15290-22-9Relevant articles and documents
Reactions of 1-Nitro-2-(trialkylsilyl)acetylenes
Bottaro, Jeffrey C.,Schmitt, Robert J.,Bedford, Clifford D.,Gilardi, Richard,George, Clifford
, p. 1916 - 1919 (1990)
The chemistry of nitroacetylenes has been relatively unexplored owing to the lack of stable nitoacetylene derivatives.Our discovery of methods to prepare stable nitroacetylenes allows us the opportunity to investigate their chemistry.We report here on the reactions of (trialkylsilyl)nitroacetylenes in Diels-Alder, 1,3-cycloaddition reactions, and the thermolysis of nitroacetylene adducts.
Copper-Free Double Silylation of 1,2-Dibromobenzenes Using a Mg/LiCl/DMI System
Kitamura, Tsugio,Yamada, Rin,Gondo, Keisuke,Eguchi, Nobuo,Oyamada, Juzo
, p. 2495 - 2500 (2017/05/22)
The reaction of 1,2-dibromobenzenes with chlorotrimethylsilane efficiently proceeded in the presence of Mg and LiCl in DMI under mild conditions, giving 1,2-bis(trimethylsilyl)benzenes in good to high yields. The reaction of 1,2-dibromobenzenes with chlorodimethylsilane under the same conditions afforded the corresponding 1,2-bis(dimethylsilyl)benzenes in high yields. Functional group transformations of 1,2-bis(trimethylsilyl)benzene were conducted to demonstrate the synthetic utility.
GAS-PHASE REACTIONS OF ARYLSILANES WITH NITRATING CATIONS. NITRATION vs. NITRODESILYLATION
Attina, Marina,Cacace, Fulvio,Ricci, Andreina
, p. 217 - 224 (2007/10/02)
The mass spectrometric and radiolytic study of the reaction of (MeNO3)H(+) with phenyl- and tolyl-trimethylsilanes has allowed to demonstrate the first example of gas-phase aromatic nitro desilylation.The process accompanies predominant nitration of the substrate, the ratio of the two channels ranging from ca. 1:2 in the case of C6H5Si(CH3)3 to ca. 1:4 in the case of m-CH3C6H4Si(CH3)3, measured in CH4 at 37 deg C, 750 Torr.Nitro desilylation of trimethylsilanes gives nitrotoluenes in which the NO2 group is not exclusively bound to the ring position formerly occupied by the SiMe3 group.Such observation bears directly on an unsettled problem concerning the detailed course of aromatic substitution by gaseous (RNO3)H(+) ions, in that it favours the classical pathway, involving intermediacy of arenium ions, excluding the alternative, concerted mechanism.The gas-phase nitration of C6H5Si(CH3)3 is characterized by a kPhSiMe3/kPhH ratio of 6.5 +/- 0.5 and by a 25percent ipso, 28percent ortho, 23percent meta, 24percent para orientation.These data can be combined with the known ρ constant of the reaction to derive the SiMe3 substituent constants, i. e. ?m(+) = -0.17 and ?p(+) = -0.25.The mechanistic features of the gas-phase reactions of (MeNO3)H(+) with phenylsilanes are discussed, and compared with relevant data from condensed-phase studies.
