5-单硝酸异山梨醇酯的合成研究(Ⅱ)

Study on the Synthesis of Isosorbide5mononitrate(Ⅱ)

山梨醇经脱水、酯化、硝酸酯化及皂化，合成了５单硝酸异山梨醇酯。山梨醇脱水反应：山梨醇与硫酸质量比为１∶００１４，二甲苯作带水剂，反应温度１４０℃，反应时间３５ｈ，得异山梨醇（Ⅰ），收率６９％；酯化反应：异山梨醇、冰乙酸及对甲基苯磺酸的质量比为１∶０４９∶００３４，溶剂Ｓ兼作带水剂，回流反应，得２乙酸异山梨醇酯混合物（Ⅱ）；在１０℃，Ⅱ与硝酸质量比为１∶０３６，２ｈ内进行硝酸酯化，得２乙酸５硝酸异山梨醇酯混合物（Ⅲ）；Ⅲ在５０℃、ｐＨ＝１０～１２条件下皂化１５ｈ，得５单硝酸异山梨醇酯。总收率２５％。

Isosorbite5mononitrate was synthesized from Dglucitol by dehydration,esterification,nitric acid esterification and saponification.The yield of isosorbite(Ⅰ) was 69% when using mass ratio of Dglucitol to sulfuric acid was 1∶0.014,xylene as watercarrying agent at 140℃ for 3.5h.Isosorbite2monoacetate admixture(Ⅱ)was synthesized from the esterification through(Ⅰ)with glacial acetic acid by using ptoluene sulfonic acid as catalyst and “S”as refluxing solvent.Their mass ratio was (I∶glacial acetic acid∶ptoluene sulfonic acid)1∶0.49∶0.034.With the nitric acid esterification of(Ⅱ),isosorbite2monoacetate5mononitrate admixture(Ⅲ)was prepared when using mass ratio of Ⅱ to nitric acid was 1∶0.36 at 10℃ for 2h.Isosorbite5mononitrate was abtained at 50℃ and pH=10～12 for 1.5h.The overall yield was 25%.