摘要
以苯硫酚为起始原料,经脱水反应、碘代反应、Suzuki-Miyaura偶联反应和氧化反应制得4-酮基-3-苯基-4H-苯并噻喃-2-甲醛(4);4经间氯过氧苯甲酸氧化后与对甲苯磺酰肼于室温反应制得2-甲苯磺酰腙-3-苯基-4H-磺酰基苯并噻喃(6);6经Bamford-Stevens反应合成了一种新型磷酸基光控保护基——2-重氮基-3-苯基-4H-磺酰基苯并噻喃(7),其结构经~1H NMR,^(13)C NMR和HR-MS表征。将7应用于磷酸基团的保护和光控脱保护反应中。结果表明:保护反应可在温和条件下顺利进行。紫外光谱法和荧光光谱法对光控脱保护反应的监测结果表明:光控脱保护反应迅速(≤15 min),被保护化合物脱保护收率高(≥95%)。
4-Oxo-3-phenyl-4H-thiochromene-2-carbaldehyde（ 4） was prepared by dehydration reaction,iodine substitution reaction,Suzuki- Miyaura coupling and oxidation,using thiophenol and ethyl acetoacetate as starting material. Furthermore oxidation of the sulfur atom of 4 with m-CPBA,and then reaction with Ts NHNH2 to obtain tosylhydrazone（ 6）. 2-Diazomethyl- 3-phenyl-4H-thiochromen-4-one1,1-dioxide（ 7） was synthesized by Bamford- Stevens reaction from 6. The structures were characterized by ~1 H NMR,^（13） C NMR and HR-MS. 7 was designed as a novel photolabile protecting group for the protection and photodeprotection of phosphate derivatives. Protection reaction proceeded smoothly under mild reaction. The photodeprotection yields were more than 95% in 15 min monitored by UV-Vis and fluorescence spectroscopies.
出处
《合成化学》
CAS
CSCD
2016年第3期198-202,210,共6页
Chinese Journal of Synthetic Chemistry
基金
国家自然科学基金资助项目(21303120)
天津市自然科学基金资助项目(13JCYBJC42100)
天津市"131"创新型人才培养工程第三层次
天津市高等学校大学生创新创业训练计划项目(201410060024)
关键词
磷酸基
苯并噻喃
2-重氮基-3-苯基-4H-磺酰基苯并噻喃
光控保护基
合成
光反应
phosphates
thiochromone S
S-dioxide
2-diazomethyl-3-phenyl-4H-thiochromen-4-one 1
1-dioxide
photolabile protecting group
synthesis
photochemistry
