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2000 (1)
1998 (1)
1Author    ChlorotrimethylsilaneJan Schneider3, Eckhard Popowski, Hans FuhrmannbRequires cookie*
 Title    Reaktionen von Lithiumhydridosilylamiden mit Carbonylverbindungen und Gemischen von Carbonylverbindungen und Chlortrimethylsilan Reactions of Lithium Hydridosilylamides with Carbonyl Compounds and Mixtures of Carbonyl Compounds  
 Abstract    The lithium hydridosilylamides Me2(H)SiN(Li)R (1: R = CM e3, 2: R = SiMe3) were allowed to react either with the non-enolizable carbonyl compounds CH2=C(Me)CHO, PhCHO and Ph2CO followed by trapping with chlorotrimethylsilane (A), or with mixtures of these carbonyl compounds and chlorotrimethylsilane (B). In the second case the course of the reactions is determined by the carbonyl compound. The composition of the reaction mixtures is nearly the same according to A and B. Main products in the reactions with the aldehydes are the corresponding imines R'CH=NR (R' = CH2=C(Me), Ph) 3 , 4 , 8 ,9 formed by addition of the hydridosilylamides to the C = 0 group of the aldehydes and subsequent LiOSiM e2H elimination. Partial hydrosilylation of the alde­ hydes by the hydridosilanolate followed by the trimethylsilylation yields the alkoxydisiloxanes R'CH2OSiMe2OSiMe3 6 , 11. In some cases 2 partially reacts under hydrosilylation to give the alkoxydisilazanes R'CH2OSiM e2NHSiM e3 7,12. The hydrosilylation is the preferred reaction of 1 and 2 with benzophenone. The compounds Ph2CHOSiMe2NHR 13, 14 are obtained. This difference in the reaction behaviour of 1 and 2 towards the aldehydes and benzophenone is mainly due to steric reasons. Depending on the conditions the imines Ph2C=NR 20, 21 may be formed. Ph2CHOSiM e2OSiMe3 (22) is a secondary product of imine formation. In all reactions of 1 and 2 with the carbonyl compounds the corresponding alkoxysilanes R'CH2OSiMe3 (5: R' = CH 2=C(Me), 6 : R' = Ph) and Ph2CHOSiM e3 (15) are generated. Compounds resulting from a reaction of 1 and 2 with chlorotrimethylsilane are produced to minor extent, but only if the molar ratio of amide to carbonyl compounds is not greater than one. The formation of a silanimine intermediate in reaction according to B is not observed. 
  Reference    Z. Naturforsch. 53b, 663—672 (1998); eingegangen am 9. April 1998 
  Published    1998 
  Keywords    Hydridosilylamides, Reaction Behaviour, Imines, Hydrosilylation 
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 TEI-XML for    default:Reihe_B/53/ZNB-1998-53b-0663.pdf 
 Identifier    ZNB-1998-53b-0663 
 Volume    53 
2Author    Jan Schneider, Eckhard Popowski, Normen PeuleckeRequires cookie*
 Title    Reaktionen der Lithiumhydridosilylamide Me2(H)Si-N(Li)R (R = CMe3, SiMe3) mit Chlortrimethylstannan und Chlormethylsilanen M e^ SiC l« {n = 1 -3) Reactions of Lithium Hydridosilylamides Me2(H)Si-N(Li)R (R = CMe3, SiMe3) with Chlorotrimethylstannane and Chloromethylsilanes Me4_" SiCl, in = 1 -3)  
 Abstract    The under reflux conditions in /7-octane stable lithium hydridosilylamides Me2(H)Si-N(Li)R (1: R = CM e3, 2: SiMe3) were allowed to react with chlorotrimethylstannane and chlorom e­ thylsilanes Me4_"SiCl" (n = 1 -3) in different molar ratios. 1 reacts with Me3SnCl in n-pentane to give the cyclodisilazane [Me2Si-NCMe3]2 (3) and Me3SnH. The reaction of 2 with Me3SnCl under the same conditions leads to a mixture of Me2 (H)Si-N(SnM e3)SiMe3 (5), [Me2Si-NSiM e3]2 (4), and to Me3SnH. In the reactions of 1 and 2 with chlorotrimethylstannane in tetrahydrofuran the corresponding N-stannylation products Me2(H)Si-N(SnMe3)R 5, 6 and very small amounts of (M e3Sn)2 are formed. The results of the reactions of 1 and 2 with Me2SiCl2 and of 1 with MeSiCl3 in n-hexane show that hydrogen-chlorine-exchange proceeds between the reactants. With Me2SiCl2 the cor­ responding cyclodisilazanes [Me2Si-NR]2 3, 4, N-silylation products Me2(H)Si-N(SiM e2Cl)R 7b, 8b, and Me2(H)Si-N(SiMe2H)R 7c, 8c, and the silanes Me2SiHCl and M e2SiH2 are formed, the cyclodisilazanes being the main products. 1 and M eSiCl3 produce 3, Me2(H)Si-N(R')CM e3 (7d: R' = SiMeCl2, 7e: R' = SiMeCIH, 7f: R' = SiM eH2) and MeSiH3. In comparison with the reaction of 1 with Me2SiCl2 the yield o f cyclodisilazane is smaller and that of N-silylated compounds is higher. The reaction behaviour of 1 towards M e2SiCl2 and M eSiCl3 in THF is comparable to that in n-hexane. No silanimine intermediates are observed in the reactions of 1 or 2 with the chloromethylsi­ lanes Me4_,7SiCl" (n = 1 -3) in the molar ratios 1:5 and 1:10. 
  Reference    Z. Naturforsch. 55b, 924—934 (2000); eingegangen am 25. Mai 2000 
  Published    2000 
  Keywords    Hydridosilylamides, Cyclodisilazanes, Hydrogen-Chlorine-Exchange 
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 TEI-XML for    default:Reihe_B/55/ZNB-2000-55b-0924.pdf 
 Identifier    ZNB-2000-55b-0924 
 Volume    55