1560-28-7Relevant articles and documents
5,6-Disubstituted 1,2,3-trisilaindanes as silicon analogues of phantolide-type musk odorants: Synthesis, structure, reactivity, and olfactory properties
Gluyas, Josef B. G.,Burschka, Christian,Kraft, Philip,Tacke, Reinhold
, p. 5897 - 5903 (2010)
In an extension of earlier studies concerning drugs and odorants based on disila-substituted tetrahydronaphthalene and indane skeletons, such as the musk odorant disila-phantolide (1), 1-(1,1,2,2,3,3,6-heptamethyl-1,2,3-trisilaindan- 5-yl)ethanone (methyltrisila-phantolide, 2) and a series of related 5,6-disubstituted 1,2,3-trisilaindanes (3-5) were prepared in multistep syntheses. Compounds 2-5 were characterized by 1H, 11B (5 only), 13C, and 29Si NMR studies. In addition, compounds 3-5 were studied by single-crystal X-ray diffraction. The 1,2,3-trisilaindane skeleton proved to have limited stability toward oxidation agents. The oxidation product 6, a novel 1,3,4-trisilaisochroman system, was isolated and characterized. The trisila-phantolide derivatives 2 and 3 do not display a typical musk odor, but instead possess a slightly creamy-lactonic odor with coumarinic aspects of very weak intensity (odor thresholds, >500 ng L -1 air).
Gas-phase reactions of silicon-centred intermediates with chlorofluorocarbons
Clarke, Michael P.,Conqueror, Martin,Morgan, Geraint H.,Davidson, Iain M.T.
, p. 395 - 396 (1996)
Pyrolysis of pentamethyldisilane in the presence of a CFC, dichlorodifluoromethane, efficiently replaced chlorine by hydrogen in the CFC, with concomitant formation of chlorosilanes. Although the primary intermediate in this pyrolysis is dimethylsilylene, there was strong evidence that conversions resulted from reactions of organosilyl and alkyl radicals. Experiments to confirm this conclusion are described, and mechanisms are discussed. Two independent measurements of the activation energy difference between chlorine-and fluorine-abstraction from dichlorodifluoromethane by trimethylsilyl radicals gave concordant values of 52 ± 5 kJ mol-1. The reactions described are of interest in relation to the environmental importance of dechlorinating CFCs.
Making Use of the Direct Process Residue: Synthesis of Bifunctional Monosilanes
Sturm, Alexander G.,Santowski, Tobias,Schweizer, Julia I.,Meyer, Lioba,Lewis, Kenrick M.,Felder, Thorsten,Auner, Norbert,Holthausen, Max C.
supporting information, p. 8499 - 8502 (2019/06/13)
The industrial production of monosilanes MenSiCl4?n (n=1–3) through the Müller–Rochow Direct Process generates disilanes MenSi2Cl6?n (n=2–6) as unwanted byproducts (“Direct Process Residue”, DPR) by the thousands of tons annually, large quantities of which are usually disposed of by incineration. Herein we report a surprisingly facile and highly effective protocol for conversion of the DPR: hydrogenation with complex metal hydrides followed by Si?Si bond cleavage with HCl/ether solutions gives (mostly bifunctional) monosilanes in excellent yields. Competing side reactions are efficiently suppressed by the appropriate choice of reaction conditions.
One-Step Synthesis of Siloxanes from the Direct Process Disilane Residue
Neumeyer, Felix,Auner, Norbert
supporting information, p. 17165 - 17168 (2016/11/23)
The well-established Müller–Rochow Direct Process for the chloromethylsilane synthesis produces a disilane residue (DPR) consisting of compounds MenSi2Cl6?n(n=1–6) in thousands of tons annually. Technologically, much effort is made to retransfer the disilanes into monosilanes suitable for introduction into the siloxane production chain for increase in economic value. Here, we report on a single step reaction to directly form cyclic, linear, and cage-like siloxanes upon treatment of the DPR with a 5 m HCl in Et2O solution at about 120 °C for 60 h. For simplification of the Si?Si bond cleavage and aiming on product selectivity the grade of methylation at the silicon backbone is increased to n≥4. Moreover, the HCl/Et2O reagent is also suitable to produce siloxanes from the corresponding monosilanes under comparable conditions.
