Eine neue in situ ‐Darstellung von (Trimethylsilyl)‐trifluormethansulfonat durch thermisch induzierte Umlagerung

Abstract

A new in situ preparation of trirnethylsilyl tnfluoromethanesulfonate (3) is described: 3 is generated by a thermally induced rearrangement of (dimethylsily1)methyI trifluoromethanesulfonate (2), which can be prepared by reaction of (CH3)&(H)CH20H (1) with (CF3S0&0. Starting with C6H5(CH3)Si(H)CH,0H (5), the derivative (methylphenylsily1)-methyl trifluoromethanesulfonate (6) can be obtained by a similar method. Its thermally induced rearrangement leads to dimethylphenylsilyl trifluoromethanesulfonate (7). The rearrangements 2+3 and 6-7 were found to be first-order reactions with half-lifes at 80°C of 0.75 and 1.7 h, respectively.

A Novel Type of Dyotropic Rearrangement. Palladium-Catalyzed Rearrangement of Alkoxymethyl-Substituted Silanes to Alkyl Silyl Ethers

“…IR: additional signal at 1163 m. 1H NMR: additional signal at 0.09 (t, J = 2.2, DCH2Si). MS: 241 (100), 240 (66), 224 (12), 223 (7).…”

(Acetoxymethyl)methylphenylgerman: Synthese, thermisches Verhalten und olfaktorische Eigenschaften / (Acetoxymethyl)methylphenylgermane: Synthesis, Thermal Behaviour and Olfactoric Properties

“…Wir haben uns deshalb für das thermische Verhalten des von la und lb abzuleitenden Germanium-Analogons (Acetoxymethyl)methylphenylgerman (lc) interessiert und untersucht, ob dieses ther misch zu Acetoxydimethylphenylgerman (2 c) um gelagert werden kann. C PH 16G e 0 4 (296, 9) Ber. C 48,55 H 5,43, Gef.…”

(Thioacetoxy-S-methyl)diorganylsilane und (Mercaptomethyl)diorganylsilane: Synthese und Eigenschaften

“…hierzu Ref. [2][3][4][5][6] waren wir vor allem an der Fr~ge interessiert, ob die (Thioacetoxy-Smethyl)diorganylsilane 9 und 10 in Analogie zu den entsprechenden (Acetoxymethyl)diorganylsilanen 3 und 4 einer thermisch induzierten Umlagerung unterliegen.…”