二苯基重氮甲烷的合成研究

Synthesis of diphenyldiazomethane

二苯基重氮甲烷(DPM)是优良的羧酸基保护试剂,以二苯甲酮腙为原料通过氧化反应制备DPM,探讨了物料配比、催化剂用量、反应时间、温度和氧化剂加料时间等因素对反应的影响.结果表明以氯胺-T为氧化剂,N,N-二甲基乙酰胺(DMAC)为溶剂,碘为催化剂时较佳反应条件∶n(二苯甲酮腙)∶n(氯胺-T)∶n(DMAC)∶n(碘)=1∶1∶10.76∶2.28×10-4,温度25℃,总反应时间85 min,氯胺-T加料时间45 min,DPM纯度为98.57%,收率85.23%.产品结构经1H NMR表征确认.并推测得到了氯胺-T氧化二苯甲酮腙制备二苯基重氮甲烷的反应历程.

Diphenyldiazomethane（DPM）has been widely used as a protective agent of the carboxyl.DPM was synthesized by using chloramine-T and benzophenone hydrazone as the materials,dimethylacetamide as solvent,and iodine as a catalyst.In this paper,the influential factors of oxidation reaction such as the molar ratio,the amount of catalyst,reaction time,the best time to add oxidant and temperature were studied.The optimal experimental conditions were n（benzophenone hydrazone）∶n（chloramine-T）∶n（DMAC）∶n（iodine）=1∶1∶10.76∶2.28×10-4,reaction temperature 25 ℃,total reaction time 85 min.The yield of DPM was 85.23% based on benzophenone hydrazone,the purity of HPLC was 98.57%,and its molecular structure was exactly identified by 1H-NMR and FT-IR.The reaction mechanism for preparation of DPM was obtained by the oxidation of benzophenone hydrazone with chloramine-T.