腺嘌呤葡萄糖苷的合成  

SYNTHESIS OF 9-(β-D-GLUCOPYRANOSYL)ADENINE

作　　者：孙莉萍 孙明明 夏然[2] 渠桂荣[3] Sun Liping;Sun Mingming;Xia Ran;Qu Guirong(School of Life Science and Technology,Xinxiang University,Xinxiang 453003,He＇nan,China;College of Chemistry and Chemical Engineering,Xinxiang University,Xinxiang 453003,He＇nan,China;College of Chemistry and Chemical Engineering,He＇ nan Normal University,Xin~ciang 453007,He＇ nan,China)

机构地区：[1]新乡学院生命科学技术学院,河南新乡453003 [2]新乡学院化学化工学院,河南新乡453003 [3]河南师范大学化学化工学院,河南新乡453007

出　　处：《精细石油化工》2018年第4期41-45,共5页Speciality Petrochemicals

基　　金：国家自然科学基金(21602189);河南省科技发展计划项目(172102310212和172102310213);河南省高等学校重点科研项目(16A150042和16A180035);新乡学院科技创新团队项目(XXUTD20170106)资助

摘　　要：以β-D-(+)-五乙酰基葡萄糖和HCl气体反应,得到1-氯-2,3,4,6-四-O-乙酰基葡萄糖,继而和硅醚化的6-氯嘌呤反应得到缩合物,缩合物在Na_2CO_3催化下脱除乙酰基,不经分离"一锅法"在饱和的NH_3/MeOH溶液中反应使6位氨解,最终以4步和80%的总收率得到腺嘌呤葡萄糖苷。考察了关键步骤缩合反应中催化剂、溶剂、投料比、反应时间、反应温度及反应规模对缩合物收率的影响,得到了较佳的反应条件:乙腈为溶剂,2%四氯化锡为催化剂,n(6-氯嘌呤)∶n[β-D-(+)-五乙酰基葡萄糖]=1∶1,60℃反应30 min,收率87%,不需要柱层析。缩合反应的反应规模可以扩大到200g,收率75%。A new new method for the synthesis of 9-（β-D-glucopyranosyl）adenine was developed.The starting material penta-O-acetyl-β-D-glucopyranose reacted with HCl gas in the presence of acetic chloride to afford 1-chloro-tetra-O-acetyl-β-D-glucopyranose,which was glycosylated with sily-protected 6-chloropurine.The acetyl groups of glycosylated intermediate were removed by catalytic Na2CO3 in MeOH,and then the saturated NH3/MeOH solution was added in order to ammonolysis of C6 chloride.The 9-（β-D-glucopyranosyl）adenine was synthesized in 4 steps and 80%total yield.The effects of catalysts,solvents,substrate ratio,reaction time,reaction temperature and reaction scale for glycosylated intermediate were investigated,and the optimized reaction conditions were obtained：CH3CN as solvent,2% SnCl4 as catalyst,n（6-chloropurine）∶n[penta-O-acetyl-β-D-glucopyranose]=1∶1,60 ℃ for 30 min,87% yield,and the chromatography was avoided.The glycosylated step could enlarge to 200 grams in 75% yield.

关 键 词：腺嘌呤葡萄糖苷 β-D-(+)-五乙酰基葡萄糖 糖苷化 核苷合成 

分 类 号：TQ463.5[化学工程—制药化工]