Patent DE-10158803-A1 (DE)
Title: Production of difluoromethoxy-bridged compounds, involves addition of acid to ketene dithioketal, reaction of the carbenium salt with hydroxy compound and fluorodesulfurisation of the dithio-ortho-ester
Inventor: HECKMEIER MICHAEL
IPC: C07C205/37
Filed: 2001-11-30
Abstract: A method for producing compounds with -CF2O- bridge(s) involves (a) addition of an acid to a ketene dithioketal, (b) reaction of the resulting bis-(alkylthio)-carbenium salt with a hydroxy compound in presence of base and (c) oxidative fluorodesulfurisation of the resulting dithio-ortho-ester with a fluorinating agent and an oxidizing agent.  Independent claims are also included for: (1) ketene dithioketals of formula (IIa)and/or corresponding bis-(alkylthio)-carbenium salts of formula (IIIa); (2) dithioketals and corresponding carbenium salts of formula (IIb1) and (IIIb1); (3) compounds of formula (Vb) and (Vc) and corresponding ketals (Vb1) and (Vc1); (4) dithioketals and carbenium salts of formula (IIb2), (IIc1) and (IIc2); (IIIb2), (IIIc1) and (IIIc2); and (5) diketones of formula (Ic1) and corresponding ketals of formula (Ic1.1).  Full definitions and structures are given in the DEFINITIONS (Full Definitions) Field.  Rc = H, halogen, CN, NCS, SF5 or 1-18C alkyl (optionally with one or more non-adjacent CH2 replaced by T, COO, E and/or -CC- and/or with one or more H substituted by halogen and/or CN); Ra = H, halogen, CN or 1-18C alkyl (optionally with 1-2 non-adjacent CH2 groups replaced by T, E and/or CC and/or with one or more H replaced by halogen and/or CN); A<1> = 1,4-phenylene (optionally with one or more CH replaced by N), 1,4-cyclohexylene (optionally with one or more non-adjacent CH2 replaced by O and/or S), 1,4-cyclohexenylene, 1,4-bicyclo(2.2.2)-octylene, piperidine-1,4-diyl, or naphthalene-2,6-diyl and the corresponding decahydro- and 1,2,3,4-tetrahydro- derivatives (all optionally substituted with halogen, CN and/or with one or more non-adjacent CH2 groups replaced by T, COO, CH=CH, CC, NH or N(CH3); R<6>, R<7> = 1-12C alkyl (optionally bridged so that R<6>-S-C-S-R<7> forms a 4 - 8 membered ring, and/or optionally with one or more H replaced by halogen and/or other optionally substituted alkyl and/or aryl groups and/or optionally with one or more non-adjacent CH2 groups replaced by CO, O, S, CH=CH, CC, NH or N(CH3)) and/or aryl (optionally substituted with one or more halogen, alkyl and/or aryl groups); R<8>-R<11> = H or optionally substituted 1-6C alkyl or alkenyl, or one or both of the groups (CR<8>R<9>)m and/or (CR<10>R<11>)M may form a cycloalkyl or aryl group; T = O, S, CO, OCO E = CR<4>=CR<5> or-CHR<4>CHR<5>; R<4>, R<5> = H, 1-6C alkyl, F, Cl, Br, CF3 or CN; Z<1> = OCO, COO, C2H4, CH2CF2, CF2CH2, CF2CF2, CH2O, CF2O, OCH2, OCF2, CH=CH, CF=CH, CH=CF, CF=CF, CC or a single bond; p = 0, 1 or 2; Y = a non-coordinating or weakly-coordinating anion; m, M = 2, 3 or 4; Rc = H, halogen, CN, NCS, SF5 or 1-18C alkyl (optionally with one or more non-adjacent CH2 replaced by T, COO, E and/or -CC- and/or with one or more H substituted by halogen and/or CN); Z<3> = as for Z<1>; A<3> = as for A<1>; r = 0 - 2; A<2> = as for A<1>; Z<2> = as for Z<1>; and v = 0 - 2.