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2‐Alkyliden‐1, 3‐dithia‐Heterocyclen aus 5‐Sulfonyl‐1, 2‐dithiol‐3‐onen und Alkoholaten
Author(s) -
Bader JÖRg
Publication year - 1968
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19680510626
Subject(s) - chemistry , dithiol , sodium methoxide , sulfonyl , medicinal chemistry , methoxide , sulfone , alkoxy group , methanol , polymer chemistry , organic chemistry , alkyl
Asymmetrically substituted 5‐sulfonyl‐1, 3‐dithiafulvenes ( 9a–g ), all of which have the same configuration (called α), are obtained by reaction of 4‐chloro‐5‐sulfonyl‐1, 2‐dithiol‐3‐ones ( 3a–e ) with sodium alkoxides. Side‐products formed are 4‐chloro‐5‐alkoxy‐1, 2‐dithiol‐3‐ones ( 5a and 5b ), 3, 5‐bis‐alkylidene‐1, 2, 4‐trithiacyclopentanes ( 21 and 22 ), and (in some instances) minor amounts of compounds 33, 34 , or 35 . Reaction of 4‐phenyl‐5‐methylsulfonyl‐1, 2‐dithiol‐3‐one with sodium methoxide results in the formation of 4‐phenyl‐5‐methoxy‐1, 2‐dithiol‐3‐one ( 5c ), the two cis‐ trans ‐isomers of 2, 4‐bis‐alkylidene‐1, 3‐dithiacyclobutane 24 and 25 , and the 2, 5‐bis‐alkylidene‐1, 2, 4, 5‐tetrathiacyclohexane 26 . Some conceivable reaction mechanisms are discussed, and proof is given for the structure of the major compounds. By treating 4‐chloro‐5‐(2′‐chloro‐ethylthio)‐1, 2‐dithiol‐3‐one with sodium methoxide, the 2‐alkylidene‐1, 3‐dithiolane 13 is obtained. The sulfonyl groups of the 1, 3‐dithiafulvenes 9a–g described may be easily replaced by hydrogen or secondary amines, yielding compounds 14, 16 and 19 , respectively. When dissolved in strong acids and reprecipitated, asymmetrically substituted 2‐alkylidene‐1, 3‐dithia compounds may be converted into mixtures of all possible cis‐trans ‐isomers thereof. Those isomers may be separated by fractional crystallization. Isomers 31 (called β) of 9 a‐‐g , and 32 of 16a, b , are obtained accordingly.