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以2-氨基-6-氯嘌呤为原料,与2-溴乙基乙酸酯反应得到9-乙酰氧基乙基-2-氨基-6-氯嘌呤(Ⅰ),收率65.6%;Ⅰ经重氮-烷硫化得到9-乙酰氧基乙基-2-烷硫基-6-氯嘌呤(Ⅱ),收率58.3%~72.1%;Ⅱ与叠氮化钠反应得到9-乙酰氧基乙基-2-烷硫基-6-叠氮嘌呤(Ⅲ),收率86.4%~92.0%。经核磁检测Ⅲ在溶液中存在叠氮结构(A)和四氮唑结构(T)的互变异构现象,CDCl3中叠氮结构比例在61.5%~67.2%。采用PPh3-HCl-DMSO为反应体系,“一锅法”将叠氮基还原为氨基同时将酯基彻底水解,高收率(~90%)得到9-(2-羟基乙基)-6-氨基-2-烷硫基嘌呤衍生物(Ⅳ)。这些化合物的结构经IR、1HNMR、13CNMR及HRMS得到确证。
2-Amino-6-chloropurine was used as the starting material to obtain 9-acetoxyethyl-2-amino-6-chloropurine with a yield of 65.6% Diazotization to give 9-acetoxyethyl-2-alkylthio-6-chloropurine (Ⅱ) in a yield of 58.3% -72.1%; reacting with sodium azide to give 9-acetoxyethyl 2-alkylthio-6-azapurine (Ⅲ) in the yield of 86.4% -92.0%. The results of NMR showed that there existed the tautomerism of azide structure (A) and tetrazolium structure (T) in solution. The proportion of azide structure in the solution was between 61.5% and 67.2%. Using PPh3-HCl-DMSO as the reaction system, the azido group was reduced to amino group by one-pot method while the ester group was completely hydrolyzed to give 9- (2-hydroxyethyl) - 6-Amino-2-alkylthiopurine derivatives (IV). The structures of these compounds were confirmed by IR, 1H NMR, 13CNMR and HRMS.