Patent FR-2844264-A1 (FR)
Title: New halogenated S-alpha-aminoalkyl thicarbonylsulfanyl compounds, useful as reagents in radical addition reactions, especially for the preparation of biologically active trifluoromethylamine compounds
Inventor: ZARD SAMIR
IPC: C07F7/08
Filed: 2002-09-11
Abstract: Halogenated S-alpha-aminoalkyl dithiocarboxylate, dithiocarbamate or di- or tri-thiocarbonate compounds (I) are new. Also new are S-gamma-aminoalkyl thiocarbamylsulfanyl compounds (II) and 1,2-diamines (VIII).  Thiocarbonylsulfanyl compounds of formula (I) and their salts are new. Z1 = alkyl, acyl, aryl, aralkyl, alkenyl, alkynyl, carbocyclyl, heterocyclyl, ORa, SRa or NRiRj;  Ra = alkyl, haloalkyl, alkenyl, alkynyl, acyl, aralkyl, aralkenyl, aralkynyl, carbocyclyl, heterocyclyl, polymer chain or -CRbRc-P(O)(ORd)(ORe);  Rb, Rc = H, alkyl, perfluoroalkyl, carbocyclyl, heterocyclyl, NO2, NCO, CN, Rf, SO3Rf, SRf, NRfRg, COORf, OCORf, CONRfRg or -NCORfRg; or CRbRc = CO, CS, carbocycle or heterocycle;  Rf, Rg = alkyl, alkenyl, alkynyl, cycloalkenyl, cycloalkynyl, aryl (optionally fused with a heterocycle), alkaryl, aralkyl or heteroaryl;  Rd, Re = as for Rf;  or Rd + Re = 2-4C hydrocarbon chain (optionally interrupted by O, S or NRh);  Rh = as for Rf;  Ri, Rj = alkyl, haloalkyl, alkenyl, alkynyl, acyl, ester group, aryl, aralkyl, aralkenyl, aralkynyl, carbocyclyl or heterocyclyl;  or Ri + Rj = 2-4C hydrocarbon chain (optionally interrupted by O, S or NRh);  Z2, Z3 = H, alkyl, aryl, cycloalkyl or an electron attracting group, provided that at least one of Z2 and Z3 is a group inducing an electron attractive effect to the N atom to which it is bonded;  Z4 = H, alkyl or cycloalkyl;  RF = halogen (preferably F), haloalkyl, poly- or perhalogenated aryl, RA-CF2-, RA-CF2CF2-, RA-CF2CF(CF3)-, CF3-CF(RA)- or )CF3)RA-;  RA = alkyl, acyl, aryl, aralkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl. Independent claims are also included for: (1) The preparation of (I);  (2) New thiocarbonylsulfanyl compounds of formula (II);  (3) The preparation of (II);  (4) The preparation of amines of formula (IV) by reduction of (II);  (5) The preparation of unsaturated amines of formula (V) by subjecting (II; R7 = H) to elimination reaction;  (6) The preparation of thiocarbonylsulfanyl compounds of formula (VI) by radical addition reaction of (II) with an olefin;  (7) The preparation of amino-aldehydes of formula (VII) by subjecting (II; R6 and R8 = H and acyloxy) to conversion, in the presence of an organic or mineral acid;  (8) The specific new compounds (conversion products of (II)) N-(3-(2-oxo-pyrrolidin-1-yl)-1-trifluoromethyl-allyl)-acetamide, N-(4-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-1-trifluoromethyl-butyl)-acetamide, O-ethyl S-(1-(5-(1-acetylamino-2,2,2-trifluoroethyl)-2-oxo-(1,3)-dioxolan-4-ylmethyl)-2,2-diethoxy-ethyl)-dithiocarbonate, N-(1-(5-bromo-1-methanesulfonyl-2,3-dihydro-1H-indol-3-ylmethyl)-2,2,2-trifluoroethyl)-acetamide and N-(3,3-dimethoxy-1-trifluoromethyl-propyl)-acetamide;  (9) New diamines of formula (VIII); and  (10) The preparation of (VIII). Z5 - Z8 = H, halo, alkyl, haloalkyl, alkenyl, alkynyl, acyl, aryl, aralkyl, aralkenyl, aralkynyl, carbocyclyl, heterocyclyl, polymer chain, -(CH2)m-ORk, -CH(ORk)(ORl). -(CH2)m-SRk, -(CH2)m-SO3Rk, -(CH2)m-NO2, -(CH2)m-CN, -(CH2)m-Rk, -(CH2)m-PO(ORkRl)2, -(CH2)m-SiRkRlRm, -(CH2)m-COORk, -(CH2)m-NCORk or -(CH2)m-NRkRl; or pairs of groups Z5 - Z8 may together form one or more carbocyclic or heterocyclic rings;  Rk, Rl, Rm = alkyl, acyl, aryl, alkenyl, alkynyl, aralkyl, alkaryl, aralkynyl, carbocyclyl or heterocyclyl;  m = 1 or more;  Z9 - Z12 = as for Z5 - Z8.