Electrochemical Trimethylsilylation of o-Dichlorobenzene: A Selective Route to Silylated Cyclo-C6 Synthons

Gas chromatography/mass spectrometry for the study of the polysilylation of 1-bromonaphthalene. Detection of new persilylated products

“…The electrolysis of magnetically stirred solutions was performed under nitrogen, in a previously described undivided cell 8 fitted with a sacrificial aluminium rod as the anode, a cylindrical stainless steel grid as the cathode. Constant current (i = 0.1A, j = 0.1 AE 0.05A dm…”

“…Compounds 10 and 13 are tris(trimethylsilyl)naphthalenes, very likely substituted in positions (1, 3,8) and (1, 4, 8), but assignments have not been made with certainty. …”

“…These chemical routes have been particularly improved using the more efficient silylation reagent Me 3 SiCl/Mg/HMPA (hexamethylphosphoramide) which affords (poly)trimethylsilylnaphthalene compounds with up to six trimethylsilyl groups on the naphthalene skeleton. [4][5][6][7] Moreover, it has been shown that electrochemical synthesis using the sacrificial anode technique is a competitive tool for silylation and a good alternative for the reductive silylation of aryl halides 8,9 and of partial reduction of the aromatic ring(s). 10,11 In particular, for naphthalenic compounds, the electrochemical route gives notable results to access selectively 1-trimethylsilylnaphthalene from 1-bromonaphthalene.…”

“…Here, we report a mass spectrometric study of the fragmentation of polytrimethylsilylnaphthalenes formed by electrochemical polysilylation of 1-bromonaphthalene, including mass spectrometry data checked at different stages of silylation. Concerning the mass spectral data of polytrimethylsilylnaphthalenes in the literature, only two derivatives 1, [8][9][10][11][12][13] and 1,2-bis(trimethylsilyl)naphthalene 14a have been characterized.…”

Synthesis and Structural Characterization of Isomeric Bis[3,4,5,6-tetrakis(trimethylsilyl)cyclohexen-1-yl]dimethoxysilanes

“…[15][16][17][18][19] Although the strategy of Birch type reductive silylation has several drawbacks vs electrochemical silylation such as using metal reducing agents, and irregular yields, it has been well developed as one of useful methods for the formation of carbon-silicon bonds in both carbon and organosilicon chemistry. [20][21][22][23][24][25] Reductive polysilylations of PhSiCl3 and PhMeSiCl2 were reported to occur with excess lithium and Me3SiCl in THF to yield tetrasilylated cyclohexene (Ttc = tetrakis(trimethylsilyl)cyclohex-1-ene) derivatives.…”