Direct alkoxysilylation of alkoxysilanes for the synthesis of explicit alkoxysiloxane oligomers
摘要:
Direct alkoxysilylation, which is a powerful tool to provide explicit alkoxysiloxanes, is developed and its versatility is investigated. Siloxane pentamers Si[OSiR1(OMe)(2)](4) having various functional groups (R-1 = methyl, vinyl, phenyl, chloropropyl and n-butyl groups) were successfully obtained by direct alkoxysilylation of Si(OR)(4) (R= t-Bu, CHPh2). Thus, the versatility of the reaction is confirmed on organic functional groups R-1. Functional group tolerance of the reaction is discussed on the basis of electro-negativity of the R-1 groups. Alkoxysilylation of Si(Ot-Bu)(2)(OMe)(2) and Si(Ot-Bu)(OMe)(3) selectively gives trimer (MeO)(2)Si[OSiMe(OMe)(2)](2) and dimer (MeO)(3)SiOSiMe(OMe)(2), respectively. Thus, the feasibility on siloxane structure is also confirmed. Various siloxane compounds are synthesized by this newly developed reaction for the first time. (C) 2012 Published by Elsevier B.V.
Novel organylthio(alkoxy)silanes (I, II, III and XII) and organylthio(diethylamino)silanes (IV, V) are described. They were prepared by treating lithium or lead thiolates with the corresponding chlorosilanes or by cleavage of dimethylbis(diethylamino)silane with thiols. Phenylthiosilanes (Me3SiSPh, III and XIII) furthermore can be obtained by reaction of chlorosilanes with benzenethiol in the presence
The concept of protecting groups in organic synthesis is applied to the synthesis of siloxane oligomers with alkoxy groups. Several alkoxysiloxane oligomers were successfully synthesized by substitution of trimethysilyl groups with alkoxysilyl groups.
Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates
作者:Yujing Zhou、Jeffrey S. Bandar、Stephen L. Buchwald
DOI:10.1021/jacs.7b04937
日期:2017.6.21
(CuH)-catalyzed coupling of α,β-unsaturated carboxylic acids to aryl alkenes to access chiral α-aryl dialkyl ketones is reported. A variety of substrate substitution patterns, sensitive functional groups, and heterocycles are tolerated in this reaction, which significantly expands the range of accessible products compared with existing hydroacylation methodology. Although mechanistic studies are ongoing, we propose
The effect of methyl substitution on the electronic structure of bis(dimethyl ether) pentadienyllithium
作者:John F. Sebastian、Bennett Hsu、John R. Grunwell
DOI:10.1016/s0022-328x(00)91966-1
日期:1976.1
ether) pentadienyllithium has been calculated by the CNDO/2 method. The metal—anion interaction involves both σ and π bonding. The effect of methylSubstitution on the electronic structure of the solvated species has been evaluated. In general, the electroniceffect of a methyl group is substantially less for the solvated structure than for the isolated anion.
Arylaminosilane Compound, Propylene Polymerization Catalyst And Preparation Thereof
申请人:PetroChina Company Limited
公开号:US20200369689A1
公开(公告)日:2020-11-26
The present disclosure discloses an arylaminosilane compound, a propylene polymerization catalyst and preparation thereof. The arylaminosilane compound has a structure of
wherein R
1
is a C
1
-C
8
alkyl group or a C
1
-C
8
silanyl group; R
2
, R
3
, R
4
, R
5
and R
6
are each independently H or a C
1
-C
12
alkyl group; R
7
, R
8
and R
9
are each independently a C
1
-C
8
alkyl group or a C
1
-C
8
alkoxy group. When the arylaminosilane compound is used as an external electron donor of a propylene polymerization catalyst in propylene polymerization reaction, the catalyst has good hydrogen response.