公开(公告)号：US06833468B2

公开(公告)日：2004-12-21

申请号：US10202833

申请日：2002-07-26

申请人： Akihiro Ishii ,  Masatomi Kanai ,  Takashi Hayami ,  Katsuyoshi Shibata ,  Masaki Matsui ,  Kazumasa Funabiki ,  Yokusu Kuriyama ,  Manabu Yasumoto

发明人： Akihiro Ishii ,  Masatomi Kanai ,  Takashi Hayami ,  Katsuyoshi Shibata ,  Masaki Matsui ,  Kazumasa Funabiki ,  Yokusu Kuriyama ,  Manabu Yasumoto

IPC分类号： C07C6900

CPC分类号： C07C69/675 ,  C07B2200/07 ,  C07C29/143 ,  C07C45/516 ,  C07C45/78 ,  C07C45/81 ,  C07C49/82 ,  C07C49/84 ,  C07C31/42

摘要： A first process for producing an optically active perfluoroalklylcarbinol derivative includes (a) reacting an optically active imine with a compound that is a hemiacetal of a perfluoroalkylaldehyde or a hydrate of a perfluoroalkylaldehyde to obtain a condensate; and (b) hydrolyzing the condensate under an acid condition. A second process for increasing optical purity of an optically active 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone derivative includes (a) precipitating a racemic crystal of the derivative, from the derivative; and (b) removing the racemic crystal from the derivative. A third process for increasing optical purity of the butanone derivative includes recrystallizing the derivative. Novel compounds are optically active and inactive 4,4,4-trifluoro-3-hydroxybotanoic aryl ester derivatives. A fourth or fifth process for producing an optically active and inactive 4,4,4-trifluoro-3-hydroxybutyric acid aryl ester derivative includes oxidizing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone derivative. A sixth process for increasing optical purity of the optically active aryl ester derivative includes recrystallizing the derivative. A seventh process for producing an optically active 4,4,4-trifluoro-3-butanediol includes reducing the optically active aryl ester derivative by a hydride. An eighth or ninth process for producing an optically active or inactive 4,4,4-trifluoro-3-hydroxybutyric acid alkyl ester derivative includes reacting under an acid condition the optically active or optically inactive aryl ester derivative with a lower alcohol. It is possible to suitably combine at least two of the first to ninth processes.

摘要翻译： 制备光学活性全氟烷基甲醇基衍生物的第一种方法包括（a）使光学活性亚胺与全氟烷基醛的半缩醛化合物或全氟烷基醛的水合物反应得到缩合物; 和（b）在酸性条件下水解冷凝物。 提高光学活性4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物的光学纯度的第二种方法包括（a）衍生物沉淀衍生物的外消旋晶体; 和（b）从衍生物中除去外消旋晶体。 提高丁酮衍生物的光学纯度的第三种方法包括使衍生物重结晶。 新型化合物是光学活性和无活性的4,4,4-三氟-3-羟基伯烷基酯衍生物。 用于制备光学活性和无活性的4,4,4-三氟-3-羟基丁酸芳基酯衍生物的第四或第五种方法包括将光学活性或光学活性的4,4,4-三氟-3-羟基-1-芳基 -1-丁酮衍生物。 提高光学活性芳基酯衍生物的光学纯度的第六种方法包括使衍生物重结晶。 制备光学活性4,4,4-三氟-3-丁二醇的第七种方法包括用氢化物还原光学活性芳基酯衍生物。 用于制备光学活性或无活性的4,4,4-三氟-3-羟基丁酸烷基酯衍生物的第八或第九方法包括在酸性条件下使光学活性或光学惰性的芳基酯衍生物与低级醇反应。 可以适当地组合第一至第九工艺中的至少两个。

公开(公告)号：US06642409B2

公开(公告)日：2003-11-04

申请号：US09770671

申请日：2001-01-29

申请人： Akihiro Ishii ,  Masatomi Kanai ,  Takashi Hayami ,  Katsuyoshi Shibata ,  Masaki Matsui ,  Kazumasa Funabiki ,  Yokusu Kuriyama ,  Manabu Yasumoto

发明人： Akihiro Ishii ,  Masatomi Kanai ,  Takashi Hayami ,  Katsuyoshi Shibata ,  Masaki Matsui ,  Kazumasa Funabiki ,  Yokusu Kuriyama ,  Manabu Yasumoto

IPC分类号： C07C6993

CPC分类号： C07C69/675 ,  C07B2200/07 ,  C07C29/143 ,  C07C45/516 ,  C07C45/78 ,  C07C45/81 ,  C07C49/82 ,  C07C49/84 ,  C07C31/42

摘要： A first process for producing an optically active perfluoroalklylcarbinol derivative includes (a) reacting an optically active imine with a compound that is a hemiacetal of a perfluoroalkylaldehyde or a hydrate of a perfinoroalkylaldehyde to obtain a condensate; and (b) hydrolyzing the condensate under an acid condition. A second process for increasing optical purity of an optically active 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone derivative includes (a) precipitating a racemic crystal of the derivative, from the derivative; and (b) removing the racemic crystal from the derivative. A third process for increasing optical purity of the butanone derivative (includes recrystallizing the derivative. Novel compounds are optically active and inactive 4,4,4-trifluoro-3-hydroxybotanoic aryl ester derivatives. A fourth or fifth process for producing an optically active and inactive 4,4,4-trifloro-3-hydroxybutyric acid aryl ester derivative includes oxidizing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone derivative. A sixth process for increasing optical purity of the optically active aryl ester derivative includes recrystallizing the derivative. A seventh process for producing an optically active 4,4,4-trifluoro-3-butanediol includes reducing the optically active aryl ester derivative by a hydride. An eighth or ninth process for producing an optically active or inactive 4,4,4-trifluoro-3-hydroxybutyric acid alkyl ester derivative includes reacting under an acid condition the optically active or optically inactive aryl ester derivative with a lower alcohol. It is possible to suitably combine at least two of the first to ninth processes.

摘要翻译： 制备光学活性全氟烷基甲醇基衍生物的第一种方法包括（a）使光学活性亚胺与全氟烷基醛的半缩醛化合物或全氟烷基醛的水合物反应得到一种缩合物; 和（b）在酸性条件下水解冷凝物。 提高光学活性4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物的光学纯度的第二种方法包括（a）衍生物沉淀衍生物的外消旋晶体; 和（b）从衍生物中除去外消旋晶体。 提供丁酮衍生物的光学纯度的第三种方法（包括重结晶衍生物）新型化合物是光学活性和无活性的4,4,4-三氟-3-羟基己酸芳基酯衍生物。第四或第五种光学活性和 不活泼的4,4,4-三氟-3-羟基丁酸芳酯衍生物包括氧化光学活性或光学活性的4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物。第六种增加方法 光学活性芳基酯衍生物的光学纯度包括使​​该衍生物重结晶。第四种制备光学活性4,4,4-三氟-3-丁二醇的方法包括用氢化物还原光学活性芳基酯衍生物，第八或第九种方法 用于制备光学活性或无活性的4,4,4-三氟-3-羟基丁酸烷基酯衍生物包括在酸性条件下使光学活性或光学惰性的芳基酯衍生物 e与低级酒精。 可以适当地组合第一至第九工艺中的至少两个。

公开(公告)号：US06797842B2

公开(公告)日：2004-09-28

申请号：US09853085

申请日：2001-05-11

申请人： Akihiro Ishii ,  Manabu Yasumoto ,  Yokusu Kuriyama ,  Masatomi Kanai ,  Takashi Hayami

发明人： Akihiro Ishii ,  Manabu Yasumoto ,  Yokusu Kuriyama ,  Masatomi Kanai ,  Takashi Hayami

IPC分类号： C07C21100

CPC分类号： C07C209/52 ,  C07B2200/07 ,  C07C211/29

摘要： An optically active 1-(fluoro- or trifluoromethyl-substituted phenyl)ethylamine is produced with high optical purity and in an industrially simple and efficient manner by asymmetrically reducing an optically active imine, obtained by dehydration and condensation of a fluoro- or trifluoromethyl-substituted phenylmethyl ketone and an optically active primary amine under acidic conditions, using a hydride reducing agent to convert to an optically active secondary amine, and subjecting the secondary amine or its salt of an inorganic acid or organic acid to hydrogenolysis. In addition, an optically active 1-(fluoro- or trifluoromethyl-substituted phenyl)ethylamine is purified to an even higher optical purity in an industrially simple and efficient manner by converting the optically active secondary amine of the synthetic intermediate obtained by asymmetric reduction, or an optically active 1-(3,5-bis-trifluoromethylphenyl)ethylamine, one of the target compounds, to an inorganic or organic acid salt followed by recrystallization purification. This ethylamine is an important intermediate of pharmaceuticals and agricultural chemicals.

摘要翻译： 以光学纯度高的光学活性的1-（氟代或三氟甲基取代的苯基）乙胺，以工业上简单有效的方式，通过不对称地还原通过氟 - 或三氟甲基取代的脱水和缩合得到的光学活性亚胺 苯甲基酮和光学活性伯胺在酸性条件下，使用氢化物​​还原剂转化成光学活性仲胺，并使无机酸或有机酸的仲胺或其盐进行氢解。 此外，通过将通过不对称还原得到的合成中间体的光学活性仲胺转化成光学活性的1-（氟代或三氟甲基取代的苯基）乙胺，以工业简单且有效的方式纯化至更高的光学纯度，或 光学活性的1-（3,5-双三氟甲基苯基）乙胺，一种目标化合物，与无机或有机酸盐接着重结晶纯化。 该乙胺是药物和农药的重要中间体。

公开(公告)号：US06639100B2

公开(公告)日：2003-10-28

申请号：US10212840

申请日：2002-08-07

申请人： Akihiro Ishii ,  Masatomi Kanai ,  Takashi Hayami ,  Katsuyoshi Shibata ,  Masaki Matsui ,  Kazumasa Funabiki ,  Yokusu Kuriyama ,  Manabu Yasumoto

发明人： Akihiro Ishii ,  Masatomi Kanai ,  Takashi Hayami ,  Katsuyoshi Shibata ,  Masaki Matsui ,  Kazumasa Funabiki ,  Yokusu Kuriyama ,  Manabu Yasumoto

IPC分类号： C07C6963

CPC分类号： C07C69/675 ,  C07B2200/07 ,  C07C29/143 ,  C07C45/516 ,  C07C45/78 ,  C07C45/81 ,  C07C49/82 ,  C07C49/84 ,  C07C31/42

摘要： A process for producing an optically active perfluoroalkylcarbinol by reacting an optically active imine with a hemiacetal or hydrate of a perfluoroalkylaldehyde to obtain a condensate, and hydrolyzing the condensate under acidic conditions. Optical purity of optically active 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone compounds may be increased by precipitating and removing a racemic crystal, and also recrystallizing the compound. Novel compounds include optically active and inactive 4,4,4-trifluoro-3-hydroxybutanoic aryl esters. A process for producing optically active or incactive 4,4,4-trifluoro-3-hydroxybutyric acid aryl esters includes oxidizing an optically active or inactive 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone. Optical purity of optically active aryl esters may be increased by recrystallization. Optically active 4,4,4-trifluoro-1,3-butanediol may be produced by reducing the optically active aryl ester with a hydride. Optically active or inactive 4,4,4-trifluoro-3-hydroxybutyric acid alkyl esters are produced by reacting optically active or inactive aryl esters with lower alcohols under acid conditions.

摘要翻译： 通过使光学活性亚胺与全氟烷基醛的半缩醛或水合物反应得到缩合物，并在酸性条件下水解缩合物，制备光学活性全氟烷基甲醇的方法。 光学活性的4,4,4-三氟-3-羟基-1-芳基-1-丁酮化合物的光学纯度可以通过沉淀和除去外消旋晶体而增加，也可以使化合物重结晶。 新型化合物包括光学活性和无活性的4,4,4-三氟-3-羟基丁酸芳酯。 制备光学活性或不活泼的4,4,4-三氟-3-羟基丁酸芳基酯的方法包括氧化光学活性或无活性的4,4,4-三氟-3-羟基-1-芳基-1-丁酮。 光学活性芳基酯的光学纯度可通过重结晶而增加。 可以通过用氢化物还原光学活性芳基酯来制备光学活性的4,4,4-三氟-1,3-丁二醇。 光学活性或无活性的4,4,4-三氟-3-羟基丁酸烷基酯是通过在酸性条件下使光学活性或惰性芳基酯与低级醇反应来制备的。