WO2000039071A1 - Procede de production de l-erythro-(1r, 2s)-2-amino-1-phenylpropan-1-ol - Google Patents
Procede de production de l-erythro-(1r, 2s)-2-amino-1-phenylpropan-1-ol Download PDFInfo
- Publication number
- WO2000039071A1 WO2000039071A1 PCT/JP1999/007206 JP9907206W WO0039071A1 WO 2000039071 A1 WO2000039071 A1 WO 2000039071A1 JP 9907206 W JP9907206 W JP 9907206W WO 0039071 A1 WO0039071 A1 WO 0039071A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- compound
- amino
- represented
- catalytic reduction
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Definitions
- the present invention provides a method for stereoselectively producing L-erythro (1R, 2S) -2-amino-1-phenylpropane-1-ol from L- (R) -phenylacetylcarpinol.
- L-erythro (1R, 2S) -2-amino-1-phenylpropane-1-ol from L- (R) -phenylacetylcarpinol.
- L-wellis (1R, 2S) -2-amino-11-phenylpropane-11-ol is used as an optical resolving agent and a chiral auxiliary in asymmetric synthesis.
- An object of the present invention is to convert L-erythro- (1R, 2S) -2-amino-1-phenylpropane-1-1-ol into a steric compound using L-erythro (R) -phenylacetylcarbinol as a raw material. It is to provide a method for selective manufacture.
- N-aralkyl group of L-elislow (1 R, 2 S)-2- (N-aralkylamino)-1-phenylpropane-l-ol is catalytically hydrogenated and finally (IV):
- the present invention relates to a method for reductive amination of L- (R) -phenylacetylcarbinol represented by the formula (I) with a primary aralkylamine represented by the formula ⁇ under catalytic reduction conditions to obtain a compound represented by the formula L-Erythro (1R, 2S) shown by (III) (L-alkylamino) -l-phenylpropane-l-ol is successively subjected to catalytic reduction to remove the N-aralkyl group by hydrogenolysis. It is intended to provide a method for producing 1- (1R, 2S) -2-amino-11-phenylpropane-11-all. BEST MODE FOR CARRYING OUT THE INVENTION
- a compound of formula (II) is reacted with a compound of formula (II) in a hydrogen atmosphere in a suitable solvent in the presence of a catalytic reduction catalyst. Can be obtained.
- L- (R) -phenylacetylcarbinol represented by the formula (I) is a known substance.
- DHG Crout et al. J. Chem. So Chem. Commun. 1993, 341
- It can be prepared according to the method.
- Aryl groups include phenyl and naphthyl, etc., which may be anywhere in any number of lower alkyl groups such as methyl, ethyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or any It may be substituted by a number of lower alkoxy groups such as methoxy, ethoxy, isopropoxy and the like.
- Preferred as compounds of formula (11) are unsubstituted primary aralkylamines, most preferred is benzylamine.
- the compound of the formula (I) and the compound of the formula (II) can be used in a molar ratio of 1.2: 1 to 1: 5, and a preferable molar ratio is 1.1: 1 to 1: 1.5. is there.
- the hydrogen pressure may be in the range of 1 to 5 O kg m 2 , preferably in the range of 2 to 30 kg / cm 2 .
- the solvent used may be any solvent that does not hinder the progress of the reaction. Alcohol solvents are preferred, with lower alcohols such as methanol, ethanol, propanol, 2-propanol and butanol being preferred. Most preferred solvents are methanol and ethanol.
- the amount of the solvent used is 1.5 to 50 times (volume / weight), preferably 5 to 4 times, relative to the compound of the formula (I). It is 0 times.
- the catalytic reduction catalyst may be any catalyst that causes reductive amination. Platinum catalysts are preferred, and Pt / C, pto 2 and the like can be used.
- the catalyst may be used in an amount of 1 to 30% (weight / weight), preferably 5 to 20%, based on the compound of the formula (I).
- the reaction can be carried out in a temperature range from 0 ° C to 150 ° C, with a preferred temperature range from 0 ° C to 50 ° C.
- the reaction time is 10 minutes to 10 hours, preferably 1 hour to 8 hours.
- the acid used for this purpose may be any as long as it provides a crystalline salt suitable for such purification, but an inorganic acid is preferred, and hydrochloric acid is most preferred.
- any solvent can be used as long as it gives such a purification effect, but a lower alcohol-based solvent such as methanol, ethanol, propanol, or 2-propanol is preferable. More preferably 2-prono. It is Knoll.
- the recrystallization temperature is not particularly limited as long as the desired purification is achieved, but is in the range of ⁇ 30 ° C. to the boiling point of the solvent used, preferably in the range of 0 ° C. to 80 ° C. is there.
- the salt purified by recrystallization is treated with an aqueous solution of Arikari according to a conventional method, and the pure compound represented by the formula (III) can be isolated as a free amine.
- the compound of formula (IV) can be obtained by subjecting the compound of formula ( ⁇ ) to hydrogenolysis of an N-aralkyl group in a hydrogen atmosphere in a suitable solvent in the presence of a catalytic reduction catalyst. .
- the hydrogen pressure may be in the range of 1 to 5 Okg m 2 , preferably in the range of 1 to 30 kg / cm 2 .
- Any solvent may be used as long as it does not hinder the progress of the reaction. Is also good. Alcohol solvents are preferred, with lower alcohols such as methanol, ethanol, propanol, 2-propanol and butanol being preferred. Most preferred solvents are methanol and ethanol.
- the amount of the solvent used is 1.5 to 50 times (volume / weight), preferably 5 to 50 times, relative to the compound of the formula (III).
- the catalytic reduction catalyst may be any catalyst that causes hydrogenolysis. Palladium-based catalysts are preferred, and Pd / C, Pd (OH) 2 / C and the like can be used.
- the catalyst may be used in an amount of 0.5 to 40% (weight / weight), preferably 5 to 30%, based on the compound of the formula ( ⁇ ).
- the reaction can be carried out in a temperature range from 0 ° C. to 150 ° C., but a preferred temperature range is from 0 ° C. to 50 ° C.
- the reaction time is 10 minutes to 10 hours, preferably 1 hour to 8 hours.
- the compound of formula (IV) thus obtained can be purified, if necessary, as a crystalline salt by the method described below.
- the compound of the formula (I) is directly reacted with the compound of the formula (II) in a hydrogen atmosphere in a suitable solvent in the presence of a suitable catalytic reduction catalyst.
- a compound of formula (IV) can be obtained.
- the hydrogen pressure may be in the range of 1 to 50 kg / cm 2 , preferably in the range of 2 to 30 kg / cm 2 .
- the solvent used may be any solvent that does not hinder the progress of the reaction. Alcohol solvents are preferred, with lower alcohols such as methanol, ethanol, propanol, 2-propanol and butanol being preferred. Most preferred solvents are methanol and ethanol.
- the amount of the solvent used is 1.5 to 50 times (volume / weight), preferably 5 to 20 times, the compound of the formula (I).
- the catalytic reduction catalyst in this case may be any catalyst capable of causing both reductive amination and hydrogenolysis. Palladium catalysts are preferred, and Pd / C, Pd (OH) 2 / C and the like can be used.
- the catalyst may be used in an amount of 0.5 to 40% (w / w) based on the compound of the formula (I), preferably Use in an amount of 3 to 30%.
- the above-mentioned catalytic reduction catalyst may be separately charged during the reductive amination reaction and the hydrogenolysis reaction. By introducing the catalyst in this manner, the amount of the entire catalyst used can be reduced as compared with the case where the entire catalyst is charged during the reductive amination reaction.
- the reaction can be carried out in a temperature range from 0 ° C to 150 ° C, but a preferred temperature range is from 0 ° C to 60 ° C.
- the reaction time is 10 minutes to 10 hours, preferably 1 hour to 8 hours.
- the acid used for this purpose may be any as long as it provides a crystalline salt suitable for such purification, but an inorganic acid is preferred, and sulfuric acid is most preferred in terms of purification efficiency. is there.
- the solvent used for the recrystallization may be any solvent as long as it provides such a purification effect, and a mixture of a plurality of solvents may be used.
- Preferred solvents are lower alcohol solvents such as methanol, ethanol, propanol and 2-propanol.
- a more preferred solvent is a mixed solvent of a lower alcohol and water, and a most preferred solvent is a mixed solvent of methanol and water.
- the temperature of the recrystallization is not particularly limited as long as the desired purification is achieved, but is in a range from ⁇ 20 ° C. to the boiling point of the solvent used, preferably from 0 ° C. to 60 ° C. Range.
- the Eris mouth Z threo ratio was indicated by the area ratio of HP LC (high performance liquid chromatography) analysis or GLC (gas-liquid mouth chromatography) analysis.
- the optical purity was shown by the enantiomeric excess (% ee).
- Example 1 L-Ellis port one (1 R, 2 S) - 2- (N- Benjiruamino) one 1-off Enirupurono ⁇ 0 down one 1 one-ol
- Carrier gas He Flow rate: 5.0 mL / min
- the method of the present invention is superior in terms of stereoselectivity as compared with the conventional method, and can efficiently convert L- (R) -phenylacetylcarbinol into L-Eris (1R, 2S) — Can be converted to 2-amino-1-phenylpropane.
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU17982/00A AU1798200A (en) | 1998-12-24 | 1999-12-22 | Process for producing l-erythro-(1r,2s)-2-amino-1-phenylpropan-1-ol |
EP99961308A EP1142864A4 (en) | 1998-12-24 | 1999-12-22 | PROCESS FOR PRODUCING L-ERYTHRO- (1R, 2S) -2-AMINO-1-PHENYLPROPAN-1-OL |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10/367339 | 1998-12-24 | ||
JP36733998 | 1998-12-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000039071A1 true WO2000039071A1 (fr) | 2000-07-06 |
Family
ID=18489067
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1999/007206 WO2000039071A1 (fr) | 1998-12-24 | 1999-12-22 | Procede de production de l-erythro-(1r, 2s)-2-amino-1-phenylpropan-1-ol |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1142864A4 (ja) |
AU (1) | AU1798200A (ja) |
WO (1) | WO2000039071A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1421055A1 (en) * | 2001-08-28 | 2004-05-26 | Polychip Pharmaceuticals Pty. Ltd. | Methods for the synthesis of amines such as ephedrine and intermediates |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7408084B2 (en) | 2002-06-11 | 2008-08-05 | Kaneka Corporation | Process for producing optically active β-amino alcohol |
ES2328502T3 (es) | 2004-04-15 | 2009-11-13 | Emmellen Biotech Pharmaceuticals Limited | Procedimiento para la preparacion de 1-eritro-2-amino-1-fenil-1-propanol optimamente activo. |
JP2009106923A (ja) * | 2007-10-29 | 2009-05-21 | Emmellen Biotech Pharmaceuticals Ltd | 接触水素化方法及びそのための新規触媒 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4533172B1 (ja) * | 1967-04-01 | 1970-10-26 |
-
1999
- 1999-12-22 AU AU17982/00A patent/AU1798200A/en not_active Abandoned
- 1999-12-22 WO PCT/JP1999/007206 patent/WO2000039071A1/ja not_active Application Discontinuation
- 1999-12-22 EP EP99961308A patent/EP1142864A4/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4533172B1 (ja) * | 1967-04-01 | 1970-10-26 |
Non-Patent Citations (7)
Title |
---|
CHEMICAL ABSTRACTS, vol. 108, no. 15, 11 April 1988, Columbus, Ohio, US; abstract no. 131150V, SUBRAMANIAN PREMA M.: "Synthesis of (1RS,2SR)-(+/-)-2-amino-1-phenyl-2-propanone" page 692; column 1; XP002926457 * |
CHEMICAL ABSTRACTS, vol. 113, no. 11, 10 September 1990, Columbus, Ohio, US; abstract no. 97101W, JACKSON W. ROY: "Stereoselective synthese of ephedrine and related 2-amino alcohols of high optical purity from protected cyanohydrins" page 662; column 1; XP002926456 * |
CHEMICAL ABSTRACTS, vol. 124, no. 21, 20 May 1996, Columbus, Ohio, US; abstract no. 288979A, SUBRAMANIAN: "Fermentation of benzaldehyde and urea and molasses followed by catalytic reductive amination" page 1287; column 2; XP002926455 * |
J. CHEM. TECHNOL. BIOTECHNOL., vol. 39, no. 4, 1987, pages 215 - 218 * |
JACKSON W. ROY: "Applications of Optically Active Aryl Cyanohydrins in the Synthesis of alpha-Hydroxy Aldehydes, alpha-Hydroxy Ketones and beta-Hydroxy Amines", AUST. J. CHEM., 1990, pages 2045 - 2062, XP002926454 * |
See also references of EP1142864A4 * |
TETRAHEDRON LETTERS, vol. 31, no. 10, 1990, pages 1447 - 1450 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1421055A1 (en) * | 2001-08-28 | 2004-05-26 | Polychip Pharmaceuticals Pty. Ltd. | Methods for the synthesis of amines such as ephedrine and intermediates |
EP1421055A4 (en) * | 2001-08-28 | 2005-01-19 | Polychip Pharmaceuticals Pty | METHODS OF SYNTHESIZING AMINES, SUCH AS EPHEDRINE AND INTERMEDIATES |
US7176332B2 (en) | 2001-08-28 | 2007-02-13 | Victoria University Of Technology | Methods for the synthesis of amines such as ephedrine and intermediates |
Also Published As
Publication number | Publication date |
---|---|
AU1798200A (en) | 2000-07-31 |
EP1142864A1 (en) | 2001-10-10 |
EP1142864A4 (en) | 2003-06-25 |
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