2-聚苯乙烯磺酰基乙醇树脂的合成及其在海因和脲固相成中的应用

合成了一种新型的聚合物载体—2-聚苯乙烯磺酰基乙醇，并研究其在固相有机合成中应用，聚苯乙烯亚磺酸钠树脂（1）在相转移催化剂BU4NI和助催化KI的作用下，与氯乙进行砜化反应，得到含羟基功能基的2-聚苯乙烯磺酰基乙醇树脂2。树脂2用Boc保护的氨基酯化，封闭树脂上未反应的羟基，用酸脱保护并用三乙胺中和，再与异（硫）氰酸苯酯反应生成聚合生物支载的脲树脂6树脂6用酸解脱得到海因和硫代海因化合物，用碱处理树脂6是得到取代的脲和硫脲，优化了合成反应的全过程，探讨了树脂在酸性和碱性条件下的解脱方法，结果表明，2-聚苯乙烯磺酰基乙醇树脂易与羧基形成含酯键的连接桥，连接桥在强酸性和碱性条件下均可解脱得到产物。

Synthesis of 2-Polystyrylsulfonylethanol and Its Application in Solid-phase Organic Synthesis of Hydantoins and Ureas

In this article a new kind of polymer\|support: 2\|polystyrylsulfonylethanol was prepared and used in solid\|phase organic synthesis. Sodium polystyrylsulfinate resin 1 reacted with chloroethanol in the presence of phase transfer catalyst Bu\-4NI and KI as a cocatalyst to give 2\|polystyrylsulfonylethanol resin 2. After the esterification of resin 2 with Boc\|Gly, deprotection of Boc group with HCl, neutralization by Et\-3N, conversion of the free amino group with phenyl isocyanate or phenyl isothiocanate to urea to give urea resin 6. The urea resins 6a and 6b were cleaved with \{6 mol/L\} HCl to obtain the hydantoin derivatives 7a and 7b in an overall yields of 29%\_30%. While the resin 6 was treated with 4 mol/L NaOH then HCl to give the urea derivatives 8a and 8b in an overall yields of 20%\_21%. The whole synthesis processes were optimized by the trace of the reactions by using IR spectra. The results show that resin 2 can easily form a stable ester linker with carboxylic acids and this kind of linker can be cleaved by the use of both strong acid or dilute base.