公开(公告)号：JPH0987255A

公开(公告)日：1997-03-31

申请号：JP19017396

申请日：1996-07-19

Applicant: TORAY INDUSTRIES

Inventor： FUJINO TOSHIHIRO ,  SATOU HARUYO

IPC: C07D241/04 ,  B01J23/04 ,  B01J31/02 ,  C07B55/00 ,  C07B61/00

Abstract: PROBLEM TO BE SOLVED: To efficiently racemize an optically active 2-piperazinecarboxylic acid derivative, racemize an unnecessary optical antipode formed as a by-product in optical resolution and enable the recycling thereof as a raw material for the optical resolution by heating the 2-piperazinecarbxylic acid derivative in the presence of a base. SOLUTION: An optically active 2-piperazinecarboxylic acid is heated in the coexistence of a base (preferably an alkali metallic hydroxide, etc.), preferably at 0-150 deg.C. For example, compounds of formulas I to III (R , R , R and R are H, a 1-10C alkyl, etc.; R is H, an aryl, etc.; R and R are each H, a 1-10C straight-chain alkyl, etc.; R and r are each H, a halogen-substituted aralkyl, etc.) are cited as the optically active 2-piperazinecarboxylic acid derivative and, among them, optically active N-tert-butyl-2-piperazinecarboxamide is preferred. The racemizing reaction is preferably carried out in an inert organic solvent such as benzene. The base is used in an amount of preferably 1-200mol% based on the optically active 2-piperazinecarboxylic acid derivative.

公开(公告)号：JPH0971576A

公开(公告)日：1997-03-18

申请号：JP22894295

申请日：1995-09-06

Applicant: TORAY INDUSTRIES

Inventor： NAKAI SAKIE ,  SATOU HARUYO ,  IWATA SHIHO

IPC: C07D307/24 ,  C07C27/02 ,  C07C51/02 ,  C07C67/14 ,  C07D309/08

Abstract: PROBLEM TO BE SOLVED: To isolate carboxylic acid or its ester which is useful as an intermediate for medicines or as a starting material for liquid crystal in high purity and high yield by bringing a salt of carboxylic acid into contact with a hydrogen halide to effect salt dissolution in a substantially water-free (anhydrous) organic solvent. SOLUTION: Preferably, in an alcohol solvent or in at least one of organic solvent selected from ethers, halogenated hydrocarbons and hydrocarbons containing an alcohol, (A) a salt of carboxylic acid (a salt of tetrahydrofrancarboxylic acid or tetrahydropyranecarboxylic acid with an alkali metal ion, an alkaline earth metal ion or an organic amine) is brought into contact with (B) a hydrogen halide such as hydrogen chloride, hydrogen bromide or hydrogen iodide to dissolve the salt to give the objective carboxylic acid or its ester. The component A is preferably brought into contact with the component B at 0 deg.C-50 deg.C. The amount of the organic solvent is preferably 0.5-20 times, more preferably 1-10 times the component A in weight.

公开(公告)号：JPH07188121A

公开(公告)日：1995-07-25

申请号：JP33118293

申请日：1993-12-27

Applicant: TORAY INDUSTRIES

Inventor： SATOU HARUYO ,  NAKAI SAKIE

IPC: C07B57/00 ,  C07C59/255 ,  C07C209/86 ,  C07C211/36

Abstract: PURPOSE:To produce optically active trans-DACH by an industrially suitable process from a mixture containing cis-DACH and trans-DACH and available as an inexpensive industrial raw material. CONSTITUTION:An optically active trans-1,2-diaminocyclohexane is produced by the direct optical resolution of a mixture containing trans-1,2- diaminocyclohexane and cis-1,2-diaminocyclohexane in an aqueous solvent. The optical resolution is carried out by adding D or L-tartaric acid as a resolution agent and separating an optically active tartaric acid salt of an optically active trans-1,2-diaminocyclohexane in the form of crystal.

公开(公告)号：JPH07188097A

公开(公告)日：1995-07-25

申请号：JP33118593

申请日：1993-12-27

Applicant: TORAY INDUSTRIES

Inventor： NAKAI SAKIE ,  SATOU HARUYO

IPC: C07B57/00 ,  C07C51/487 ,  C07C59/255 ,  C07C209/88 ,  C07C211/11 ,  C07C211/27 ,  C07C211/36

Abstract: PURPOSE:To provide a method for recovering optically active tartaric acid from a diastereomer salt obtained by optical resolution, suitable for industrial production. CONSTITUTION:In subjecting a racemic amine to optical resolution by using optically active tartaric acid as a resolving agent, in recovering optically active tartaric acid from the prepared optically active amine.optically active tartaric acid, an inorganic alkali is brought into contact with the optically active amine.optically active tartaric acid in an alcohol solution to provide a method for recovering optically active tartaric acid as an inorganic alkali salt of optically active tartaric acid. High-purity optically active tartaric acid can be recovered from a diastereomer salt obtained by the optical resolution and the recovered optically active tartaric acid can be recycled.

公开(公告)号：JPH0776571A

公开(公告)日：1995-03-20

申请号：JP22334793

申请日：1993-09-08

Applicant: TORAY INDUSTRIES

Inventor： ONO TAKAE ,  SATOU HARUYO

IPC: C07C403/20

Abstract: PURPOSE:To carry out efficient isolation of abscisic acid in a high yield from a dilute solution containing abscisic acid using a reduced amount of the solvent. CONSTITUTION:The isolation process for abscisic acid comprises the extraction step of bringing the aqueous abscisic acid into contact with an organic solvent immiscible with water to transfer the abscisic acid into the organic solvent, the concentration step of concentrating the separated organic layer containing abscisic acid into abscisic acid and the organic solvent, the recycling step of recycling the organic layer separated in the concentration step to the extraction step, and the isolation step of crystallizing out abscisic acid from the concentrated solution. The isolated abscisic acid lowers the purification load thereafter to give ABA of high purity inexpensively in an industrial scale.

公开(公告)号：JPH06107603A

公开(公告)日：1994-04-19

申请号：JP26042492

申请日：1992-09-30

Applicant: TORAY INDUSTRIES

Inventor： NAKAI SAKIE ,  SATOU HARUYO

IPC: C07B57/00 ,  C07C209/88 ,  C07C211/27 ,  C07C213/10 ,  C07C217/58

Abstract: PURPOSE:To obtain an optically active 1-phenylethylamine by carrying out the optical resolution of an (RS)-1-phenylethylamine derivative using a resolution agent consisting of a specific optically active substance having extremely high chemical stability and producible from an inexpensive raw material in high yield. CONSTITUTION:An (RS)-1-phenylethylamine derivative of formula II (R is methyl or methoxy) is made to contact with a resolution agent selected from an optically active N-formylphenylglycine and an optically active tartaric acid anilide derivative of formula I (R is Cl or nitro) in a solvent to form a diastereomer salt. A solution containing the diastereomer salt is cooled or concentrated to crystallize the scarcely soluble diastereomer salt. The remaining mother liquor is cooled or concentrated to crystallize the remaining easily soluble diastereomer salt. Since the resolution agent used in the above process has extremely high chemical stability, it can be recovered from the diastereomer salt solution in high yield without causing the racemization of the agent. The process is excellent in yield and optical purity.

公开(公告)号：JPH04128270A

公开(公告)日：1992-04-28

申请号：JP28467690

申请日：1990-10-22

Applicant: TORAY INDUSTRIES

Inventor： NAKAI SAKIE ,  SATOU HARUYO ,  FUJIKAWA KAZUHIRO

IPC: C07D241/04 ,  C07B57/00 ,  C07C229/24 ,  C07C233/47 ,  C07C311/19

Abstract: PURPOSE:To readily obtain the subject compound useful as an intermediate for synthesis of medical drugs such as a quinolone-based antibacterial agent in high yield at a low cost by optically dissolving (RS)-2-methylpiperazine using an optically active N-substituted dicarboxylic acid. CONSTITUTION:An optically active N-substituted dicarboxylic acid represented by the formula ((n) is 1-2; R is acetyl, benzoyl, benzenesulfonyl or p- toluenesulfonyl) is used as an optical resolution agent and brought into contact with (RS)-2-methylpiperazine in a solvent such as methanol. The resultant mixture solution is subsequently cooled and/or concentrated to deposit sparingly soluble diastereomer salts and the residual mother liquid is cooled after concentration or without any treatment to deposit readily soluble diastereomer salts. As the N-substituted dicarboxylic acid as the resolution agent, N-acetylglutamic acid, etc., are exemplified and used in an amount of 0.1-1.5mol based on 1mol (RS)-2-methylpiperizine.

公开(公告)号：JPH0413670A

公开(公告)日：1992-01-17

申请号：JP11949490

申请日：1990-05-08

Applicant: TORAY INDUSTRIES

Inventor： NAKAI SAKIE ,  SATOU HARUYO

IPC: C07D241/04

Abstract: PURPOSE:To carry out optical resolution of (RS)-2-methylpiperazine in high yield and optical purity with an extremely simple procedure by using D- camphoric acid as a resolution agent. CONSTITUTION:(RS)-2-methylpiperazine is brought into contact with 0.1-2.0mol of D-camphoric acid (based on 1mol of the methylpiperazine) in a solvent (e.g. water or methanol) optionally in the presence of a mineral acid or organic acid. The system is cooled and/or concentrated to crystallize a scarcely soluble diastereomer salt. The remaining mother liquor is used as it is or concentrated and/or cooled to precipitate and separate an easily soluble diastereomer salt. Each diastereomer salt obtained by the above process is decomposed into the resolution agent and (R)-2-methylpiperazine or (S)-2-methylpiperazine and the objective compound is separated and collected.

公开(公告)号：JPH02306943A

公开(公告)日：1990-12-20

申请号：JP12823389

申请日：1989-05-22

Applicant: TORAY INDUSTRIES

Inventor： HASEGAWA SAKIE ,  SATOU HARUYO

IPC: C07C209/88 ,  C07C211/29

Abstract: PURPOSE:To easily obtain the subject compound having high optical purity and useful as an optical resolution agent for racemic acids in high yield by carrying out optical resolution using an optically active N-acetylmethionine as a resolution agent. CONSTITUTION:1Mol of (RS)-1-(p-bromophenyl)ethylamine is brought into contact with 0.1-2.0mol of an optically active (D)- or (L)-Nacetylmethionine as a resolution agent in a solvent (e.g. water or lower alcohol) at 0-80 deg.C to effect the optical resolution of the raw material. The obtained solution is cooled and/or concentrated to crystallize the scarcely soluble diastereomer salt, which is easily separated by a solid-liquid separation means such as filtration to obtain the objective compound. The resolution agent can be easily recovered by treating the diastereomer salt with an acid and alkali and the recovered optically active N-acetylmethionine can be reused.

公开(公告)号：JPH0232046A

公开(公告)日：1990-02-01

申请号：JP18008588

申请日：1988-07-19

Applicant: TORAY INDUSTRIES

Inventor： HASEGAWA SAKIE ,  SATOU HARUYO ,  KATO TETSUYA ,  KOYAMA YOSHIHIRO

IPC: C07C209/88 ,  C07B57/00 ,  C07C67/00 ,  C07C209/00 ,  C07C211/27

Abstract: PURPOSE:To easily perform the optical resolution of (RS)-1-methyl-3- phenylpropylamine via a diastereomer salt in high optical purity and yield by using an optically active cis-2-benzamide cyclohexanecarboxylic acid as a resolution agent. CONSTITUTION:An optically active 1-methyl-3-phenylpropylamine useful as an intermediate for a drug such as beta-blocker can be easily produced in high yield and optical purity by using an optically active cis-2-benzamide cyclohexanecarboxylic acid as a resolution agent, forming two kinds of diastereomer salts of said resolution agent and (RS)-1-methyl-3-phenylpropylamine and carrying out the optical resolution of the (RS)-1-methyl-3-phenylpropylamine taking advantage of the solubility difference between said two kinds of diastereomer salts. The resolution agent can be easily recovered and reused by treating the diastereomer salt with an acid or alkali.