摘要
报道了以化学合成和生物转化的方法制备光学纯D-谷氨酰胺.首先在中试规模上用化学方法合成DL-谷氨酰胺.即以廉价的DL-谷氨酸为原料,采用邻苯二甲酰基作为保护基保护L-谷氨酸的α-氨基,醋酐回流15min,使其分子内脱水生成N-邻苯二甲酰-DL-谷氨酸酐,在常温、常压条件下,分别与2mol/L氨水反应生成中间产物N-邻苯二甲酰-DL-谷氨酰胺,中间产物在室温条件下与0.5mol/L水合肼反应48h脱除保护基,以57%总收率得到DL-谷氨酰胺.在37℃,pH4.8的条件下,利用大肠杆菌(E.coli.AS1.505)脱羧酶将底物浓度30g/L的DL-谷氨酰胺中L型对映体在8h内完全转化为4-氨基丁酰胺,分离得到D-谷氨酰胺.
Optically pure D-glutamine was prepared by biotransformations of DL-glutamine manufactured by chemical synthesis. Firstly, DL-glutamine was synthesized from DL-glutamic acid on larger scale. Protected DL-glutamic acid was prepared by using inexpensive phthaloyl as protecting group. Then N-phthaloyl-DL-glutamic acid anhydride was synthesized with protected DL-glutamic acid and acetic anhydride under reflux for 15min. Under ambient temperature and normal pressure, N-phthaloyl.DL.glutamine was produced by reacting N-phthaloyl-DL-glutamic acid anhydride with 2 mol/L ammonia solution. After the phthaloyl was removed from the intermediate with 0.5 mol/L hydrazine hydrate under ambient temperature for 48 h DL-glutamine mixture was obtained in 57% yields. L-Glutamine in the racemic mixture was selectively decarboxylated to 4-aminobutanamide by the decarboxylase of E. coli AS 1.505. Under the following conditions： temperature of 37 ℃, reaction time of 8 h, pH of 4.8, substrate concentration of 30 g/L, D-glutamine was efficiently produced.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
2006年第4期514-517,共4页
Chinese Journal of Organic Chemistry
基金
国家技术创新基金(No.02CJ-13-01-16)资助项目
