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Synthesis and reactions of poly[(4-chlorobutyl)thiirane]: evidence for backbone-assisted solvolysis

Shih, Jenn S. and Tirrell, David A. (1984) Synthesis and reactions of poly[(4-chlorobutyl)thiirane]: evidence for backbone-assisted solvolysis. Chemical Engineering Communications, 30 (3-5). pp. 219-228. ISSN 0098-6445. https://resolver.caltech.edu/CaltechAUTHORS:SHIHcec84

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Abstract

(4-Chlorobutyl)thiirane is prepared in 80% yield in a single step from (4-chlorobutyl)oxirane. Homopolymerization of (4-chlorobutyl)thiirane with ZnEt2—CH3OH or CdCO3 initiator systems provides poly[(4-chlorobutyl)thiirane] as a soft elastomer with inherent viscosity 0.2dL/g. Reaction of poly[(4-chlorobutyl)thiirane] with tetra-n-butylammonium benzoate in N,N-dimethylacetamide proceeds by direct displacement, without involvement of the backbone sulfur atom. Solvolysis under more strongly ionizing conditions (acetic acid/chloroform) occurs with repeating unit isomerization, most probably via a cyclic intermediate formed by attack of the backbone sulfur atom on the chloromethyl group at the side chain terminus.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1080/00986448408911129DOIArticle
http://www.tandfonline.com/doi/abs/10.1080/00986448408911129PublisherArticle
ORCID:
AuthorORCID
Tirrell, David A.0000-0003-3175-4596
Additional Information:© 1984 Gordon & Breach. (Received February 16, 1984; in final form March 19, 1984) Dedicated to Professor E. W. Merrill on the occasion of his 60th birthday, with best wishes. This work was supported by an Alfred P. Sloan Research Fellowship to David A. Tirrell and by a grant from the Polymers Program of the National Science Foundation (DMR82-01180). The Bruker WM-300 spectrometer was purchased with the aid of a grant from the National Institutes of Health (GM27390). NMR spectra at 600 MHz were recorded at the NIH NMR Facility for Biomedical Studies (RR00292).
Funders:
Funding AgencyGrant Number
Alfred P. Sloan FoundationUNSPECIFIED
NSFDMR 82-01180
NIHGM27390-01
NIHRR00292
Subject Keywords:Solvolysis, (4-chlorobutyl)thtirane, (4-chlorobutyl)oxirane, Polythiiranes
Issue or Number:3-5
Record Number:CaltechAUTHORS:SHIHcec84
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:SHIHcec84
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:56127
Collection:CaltechAUTHORS
Deposited By: Anne Hormann
Deposited On:27 Mar 2015 23:37
Last Modified:03 Oct 2019 08:11

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