally in a solvent, to give an N-(chloro(thio)carbonyl)-chloro-enamine compound of formula (V) and (ii) reacting (V) with a hydrazide of formula QNHNHCOR<26> (VI) or its acid addition salt, optionally in presence of a diluent, optionally  initially in presence of a base then in presence of an acid and optionally with elevation of temperature. X = O or S; R<1> = 2-8C alkoxyalkyl, 2-8C haloalkoxyalkyl, alkyl, haloalkyl, cyanoalkyl, 2-8C alkylthioalkyl, 2-8C alkylsulphinylalkyl, 2-8C alkylsulphonylalkyl, 7-8C aralkyl (e.g. benzyl), 2-8C alkenyl, 2-8C haloalkenyl, 2-8C alkynyl, 2-8C haloalkynyl, aryl such as phenyl or naphthyl (optionally substituted by one or more of halogen, 1-3C alkyl and 1-3C alkoxy), or heteroaryl such as pyridyl (optionally substituted by halogen); R<2>,R<3> = H, 2-6C alkoxyalkyl, 2-6C haloalkoxyalkyl, 1-6C alkyl, 1-6C haloalkyl, (1-6C)cyanoalkyl, 1-6C alkylthio, 2-6C alkylthioalkyl, 2-6C alkylsulphinylalkyl, 2-6C alkylsulphonylalkyl, 2-6C alkenyl, 2-6C haloalkenyl, 2-6C alkynyl or 2-6C haloalkynyl; or aralkyl or optionally substituted aryl as defined for R<1>; or heteroaryl such as pyridyl; alternatively R<1>+R<2> complete a ring, so that (I) is a bicyclic compound of formula (I'); n,m = 0-3; Z = CR<4>R<5>, O, S, SO, SO2, N(1-4C alkyl), N(1-4C haloalkyl), CO, C=NR<4> or CS; R<4> = H, 1-3C alkyl, halogen, 1-6C alkoxy, 1-6C haloalkyl, 1-6C haloalkoxy, 2-6C alkylcarbonyloxy or 2-6C haloalkylcarbonyloxy; R<5> = H, 1-3C alkyl or halogen; R<4> and R<5> may each substitute the ring in one or more positions, up to a total of 12 substituents (m = n = 3); Q = aryl or benzo-heterocyclic group of formula (Q1)-(Q7); W = O or S; R<6> = H or halogen; R<7> = H, alkyl, haloalkyl, halogen, OH, OR<12>, SH, S(O)pR<12>, COR<12>, COOR<12>, C(O)SR<12>, CONR<14>R<15>, CHO, CR<14>=NOR<21>, CHCR<22>COOR<12>, CH2CHR<22>COOR<12>, COON=CR<16>R<17>, NO2, CN, NHSO2R<18>, NR<12>R<23>, NH2 or phenyl (optionally substituted by R<24>); p = 0-2; R<8> = 1-2C alkyl, 1-2C haloalkyl, OMe, SMe, OCHF2, halogen, CN or NO2; R<9> = H, 1-3C alkyl or halogen; R<10> = H, 1-3C alkyl, halogen, 1-3C haloalkyl, cyclopropyl, vinyl, ethynyl, CN, COR<23>, COOR<23>, CONR<23>R<25>, CR<19>R<20>CN, CR<19>R<20>COR<23>, CR<19>R<20>COOR<23>, CR<19>R<20>CONR<23>R<25>, CHR<19>OH, CHR<19>OCOR<23> or OCHR<19>OCONR<23>R<25>; or in (Q2), CR<9>R<10> may be CO; R<11> = H, 1-6C alkyl, 1-6C haloalkyl, 3-6C haloalkenyl, 2-6C alkoxyalkyl, 3-6C alkenyl, 3-6C alkynyl, 3-6C haloalkynyl, 4-7C cycloalkylalkyl, CHR<27>COOR<28>, CHR<27>CN, CHR<27>CH=CHCOOR<28> or glycidyl; R<12> = alkyl, 3-8C cycloalkyl, 3-8C alkenyl, 3-8C alkynyl, haloalkyl, 2-8C alkoxyalkyl, 2-8C alkylthioalkyl, 2-8C alkylsulphinylalkyl, 2-8C alkylsulphonylalkyl, 4-8C alkoxyalkoxyalkyl, 4-8C cycloalkylalkyl, 6-8C cycloalkoxyalkyl, 4-8C alkenyloxyalkyl, 4-8C alkynyloxyalkyl, 3-8C haloalkoxyalkyl, 4-8C haloalkenyloxyalkyl, 4-8C haloalkynyloxyalkyl, 6-8C cycloalkylthioalkyl, 4-8C alkenylthioalkyl, 4-8C alkynylthioalkyl, 1-4C alkyl substituted by phenoxy or benzyloxy (both optionally ring-substituted by halogen, 1-3C alkyl or 1-3C haloalkyl), 4-8C trialkylsilylalkyl, 3-8C cyanoalkyl, 3-8C halocycloalkyl, 3-8C haloalkenyl, 5-8C alkoxyalkenyl, 5-8C haloalkoxyalkenyl, 5-8C alkylthioalkenyl, 3-8C haloalkynyl, 5-8C alkoxyalkynyl, 5-8C haloalkoxyalkynyl, 5-8C alkylthioalkynyl, 2-8C alkylcarbonyl, benzyl (optionally substituted by halogen, 1-3C alkyl or 1-3C haloalkyl), CHR<19>COR<13>, CHR<19>P(O)(OR<13>)2, CHR<19>P(S)(OR<13>)2, P(O)(OR<13>)2, P(S)(OR<13>)2, CHR<19>CONR<14>R<15>, CHR<19>CONH2, CHR<19>COOR<13>, COOR<13>, SO2R<13>, phenyl (optionally substituted by R<24>), 1,3-dioxolan-2-ylmethyl or glycidyl; R<13> = 1-6C alkyl, 1-6C haloalkyl, 3-6C alkenyl or 3-6C alkynyl; R<14>,R<16>,R<23>,R<24>,R<28> = H or 1-4C  alkyl moieties have 1-8C unless specified otherwise.  The following intermediates are new compounds: formic acid N'-(2,4-dichloro-5-hydroxyphenyl)hydrazide (VIb) and formic acid N'-(2,4-dichloro-(5-prop-2-ynyloxy)phenyl)hydrazide (VIa).