Reactions of halothiophenes with metal amides
Adickes, H. Wayne
Adickes, H. Wayne
item.page.creator
Citations
Altmetric:
Soloist
Composer
Publisher
Date
1968
Additional date(s)
Abstract
In an attempt to generate and study 2,3-dehydrothiophene a variety of halothiophenes were treated with several metal amides in liquid ammonia. Reaction of 2-bromothiophene with amide ion results in the formation of either 3-aminothiophene or 3-bromothiophene; the product distribution being highly dependent upon the reaction conditions. Four mechanisms for the cine-amination of 2-bromothiophene were considered: (1) a normal substitution, either preceded by the rearrangement of 2- to -3-bromothiophene or followed by rearrangement of 2- to 3-aminothiophene, (11) an elimination- addition (aryne) mechanism, (111) an addition-elimination mechanism, and (iv) a mechanism involving a nucleophilic displacement on a polybromothiophene intermediate which arises from a series of displacements on halogen by thiophene anions. The latter mechanism was found to explain most satisfactorily the results obtained from the various reactions. This mechanism represents a new pathway for the formation of cine-substituted products. A detailed discussion of the mechanism, application of this mechanism to explain cine-substitution observed in other five-membered heterocycles, and a discussion of the synthetic utility of these reactions are presented.
Contents
Subject
Subject(s)
Thiophenes
Amides
Amides
Research Projects
Organizational Units
Journal Issue
Genre
Dissertation
Description
Format
158 leaves
Department
Chemistry and Biochemistry