Premium
Mercuric ion‐catalyzed hydration of derivatives of 1,4‐dichloro‐2‐butyne. Hydration of 1‐aryloxy‐4‐arylthio‐2‐butynes, 1,4‐ bis (arylthio)‐2‐butynes, and 1,4‐ bis (arylsulfonyl)‐1‐butynes
Author(s) -
Thyagarajan B. S.,
Majumdar K. C.,
Bates Dallas K.
Publication year - 1975
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570120110
Subject(s) - chemistry , ketone , nucleophile , catalysis , medicinal chemistry , methanol , acetic acid , butanone , intramolecular force , solvent , organic chemistry
The mercuric ion‐catalyzed hydration of 1,4‐ bis (arylthio)‐2‐butynes and 1‐aryloxy‐4‐arylthio‐2‐butynes was studied. The 1,4‐ bis (arylsulfonyl)‐2‐butynes afforded 1,4‐ bis (arylsulfonyl)‐2‐butanones (7). The 1,4‐ bis (arylthio)‐2‐butynes afforded a variety of products in acetic acid among which were: 1,4‐ bis (arylthiomethyl)vinyl acetate ( 18 ); 1,4‐ bis (arylthio)‐2‐butanone ( 15 ); 1‐(arylthio)‐3‐buten‐2‐one ( 16 ); and 1‐(arylthio)‐4‐acetoxy‐2‐butanone ( 17 ). Ketone 15 eliminates arylthiol in an acidic medium yielding 16 which undergoes Michael addition of solvent to give 17. Treatment of 7 with base in the presence of a nucleophile (ArSH) analogously leads to elimination of arylsulfinic acid, followed by Michael addition of arylthiol. Hydration of 5 in methanol cleanly gave 1‐(arylthio)‐4‐methoxy‐2‐butanones ( 19 ). In contrast, 1‐aryloxy‐4‐arylthio‐24)utynes afforded chromenes ( 8 ) by intramolecular cyclization. No thiochromenes were formed in any of the examples investigated.