CN101973890B - 一种手性(R)-α-苯乙胺醋酸盐的制备及合成方法 - Google Patents

一种手性(R)-α-苯乙胺醋酸盐的制备及合成方法 Download PDF

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CN101973890B
CN101973890B CN 201010518321 CN201010518321A CN101973890B CN 101973890 B CN101973890 B CN 101973890B CN 201010518321 CN201010518321 CN 201010518321 CN 201010518321 A CN201010518321 A CN 201010518321A CN 101973890 B CN101973890 B CN 101973890B
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罗梅
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Liuan Jianuo Biochemical Technology Co., Ltd
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Abstract

一种新型手性(R)-α-苯乙胺醋酸盐化合物，该化合物的合成方法是(R)-α-苯乙胺与四水合乙酸钴在无水乙醇溶液中反应一天，将反应液热过滤，自然挥发滤液，得到产物手性(R)-α-苯乙胺醋酸盐。该化合物在苯甲醛的亨利反应中显示良好的催化性能，其产率高达96％。

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一种手性(R)-α-苯乙胺醋酸盐的制备及合成方法
一、技术领域
本发明涉及一种季铵盐的制备及合成方法，确切地说是一种手性α-苯乙胺醋酸盐的制备及合成方法。
二、背景技术
季铵盐的合成方法已有许多文献报道。早在1956年，J.Chem.Soc.报道了一些季铵盐的合成方法，1959年，J.Am.Chem.Soc.也报道了季铵盐类的合成方法。(1.Surrey，Alexander R.；Lesher，George Y.；Mayer，J.Richard；Webb，Wm.G.Journal of the American Chemical Society(1959)，81 2894-7；2.Davis，M.Journal of the Chemical Society(1956)，337-43.)。
申请人在合成手性(R)-α-苯乙胺乙酸钴配合物的实验中，未得到目标产物配合物，却得到了另一种化合物手性(R)-α-苯乙胺醋酸盐。
三、发明内容
本发明旨在提供化合物手性(R)-α-苯乙胺醋酸盐，所要解决的技术问题是一步合成得到目标产物。
本发明所称的一种手性(R)-α-苯乙胺醋酸盐是由(R)-α-苯乙胺与四水合醋酸钴制备的由以下化学式所示的化合物：
Figure BSA00000316843500011
化学名称：(R)-α-苯乙胺醋酸盐，简称化合物(I)。
本合成方法包括合成和分离，所述的合成2.2∶1的(R)-α苯乙胺与四水合乙酸钴在无水乙醇溶液中反应一天，将反应液热过滤，自然挥发滤液，得到产物手性(R)-α-苯乙胺醋酸盐。
本合成方法一步得到目标产物，工艺简单，操作方便。
四、附图说明
图1是(R)-α-苯乙胺醋酸盐的X-衍射分析图。
五、具体实施方式
1.手性(R)-α-苯乙胺醋酸盐的制备
在100mL烧瓶中，无水无氧条件下，加入乙酸钴2.499g(10mmol)，(R)-α-苯乙胺3.0mL(23.8mmol)，无水乙醇30mL，将混合物回流24h，停止反应，反应液热过滤，自然挥发滤液，得到产物手性(R)-α-苯乙胺醋酸盐无色晶体。熔点：110-112℃.元素分析结果如下：理论值：C，66.27％；H，8.34％；N，7.725％，实测值：C，66.36％；H，8.21％；N，7.734％.
2.亨利反应应用
反应原理：
Henry反应是Louis Henry于1895年最早发现并命名的。它是基于羰基和含有α-活泼氢的硝基烷烃类化合物之间的碳碳键形成反应，其产物是一类含β-硝基醇的双官能团化合物。到目前为止它仍然是一种经典的碳碳键形成反应。Henry反应中，含α-活泼氢的硝基化合物在碱等夺质子试剂作用下成为碳负离子，再进攻羰基形成新的碳碳键，而得到双官能团化合物β-硝基醇。方程式如下：
Figure BSA00000316843500021
2-硝基-1苯基乙醇的制备
取0.15mmol化合物(I)(催化用量为15％)于25mL的小烧瓶中，加入2毫升的甲醇溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.5mL的硝基甲烷，常温搅拌，反应72小时，用石油醚/二氯甲烷淋洗，进行柱层析，产率96％，1H NMR(300MHz，CDCl3)7.28～7.32(m，5H，Ar-H)，5.32～5.35(d，J＝9.18Hz，1H，-CH)，4.38～4.56(m，2H，-CH2)，3.89(br，1H，-OH).

Claims (1)

1.一种手性(R)-α-苯乙胺醋酸盐的合成方法，包括合成和分离，其特征在于2.2∶1的(R)-α-苯乙胺与四水合乙酸钴在无水乙醇溶液中反应一天，将反应液热过滤，自然挥发滤液，得到产物手性(R)-α-苯乙胺醋酸盐。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006124325A (ja) * 2004-10-28 2006-05-18 Fuji Molecular Planning Co Ltd ｄｌ−１，２−ジフェニルエチレンジアミンの製造方法
CN101016311A (zh) * 2007-03-09 2007-08-15 合肥工业大学 手性(R/S)－a－苯乙胺(+/－)－酒石酸盐的新用途

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006124325A (ja) * 2004-10-28 2006-05-18 Fuji Molecular Planning Co Ltd ｄｌ−１，２−ジフェニルエチレンジアミンの製造方法
CN101016311A (zh) * 2007-03-09 2007-08-15 合肥工业大学 手性(R/S)－a－苯乙胺(+/－)－酒石酸盐的新用途

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Title
(士)-α-苯乙胺的光学拆分;李科;《中国医药工业杂志》;19941231;第25卷(第10期);第462页 *
Hugo T.S.Braibante.Preparation of β-Enamino Carbonylic Compounds using Microwave Radiation/K-10.《Journal of the Brazilian Chemical Society》.2003,第14卷(第6期),第995页图1.
Kayoko Taniguchi等.Optical Rotation Study on Solvent Dependence of Diastereomeric Salt Discrimination Properties.《The Chemical Society of Japan》.2006,第79卷(第7期),第1085页图1.
Optical Rotation Study on Solvent Dependence of Diastereomeric Salt Discrimination Properties;Kayoko Taniguchi等;《The Chemical Society of Japan》;20060704;第79卷(第7期);第1085页 *
Preparation of β-Enamino Carbonylic Compounds using Microwave Radiation/K-10;Hugo T.S.Braibante;《Journal of the Brazilian Chemical Society》;20031128;第14卷(第6期);第995页 *
张华.手性物α-苯乙胺的制备和分析研究.《四川大学硕士学位论文》.2005,第32-34页.
手性物α-苯乙胺的制备和分析研究;张华;《四川大学硕士学位论文》;20050315;第32-34页 *
李科.(士)-α-苯乙胺的光学拆分.《中国医药工业杂志》.1994,第25卷(第10期),第462页.

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