Patent FR-2830014-A1 (FR)
Title: Preparation of halogenated monoorganoxysilanes from halogenoalkylsilanes with substitution of silicon with a divalent motif attached to an electrophile, useful as synthetic intermediates
Inventor: GUENNOUNI NATHALIE
IPC: C07F7/18
Filed: 2001-12-20
Abstract: Synthesis of halogenated monoorganoxysilanes from halogenoalkylsilanes as intermediates for the production of monoorganoxysilanes functionalized by groups other than halogen.  The halogenated monoorganoxysilanes conform to formula (R<1>O)-Si(R<2>)(R<3>)-B-(Hal)m (I); R<1> = H, 1 - 4C alkyl or 2 - 8 C alkoxyalkyl; R2, R3 = 1 - 6C alkyl, 6 - 18C aryl,arylalkyl or alkylaryl(6 - 18C aryl ; 1 - 8C alkyl); m = 1 or 2; B = 1 - 10C alkylene, When m = 1, B is a divalent residue of formula -B<1>-CR<4>H-CR<5>R<6>- : -B<1>-CR<4>-CR<5>R<6> or -(B<2>)a-CR<7>R<8>-CR<9>R<10>-CR<11>R<12> ; on condition that one of the radicals R<7> - R<13> is a valence bond; B<1> and B<2> = 1 - 10C alkylene or a divalent aromatic residue form phenylene (o, m or p)-2 - 8C alkylene, 2 - 8C alkylene-phenylene (o, m or p) or 2 - 8C alkylene-phenylene (o, m o p)-2 - 8C alkylene; a = 0 or 1; R<4> - R<13> = H or 1 - 3C alkyl; When m = 2 = B is a trivalent residue of formula -B<1>-CR<4>-CR<5>R<6>-. The preparation comprises the stages: (a) Hal-Si(R<2>R<3>)-Hal (A)+ R<0>-M-Hal --> Hal-Si(R<2>R<3>)-R<0>(C) + Hal-M-Ha ; (b) When R<0> = R<01>, either: (C) + H-Hal --> Hal-Si(R<2>R<3>)-B<1>-CR<4>H-CR<5>R<6>-Hal and/or Hal-Si(R<2>R<3>)-B<1>-CR<4>Hal-CR<5>R<6>H ; or (C) + Hal-Hal --> Hal-SI(R<2>R<3>)-B<1>-CR<4>Hal-CR<5>R<6>Hal ; When R<0> = R<02> :- (C) + Hal-Hal or SO2(Hal)2 --> Hal-Si(R<2>R<3>)-(B<2>)a-CR<7>R<8>-CR<9>R<10>-CR<11>R<12>Hal and/or Hal-Si(R<2>R<3>)-(B<2>)a-CR<7>R<8>-CR<9>Hal-CR<11>R<12>R<13> and/or Hal-Si(R<2>R<3>)-(B<2>)a-CR<7>Hal-CR<9>R<10>-CR<11>R<12>R<13> (in the case where R<13> and/or R<10> and/or R<8> = H); The mixed products obtained can be used in stage (c); (c) either as a mixture or separately isolated; R<0> = either R<01>, corresponding to CR<5>R<6>=CR<4>-B<1>-, or R<02>, corresponding to CR<11>R<12>R<13>-CR<9>R<10>-CR<7>R<8>-(B<2>)a (at least one of R<7> - R<1>3 is H) ; and M = an alkali or alkaline earth metal ; Hal-Si(R<2>R<3>)-B-(Hal)M + R<1>OH --> (R<1>O)-Si(R<2>R<3>)-B-(Hal)m + H-Hal;  The symbol Hal is preferably Cl.  More preferably, R<0> = R<0>1, and stage (b) is: (C) + H-Hal --> Hal-Si(R<2>R<3>)-B<1>-CR<4>H-CR<5>R<6>-(Hal) and/or Hal-Si(R<2>R<3>)-B<1>-CR<4>Hal-CR<5>R<6>H. Alternatively,in stages (a), (b) and (c), (a) and (b), where m = 1, may be replaced by a' or a'':- a') Hal-Si(Hal)2-B-Hal + 2R<03>-M-Hal--> Hal-Si(R<03>)2-B-Hal + 2Hal-M-Hal ; or a'') Hal-Si(Hal)(R<3>)-B-Hal + R<2>-M-Hal --> Hal-Si(R<2>R<3>)-B-Hal + Hal-M-Hal (R<03> corresponds to R<2> and/or R<3>) -or (a), (b) and (c) may be replaced by a1, b1 and c1(m = 1) : a1) Hal-Si(R<2>R<3>)-Hal(A) + 2R<1>OH --> R<1>O-Si(R<2>R<3>)-OR<1>(F) + 2H-Hal b1) R<1>O-Si(R<2>R<3>)OR<1> + R<0>-M-Hal --> R<1>O-Si(R<2>R<3>)-R<0>(G) + R<1>O-M-Hal c1) Hydrohalogenation of the group R<0>(R<0>1 or R<0>2) of formula (G) to give the group B-Hal, effected by a reactant Hal-Hal and/or SO2(Hal)2.  Preferred Uses: The silane (I) obtained may be reacted with a nucleophilic agent to produce functionalized organosilanes of general formula R<1>O)-Si(R<2>R<3>)-B-(W)m (II); W = monovalent functional organic group from alkoxyl, acyl, amino(optionally substituted), mercapto, cyano, thiocyanato, oxycyanato, or (organosilyl)organopolythio or mixtures.  An alkoxyl may be obtained by the reaction:- (I) + R<20>-O-M' --> (I)-OR<20> + M'-Hal-; M' = an alkali metal and R<20> is equivalent to R<1> ; Similarly, an acyl derivative is obtained by reaction of (I) with M'OCOR<21>; R<21> = R<1>, and in addition 2 - 10C alkenyl ; more preferably -OCOR<21> conforms to (meth)acrylate ; -similarly, substituted amino, mercapto, cyano, thiocyanato, oxycyanato and sulfide compounds can be obtained by reaction of (I) with HR<22>R<23>N, S=(NH2)2, M'CN, M'R<24>-CN(R<24> = O or S) and M'2Sx respectively. Compositions containing effective amounts of an alkoxysilane (I) or (II) are claimed.