论文部分内容阅读
2-甲基-1,5-苯并硫氮杂草(2a-2d)在苯溶液中光照生成相应的2,4-异构化产物3a-3d,其中2a和2d同时还生成双键位移产物4a和4d.4a经碱性醇解生成一对2,4-异构体2b和3b。2-甲基-4-芳酰氧基-1,5-苯并硫氮杂草(2e-2g)在苯中光照主要经Fries重排生成2-甲基-3-芳酰基-1,5-苯并硫氮杂草-4(5H)-酮(5e-5g),同时还生成少量2,4-异构化产物2-芳酰氧基-4-甲基-1,5-苯并硫氮杂草(3e-3g)。但2-甲基-4-烷基酰氧基-1,5-苯并硫氮杂草(2i,2j)在相同条件下光照只生成2,4-异构化产物2-烷基酰氧基-4-甲基-1,5-苯并硫氮杂草(3i,3j)。2-甲基-4-对硝基苯甲酰氧基-1,5-苯并硫氮杂草(2h)可发生热Fries重排,生成2-甲基-3-对硝基苯甲酰基-1,5-苯并硫氮杂草-4(5H)-酮(5h)。化学和光谱数据证明5e-5h和6e-6h为互变异构体。
2-Methyl-1,5-benzothiazepine (2a-2d) is light-irradiated in a benzene solution to give the corresponding 2,4-isomerization products 3a-3d in which 2a and 2d also give double bond displacement The products 4a and 4d.4a undergo basic alcoholysis to form a pair of 2,4-isomers 2b and 3b. 2-Methyl-4-aroyloxy-1,5-benzothiazepine (2e-2g) is mainly rearranged by Fries in 2-methyl-3-aroyl-1,5 -benzothiazepin-4 (5H) -one (5e-5g) with a small amount of 2,4-isomerization product 2-aroyloxy-4-methyl-1,5- Thionane (3e-3g). But 2-methyl-4-alkyl-acyloxy-1,5-benzothiazepine (2i, 2j) was irradiated under the same conditions to produce only 2,4-isomerization product 2-alkyl acyloxy 4-methyl-l, 5-benzothiazepine (3i, 3j). Thermal Fries rearrangement of 2-methyl-4-p-nitrobenzoyloxy-1,5-benzothiazepine (2h) can produce 2-methyl-3-p-nitrobenzoyl -1,5-benzothiazepin-4 (5H) -one (5h). Chemical and spectral data demonstrate that 5e-5h and 6e-6h are tautomers.