The Reaction of Phenyl(trichloromethyl)mercury with Substituted Norbornenes
作者:C. W. Jefford、D. T. Hill、J. Goré、B. Waegell
DOI:10.1002/hlca.19720550307
日期:1972.4.20
The addition of phenyl(trichloromethyl)mercury to five substituted norbornenes is described, and the results compared with those obtained with bicyclo[2.2.2]oct-2-ene and 3,3,5,5-tetramethylcyclopentene. The reaction proves to be useful for synthetic purposes, in that it leads usually to ring expansion. However, a possible disadvantage is that the addition step is sensitive to steric hindrance and
substituents at the silicon atom. Using the competition reactions, the relative rate constants for the reaction of dichlorocarbene insertion into the SiH bond of thienyl- and furyl-silanes (I and IV) were measured. The reactivity of these silanes was found to be greater than had been expected taking as a basis the Taft σ* constants for the substituent at the silicon atom. This is apparently due to the existence
二甲基(2-噻吩基)-,甲基[二(2-噻吩基)]-,三(2-噻吩基)-和二甲基(2-呋喃基)硅烷(分别为I-IV)与由三氯乙酸钠生成的二氯卡宾的反应在固液相转移条件下,可以提供相应的二氯甲基硅烷,收率为38-66%。噻吩基硅烷的反应性随硅原子上电子接受的噻吩基取代基的数量而降低。使用竞争反应,测量了二氯卡宾插入噻吩基和呋喃基硅烷(I和IV)的SiH键中的相对速率常数。发现这些硅烷的反应性大于以硅原子处的取代基的Taftσ *常数为基础的预期。这显然是由于存在p π - d π杂环π-系统和之间的相互作用d硅的-orbitals。
Halomethyl-metal compounds XXII. The preparation of trihalomethyl and other halogenated organotin compounds
作者:Dietmar Seyferth、Frank M. Armbrecht
DOI:10.1016/s0022-328x(00)81112-2
日期:1969.2
and Me3SnCCl2-Me have been prepared by reaction of the appropriate organolithium reagent with trimethyltin chloride at low temperature. The reaction of phenyl(bromodichloromethyl)mercury with trimethyltinbromide in refluxing benzene solution produced Me3SnCCl2Br in 63% yield. An experiment in which this mercury reagent was allowed to react with trimethyltin chloride gave both Me3SnCCl3 and Me3SnCCl2Br
Aromatization of tetrahydrocyclopropa[<i>a</i>]naphthalenes: An alternative synthesis of 1<i>H</i>-Cyclopropa[<i>a</i>]naphthalene
作者:Paul Müller、GéRald Bernardinelli、Huong Can Godoy-Nguyen Thi
DOI:10.1002/hlca.19890720723
日期:1989.11.1
1H-Cyclopropa[a]naphthalene (1a) is accessible via reduction of the dichloro compound 1c with LiAlH4/AlCl3. Several derivatives of tetrahydrocyclopropa[a]naphthalene were synthesized. However, contrary to their 1,1-dihalogeno analogues, they afforded no cycloproparenes upon attempted aromatization.
通过用LiAlH 4 / AlCl 3还原二氯化合物1c可得到1 H-环丙烷[ a ]萘(1a)。合成了四氢环丙烷[ a ]萘的几种衍生物。然而,与它们的1,1-二卤代类似物相反,它们在试图进行芳构化时没有提供环丙烷。
Trapping of the highly strained [5](2,4)quinolinophane system
作者:Maurice J. van Eis、Martin Lutz、Anthony L. Spek、Willem H. de Wolf、Friedrich Bickelhaupt
DOI:10.1016/j.tet.2006.11.075
日期:2007.2
The highlystrained [5](2,4)quinolinophane system can be generated as an intermediate (2b), which is extremely susceptible towards the attack of both nucleophilic and electrophilic species. Addition of water at the carbon bridgehead C2 occurs rapidly and is followed by rearrangements to give a strain free product 10. An unusual carbene addition at the N1C2 bond of 2b is proposed to explain the formation