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WO1997043256A1 - Procede de preparation de 3-hydroxypyrrolidine - Google Patents

Procede de preparation de 3-hydroxypyrrolidine Download PDF

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Publication number
WO1997043256A1
WO1997043256A1 PCT/JP1997/001620 JP9701620W WO9743256A1 WO 1997043256 A1 WO1997043256 A1 WO 1997043256A1 JP 9701620 W JP9701620 W JP 9701620W WO 9743256 A1 WO9743256 A1 WO 9743256A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxypyrrolidine
hydroxy
compound
proline
iii
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1997/001620
Other languages
English (en)
Japanese (ja)
Inventor
Katsumi Takahashi
Shin-Ichiro Mohri
Takehiro Ogasa
Masaji Kasai
Yasuyuki Ono
Toru Sugaya
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KH Neochem Co Ltd
Original Assignee
Kyowa Hakko Kogyo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyowa Hakko Kogyo Co Ltd filed Critical Kyowa Hakko Kogyo Co Ltd
Priority to AU27882/97A priority Critical patent/AU2788297A/en
Publication of WO1997043256A1 publication Critical patent/WO1997043256A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/12—Oxygen or sulfur atoms

Definitions

  • the present invention relates to a method for producing optically active 3- (R) -hydroxypyrrolidine useful as a raw material for medicines, agricultural chemicals and the like.
  • Japanese Patent Publication No. 110452/1990 discloses a method of performing a decarboxylation reaction using trans-14-hydroxy-1-L-proline as a starting material to obtain 3- (R) -hydroxypyrrolidine in one step.
  • This method is a decarboxylation reaction using vinyl ketones as a catalyst, and offers a milder and safer method than the conventional decarboxylation method, but there is a problem in industrial application due to the specialty of the catalyst. .
  • An object of the present invention is to use cis-3-hydroxy-L-proline or trans-14-hydroxy L-proline as a starting material, and to prepare 3- (R) -hydrogen more easily than a conventional method without using a catalyst. It is to provide a method for producing xypyrrolidine.
  • Cis-3-hydroxy-1-L-proline is an isomer of trans-4-hydroxy-L-proline, and its industrial production method is described in JP-A-7-322885.
  • the present inventors have found that the cis-l-hydroxy-l-proline can be easily heated in an alcoholic solvent without adding any catalyst, and can be easily decarboxylated to give 3- (R) -hydroxyl in a high yield.
  • the inventors have paid attention to being converted into pyrrolidine, and have reached the present invention. This method is also applicable to trans-14-hydroxy-1-L-proline, and similarly, 3- (R) -hydroxypyrrolidine can be obtained.
  • the present invention relates to a compound of the formula (I) Or formula (II)
  • the decarboxylation reaction in the present invention is carried out in the presence or absence of a solvent, but is preferably carried out in the presence of an alcohol.
  • alcohols used in the reaction include alcohols having a boiling point of 120 ° C or more, such as octanol, hexanol, and cyclohexanol.
  • the reaction is preferably carried out after charging the starting materials and, if necessary, the solvent, preferably with nitrogen or acetonitrile. Heating and stirring are performed in an inert gas atmosphere such as rugon.
  • the reaction temperature any temperature of about 120 to 250 ° C is selected, and preferably around 140 to 160 ° C.
  • the product is isolated from the reaction mixture by, for example, precipitation as a hydrogen halide salt or by distillation, and if necessary, extraction, washing, drying, concentration, recrystallization, column chromatography, or column chromatography. It is purified by a purification method commonly used in organic synthetic chemistry such as chromatography.
  • hydrogen halide gas is directly blown into the reaction mixture, or an alcohol such as methanol, ethanol, isopropanol, octanol or the like containing hydrogen halide, or an organic compound such as ethyl acetate.
  • an alcohol such as methanol, ethanol, isopropanol, octanol or the like containing hydrogen halide, or an organic compound such as ethyl acetate.
  • the desired product is precipitated by adding a solvent.
  • 3- (R) -Hydroxypyrrolidine obtained according to the present invention can be used as a synthetic intermediate for certain antibacterial agents, antidepressants, bronchodilators, analgesics, antiarrhythmic agents, etc. [Heterocycle (Heterocycles), 26, 2247 (1987)].
  • trans-4-hydroxy-1-L-proline 20 mg was suspended in 1 ml of hexane, and the mixture was heated and stirred at about 156 ° C. in an argon atmosphere. After 6 hours, water and methanol were added to the reaction mixture to make a homogeneous solution, which was quantified by a high performance liquid chromatography internal standard method. As a result, the yield of the desired product was 4%, and the residual ratio of trans-4-hydroxy-L-phosphorus, which is a starting material, was 89%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyrrole Compounds (AREA)

Abstract

Procédé facilité et simplifié de préparation de 3-(R)-hydroxypyrrolidine (III), consistant à utiliser cis-3-hydroxy-L-proline (I) ou trans-4-hydroxy-L-proline (II) en tant que composé de départ et à réchauffer ce dernier sans catalyseur afin d'effectuer une décarboxylation.
PCT/JP1997/001620 1996-05-14 1997-05-14 Procede de preparation de 3-hydroxypyrrolidine Ceased WO1997043256A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU27882/97A AU2788297A (en) 1996-05-14 1997-05-14 Process for the preparation of 3-hydroxypyrrolidine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11912796 1996-05-14
JP8/119127 1996-05-14

Publications (1)

Publication Number Publication Date
WO1997043256A1 true WO1997043256A1 (fr) 1997-11-20

Family

ID=14753616

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1997/001620 Ceased WO1997043256A1 (fr) 1996-05-14 1997-05-14 Procede de preparation de 3-hydroxypyrrolidine

Country Status (2)

Country Link
AU (1) AU2788297A (fr)
WO (1) WO1997043256A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2862970A1 (fr) * 2003-11-28 2005-06-03 Oreal Procede de preparation de derives de 16(4-nitrophenyl)-3- pyrrolidinols optiquement actifs, et paraphenylenediamines a groupement pyrolidinyle chirales
WO2007011162A1 (fr) * 2005-07-20 2007-01-25 Chiroad Incorporate Procédé synthétique de préparation de (s)-3-hydroxypyrrolidine optiquement pure
US7223873B2 (en) 2004-03-30 2007-05-29 Daisco Co., Ltd Process for preparing amines
EP4382529A1 (fr) 2022-12-07 2024-06-12 Bayer Consumer Care AG Procédé de préparation de (3s)-pyrrolidin-3-ol pur et de chlorhydrate de (3s)-pyrrolidin-3-ol pur

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6023328A (ja) * 1983-07-19 1985-02-05 Sankyo Co Ltd 脱炭酸反応
JPH02111761A (ja) * 1988-10-20 1990-04-24 Kyowa Hakko Kogyo Co Ltd ウラシルの製造法
JPH03123779A (ja) * 1989-10-07 1991-05-27 Nippon Synthetic Chem Ind Co Ltd:The ５―（４―ピリジル）オキサゾールの製造方法
JPH03161462A (ja) * 1989-11-20 1991-07-11 Occidental Chem Corp ３，４，６―トリフルオロフタル酸無水物の脱炭酸による２，４，５―トリフルオロ安息香酸の調製
JPH05255204A (ja) * 1992-03-11 1993-10-05 Kanegafuchi Chem Ind Co Ltd アミン類の製造法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6023328A (ja) * 1983-07-19 1985-02-05 Sankyo Co Ltd 脱炭酸反応
JPH02111761A (ja) * 1988-10-20 1990-04-24 Kyowa Hakko Kogyo Co Ltd ウラシルの製造法
JPH03123779A (ja) * 1989-10-07 1991-05-27 Nippon Synthetic Chem Ind Co Ltd:The ５―（４―ピリジル）オキサゾールの製造方法
JPH03161462A (ja) * 1989-11-20 1991-07-11 Occidental Chem Corp ３，４，６―トリフルオロフタル酸無水物の脱炭酸による２，４，５―トリフルオロ安息香酸の調製
JPH05255204A (ja) * 1992-03-11 1993-10-05 Kanegafuchi Chem Ind Co Ltd アミン類の製造法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMISTRY LETTERS, No. 6, (1986), HASHIMOTO, MITSUNORI et al., "A Novel Decarboxylation of alpha-Amino Acids. A Facile Method of Decarboxylation by the Use of 2-Cyclohexen-1-One as a Catalyst", Refer to p. 893-896. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2862970A1 (fr) * 2003-11-28 2005-06-03 Oreal Procede de preparation de derives de 16(4-nitrophenyl)-3- pyrrolidinols optiquement actifs, et paraphenylenediamines a groupement pyrolidinyle chirales
EP1535904A3 (fr) * 2003-11-28 2005-07-13 L'oreal Procédé de préparation de dérives de 1- (4-nitrophényl)-3-pyrrolidinols optiquement actifs, et paraphénylenediamines à groupement pyrrolidinyle chirales
US7223873B2 (en) 2004-03-30 2007-05-29 Daisco Co., Ltd Process for preparing amines
WO2007011162A1 (fr) * 2005-07-20 2007-01-25 Chiroad Incorporate Procédé synthétique de préparation de (s)-3-hydroxypyrrolidine optiquement pure
US7652152B2 (en) 2005-07-20 2010-01-26 Chiroad Incorporate Synthetic method of optically pure (S)-3-hydroxypyrrolidine
EP4382529A1 (fr) 2022-12-07 2024-06-12 Bayer Consumer Care AG Procédé de préparation de (3s)-pyrrolidin-3-ol pur et de chlorhydrate de (3s)-pyrrolidin-3-ol pur
WO2024121219A1 (fr) 2022-12-07 2024-06-13 Bayer Consumer Care Ag Procédé de préparation de (3s)-pyrrolidin-3-ol pur et de chlorhydrate de (3s)-pyrrolidin-3-ol pur

Also Published As

Publication number Publication date
AU2788297A (en) 1997-12-05

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