Reaktionen von Lithiumhydridosilylamiden mit Carbonylverbindungen und Gemischen von Carbonylverbindungen und Chlortrimethylsilan / Reactions of Lithium Hydridosilylamides with Carbonyl Compounds and Mixtures of Carbonyl Compounds and Chlorotrimethylsilane
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Jan Schneider
Abstract
The lithium hydridosilylamides Me2(H)SiN(Li)R (1: R = CMe3, 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 = O group of the aldehydes and subsequent LiOSiMe2H elimination. Partial hydrosilylation of the aldehydes 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'CH2OSiMe2NHSiMe3 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. Ph2CHOSiMe2OSiMe3 (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' = CH2=C(Me), 6 : R' = Ph) and Ph2CHOSiMe3 (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.
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Articles in the same Issue
- Titelei
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- The Partial Oxidation of Methane to Methanol with Nitrite and Nitrate Melts
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