92177-86-1Relevant academic research and scientific papers
Phenyldimethylsilyl-substituted ketenes and bisketenes
Liu, Ronghau,Marra, Romeo M.,Tidwell, Thomas T.
, p. 6227 - 6232 (1996)
The phenyldimethylsilyl-substituted monoketene PhMe2SiCH=C=O (1) and bisketene (PhMe2-SiC=C=O)2 (3) have been prepared and compared to the corresponding Me3Si- and t-BuMe2Si-substituted species. The 13C, 17O, and 29Si NMR spectra fit the pattern shown by other silylketenes and provide no evidence for transmission of a substituent effect of the Ph group through the silicon to the ketenyl group, as has been proposed for PhMe2Si-substituted radicals. The UV spectrum of 1 does show a longer λ and greater ∈ than for t-BuMe2SiCH=C=O, and this may indicate some interaction of the phenyl group with the ketene chromophore, while the greater reactivity of 1 in hydration compared to t-BuMe2SiCH=C=O is ascribed to the inductive effect of the phenyl. The very similar ring-opening reactivity of the bis(phenyldimethylsilyl)cyclobutenedione (6) to form 3 compared to the bis(Me3Si) analogues also provides no evidence of a significant interaction of the phenyl with the ketene. A new type of stabilized 1,8-bisketene based on the arylbis(dimethylsilyl) grouping, namely, 1,4-bis(ketenyldimethylsilyl)benzene (12), has been prepared for the first time.
Cycloadditions, III. - Reactions of Ynamines with Silylketenes
Himbert, Gerhard,Henn, Lothar
, p. 1358 - 1366 (2007/10/02)
The ynamines 1a-e react with the silyl aldoketenes 2a and b in a normal way under cycloaddition to give the allenecarboxamides 6 and in one case a cyclobutenone derivative.The presence of the silyl group in the adducts gives rise to 1,3-migrations of
