Synthese und umlagerungsreaktionen von o-funktionellen phenyllithium- und phenylnatrium derivaten der IVB- und VB-elemente
作者:J. Heinicke、E. Nietzschmann、A. Tzschach
DOI:10.1016/0022-328x(83)80214-9
日期:1983.2
While o-substituted bromobenzene derivatives of the type o-BrC6H4XERn (X O, S; ERn SiMe3 and N-BuLi undergo metal halogen exchange followed by silyl- X å C rearrangement, the corresponding compounds of phosphorus, arsenic or tin are split at the EXbond. o-Metal derivatives o-M1C6H4XERn (X O, NMe; E P, As, Sn) of these elements may be generated, however, by direct reaction with sodium or lithium
当o -BrC 6 H 4 XER n(X = O,S; ER n SiMe 3和N-BuLi类型)的邻位取代溴苯衍生物进行金属卤素交换,然后进行甲硅烷基-XåC重排时,相应的磷,砷或锡处于EX键分裂。ø -金属衍生物ö -M 1 C 6 ħ 4 XER ñ(XO,NME,EP,砷,锡)可以生成这些元素的但是,通过与钠或锂直接反应,它们不稳定,并提供邻羟基和邻羟基。-氨基苯基元素(IV,V)衍生物通过分子内阴离子重排。
Heteroatom-Facilitated Lithiations of N-Methyl-N-(trimethylsilyl)methyl- benzylamine and Benzyl (Trimethylsilyl)methyl Ether with Butyllithium.
作者:Seiko MITSUI、Kiyotaka MARUMO、Sumie ANDO-INOUE、Hideo KATO、Yosiro SATO
DOI:10.1248/cpb.41.2195
日期:——
Lithiation of the Si-methyl groups of N-methyl-N-[(trimethylsilyl)methyl]benzylamine (1) occurred in preference to ortho-lithiation of the benzyl group with butyllithium in ether. In a similar reaction with benzyl (trimethylsilyl)methyl ether (7), lithiation of the benzylic position competed with that of the Si-methyl groups.
Fluoride ion induced rearrangements of chloromethyl-substituted silanes: carbanionic character of groups undergoing migration
作者:Robert Damrauer、Stephen E. Danahey、Vernon E. Yost
DOI:10.1021/ja00336a060
日期:1984.11
On montre que le chloromethyl trimethyl silane reagit avec KF ou CsF en presence de 18-crown-6 dans un solvant aromatique pour conduire exclusivement au dimethyl ethyl fluoro silane. Mecanisme
在 montre que le 氯甲基三甲基硅烷反应剂 avec KF 或 CsF 上存在 de 18-crown-6 dans 非溶剂芳香剂倾倒 au 二甲基乙基氟硅烷。机制
The reaction of α-trialkylsilyl carbenes
作者:John W. Connolly
DOI:10.1016/0022-328x(68)80067-1
日期:——
Regioselective Synthesis of 1,4-Di(organo)[60]fullerenes through DMF-assisted Monoaddition of Silylmethyl Grignard Reagents and Subsequent Alkylation Reaction
Monoaddition of Grignard reagents, in particular tri(organo)silylmethyl magnesium chlorides, to [60]fullerene took place smoothly in the presence of dimethylformamideto produce (organo)(hydro)[60]fullerenes, (C60RH)-H-1, in good yield (up to 93% isolated yield). The hydrofullerene was then deprotonated to generate the corresponding anion, C60R-, which was then alkylated to obtain 58 pi-electron di(organo)[60]fullerenes, (C60RR2)-R-1, in good to high yield (up to 93% overall yield). The two-step methodology provides a wide variety of 1,4-di(organo)[60] fullerenes bearing the same or different organic addends on the [60] fullerene core. By changing the addends, one can control the chemical and physical properties of the compounds at the molecular and bulk levels.