CN1055284C - Ｎ－酰基α－氨基酸的合成方法 - Google Patents

Ｎ－酰基α－氨基酸的合成方法 Download PDF

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CN1055284C
CN1055284C CN94119285A CN94119285A CN1055284C CN 1055284 C CN1055284 C CN 1055284C CN 94119285 A CN94119285 A CN 94119285A CN 94119285 A CN94119285 A CN 94119285A CN 1055284 C CN1055284 C CN 1055284C
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罗玉忠
李红兵
赵继全
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

本发明以醛、酰胺和一氧化碳为原料，在羰基金属络合物催化剂存在下合成N-酰基α-氨基酸的方法。以三核羰基钴簇化合物YCCo3(CO)9(Y为烷基、芳香基、卤素、酯等)为催化剂，在一定的合成气压力下(5-10NPa)，100-130℃反应温度反应20-60分钟，在酰胺存在下醋羰基化反应，N-酰基α-氨基酸收率在70-90%之间。本发明选用羰基金属簇催化剂一步完成N-酰基α-氨基酸的制备，具有工艺简便，合理，收率高，产物较易分离等优点。

Description

Ｎ－酰基α－氨基酸的合成方法
本发明涉及一种以醛、酰胺和一氧化碳为原料，在羰基金属络合物催化剂存在下合成N-酰基α-氨基酸的方法。
氨基酸是精细化工重要的中间体，利用其多官能基性，光学活性或氨基酸支链的多种功能，可制成各种功能材料。在医药、生化、饲料、表面活性剂等方面具有广泛的用途。
已知的N-酰基氨基酸的合成方法不仅反应条件苛刻而且经多步完成。H.Wakamatsu及其同事在七十年代初首先发现由醛、酰胺羰化反应合成N-乙酰基α-氨基酸[1]后来又相续发表了用Co2(CO)6
Figure C9411928500031
和羰基铑催化剂的专利。
本发明的目的在于选用羰基金属簇作为催化剂，克服原来Co2(CO)6为催化剂在现有技术中的缺点，从而提供一种工艺简单合理、可行的制备方法。
本发明选用了在空气中比较稳定的有较高催化活性的羰基金属簇YCCo3(CO)9催化剂，得到较高的收率。
本发明选用金属簇化合物YCCo3(CO)9(Y＝烷基、酯、卤素、芳基)为催化剂，乙酸乙酯或二氧六环为溶剂，充入合成气(0O∶H2＝3∶1)，在100-130℃、6-10MPa压力下反应25-60分钟，然后从反应混合物中收集生成物。
本发明得到的N-酰基α-氨基酸，产率在70-90％。
本发明选用羰基金属簇催化剂一步完成N-酰基α-氨基酸的制备，具有工艺简便、合理、收率高，产物较易分离等优点。
反应温度对反应诱导期和收率的影响列于表1。
              表1、反应温度的影响
反应温度(℃)      90       100       110       120      130
诱导期(分)        -        43        17        14       4
产率(％)         0         72.9      79.3      90.6     31.4
反应条件：催化剂PhCCo3(CO)9，0.5g；乙酰胺∶丁醛＝0.1∶0.05摩尔；反应压力9MPa；CO∶H2＝3∶1，反应25分钟。
反应压力对N-乙酰基α-氨基酸收率的影响列表2。
              表2、反应压力的影响
反应压力(MPa)      6         8         9          10
诱导期(分)         28        14        14         5
产率(％)           76.5      76.7      90.6       93.1
反应条件：反应温度120℃其他条件同表1。
不同结构的醛和酰胺的影响见表3。
            表3、各种醛和酰胺醛        酰胺         反应压力(MPa)   反应时间(分)   收率(％)丁醛      乙酰胺       9               25             90.6异丁醛                 9               40             89.3异戊醛                 9               40             92.5十碳醛                 9.5             50             76.2十二碳醛               10              60             73.5丁醛      甲酰胺       9               70             0.4丁醛      苯甲酰胺     9               90             35.7丁醛      邻苯二甲酰胺 9               90             微
反应条件：酰胺∶醛＝2∶1，CO∶H2＝1∶1，其余条件同表1。
例1，0.1立升带电磁搅拌的不锈钢高压釜内加入3.6克(0.05摩尔)的丁醛，5.9克(0.1摩尔)乙酰胺，0.5克PhCCo3(CO)9，50毫升乙酸乙酯。用合成气(CO∶H2＝3∶1)置换三次。充入该比例的合成气，升温至120℃，反应压力9MPa，14分钟后反应压力开始下降，充合成气维持9MPa，25分钟后不再吸收，停止加热，冷却至室温。将反应液从高压釜中放出，减压蒸馏乙酸乙酯。残留物加入35毫升10％的碳酸钠水溶液，温热再冷却，用乙醚淬取三次除去未反应的乙酰胺。水相用磷酸酸化至pH值2-3，用乙醚淬取三次合并乙醚相，蒸除乙醚得产品7.2克，产率90.6％。重结晶得精制产物熔点114℃。
例2，在0.1立升带电磁搅拌的不锈钢高压釜内加入9.2克(0.05摩尔)十二碳醛，5.9克(0.1摩尔)乙酰胺，0.5克PhCCo3(CO)9，50毫升乙酸乙酯，实验同例1，反应温度120℃，反应压力10MPa，9分钟后开始吸收。反应60分钟停止加热，冷却至室温。开釜取出反应液，有白色晶体析出。蒸除乙酸乙酯，残留物加入10％的Na2CO3水溶液35毫升，蒸出水，残渣用乙醚抽提至无乙酰胺存在。抽提后的残渣加入25毫升水，用磷酸酸化至pH＝2-3。用乙醚萃取三次，萃取液合并蒸除乙醚得产物10克，产率73.5％。重结晶熔点109-110℃。
例3，十碳醛、乙酰胺的羰化反应同十二碳醛，反应压力9.5MPa.产率76.2％。
例4，异丁醛与乙酰胺羰化反应同例1，产率89.3％。

Claims (1)

1.一种以醛、乙酰胺和一氧化碳为原料，在羰基金属络合物催化剂存在下合成N-酰基α-氨基酸的方法，其特征在于催化剂为YCCo3(CO)9，其中Y是苯基，乙酸乙酯或二氧六环为溶剂，合成气比例CO∶H2＝3∶1，在100℃-130℃、6-10Mpa下反应25-60分钟，其中所述醛选自丁醛、异丁醛、异戊醛、十碳醛或十二碳醛。
CN94119285A 1994-12-23 1994-12-23 Ｎ－酰基α－氨基酸的合成方法 Expired - Fee Related CN1055284C (zh)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3766266A (en) * 1970-04-04 1973-10-16 Ajinomoto Kk Method of producing n acyl alpha amino acids
US3996288A (en) * 1972-12-23 1976-12-07 Ajinomoto Co., Inc. Method of producing aldehydes by hydroformylation
JPS559047A (en) * 1978-07-06 1980-01-22 Agency Of Ind Science & Technol Preparation of aldehyde
US4264515A (en) * 1977-06-21 1981-04-28 Institut Francais Du Petrole Process for manufacturing a N-acyl α-amino acid
US4497964A (en) * 1981-11-17 1985-02-05 Sagami Chemical Research Center Process for production of N-acyl-α-amino acids
EP0170830A1 (en) * 1984-07-27 1986-02-12 Texaco Development Corporation A process for amido carbonylation of an aldehyde to n-acetyl alpha-amino acids
EP0197669A2 (en) * 1985-03-12 1986-10-15 Diversified Products Corporation Racquets
US4691048A (en) * 1984-05-11 1987-09-01 Institut Francais Du Petrole Process for reducing carbonylation of aldehydes, uses as hemiacetalesters, catalyzed by cobalt carbonyl complexes

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3766266A (en) * 1970-04-04 1973-10-16 Ajinomoto Kk Method of producing n acyl alpha amino acids
US3996288A (en) * 1972-12-23 1976-12-07 Ajinomoto Co., Inc. Method of producing aldehydes by hydroformylation
US4264515A (en) * 1977-06-21 1981-04-28 Institut Francais Du Petrole Process for manufacturing a N-acyl α-amino acid
JPS559047A (en) * 1978-07-06 1980-01-22 Agency Of Ind Science & Technol Preparation of aldehyde
US4497964A (en) * 1981-11-17 1985-02-05 Sagami Chemical Research Center Process for production of N-acyl-α-amino acids
US4691048A (en) * 1984-05-11 1987-09-01 Institut Francais Du Petrole Process for reducing carbonylation of aldehydes, uses as hemiacetalesters, catalyzed by cobalt carbonyl complexes
EP0170830A1 (en) * 1984-07-27 1986-02-12 Texaco Development Corporation A process for amido carbonylation of an aldehyde to n-acetyl alpha-amino acids
EP0197669A2 (en) * 1985-03-12 1986-10-15 Diversified Products Corporation Racquets

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