青霉烷酸二苯甲酯亚砜的合成

Synthesis of Benzhydryl S-oxopenicillanate

以6 氨基青霉烷酸(Ⅰ)为原料经溴化制得6 溴青霉烷酸(Ⅱ),收率89 1%。然后以六氟异丙醇为溶剂,经w(H2O2)=30%的双氧水氧化合成6 溴青霉烷酸二苯甲酯亚砜(Ⅲ),收率97%。最后经超声波锌粉脱溴制得青霉烷酸二苯甲酯亚砜(Ⅳ),收率93%,总收率80 4%。在氧化反应,用w(H2O2)=30%的双氧水代替了高质量分数的过氧乙酸,不但反应时间从3h降低至10min,得率更是由83%提高到97%。反应过程绿色化,提高了原子经济性。产品用1HNMR、IR进行了表征。

Synthesis of benzhydryl S-oxopenicillanate(Ⅳ) using 6-aminopenicillanic acid(Ⅰ) as starting material was conducted through a green procedure in a total yield of 80.4%.Thus,Ⅰ was firstly brominated to give 6-bromopenicillanic acid(Ⅱ) in 89.1% yield,and then oxidized with 30% aqueous H2O2 in hexafluoro-2-propanol to give benzhydryl 6-bromo-S-oxopenicillanate(Ⅲ).The oxidation reaction of Ⅱ was finished within 10 min and the yield was excellent (97%).Ⅳ was eventually prepared by treatment of Ⅲ with zinc under ultrasonic in a yield of 93%.The products were corroborated by 1HNMR and IR.