ISSN:
0018-019X
Schlagwort(e):
Chemistry
;
Organic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
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.
Zusätzliches Material:
4 Tab.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/hlca.19680510626
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