含蒽基取代氧噻唑酮之1,3-偶極環化加成反應

Abstract

摘要 本論文成功地在兩個步驟內合成5-(9-蒽基)-1,3,4-氧噻唑-2-酮前驅物55，總產率53%，利用它容易進行脫CO2的性質，經由1,3-偶極環化加成反應與一系列的親偶極體進行熱化學與光化學反應的研究。 含蒽基取代氧噻唑酮55在高溫 (120-140oC) 反應時，會進行脫CO2反應得到腈硫化物偶極中間體，接著再與一系列的親偶極體進行1,3-偶極環化加成反應得到相對應的五員雜環56-60，產率45-82%。而在光化學反應中，以低壓汞燈350 nm 波長照射含蒽基取代氧噻唑酮55與一系列親偶極體在乙腈的溶液中反應六個小時，可得到與熱化學加成反應相同的產物56-60及63，總產率57-78%。 含蒽基取代氧噻唑酮55與N-苯基馬來醯亞胺進行熱化學加成反應並沒有得到預期的1,3-偶極環化加成產物，而是經過兩階段的反應，首先，含蒽基取代腈硫化物偶極中間體，進行脫硫反應得到9-氰基蒽，接著9-氰基蒽再與N-苯基馬來醯亞胺進行狄耳士－阿德爾反應得到產物61，產率82%;而在光化學反應中則得到未知產物64。

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.