WO1995023805B1 - Process for preparing [l]- or [d]-homoalanin-4-yl-(methyl)phosphinic acid and its salts by racemic resolution - Google Patents
Process for preparing [l]- or [d]-homoalanin-4-yl-(methyl)phosphinic acid and its salts by racemic resolutionInfo
- Publication number
- WO1995023805B1 WO1995023805B1 PCT/EP1995/000682 EP9500682W WO9523805B1 WO 1995023805 B1 WO1995023805 B1 WO 1995023805B1 EP 9500682 W EP9500682 W EP 9500682W WO 9523805 B1 WO9523805 B1 WO 9523805B1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- salt
- salts
- homoalanin
- methyl
- Prior art date
Links
- 150000003839 salts Chemical class 0.000 title claims abstract 22
- 239000011780 sodium chloride Substances 0.000 title claims abstract 22
- GQZXNSPRSGFJLY-UHFFFAOYSA-N Hypophosphorous acid Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 claims abstract 7
- 235000001258 Cinchona calisaya Nutrition 0.000 claims abstract 3
- 241000434299 Cinchona officinalis Species 0.000 claims abstract 3
- 229960000948 Quinine Drugs 0.000 claims abstract 3
- 150000001413 amino acids Chemical class 0.000 claims abstract 3
- 125000005842 heteroatoms Chemical group 0.000 claims abstract 3
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims 22
- 125000003172 aldehyde group Chemical group 0.000 claims 4
- BCDIWLCKOCHCIH-UHFFFAOYSA-N Methylphosphinic Acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 claims 3
- 239000003960 organic solvent Substances 0.000 claims 3
- FLJXIBHYDIMYRS-UHFFFAOYSA-N 3,5-Dinitrosalicylaldehyde Chemical compound OC1=C(C=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O FLJXIBHYDIMYRS-UHFFFAOYSA-N 0.000 claims 2
- 150000001299 aldehydes Chemical class 0.000 claims 2
- 235000001014 amino acid Nutrition 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 150000007524 organic acids Chemical class 0.000 claims 2
- 235000005985 organic acids Nutrition 0.000 claims 2
- 239000011877 solvent mixture Substances 0.000 claims 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N t-BuOH Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000003797 alkaloid derivatives Chemical class 0.000 claims 1
- 229930013930 alkaloids Natural products 0.000 claims 1
- 150000001371 alpha-amino acids Chemical class 0.000 claims 1
- 235000008206 alpha-amino acids Nutrition 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- KMPWYEUPVWOPIM-CFGMGRTJSA-N (S)-[(2R,4S,5S)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-quinolin-4-ylmethanol Chemical compound C1=CC=C2C([C@@H]([C@@H]3N4CC[C@H]([C@@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-CFGMGRTJSA-N 0.000 abstract 1
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N Glufosinate Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000001376 precipitating Effects 0.000 abstract 1
Abstract
The title compounds are obtained by racemic resolution of D, L-homoalanin-4-yl-(methyl)phosphinic acid by precipitating out one of the diastereomeric salts with chiral bases such as quinine or cinchonine. The yield of desired enantiomers can be increased by transformed racemic resolution, the diastereomeric salt being precipitated when the undesired enantiomer is racemised in the presence of (hetero)aromatic aldehydes. The racemisation method is also suitable for optically active amino acids having other structures.
Claims
1. Verfahren zur Herstellung von [L]-Homoalanin-4-yl-(methyl)phosphinsäure (L-Säure) und deren Salzen1. Process for the preparation of [L] -Homoalanin-4-yl- (methyl) phosphinic acid (L-acid) and its salts
H 3 C - b ) 
oder von [D]-Homoalanin-4-yl-(methyl)phosphinsäurβ (D-Säure) und deren Salzen aus racemischer [DL]-Homoalanin-4-yl-(methyl)phosphinsäure (DL-Säure) oder deren Salzen durch Racematspaltung, dadurch gekennzeichnet, daß man a) DL-Säure oder deren Salz mit einer chiralen Base umsetzt, b) aus einer Lösung des erhaltenen Gemischs der diastereomeren Salze aus D-Säure, L-Säure und der chiralen Base in einem wäßrigen oder wäßrig¬ organischen Lösungsmittel, in welchem das Salz der D-Säure bzw. L-Säure eine höhere Löslichkeit als das Salz der L-Säure bzw. D-Säure aufweist, das Salz der L-Säure bzw. D-Säure und der chiralen Base auskristallisieren läßt (Racematspaltung) und c) im Falle, daß die freie L-Säure bzw. D-Säure hergestellt wird, das erhaltene Salz mit einer Säure neutralisiert oder, im Falle, daß ein anderes Salz als das nach b) erhaltene hergestellt wird, eine Umsalzung durchführt.H 3 C - b ) or of [D] -homoalanin-4-yl- (methyl) phosphinic acid (D-acid) and its salts of racemic [DL] -homoalanin-4-yl- (methyl) phosphinic acid (DL-acid) or salts thereof by racemate resolution , a) characterized in that a) DL acid or its salt is reacted with a chiral base, b) from a solution of the resulting mixture of the diastereomeric salts of D acid, L acid and the chiral base in an aqueous or aqueous organic Solvent in which the salt of D-acid or L-acid has a higher solubility than the salt of L-acid or D-acid, crystallizes the salt of L-acid or D-acid and the chiral base ( Racemate resolution) and c) in the case that the free L-acid or D-acid is prepared, the resulting salt is neutralized with an acid or, in the case that a salt other than that obtained according to b) is prepared, performs a salination ,
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man L-Säure oder deren Salze hergestellt.2. The method according to claim 1, characterized in that one produces L-acid or its salts.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man als chirale Base Chinin verwendet.3. The method according to claim 2, characterized in that one uses quinine as the chiral base.
4. Verfahren nach Anspruch 2 oder 3. dadurch gekennzeichnet, daß man als Lösungsmittel Lösungsmittelgemische aus Wasser und organischen Lösungsmitteln aus der Gruppe der Alkohole und Ketone einsetzt. 4. The method according to claim 2 or 3, characterized in that one uses as the solvent solvent mixtures of water and organic solvents from the group of alcohols and ketones.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man ein Lösungsmittelgemisch aus Wasser und Isopropanol oder tert.-Butanol einsetzt.5. The method according to claim 4, characterized in that one uses a solvent mixture of water and isopropanol or tert-butanol.
6. Verfahren nach einem der Ansprüche 2-5, dadurch gekennzeichnet, daß die Stufe b) bei Temperaturen von O-100°C durchgeführt wird.6. The method according to any one of claims 2-5, characterized in that the stage b) is carried out at temperatures of O-100 ° C.
7. Verfahren nach einem der Ansprüche 2-6, dadurch gekennzeichnet, daß das D-Isomer (D-Ia) oder dessen Salze racemisiert und die erhaltene racemische Verbindung (DL-Ia) für die Racematspaltung verwendet wird.7. The method according to any one of claims 2-6, characterized in that the D-isomer (D-Ia) or its salts are racemized and the resulting racemic compound (DL-Ia) is used for the resolution of racemates.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß man das D-Isomer (D-Ia) in Gegenwart von sechsgliedrigen (hetero)aromatlschen Aldehyden, die eine Hydroxygruppe in 2-Position zur Aldehydgruppe und elektronenziehende Reste in 3- oder 5-Position zur Aldehydgruppe aufweisen und gegebenenfalls weiter substituiert sind, in wäßrigem oder wäßrig¬ organischen Medium ohne Zusatz von organischen Säuren umsetzt.8. The method according to claim 7, characterized in that the D-isomer (D-Ia) in the presence of six-membered (hetero) aromat aldehydes containing a hydroxy group in the 2-position to the aldehyde group and electron-withdrawing radicals in the 3- or 5-position to the aldehyde group and optionally further substituted, in aqueous or aqueous organic medium without the addition of organic acids.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß man 5-Nitrosalicylaldehyd oder 3,5-Dinitrosalicylaldehyd einsetzt.9. The method according to claim 8, characterized in that one uses 5-nitrosalicylaldehyde or 3,5-dinitrosalicylaldehyde.
10. Verfahren nach einem der Ansprüche 7-9, dadurch gekennzeichnet, daß die Racemisierung bei Temperaturen von 0- 120°C durchgeführt wird.10. The method according to any one of claims 7-9, characterized in that the racemization is carried out at temperatures of 0-120 ° C.
11. Verfahren nach einem der Ansprüche 8-10, dadurch gekennzeichnet, daß man ein Gemisch der diastereomeren Salze aus D-Säure bzw. L-Säure und der chiralen Base, gelöst in einem wäßrigen oder wäßrig-organischen Lösungsmittel, in welchem das Salz der D-Säure eine höhere Lδslichkeit als das Salz der L-Säure aufweist, bei Temperaturen von 0-85 °C in Gegenwart des Aldehyds umsetzt, wobei die Temperatur so niedrig eingestellt ist, daß zugleich das Salz der L-Säure und der chiralen Base auskristallisiert. nπ. ™. 5 PCT/EP95/0068211. The method according to any one of claims 8-10, characterized in that a mixture of diastereomeric salts of D-acid or L-acid and the chiral base, dissolved in an aqueous or aqueous-organic solvent in which the salt of D acid has a higher solubility than the salt of L acid, at temperatures of 0-85 ° C in the presence of the aldehyde, the temperature being set so low that at the same time the salt of the L acid and the chiral base crystallized out , nπ . ™ . 5 PCT / EP95 / 00682
12. Salze von [L]- oder [D]-Homoalanin-4-yl-(methyl)phosphinsäure und chiralen Alkaloidbasen.12. Salts of [L] - or [D] -homoalanin-4-yl (methyl) phosphinic acid and chiral alkaloid bases.
13. Salz von [L]-Homoalanin-4-yl-(methyI)phosphinsäure (L-Säure) und Chinin.13. Salt of [L] -homoalanin-4-yl (methyl) phosphinic acid (L-acid) and quinine.
14. Verfahren zur Racemisierung von optisch aktiven freien alpha-Aminosäuren und deren Salzen, dadurch gekennzeichnet, daß man die optisch aktiven Aminosäuren in Gegenwart von sechsgliedrigen (hetero)aromatischen Aldehyden, die eine Hydroxygruppe in 2-Positioπ zur Aldehydgruppe und elektronenziehende Reste in 3- oder 5-Position zur Aldehydgruppe aufweisen und gegebenenfalls weiter substituiert sind, in wäßrigem oder wäßrig- organischen Medium ohne Metallionen-Katalyse und ohne Zusatz von organischen Säuren umsetzt.14. A process for the racemization of optically active free alpha-amino acids and their salts, which comprises reacting the optically active amino acids in the presence of six-membered (hetero) aromatic aldehydes containing a hydroxy group in 2-position to the aldehyde group and electron-withdrawing radicals in 3 or 5-position to the aldehyde group and optionally further substituted, in aqueous or aqueous organic medium without metal ion catalysis and without addition of organic acids.
15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß man 5-Niτrosalicylaldehyd oder 3,5-Dinitrosalicylaldehyd einsetzt.15. The method according to claim 14, characterized in that one uses 5-Niτrosalicylaldehyd or 3,5-dinitrosalicylaldehyde.
16. Verfahren nach Anspruch 14 oder 15, dadurch gekennzeichnet, daß man die Racemisierung bei pH 4-9 und bei Temperaturen von 0-120° C durchführt.16. The method according to claim 14 or 15, characterized in that one carries out the racemization at pH 4-9 and at temperatures of 0-120 ° C.
17. Verfahren nach einem der Ansprüche 14-16, dadurch gekennzeichnet, daß man optisch aktive Aminosäuren aus der Gruppe [D]- oder [Ll-Alanin, [D]- oder [L]-Phenylglycin, [DJ- oder [L]-HydroxypheπylgJycin, [D]- oder [L]-Leuclne, [Di¬ oder [Ll-Homoalanin-4-yl-(methyl)phosphinsäure, [Dl- oder [Ll-Homoalanin-4-γl- (methyl)phosphinsäure-ammoniumsalz und [Dl- oder [Ll-Homoalanin-4-yl- (methyDphosphinsäure/Chininsalz einsetzt. 17. The method according to any one of claims 14-16, characterized in that optically active amino acids from the group [D] - or [Ll-alanine, [D] - or [L] -phenylglycine, [DJ- or [L] Hydroxyphenylgycin, [D] or [L] -Leuclne, [di- or [LI-homoalanin-4-yl (methyl) phosphinic acid, [Dl- or [ll-homoalanine-4-yl- (methyl) -phosphinic acid] ammonium salt and [Dl or [Ll-homoalanin-4-yl (methylphosphine / quinine salt.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE59505034T DE59505034D1 (en) | 1994-03-04 | 1995-02-24 | METHOD FOR THE PRODUCTION OF [L] - OR [D] -HOMOALANIN-4-YL- (METHYL) PHOSPHINIC ACID AND THE SALTS THEREOF BY RACEMATE CLEARANCE |
| JP52267995A JP4303785B2 (en) | 1994-03-04 | 1995-02-24 | Process for producing [L]-or [D] -homoalanin-4-yl- (methyl) phosphinic acid and salts thereof by racemate resolution |
| EP95910520A EP0748325B1 (en) | 1994-03-04 | 1995-02-24 | Process for preparing [l]- or [d]-homoalanin-4-yl-(methyl)phosphinic acid and its salts by racemic resolution |
| MX9603873A MX9603873A (en) | 1994-03-04 | 1995-02-24 | Process for preparing [l]- or [d]-homoalanin-4-yl-(methyl)phosphinic acid and its salts by racemic resolution. |
| AU17595/95A AU704175B2 (en) | 1994-03-04 | 1995-02-24 | Process for preparing {l}- or {d}-homoalanin-4-yl- (methyl)phosphinic acid and salts thereof by racemate resolution |
| BR9506986A BR9506986A (en) | 1994-03-04 | 1995-02-24 | Process for the preparation of (l) - or (d) - homoalanin-4-yl- (methyl) phosphinic acid and its salts by means of racemate separation |
| FI963422A FI963422A (en) | 1994-03-04 | 1996-09-02 | Process for the preparation of (L) - or (D) -homoalanin-4-yl (methyl) phosphinic acid and its salts by racemate cleavage |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4407197.3 | 1994-03-04 | ||
| DE4407197A DE4407197A1 (en) | 1994-03-04 | 1994-03-04 | Process for the preparation of / L / -Homoalanin-4-yl- (methyl) phosphinic acid and its salts by resolution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO1995023805A1 WO1995023805A1 (en) | 1995-09-08 |
| WO1995023805B1 true WO1995023805B1 (en) | 1995-10-26 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1995/000682 WO1995023805A1 (en) | 1994-03-04 | 1995-02-24 | Process for preparing [l]- or [d]-homoalanin-4-yl-(methyl)phosphinic acid and its salts by racemic resolution |
Country Status (19)
| Country | Link |
|---|---|
| US (2) | US5767309A (en) |
| EP (1) | EP0748325B1 (en) |
| JP (1) | JP4303785B2 (en) |
| CN (1) | CN1053669C (en) |
| AT (1) | ATE176475T1 (en) |
| AU (1) | AU704175B2 (en) |
| BR (1) | BR9506986A (en) |
| CA (1) | CA2184718A1 (en) |
| CZ (1) | CZ260196A3 (en) |
| DE (2) | DE4407197A1 (en) |
| ES (1) | ES2128717T3 (en) |
| FI (1) | FI963422A (en) |
| HU (1) | HU215583B (en) |
| IL (1) | IL112851A (en) |
| MX (1) | MX9603873A (en) |
| TR (1) | TR28265A (en) |
| TW (1) | TW293012B (en) |
| WO (1) | WO1995023805A1 (en) |
| ZA (1) | ZA951779B (en) |
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| EP3613750A4 (en) * | 2017-04-17 | 2021-01-13 | Kyoto University | Optically-active 2-amino-phosphonoalkane acid, optically-active 2-amino-phosphonoalkane acid salt, and hydrates of these |
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| TW353663B (en) * | 1991-04-06 | 1999-03-01 | Hoechst Ag | Process for the preparation of phosphorus-containing L-amino acids, their derivatives and intermediates for this process |
| DE9202282U1 (en) * | 1991-04-09 | 1992-04-30 | Siemens AG, 8000 München | Slide switch |
| ATE137498T1 (en) * | 1991-08-03 | 1996-05-15 | Hoechst Schering Agrevo Gmbh | OPTICALLY ACTIVE OMEGA-HALOGENE-2-AMINO-ALKANE CARBOXYLIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR PRODUCING OPTICALLY ACTIVE PHOSPHORUS-CONTAINING ALPHA-AMINO ACIDS |
| JPH05165305A (en) * | 1991-12-11 | 1993-07-02 | Sharp Corp | Electrostatic charging device |
| IL104056A (en) * | 1991-12-13 | 1997-02-18 | Hoechst Ag | Process for the preparation of L-phosphinothricin and its derivatives |
-
1994
- 1994-03-04 DE DE4407197A patent/DE4407197A1/en not_active Withdrawn
-
1995
- 1995-02-24 AT AT95910520T patent/ATE176475T1/en active
- 1995-02-24 HU HU9602411A patent/HU215583B/en unknown
- 1995-02-24 WO PCT/EP1995/000682 patent/WO1995023805A1/en not_active Application Discontinuation
- 1995-02-24 EP EP95910520A patent/EP0748325B1/en not_active Expired - Lifetime
- 1995-02-24 ES ES95910520T patent/ES2128717T3/en not_active Expired - Lifetime
- 1995-02-24 DE DE59505034T patent/DE59505034D1/en not_active Expired - Lifetime
- 1995-02-24 MX MX9603873A patent/MX9603873A/en unknown
- 1995-02-24 CZ CZ962601A patent/CZ260196A3/en unknown
- 1995-02-24 JP JP52267995A patent/JP4303785B2/en not_active Expired - Lifetime
- 1995-02-24 BR BR9506986A patent/BR9506986A/en not_active IP Right Cessation
- 1995-02-24 CA CA002184718A patent/CA2184718A1/en not_active Abandoned
- 1995-02-24 CN CN95191936A patent/CN1053669C/en not_active Expired - Lifetime
- 1995-02-24 AU AU17595/95A patent/AU704175B2/en not_active Expired
- 1995-03-01 TR TR00223/95A patent/TR28265A/en unknown
- 1995-03-02 US US08/398,216 patent/US5767309A/en not_active Expired - Lifetime
- 1995-03-02 IL IL11285195A patent/IL112851A/en not_active IP Right Cessation
- 1995-03-03 ZA ZA951779A patent/ZA951779B/en unknown
- 1995-03-10 TW TW084102260A patent/TW293012B/zh active
-
1996
- 1996-09-02 FI FI963422A patent/FI963422A/en unknown
-
1998
- 1998-03-27 US US09/049,404 patent/US5869668A/en not_active Expired - Lifetime
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