Publication Date

1974

Document Type

Dissertation/Thesis

First Advisor

Cunico, Robert F.

Degree Name

M.S. (Master of Science)

Legacy Department

Department of Chemistry

LCSH

Silane; Organolithium compounds

Abstract

The reaction of both cis- and trans-beta-chlorovinyltrimethyl-silane with lithium in ether proceeds readily under high speed stirring. Half of the resulting organolithium compound mixture was treated with chlorotrimethylsilane and the other portion carbonated. The products of silylation were bis-trimethylsllylethylene, bis-trimethylsilylacetylene and higher boiling compounds, two of which are 1,4-bis-trimethylsilylbutadienes. Diazomethane treatment of the acids obtained from the carbonated portion produced methyl 3-trimethylsilylpropenoate and methyl 4-trimethylsilyl-2-butenoate resulting from the stereospecific insertion of methylene by diazomethane. The carbonated portion also contained bis-trimethylsilylethylene and higher boiling compounds from the coupling of starting material and organolithium compounds, Trans-beta- chlorovinyltrimethylsilane gave products of retained configuration whereas its cis isomer gave products of inverted configuration at room temperature. Products of retained configuration were obtained for the latter only when in situ trapping of the organolithium compound by chlorotrimethylsilane was employed or when chlorotrimethylsilane derivatization was carried out at low temperature (-20°C), Lithiation does not proceed below -30°C. Reaction of cis-beta-chlorovinyltri- methylsilane with lithium in pentane led to in situ elimination; bis-trimethylsilylacetylene was obtained from silylation. and only methyl propargylate from carbonation.

Comments

Includes bibliographical references.||Includes illustrations.

Extent

xi, 98 pages

Language

eng

Publisher

Northern Illinois University

Rights Statement

In Copyright

Rights Statement 2

NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.

Media Type

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