CN101830821A - Chemical synthesis method of N-alcoxyloxalyl alanine ester - Google Patents
Chemical synthesis method of N-alcoxyloxalyl alanine ester Download PDFInfo
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Abstract
The invention relates to a chemical synthesis method of N-alcoxyloxalyl alanine ester shown as a formula (I). The method comprises the following steps of: reacting alanine shown and oxalic acid which are shown as the formula (I) in alcohol of C1-C8 for 5-150 hours at 50-150 DEG C under the catalysis of bisulfate shown as a formula (II), wherein water generated in the reaction is timely evaporated out with a water taking agent through a rectifying column and a water knockout drum; and after the reaction ends, carrying out after-treatment on reaction liquid to obtain the N-alcoxyloxalyl alanine ester, wherein the mass ratio of the alanine to the oxalic acid to the bisulfate is 1:(1-10):(0.001-1), and the bisulfate is sodium bisulfate or potassium bisulfate or a mixture of the sodium bisulfate and the potassium bisulfate in arbitrary proportion. In the invention, since the bisulfate is used as a catalyst, and the method has high esterification speed, high reaction yield, low production cost, high catalyst activity, good selectivity, basically no monoesterification by-product, high product purity, easy separation and purification, moderate reaction condition and easy industrialization.
Description
(1) technical field
The present invention relates to a kind of chemical synthesis process of N-alcoxyl oxalyl alanine ester, particularly a kind of method of high produced in yields N-alcoxyl oxalyl alanine ester.
(2) background technology
N-alcoxyl oxalyl alanine ester is widely used in medicine, agricultural chemicals, chemical industry, has very high practical value, is the key intermediate of vitamin B6 such as N-ethoxalyl alanine ethyl ester.
Before the present invention makes, the chemical synthesis process of original technology N-alcoxyl oxalyl alanine ester is to be raw material with L-Ala or alanine ester, through over-churning or the synthetic target product of acidylate, such as (1) under concentrated hydrochloric acid catalysis, L-Ala, oxalic acid, careless diester, ethanol is continuous rectification dehydration esterification [Chinese Journal of Pharmaceuticals under the effect of water liquid benzene, 1994,25 (9), 385; Chinese Journal of Pharmaceuticals, 2004,35 (1), 1].This method long reaction time, and used a large amount of concentrated hydrochloric acids, equipment corrosion is serious, inconvenient operation.(2) with alanine ethyl ester and hydrochloric acid salify, under the catalysis of triethylamine, react synthesising target compound [Bull.Chem.Soc.Jpn, 1969,1435] again with careless diester, this method is a raw material with the expensive alanine ethyl ester of price, the triethylamine consumption is big, the cost height.(3) under the nonacid condition or in the presence of the organic alkali catalyst, L-Ala and oxalic acid, careless diester prepared in reaction target product in alcoholic solution, this method easily generates the by product of L-Ala mono-esterification, and not easily separated, the not high [CN200480009214.X of yield; WO2004087640].The synthetic method of other N-alcoxyl oxalyl alanine esters exists more or less that yield is low, troublesome poeration, product are difficult for shortcomings such as separation and purification, severe reaction conditions, therefore develops a new synthetic method that is easy to the N-alcoxyl oxalyl alanine ester of suitability for industrialized production and is badly in need of.
(3) summary of the invention
The technical problem to be solved in the present invention provides that a kind of technology is reasonable, reaction yield is high, production cost is low, is easy to the chemical synthesis process of the N-alcoxyl oxalyl alanine ester of suitability for industrialized production.
For solving the problems of the technologies described above, the present invention prepares N-alcoxyl oxalyl alanine ester with L-Ala and oxalic acid in the presence of catalyzer, and concrete technical scheme is as follows:
The chemical synthesis process of the N-alcoxyl oxalyl alanine ester shown in a kind of formula (I): in the alcohol of C1~C8, L-Ala shown in the formula (II) and oxalic acid (reacted 5~150 hours in 50 ℃~150 ℃ under the catalysis of the hydrosulfate shown in (III) in formula, reaction process in time steams the water that reaction produces by the band aqua through rectifying column and water trap, after reaction finished, reaction solution obtained described N-alcoxyl oxalyl alanine ester through aftertreatment; The amount of substance ratio of described L-Ala, oxalic acid, hydrosulfate is 1: 1~10: 0.001~1; Described hydrosulfate is sodium pyrosulfate or sal enixum, or the mixing of both arbitrary proportions;
In the formula (I), R is selected from the alkyl of C1~C8, and M is sodium or potassium in the formula (III).The quality consumption of described band aqua is generally 1~10 times of L-Ala quality.
The inventive method concrete operations step is: in the reaction that has rectifying column, water trap and prolong device is irritated, earlier with L-Ala, oxalic acid heating for dissolving in the alcohol of C1~C8, add catalyst sulfuric acid hydrogen salt and band aqua then 50 ℃~150 ℃ reactions 5~150 hours, the quality consumption of described band aqua is 1~10 times of L-Ala quality, and reaction solution obtains described N-alcoxyl oxalyl alanine ester through aftertreatment.
Further, it is 60~100 ℃ that the present invention recommends described temperature of reaction, and the reaction times is 10~40 hours.
Further again, the present invention is one of following or the mixture of any several arbitrary proportions with aqua preferably: benzene, toluene, normal hexane, hexanaphthene.It is one of following that alcohol of the present invention is preferably: ethanol, n-propyl alcohol or propyl carbinol.
Further, the amount of substance ratio of preferred L-Ala, oxalic acid, hydrosulfate is 1: 1~3: 0.05~0.1; Preferred described alcohol is 1~100: 1 with L-Ala amount of substance ratio.
The present invention recommends post-treating method to be: after reaction finished, reaction solution added water washing, branch vibration layer, get organic phase with anhydrous sodium sulfate drying after, normal pressure boils off solvent to interior temperature and reaches 120 ℃, and reclaim under reduced pressure grass diester obtains described N-alcoxyl oxalyl alanine ester.
Concrete, the present invention recommends described preparation method to carry out according to following steps: in the reaction that has rectifying column, water trap and prolong device is irritated, elder generation is heating for dissolving in the alcohol of C1~C8 with L-Ala and oxalic acid, add hydrosulfate and band aqua then, be warmed up to 60~100 ℃ after finishing, reaction times is 10~40 hours: after reaction finishes, reaction solution adds water washing, branch vibration layer, get organic phase with anhydrous sodium sulfate drying after, boil off solvent, reach 120 ℃ to interior temperature, reclaim under reduced pressure grass diester obtains described N-alcoxyl oxalyl alanine ester again; The amount of substance ratio of described amino acid, oxalic acid, hydrosulfate is 1: 1~3: 0.05~0.1, band aqua quality consumption is 1~5 times of L-Ala quality, described alcohol is 5~10: 1 times with L-Ala amount of substance ratio, and described alcohol is ethanol, n-propyl alcohol or propyl carbinol.Reaction unit as shown in Figure 1.
The product yield that synthetic method of the present invention makes can reach more than 80%.
The present invention compares with original technology, and advantage is embodied in:
1. use hydrosulfate as catalyzer, esterification rate is fast, reaction yield height (generally more than 80%), and production cost is low;
2. catalyst activity height, selectivity is good, does not have the mono-esterification by product substantially, product purity height, easily separated purification;
3. add the band aqua in the reaction, in time take away the water that reaction is given birth in the reaction process, reduce side reaction.
Operational path advanced person, reaction conditions gentleness, be easy to industrialization.
(4) Figure of description
Fig. 1 is the used reaction unit synoptic diagram of the embodiment of the invention, and 1 is condenser, and 2 is water trap, and 3 is rectifying column, and 4 is reaction flask.
(5) embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto.
In thermometer, rectifying column, water trap, reflux condensing tube and churned mechanically 2L four-hole boiling flask are housed, add L-Ala 89g (1mol), oxalic acid 180g (2mol), ethanol 460g, heating for dissolving adds sodium pyrosulfate 6g (0.05mol), band aqua toluene 200g, be warming up to backflow, rectification 40 hours.After reaction finishes, add entry 50mL, branch vibration layer, organic phase 50g anhydrous sodium sulfate drying, normal pressure boil off solvent to interior temperature and reach 120 ℃, and 2mmHg is lower than 120 ℃ of reclaim under reduced pressure grass diester, obtain weak yellow liquid N-ethoxalyl alanine ethyl ester 198.7g, gas chromatographic detection content 95%, yield 87%, MS (EI): 217.3.
In thermometer, rectifying column, water trap, reflux condensing tube and churned mechanically 2L four-hole boiling flask are housed, add L-Ala 89g (1mol), oxalic acid 180g (2mol), n-propyl alcohol 600g, heating for dissolving adds sodium pyrosulfate 6g (0.05mol), band aqua normal hexane 100g, be warming up to backflow, rectification 40 hours.After reaction finishes, add entry 50mL, branch vibration layer, organic phase 50g anhydrous sodium sulfate drying, normal pressure boil off solvent to interior temperature and reach 120 ℃, and 2mmHg is lower than 120 ℃ of reclaim under reduced pressure grass diester, obtain the weak yellow liquid N-third oxygen oxalyl L-Ala n-propyl 213.7g, content 94%, yield 82%, MS (EI): 245.2.
In thermometer, rectifying column, water trap, reflux condensing tube and churned mechanically 2L four-hole boiling flask are housed, add L-Ala 89g (1mol), oxalic acid 180g (2mol), propyl carbinol 740g, heating for dissolving adds sodium pyrosulfate 6g (0.05mol), water liquid benzene 200g, be warming up to backflow, rectification 40 hours.After reaction finishes, add entry 50mL, branch vibration layer, organic phase 50g anhydrous sodium sulfate drying, normal pressure boil off solvent to interior temperature and reach 120 ℃, and 2mmHg is lower than 120 ℃ of reclaim under reduced pressure grass diester, obtain the positive butyl ester 246.9g of weak yellow liquid N-fourth oxygen oxalyl L-Ala, content 94%, yield 85%, MS (EI): 273.3.
Embodiment 4
The charging capacity of oxalic acid is 90g (1mol), and other are operated with embodiment 1, obtains weak yellow liquid N-ethoxalyl alanine ethyl ester 168.8g, content 90%, yield 70%.
Embodiment 5
The charging capacity of oxalic acid is 900g (10mol), and other are operated with embodiment 1, obtains weak yellow liquid N-ethoxalyl alanine ethyl ester 188.1g, content 90%, yield 78%.
Embodiment 6
Catalyst sulfuric acid hydrogen sodium consumption is 24g (0.2mol), and other are operated with embodiment 1, obtains weak yellow liquid N-ethoxalyl alanine ethyl ester 188.4g, content 91%, yield 79%.
Embodiment 7
Catalyst sulfuric acid hydrogen sodium consumption is 120g (1mol), and other are operated with embodiment 1, obtains weak yellow liquid N-ethoxalyl alanine ethyl ester 175.6g, content 89%, yield 72%.
Embodiment 8
Catalyzer is a sal enixum, and consumption is 6.8g (0.05mol), and other are operated with embodiment 1, obtains weak yellow liquid N-ethoxalyl alanine ethyl ester 205.5g, content 94%, yield 89%.
Embodiment 9
The reflux water-dividing time is 5 hours, and other are operated with embodiment 1, obtains weak yellow liquid N-ethoxalyl alanine ethyl ester 167.9g, content 84%, yield 65%.
Embodiment 10
The reflux water-dividing time is 150 hours, and other are operated with embodiment 1, obtains pale brown look liquid N-ethoxalyl alanine ethyl ester 187.4g, content 88%, yield 76%.
Claims (9)
1. the chemical synthesis process of the N-alcoxyl oxalyl alanine ester shown in the formula (I), it is characterized in that described synthetic method is: in the alcohol of C1~C8, L-Ala shown in the formula (II) and oxalic acid reacted 5~150 hours in 50 ℃~150 ℃ under the catalysis of the hydrosulfate shown in the formula (III), in time steam the water that reaction produces by the band aqua through rectifying column and water trap in the reaction process, after reaction finished, reaction solution obtained described N-alcoxyl oxalyl alanine ester through aftertreatment; The amount of substance ratio of described L-Ala, oxalic acid, hydrosulfate is 1: 1~10: 0.001~1; Described hydrosulfate is sodium pyrosulfate or sal enixum, or the mixing of both arbitrary proportions;
In the formula (I), R is selected from the alkyl of C1~C8, and M is sodium or potassium in the formula (III).
2. the method for claim 1, it is characterized in that described synthetic method is: in the reaction that has rectifying column, water trap and prolong device is irritated, earlier with L-Ala, oxalic acid heating for dissolving in the alcohol of C1~C8, add catalyst sulfuric acid hydrogen salt and band aqua then 50 ℃~150 ℃ reactions 5~150 hours, the quality consumption of described band aqua is 1~10 times of L-Ala quality, and reaction solution obtains described N-alcoxyl oxalyl alanine ester through aftertreatment.
3. method as claimed in claim 2 is characterized in that described temperature of reaction is 60~100 ℃, and the reaction times is 10~40 hours.
4. the method for claim 1 is characterized in that described band aqua can be the mixture of one of following or any several arbitrary proportions: benzene, toluene, normal hexane, hexanaphthene.
5. the method for claim 1 is characterized in that the amount of substance ratio of L-Ala, oxalic acid, hydrosulfate is 1: 1~3: 0.05~0.1
6. as the described method of one of claim 1~4, it is characterized in that described alcohol and L-Ala amount of substance ratio are 1~100: 1.
7. as the described method of one of claim 1~4, it is characterized in that described post-treating method is: after reaction finishes, reaction solution adds water washing, branch vibration layer, get organic phase with anhydrous sodium sulfate drying after, normal pressure boils off solvent, reaches 120 ℃ to interior temperature, reclaim under reduced pressure grass diester obtains described N-alcoxyl oxalyl alanine ester again.
8. as the described method of one of claim 1~4, it is characterized in that described alcohol is one of following: ethanol, n-propyl alcohol, propyl carbinol.
9. the method for claim 1, it is characterized in that described preparation method carries out according to following steps: having rectifying column, during the reaction of water trap and prolong device is irritated, elder generation is heating for dissolving in the alcoholic solution of C1~C8 with L-Ala and oxalic acid, add hydrosulfate and band aqua then, be warmed up to 60~100 ℃ after finishing, reaction times is 10~40 hours, the water that divides the dereaction generation in the reaction process by the band aqua through rectifying column and water trap, after reaction finishes, reaction solution adds water washing, branch vibration layer, get organic phase with anhydrous sodium sulfate drying after, boil off solvent, reach 120 ℃ to interior temperature, reclaim under reduced pressure grass diester obtains described N-alcoxyl oxalyl alanine ester again; The amount of substance ratio of described amino acid, oxalic acid, hydrosulfate is 1: 1~3: 0.05~0.1, and band aqua quality consumption is 1~5 times of L-Ala quality, and described alcohol is 5~10: 1 times with L-Ala amount of substance ratio.
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Cited By (10)
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CN102249946A (en) * | 2011-05-13 | 2011-11-23 | 上海海嘉诺医药发展股份有限公司 | Preparation method of N-alkyloxy oxalyl alanine alkyl ester |
CN102898321A (en) * | 2011-07-24 | 2013-01-30 | 上海海嘉诺医药发展股份有限公司 | Method for preparing N-butoxy oxalyl butyl alaninate |
CN104725262A (en) * | 2013-12-23 | 2015-06-24 | 大丰海嘉诺药业有限公司 | Method for continuously preparing N-ethyloxyl oxalyl alanine ethyl ester |
CN111808434A (en) * | 2020-07-20 | 2020-10-23 | 青岛科技大学 | Method for preparing naphthol AS series azo dye |
CN113214145A (en) * | 2020-12-11 | 2021-08-06 | 安徽泰格维生素发展有限公司 | Production method of vitamin B6 |
CN114195666A (en) * | 2021-11-29 | 2022-03-18 | 湖北文理学院 | Preparation method of N-ethoxyoxalyl-L-alanine ethyl ester |
CN114213274A (en) * | 2021-11-29 | 2022-03-22 | 湖北文理学院 | Synthesis process of N-ethoxyoxalyl-L-alanine ethyl ester |
CN114671823A (en) * | 2022-04-25 | 2022-06-28 | 浙江花园营养科技有限公司 | Preparation method of 4-methyl-5-ethoxy oxazole acid ethyl ester |
CN114702405A (en) * | 2022-04-25 | 2022-07-05 | 浙江花园营养科技有限公司 | Preparation method of N-ethoxy oxalyl alanine ethyl ester |
CN116332783A (en) * | 2021-12-23 | 2023-06-27 | 杭州鑫富科技有限公司 | Continuous preparation method of N-ethoxyoxalyl alanine ethyl ester |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86101512A (en) * | 1986-07-07 | 1988-01-13 | 国家医药管理局上海医药工业研究院 | The synthesis technique of vitamin B6 intermediate 4-methyl-5-alkoxy-oxazole |
CN1470503A (en) * | 2003-06-20 | 2004-01-28 | 江苏常顺化工有限公司 | Method for preparing N-ethoxy oxalyl-alanine ethyl ester |
WO2004087640A1 (en) * | 2003-04-04 | 2004-10-14 | Dsm Ip Assets B.V. | Process for the manufacture of n-alkoxalyl-alaninates |
-
2010
- 2010-05-12 CN CN 201010170305 patent/CN101830821B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86101512A (en) * | 1986-07-07 | 1988-01-13 | 国家医药管理局上海医药工业研究院 | The synthesis technique of vitamin B6 intermediate 4-methyl-5-alkoxy-oxazole |
WO2004087640A1 (en) * | 2003-04-04 | 2004-10-14 | Dsm Ip Assets B.V. | Process for the manufacture of n-alkoxalyl-alaninates |
CN1470503A (en) * | 2003-06-20 | 2004-01-28 | 江苏常顺化工有限公司 | Method for preparing N-ethoxy oxalyl-alanine ethyl ester |
Non-Patent Citations (1)
Title |
---|
《中国医药工业杂志》 19941231 周后元 等 维生素B6噁唑法合成新工艺 385-389 1-9 第25卷, 第9期 * |
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CN102249946A (en) * | 2011-05-13 | 2011-11-23 | 上海海嘉诺医药发展股份有限公司 | Preparation method of N-alkyloxy oxalyl alanine alkyl ester |
CN102249946B (en) * | 2011-05-13 | 2013-11-06 | 上海海嘉诺医药发展股份有限公司 | Preparation method of N-alkyloxy oxalyl alanine alkyl ester |
CN102898321A (en) * | 2011-07-24 | 2013-01-30 | 上海海嘉诺医药发展股份有限公司 | Method for preparing N-butoxy oxalyl butyl alaninate |
CN102898321B (en) * | 2011-07-24 | 2015-10-28 | 上海海嘉诺医药发展股份有限公司 | A kind of method preparing N-fourth oxygen butoxalyl-alaninate |
CN104725262A (en) * | 2013-12-23 | 2015-06-24 | 大丰海嘉诺药业有限公司 | Method for continuously preparing N-ethyloxyl oxalyl alanine ethyl ester |
CN104725262B (en) * | 2013-12-23 | 2018-05-15 | 大丰海嘉诺药业有限公司 | A kind of continuous method for preparing N- ethyoxyl oxalyl alanine ethyl esters |
CN111808434A (en) * | 2020-07-20 | 2020-10-23 | 青岛科技大学 | Method for preparing naphthol AS series azo dye |
CN113214145A (en) * | 2020-12-11 | 2021-08-06 | 安徽泰格维生素发展有限公司 | Production method of vitamin B6 |
CN114195666A (en) * | 2021-11-29 | 2022-03-18 | 湖北文理学院 | Preparation method of N-ethoxyoxalyl-L-alanine ethyl ester |
CN114213274A (en) * | 2021-11-29 | 2022-03-22 | 湖北文理学院 | Synthesis process of N-ethoxyoxalyl-L-alanine ethyl ester |
CN114195666B (en) * | 2021-11-29 | 2024-05-28 | 湖北文理学院 | Preparation method of N-ethoxyoxalyl-L-alanine ethyl ester |
CN116332783A (en) * | 2021-12-23 | 2023-06-27 | 杭州鑫富科技有限公司 | Continuous preparation method of N-ethoxyoxalyl alanine ethyl ester |
CN114671823A (en) * | 2022-04-25 | 2022-06-28 | 浙江花园营养科技有限公司 | Preparation method of 4-methyl-5-ethoxy oxazole acid ethyl ester |
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