CN104152526A - 一种拆分制备光学纯r-1-苯乙胺的方法 - Google Patents
一种拆分制备光学纯r-1-苯乙胺的方法 Download PDFInfo
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- RQEUFEKYXDPUSK-SSDOTTSWSA-N (1R)-1-phenylethanamine Chemical compound C[C@@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-SSDOTTSWSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 13
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 230000006340 racemization Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 108010084311 Novozyme 435 Proteins 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 12
- PAVMRYVMZLANOQ-MRVPVSSYSA-N (R)-N-acetyl-1-phenylethylamine Chemical compound CC(=O)N[C@H](C)C1=CC=CC=C1 PAVMRYVMZLANOQ-MRVPVSSYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 5
- 229960002510 mandelic acid Drugs 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- PAVMRYVMZLANOQ-UHFFFAOYSA-N N-(1-phenylethyl)acetamide Chemical compound CC(=O)NC(C)C1=CC=CC=C1 PAVMRYVMZLANOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- ZUBRUEJEJSFAFR-JTQLQIEISA-N N-[(1R)-1-ethylcyclohexa-2,4-dien-1-yl]acetamide Chemical compound C(C)(=O)N[C@@]1(CC=CC=C1)CC ZUBRUEJEJSFAFR-JTQLQIEISA-N 0.000 abstract 1
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- -1 glyceryl alcohol derivative Chemical class 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004540 process dynamic Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种动态动力学拆分制备R-1-苯乙胺的方法。以1-苯乙胺为原料，Novozym435为拆分催化剂， D-(-)-O-乙酰基扁桃酸为酰基供体，KT-02（镍型催剂）为消旋催化剂，在高压釜中通入氢气进行反应，1-苯乙胺转化完全得(R)-(1-苯基乙基)乙酰胺（ee值99%）；酰胺纯化后进行酸解得R-1-苯乙胺盐，盐再通过碱化、萃取、干燥、浓缩等操作得R-1-苯乙胺，整个步骤产品收率和ee值均可达90%以上。本发明具备消旋催化剂廉价易得、原料利用完全、产品收率好、纯度高等特点。在R-1-苯乙胺的生产制备中，具有极大的指导和应用价值。
Description
技术领域
本发明涉及一种光学纯手性胺的拆分制备方法，尤其涉及光学纯R-1-苯乙胺的拆分及制备方法。
背景技术
光学纯的手性胺是一种非常重要的药物中间体。目前获得光学纯的手性胺主要通过以下几种方法：酶拆分(Indian J. Chem. Sect. B 2005, 44, 1312-1316; J. Org. Chem. 1997, 62, 3488-3495)；化学拆分：用手性α-羟基苯乙酸（US6342636; Tetrahedron: asymmetry, 1998, 9, 2219-2212）或保护的手性甘油醇衍生物拆分（Tetrahedron: asymmetry, 1996, 7, 1117-1122; Tetrahedron: asymmetry, 2002, 13, 2277-2282）；通过相应的醛经不对称合成得到（WO2004/110976; J. Org. Chem. 1992, 57, 1237-1241）。
在现有的方法中，不对称合成法成本高且经常难得到光学纯度高的产物；化学拆分法及酶法动力学拆分存在原料的利用率低的缺点，最多只有50%；而现报道的酶法动态动力学拆分法中，所使用的消旋催化剂通常是一些钌、铑等贵金属的复合物，这些消旋催化剂成本极高，有些方法虽然实现了高转化率，但是产品难以获得让人满意的光学纯度。。
发明内容
本发明要解决的技术问题是找到一种价格低廉的消旋催化剂，同时实现R-1-苯乙胺在拆分制备过种中的高收率以及高光学纯度。
为了解决上述问题，本发明提供了一种光学纯R-1-苯乙胺的拆分制备方法：1）在高压釜中，以甲苯为溶剂，按摩尔比1:1.0~2.0的比例加入原料1-苯乙胺和酰基供体D-(-)-O-乙酰基扁桃酸，最后再按原料1-苯乙胺质量分数1%-10%的比例加入脂肪酶Novozym 435和KT-02，高压釜密封进行氮气置换后，通入氢气至压力0.1-1.0MPa并升温至40-70℃反应20小时，即可将1-苯乙胺完全转化为(R)-(1-苯基乙基)乙酰胺，且产物ee值可达99%；反应结束后，将溶液进行浓缩，柱层析，得纯(R)-(1-苯基乙基)乙酰胺，2）将步骤1中制得的(R)-(1-苯基乙基)乙酰胺溶解在10倍体积比的醇与酸液（v/v=1:1）的混合溶液中，然后加热回流反应24小时，(R)-(1-苯基乙基)乙酰胺完全水解得R-1-苯乙胺盐；3）将步骤2所得R-1-苯乙胺盐进行碱化处理，然后通过有机溶剂萃取、干燥、浓缩即可得到光学纯的R-1-苯乙胺，最终整个步骤产品收率可达90%以上，且产品纯度为99%。
本发明在制备光学纯R-1-苯乙胺过程中使用的消旋催化剂为KT-02具有低廉易得、可重复使用的特点，使用D-(-)-O-乙酰基扁桃酸做为酰基供体，可以保证在获得较高收率的同时，最终产品R-1-苯乙胺具有极好的光学纯度高。
具体实施方法
1）拆分制备(R)-(1-苯基乙基)乙酰胺
1000mL的高压釜中加入500mL甲苯作为溶剂，依次加入60.5g1-苯乙胺、106.7g D-(-)-O-乙酰基扁桃酸，5g脂肪酶Novozym 435和8gKT－02，加入完毕后，密封高压釜后用氮气将釜内空气进行置换，然后往高压釜内通入氢气至压力1.0MP，开启搅拌，并升温至60℃进行反应；19小时后，取样检测，1-苯乙胺消失完全转化为(R)-(1-苯基乙基)乙酰胺，且产物ee值达99%；反应结束后，将溶液进行浓缩，然后用体积比为10:1的正已烷与乙醇混合溶剂进行柱层析，得纯(R)-(1-苯基乙基)乙酰胺102.3g，收率为96%。
2）酸解获得R-1-苯乙胺盐
将上步中制得的(R)-(1-苯基乙基)乙酰胺40g加入到400ml的乙醇和浓盐酸以体积比1:1混合的溶液中，然后加热回流，反应24小时后，TLC检测(R)-(1-苯基乙基)乙酰胺完全水解得R-1-苯乙胺对映体盐。
3）碱化获得R-1-苯乙胺
往步骤2所得反应完全的溶液加入400mL的二氯甲烷，然后缓慢加入氢氧化钠溶液，并进行搅拌，检测溶液PH值至13，停止添加氢氧化钠溶液，分液，上层水液再次用200mL的二氯甲烷萃取3次，将几次萃取得到的二氯甲烷溶液用无水硫酸钠进行干燥、浓缩得R-1-苯乙胺29.2g，收率为97.4%，HPLC检测最终产品的ee值为99.5%
Claims (4)
1.光学纯R-1-苯乙胺的拆分制备方法其特征在于：1）在高压反应釜中，以甲苯为溶剂，按摩尔比1:1.0-2.0的比例加入原料1-苯乙胺和酰基供体D-(-)-O-乙酰基扁桃酸，然后按原料1-苯乙胺质量分数1%-10%的比例加入脂肪酶Novozym 435和KT-02(镍型催化剂)，高压釜密封进行氮气置换后，通入氢气至压力0.1-1.0MPa并升温至40-70℃反应20小时，即可将1-苯乙胺完全转化为(R)-(1-苯基乙基)乙酰胺，且产物ee值达99%；反应结束后，将溶液进行浓缩，柱层析，得纯(R)-(1-苯基乙基)乙酰胺，2）将步骤1中制得的(R)-(1-苯基乙基)乙酰胺溶解在10倍（v/w）的醇与酸液（v/v=1:1）的混合溶液中，加热回流反应24小时，(R)-(1-苯基乙基)乙酰胺完全水解得R-1-苯乙胺盐；3）将步骤2所得R-1-苯乙胺盐进行碱化处理，然后通过有机溶剂萃取、干燥、浓缩即可得到光学纯的R-1-苯乙胺，最终整个步骤产品收率可达93%以上，且产品纯度为99%；根据所述，其反应方程式如下： 。
2.根据权利要求1所述，光学纯R-1-苯乙胺的制备方法其特征在于步骤1)中的酰基供体为D-(-)-O-乙酰基扁桃酸，消旋催化剂为KT-02镍型催化剂。
3.根据权利要求1所述，光学纯R-1-苯乙胺的制备方法其特征在于步骤2)中的醇为甲醇或乙醇；酸为盐酸或硫酸。
4.根据权利要求1所述，光学纯R-1-苯乙胺的制备方法其特征在于步骤3)中的碱化处理所用的碱为氢氧化钠、氢氧化钾或氨水；萃取所用的有机溶剂为甲苯、二氯甲烷，1,2-二氯乙烷，乙醚等。
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Cited By (2)
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| CN109651158A (zh) * | 2019-01-29 | 2019-04-19 | 安徽高盛化工股份有限公司 | 一种对苯二胺的制备方法 |
| CN115583867A (zh) * | 2022-08-24 | 2023-01-10 | 湖南复瑞生物医药技术有限责任公司 | 一种l-2-氨基丙醇的拆分方法 |
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| US4983771A (en) * | 1989-09-18 | 1991-01-08 | Hexcel Corporation | Method for resolution of D,L-alpha-phenethylamine with D(-)mandelic acid |
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| US4983771A (en) * | 1989-09-18 | 1991-01-08 | Hexcel Corporation | Method for resolution of D,L-alpha-phenethylamine with D(-)mandelic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651158A (zh) * | 2019-01-29 | 2019-04-19 | 安徽高盛化工股份有限公司 | 一种对苯二胺的制备方法 |
| CN115583867A (zh) * | 2022-08-24 | 2023-01-10 | 湖南复瑞生物医药技术有限责任公司 | 一种l-2-氨基丙醇的拆分方法 |
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