Organometallic reactions in ionic liquids : formation and reaction of organoindium, organozinc and organomagnesium reagents with imines and carbonyl compounds

Pao Yue-kong Library Electronic Theses Database

Organometallic reactions in ionic liquids : formation and reaction of organoindium, organozinc and organomagnesium reagents with imines and carbonyl compounds

 

Author: Law, Man-chun
Title: Organometallic reactions in ionic liquids : formation and reaction of organoindium, organozinc and organomagnesium reagents with imines and carbonyl compounds
Degree: Ph.D.
Year: 2009
Subject: Hong Kong Polytechnic University -- Dissertations.
Organometallic chemistry.
Environmental chemistry -- Industrial applications.
Carbonyl compounds.
Department: Dept. of Applied Biology and Chemical Technology
Pages: xxii, 186 leaves : ill. ; 30 cm.
Language: English
InnoPac Record: http://library.polyu.edu.hk/record=b2275523
URI: http://theses.lib.polyu.edu.hk/handle/200/3608
Abstract: Because of concern for the environment, there has been extensive recent research into the use of environmentally benign reaction media to replace volatile organic solvents. The most extensively studied alternatives are water, supercritical carbon dioxide, and ionic liquids (IL). However, water and supercritical carbon dioxide are well known to react with some reactive organometallic reagents, such as Grignard or organozinc reagents which are very useful in chemical synthesis. Alternative reagents or solvent media must be sought for solving this dilemma. We have explored the possibility of metal-mediated allylation and alkylation reactions in IL systems. The challenge, under such reaction conditions, is to seek base-stable ILs which favor the in-situ generation of reactive organometallic reagents. The study of organometallic reactions in room-temperature ionic liquids (RTILs) has thus far been limited to the less-reactive allylmetal reagents or their variations. This is because the commonly used imidazolium-based RTILs react with reactive organometallic reagents to give imidazol-2-ylidenes (W-heterocyclic carbenes, NHCs). Recently, we found that the RTIL N-butylpyridinium tetrafluoroborate, [bpy][BF4], is stable toward diethylzinc and preformed diethylzinc could be used to react with aldehydes in [bpy][BF4] to give the adducts in high yields. We are therefore interested in the possibility of generating organometallic reagents directly from metal (zinc, magnesium and indium) and organohalides (alkyl and allyl) in RTILs. In this thesis, we demonstrate that (1) allylindium reagents can react with imines in IL and the mechanism of the reaction was investigated; (2) alkylzinc and functionalized alkylzinc reagents can be formed in IL and their reactions with carbonyl compounds were studied; (3) alkylmagnesium reagents can be formed in IL and their reactions with carbonyl compounds were found to be different from that in organic solvents.

Files in this item

Files Size Format
b22755238.pdf 8.122Mb PDF
Copyright Undertaking
As a bona fide Library user, I declare that:
  1. I will abide by the rules and legal ordinances governing copyright regarding the use of the Database.
  2. I will use the Database for the purpose of my research or private study only and not for circulation or further reproduction or any other purpose.
  3. I agree to indemnify and hold the University harmless from and against any loss, damage, cost, liability or expenses arising from copyright infringement or unauthorized usage.
By downloading any item(s) listed above, you acknowledge that you have read and understood the copyright undertaking as stated above, and agree to be bound by all of its terms.

     

Quick Search

Browse

More Information