The 1,3-Dipolar Cycloaddition Reaction of 9-Anthryl Substituted Oxathiazolone and its Photochemical Reactions

• Main Authors: Wang, Heng-Jhe, 王亨哲
• Other Authors: 鍾文聖
• Format: Others
• Language: zh-TW
• Published: 2012
• Online Access: http://ndltd.ncl.edu.tw/handle/83272125519230020984

碩士 === 國立交通大學 === 應用化學系碩博士班 === 100 === abstract In this thesis, 5-(anthracen-9-yl)-1,3,4-oxathiazol-2-one 55 was successfully synthesized in two steps with 53% yield. 9-Anthryl substituted oxathiazolone 55 was then used to react with a series of dipolarophiles through 1,3-dipolar cycloaddition reactions because it is known that 9-anthryl substituted oxathiazolone 55 can extrude CO2 under thermolysis and photolysis conditions. The extrusion of CO2 from 9-anthryl substituted oxathiazolone 55 at high temperature (120-140oC) led to nitrile sulfide as reactive intermediate, which subsequently reacted with a series of dipolarophiles to form corresponding five-member thiazoles or thiazolines 56-60 in 45-82% yields. Similar products were obtained 56-60 and 63 in 57-78% yields when 9-anthryl substituted oxathiazolone 55 with a series of dipolarophiles was photolyzed using 350 nm light from low pressure mercury lamp. Surprisingly, when a mixture of 9-anthracenyl substituted oxathiazolone 55 with 4 eq. of N-phenylmaleimide was heated to 120-140oC for 12.5 hours, the expected product from 1,3-dipolar cycloaddition was not obtained, insead, a Diels–Alder adduct 61 was obtained in 82% yield. When a mixture of 9-anthryl substituted oxathiazolone 55 with 10 eq. of N-phenylmaleimide was photolyzed using 350 nm light, an unkown product was obtained. The study of its structure and identity is still under investigation.