N^δ-保护鸟氨酸的微波合成

目的]用微波法合成N^δ-保护鸟氨酸。方法]以L-鸟氨酸盐酸盐为原料,与碱式碳酸铜反应得到L-鸟氨酸铜络合物,在δ-氨基上分别引入苄氧羰基、叔丁氧羰基、芴甲氧羰基、乙酰基和邻苯二甲酰基,得到了N^δ-保护鸟氨酸铜络合物,微波辐射下用EDTA-2Na脱去铜离子,得到N^δ-苄氧羰基鸟氨酸、Nδ-叔丁氧羰基鸟氨酸、N^δ-芴甲氧羰基鸟氨酸、N^δ-乙酰基鸟氨酸和N^δ-邻苯二甲酰基鸟氨酸5个N^δ-保护鸟氨酸。探讨了微波辐射功率、时间及投料比例对脱铜反应的影响。结果]脱铜反应的最佳反应条件为：n（N^δ-保护鸟氨酸铜络合物）∶n（EDTA）=1∶1.1～1∶1.2,微波辐射功率为250～300W,反应时间为4～6min,收率分别为93.2%、86.2%、88.7%、86.3%和86.4%（以N^δ-保护鸟氨酸铜络合物计）。产物结构经元素分析和1HNMR确证。结论]该合成工艺对环境友好、简便、高效,产物收率与纯度均较高。

Synthesis of Nδ-protective Ornithine under Microwave Irradiation

Objective] To synthesis Nδ-protective ornithine under microwave irradiation.Method]L-ornithine monohydrochloride was first reacted with basic curpic carbonate to give L-ornithine copper complexes.Subsequently,the δ-amino was protected with tert-butoxycarbonyl（Boc）,benzyloxycarbonyl（Z）,fluorenylmethyloxycarbonyl（Fmoc）,acetyl（Acetyl）and phthaloyl（Phthalyl）,after the use of EDTA-2Na for copper removal,the Nδ-benzyloxycarbonyl ornithine,Nδ-tert-butoxycarbonyl ornithine,Nδ-fluorenylmethyloxycarbonyl ornithine,Nδ-acetyl ornithine and Nδ-phthaloyl ornithine were obtained.And the effects of microwave irradiation power,time and the feed ratio on the removal of copper were analyzed.Results]The optimal conditions were obtained as follows：n（Nδ-protective ornithine copper complexes）∶n（EDTA）=1∶1.1-1∶1.2,microwave power was 250-300 W,reaction time was 4-6 min.The yield of Nδ-benzyloxycarbonyl-L-Ornithine,Nδ-tert-butyloxycarbonyl-L-Ornithine,Nδ-fluorenylmethyl-oxycarbonyl-L-Ornithine,Nδ-acetyl-L-Ornithine and Nδ-phthalyl-L-Ornithine were 93.2%,86.2%,88.7%,86.3% and 86.4% respectively.The structure of aimed compounds was confirmed by elementary analysis and 1H NMR.Conclusion]The improved synthetic route was environment friendly and convenient in operation with better product yield and purity.