Patent DE-10325050-A1 (DE)
Title: Thiouronium or uronium salts with various anions, e.g. triflate or tetrakis-pentafluorophenyl-borate, used as ionic liquids, non-aqueous electrolytes, phase-transfer catalysts and surfactants
Inventor: IGNATIEV NIKOLAI
IPC: C07F9/30
Filed: 2003-06-02
Abstract: New salts with thiouronium or uronium cations in which the positive charge is delocalized over several hetero-atoms. Thiouronium or uronium salts of formula (1) are new. [Image] X : O or S; R, R 0> : 1-20C alkyl, 2-20C alkenyl or alkynyl with one or more double bonds, or optionally unsaturated 3-7C cycloalkyl (optionally substituted with 1-6C alkyl groups), with the proviso that (a) R may also be hydrogen, (b) one or more of the groups R/R 0> may be partly or completely substituted with halogen or partly substituted with CN or NO 2 (but with no halogen in the alpha -position in R 0>), (c) R and R 0> may be linked together by a single or double bond and (d) one carbon or two non-adjacent carbons of one or more of the groups R/R 0> which are not directly adjacent to the hetero-atom may be replaced by -O-, -CO-, -COO-, -S-, -SO-, -SO 2-, -SO 3-, -N=, -N=N-, -NH-, -NR'-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O- or -P(R') 2=N-; halogen : F, Cl, Br or I; R' : optionally (per)fluorinated 1-6C alkyl, optionally unsaturated 3-7C cycloalkyl, optionally substituted phenyl or an optionally substituted heterocycle; A : [R 1>SO 3] ->, [RF'SO 3] ->, [(RFSO 2) 2N] ->, [(RFSO 2) 3C] ->, [(FSO 2) 3C] ->, [R 1>CH 2OSO 3] ->, [R 1>COO] ->, [RF'COO] ->, [CCl 3COO] ->, [(CN) 3C] ->, [(CN) 2CR 1>] ->, [(R 1>OOC) 2CR 1>] ->, [P(C nF 2 n + 1 - mH m) yF 6 - y] ->, [P(C 6F 5) yF 6 - y] ->, [R 1> 2P(O)O] ->, [R 1>P(O)O 2] 2> ->, [(R 1>O) 2P(O)O] ->, [(R 1>O)P(O)O 2] 2> ->, [(R 1>O)(R 1>)P(O)O] ->, [RF 2P(O)O] ->, [RFP(O)O 2] 2->, [BF zRF 4-z] ->, [BF z(CN) 4 - z] ->, [B(CN) 4] ->, [B(C 6F 5) 4] ->, [B(OR 1>) 4] ->, [N(CF 3) 2] ->, [N(CN 2] ->, [AlCl 4] -> or [SiF 6] 2> ->; RF, RF' : 1-20C perfluoroalkyl (not CF 3 in the case of RF'), 2-20C perfluoroalkenyl, perfluorophenyl or optionally unsaturated 3-7C cycloalkyl (optionally substituted with perfluoroalkyl), where pairs of RF or RF' groups may be linked by single or double bonds and carbon atom(s) (see (d) above) may be replaced by O, CO, S, SO, SO 2, -N=, -N=N-, NR', PR' or P(O)R' or may carry a terminal R'OSO 2- or R'OCO- group; R 1> : H (if A = [(CN) 2CR 1>] -> or [(R 1>OOC) 2CR 1>] -> and X is O or S, or if A = [R 1>CH 2OSO 3] ->, X is S or O and the groups R and R 0> are 1-20C alkyl groups), 1-20C alkyl, 2-20C alkenyl or alkynyl (with one or more double or triple bonds) or optionally unsaturated 3-7C cycloalkyl (optionally substituted with 1-6C alkyl), with provisos (b), (c) and (d) as above; n : 1-20; m, z : 0, 1, 2 or 3; y : 0, 1, 2, 3 or 4; if X : S and R and R 0> = 1-20C alkyl, the anions A = [BF 4] ->, CF 3COO ->, [B(C 6H 5) 4] -> and [CH 3C 6H 4SO 3] -> are also allowed; if X : O, the anions A = CF 3COO -> and [B(C 6H 5) 4] -> are also allowed; if X : O and R 0> = ethyl, the anion A = CH 3CH 2OSO 3 -> is not allowed. Independent claims are also included for: (1) a method (M1) for the production of (1) by alkylating a thiourea SC(NR 2) 2 or a urea OC(NR 2) 2 (a) with an ester of formula AR 0> or (b) with an oxonium salt of formula (R 0>) 3A ->; and (2) a method (M2) for the production of (1) by reacting salts of formula (1) in which the anion (A) is [BF 4] ->, Br ->, Cl ->, I -> or [ClO 4] -> with a salt Kt +> A -> or an acid AH. A : [R 1>CH 2OSO 3], [R 1>SO 3], [RFSO 3], [RFCOO] or [CCl 3COO] in M1 (a), or [(FSO 2) 3C] or [BF 4] in M1 (b); Kt : an alkali or alkaline earth metal.