Synthesis and Reactions of 1-Thianaphthalenes

• Published in: Chemical & pharmaceutical bulletin Vol. 36; no. 10; pp. 3816 - 3825
• Main Authors: KATAOKA, TADASHI, SHIMIZU, HIROSHI, AOKI, HARUMI, HORI, MIKIO
• Format: Journal Article
• Language: English
• Published: Tokyo The Pharmaceutical Society of Japan 1988; 公益社団法人日本薬学会; Maruzen; Japan Science and Technology Agency
• Subjects: 1, 2-rear-rangement; 1, 2-rearrangement; 1, 4-rearrangement; 1-thianaphthalene; Chemistry; cyclic sulfur ylide; dimerization; electophile; electrophile; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Organic chemistry; Preparations and properties; ring expansion; thiabenzene; Chemical rearrangement; Sulfur heterocycle; Base catalysis; Potassium Hydroxides; Bicyclic compound; Aromatic compound; Electrophilic reaction; Sodium Hydrides; Dimerization; Scission; Ring expansion; Ylide
• ISSN: 0009-2363; 1347-5223
• DOI: 10.1248/cpb.36.3816

Treatment of 1-methyl-4-phenyl-1-thio-2H-chromenium perchlorate (2) with sodium hydride yielded a dimeric compound 4 and two rearrangement products 5 and 6 via unstable 1-methy1-4-phenyl-l-thianaphthalene (3). On heating with potassium hydroxide in ethanol, 1-methy1-2, 4-dipheny1-1-thio-2H-chromenium perchlorate (9) gave a dimeric compound 13 and two ring-opened products 11a and 12a, but no rearrangement product. On the other hand, 2-cyano-l-methy1-4-phenyl-1-thianaphthalene (20) prepared from the corresponding 1-thiochromenium salt 19 by treatment with triethylamine in ethanol was quite stable, and it is the first example of a stable and crystalline 1-thianaphthalene. Reactions of the 1-thianaphthalene 20 with electrophiles such as tetracyanoethylene, maleic anhydride, and 4-phenyl-1-thianaphthylium perchlorate gave the dimeric compound 23. However, the treatment of 20 with dimethyl acetylenedicarboxylate yielded a new ring expansion product 27 having a sulfur-containing nine-membered ring.