EP0000745A1 - Salt of an optically active isomer of phenylglycine and an optically active isomer of 2-amino butanol and process for its preparation - Google Patents
Salt of an optically active isomer of phenylglycine and an optically active isomer of 2-amino butanol and process for its preparation Download PDFInfo
- Publication number
- EP0000745A1 EP0000745A1 EP7878100531A EP78100531A EP0000745A1 EP 0000745 A1 EP0000745 A1 EP 0000745A1 EP 7878100531 A EP7878100531 A EP 7878100531A EP 78100531 A EP78100531 A EP 78100531A EP 0000745 A1 EP0000745 A1 EP 0000745A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkoxy
- substituted
- optical isomer
- salt
- formula
- 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.)
- Granted
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 18
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title description 2
- ZGUNAGUHMKGQNY-ZETCQYMHSA-N L-alpha-phenylglycine zwitterion Chemical compound OC(=O)[C@@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-ZETCQYMHSA-N 0.000 title 1
- 230000003287 optical effect Effects 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- -1 C 1 -C 4 acyloxy Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000003545 alkoxy group Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000005076 adamantyloxycarbonyl group Chemical group C12(CC3CC(CC(C1)C3)C2)OC(=O)* 0.000 claims description 2
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims description 2
- 125000003435 aroyl group Chemical class 0.000 claims description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000001584 benzyloxycarbonyl group Chemical class C(=O)(OCC1=CC=CC=C1)* 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Chemical class O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001557 phthalyl group Chemical class C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 claims description 2
- 125000002221 trityl group Chemical class [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 claims 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 150000001413 amino acids Chemical class 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 4
- 229930186147 Cephalosporin Natural products 0.000 abstract description 2
- 229930182555 Penicillin Natural products 0.000 abstract description 2
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 abstract description 2
- 239000003242 anti bacterial agent Substances 0.000 abstract description 2
- 229940088710 antibiotic agent Drugs 0.000 abstract description 2
- 229940124587 cephalosporin Drugs 0.000 abstract description 2
- 150000001780 cephalosporins Chemical class 0.000 abstract description 2
- 229940049954 penicillin Drugs 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- KAGSUJOTNBINKR-UHFFFAOYSA-N 2-acetamido-2-(4-methoxyphenyl)acetic acid Chemical compound COC1=CC=C(C(NC(C)=O)C(O)=O)C=C1 KAGSUJOTNBINKR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WFRVJRZGHCTEGP-UHFFFAOYSA-N acetyl 2-acetamido-2-(4-hydroxyphenyl)acetate Chemical compound C(C)(=O)NC(C(=O)OC(C)=O)C1=CC=C(C=C1)O WFRVJRZGHCTEGP-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 229960003022 amoxicillin Drugs 0.000 description 1
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 1
- 229960000723 ampicillin Drugs 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KMPWYEUPVWOPIM-KODHJQJWSA-N cinchonidine Chemical compound C1=CC=C2C([C@H]([C@H]3[N@]4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-KODHJQJWSA-N 0.000 description 1
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B57/00—Separation of optically-active compounds
Definitions
- the present invention relates to the separation into optical antipodes of compounds of the formula I. wherein XH, OH, C 1 -C 4 alkoxy, aryloxy, C 1 -C 4 acyloxy, aralkyloxy, which is optionally.substituted with at most 3 halogen atoms or nitro groups and contains at most 4 carbon atoms in the alkyl radical, tert.-alkoxy with one tertiary carbon atom bonded to the oxygen atom, alkoxycarbonyloxy or picolyloxycarbonyloxy and Y is aliphatic acyl, which may optionally be substituted with up to 3-halogen atoms or which may contain further carbonyl groups, optionally halogen-substituted aroyl, or alkyl, alkoxy, nitro, phthalyl, trityl , optionally alkyl, alkoxy or halogen substituted Benzylidene, acetylisoprop
- optically active compounds of the formula mentioned are used as starting material for the production of semisynthetic antibiotics of the cephalosporin or penicillin type, for example ampicillin or amoxycillin.
- the invention relates to a new process for the preparation of the optically active compounds of the above formula using optically active 2-aminobutanol.
- optically active natural amines such as cinchonidine or dehydroabiethylamine
- these natural amines are very expensive and the separation yields are low.
- recovery of these natural amines for further use is limited because some of these amines are destroyed during the separation process, which is carried out at high temperatures.
- amino group of the amino acid or one of its derivatives is substituted for acidity
- the salts are generally prepared in water or a lower alkanol, preferably methanol, ethanol or isopropanol, one of the two salts precipitating out, starting from a racemi see compound of formula I and optically active 2-aminobutanol can be formed.
- the process according to the invention is superior to known processes in that the optical purity is higher than 99% and higher yields are obtained.
- amino acid derivatives are converted into the amino acids or into an amino acid which is either still substituted on the amino group or on the phenyl ring.
- the invention is illustrated by the following examples.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Trennung von Aminosäuren in optische Antipoden. Die vorliegende Anmeldung betrifft Salze, bestehend aus einem optischen Isomeren einer Verbindung der Formel <IMAGE> worin X ein Wasserstofatom oder eine gegebenenfalls verätherte oder veresterte Hydroxygruppe bedeutet und Y unter anderen eine Acylgruppe ist, und einem optischen Isomeren von 2-Aminobutanol sowie ein Verfahren zur Herstellung von solchen Salzen. Die optisch aktiven Verbindungen der genannten Formel werden als Ausgangsmaterial für die Produktion von halbsynthetischen Antibiotika des Cephalosporinoder Penicillin-Typs eingesetzt.Separation of amino acids into optical antipodes. The present application relates to salts consisting of an optical isomer of a compound of the formula <IMAGE> in which X is a hydrogen atom or an optionally etherified or esterified hydroxyl group and Y is, inter alia, an acyl group, and an optical isomer of 2-aminobutanol and a process for Production of such salts. The optically active compounds of the formula mentioned are used as the starting material for the production of semisynthetic antibiotics of the cephalosporin or penicillin type.
Description
Die vorliegende Erfindung betrifft die Trennung in optische Antipoden von Verbindungen der Formel I
Die optisch aktiven Verbindungen der genannten Formel werden als Ausgangsmaterial für die Produktion von halbsynthetischen Antibiotika des CephalosporinoderPenicillin-Typs, beispielsweise Ampicillin oder Amoxycillin eingesetzt. Die Erfindung betrifft ein neues'Verfahren zur Herstellung der optisch aktiven Verbindungen der obigen Formel unter Einsatz von optisch aktivem 2-Aminobutanol.The optically active compounds of the formula mentioned are used as starting material for the production of semisynthetic antibiotics of the cephalosporin or penicillin type, for example ampicillin or amoxycillin. The invention relates to a new process for the preparation of the optically active compounds of the above formula using optically active 2-aminobutanol.
In einem bekannten Verfahren zur Trennung von Verbindungen in optische Isomere der obigen Formel wurden optisch aktive natürliche Amine, wie Cinchonidin oder Dehydroabiethylamin, eingesetzt. Doch diese natürlichen Amine sind sehr teuer, und die Trennungsausbeuten sind niedrig. Hinzu kommtnoch der weitere Nachteil, daß eine Wiedergewinnung dieser natürlichen Amine zum'weiteren Gebrauch begrenzt ist, weil ein Teil dieser Amine während des Trennungsverfahrens, das mit hohen-Temperaturen durchgeführt wird, zerstört wird.In a known process for separating compounds into optical isomers of the above formula, optically active natural amines, such as cinchonidine or dehydroabiethylamine, have been used. However, these natural amines are very expensive and the separation yields are low. In addition, there is the further disadvantage that recovery of these natural amines for further use is limited because some of these amines are destroyed during the separation process, which is carried out at high temperatures.
Gemäß der Erfindung wird die Aminogruppe der Aminosäure oder eines ihrer Derivate substituiert, um die AciditätAccording to the invention, the amino group of the amino acid or one of its derivatives is substituted for acidity
der Aminosäure zu erhöhen. Diese Derivate der Aminosäuren bilden mit 2-Aminobutanol leichter die entsprechenden Salze als die Aminosäuren selbst. Die Salze werden im allgemeinen in Wasser oder einem niederen Alkanol, vorzugsweise Methanol, Äthanol oder Isopropanol hergestellt, wobei eines der beiden Salze ausfällt, die ausgehend von einer racemisehen Verbindung der Formel I und optisch aktivem 2-Aminobutanol gebildet werden können.to increase the amino acid. These derivatives of the amino acids form the corresponding salts more easily with 2-aminobutanol than the amino acids themselves. The salts are generally prepared in water or a lower alkanol, preferably methanol, ethanol or isopropanol, one of the two salts precipitating out, starting from a racemi see compound of formula I and optically active 2-aminobutanol can be formed.
Das erfindungsgemäße Verfahren ist bekannten Verfahren darin überlegen, daß die optische Reinheit höher als 99 % liegt und höhere Ausbeuten erhalten werden.The process according to the invention is superior to known processes in that the optical purity is higher than 99% and higher yields are obtained.
Gegebenenfalls werden die Aniinosäure-Derivate in die Aminosäuren umgewandelt oder in eine Aminosäure, die entweder noch an der Aminogruppe oder am Phenylring substituiert ist. Die Erfindung wird durch die folgenden Beispiele erläutert.If appropriate, the amino acid derivatives are converted into the amino acids or into an amino acid which is either still substituted on the amino group or on the phenyl ring. The invention is illustrated by the following examples.
Salz von 1-N,O-Diacetyl-4-hydroxy-phenylglycin und 1-2-Aminobutanol.Salt of 1-N, O-diacetyl-4-hydroxy-phenylglycine and 1-2-aminobutanol.
Zu einer Suspension von dl-Diacetyl-4-hydroxy-phenylglycin (47,5 g) in 400 ml Äthanol, wurde 1-2-Aminobutanol (18 g) unter Rühren gegeben. Die Reaktionsmischung wurde langsam bis zur Auflösung erwärmt, worauf auf Raumtemperatur abgekühlt und 2 Stunden stehengelassen wurde, um die Ausfällung des Salzes zu vervollständigen. Das Salz wurde durch Filtrieren abgetrennt und ergab ein Rohprodukt (30 g). Durch Umkristallisieren aus 80 ml Äthanol wurde das reine Salz aus 1-N,O-Diacetyl-4-hydroxy-phenylglycin und 1-2-Aminobutanol erhalten.To a suspension of dl-diacetyl-4-hydroxy-phenylglycine (47.5 g) in 400 ml of ethanol was added 1-2-aminobutanol (18 g) with stirring. The reaction mixture was slowly warmed to dissolution, then cooled to room temperature and allowed to stand for 2 hours to complete the precipitation of the salt. The salt was separated by filtration and gave a crude product (30 g). The pure salt of 1-N, O-diacetyl-4-hydroxy-phenylglycine and 1-2-aminobutanol was obtained by recrystallization from 80 ml of ethanol.
Fp. 168-170° C und (α)D 25 = 126° (C=2, H2O).Mp 168-170 ° C and (α) D 25 = 126 ° (C = 2, H 2 O).
1-4-Hydroxyphenylglycin1-4-hydroxyphenylglycine
Das gemäß obiger Arbeitsweise erhaltene Salz wurde in bekannter Weise behandelt, um 1-4-Hydroxyphenylglycin mit einer optischen Reinheit ([α]25 D = -159° (C=2, N-HCl) von mehr als 99 % zu erhalten.The salt obtained according to the above procedure was treated in a known manner in order to obtain 1- 4-hydroxyphenylglycine with an optical purity ([α] 25 D = -159 ° (C = 2, N-HCl) of more than 99%.
Salz von l-N-Acetyl-4-methoxy-phenylglycin mit 1-2-Aminobutanol.Salt of 1N-acetyl-4-methoxy-phenylglycine with 1-2-amino butanol.
Zu einer Suspension von dl-N-Acetyl-4-methoxy-phenylglycin (4,46 g) in 15 ml abs. Methanol wurde 1-2-Aminobutanol (1,8g) gegeben. Es wurde wie in Beispiel 1 verfahren und ein rohes Salz (3,1 g) von 1-N-Acetyl-4-methoxy-phenylglycin mit 1-2-Aminobutanol erhalten. Das reine Salz wurde durch Umkristallisieren aus 5 ml abs. Methanol erhalten. 2,5 g (80 %); [α]25 D =-107° (C=2, H2O).To a suspension of dl-N-acetyl-4-methoxy-phenylglycine (4.46 g) in 15 ml abs. Methanol was added to 1-2-aminobutanol (1.8 g). The procedure was as in Example 1 and a crude salt (3.1 g) of 1-N-acetyl-4-methoxy-phenylglycine with 1-2-aminobutanol was obtained. The pure salt was recrystallized from 5 ml abs. Get methanol. 2.5 g (80%); [α] 25 D = -107 ° (C = 2, H 2 O).
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772735834 DE2735834A1 (en) | 1977-08-09 | 1977-08-09 | SEPARATION OF AMINO ACIDS INTO OPTICAL ANTIPODES |
| DE2735834 | 1977-08-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000745A1 true EP0000745A1 (en) | 1979-02-21 |
| EP0000745B1 EP0000745B1 (en) | 1981-07-15 |
Family
ID=6015982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100531A Expired EP0000745B1 (en) | 1977-08-09 | 1978-07-28 | Salt of an optically active isomer of phenylglycine and an optically active isomer of 2-amino butanol and process for its preparation |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US4182899A (en) |
| EP (1) | EP0000745B1 (en) |
| JP (1) | JPS5430132A (en) |
| AT (1) | AT359997B (en) |
| BG (1) | BG35593A3 (en) |
| CA (1) | CA1110653A (en) |
| CS (1) | CS203200B2 (en) |
| DD (1) | DD137580A5 (en) |
| DE (2) | DE2735834A1 (en) |
| HU (1) | HU178248B (en) |
| IE (1) | IE47236B1 (en) |
| IL (1) | IL55293A (en) |
| IT (1) | IT1098014B (en) |
| SU (1) | SU913937A3 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041637A (en) * | 1988-07-12 | 1991-08-20 | Presidenza Del Consiglio Del Ministri-Ufficio Del Ministro Per Il Coordinamento Delle Iniziatjvo Per La Ricerca Scientifica E. Technologica | Process for the synthesis of optically active aminoacids |
| FR2672593A1 (en) * | 1991-02-08 | 1992-08-14 | Beecham Sa Laboratoires | NEW COMPOUNDS USEFUL FOR THE RESOLUTION OF DL-N-ACETYL OR DL-N-HALOACETYL-HYDROXYPHENYLGLYCINE. |
| US5583259A (en) * | 1991-02-08 | 1996-12-10 | Les Laboratoires Beecham S.A. | 2-(RO)-1-(R) ethylamines |
| CN102887836A (en) * | 2011-07-18 | 2013-01-23 | 西南大学 | L-phenylglycine derivative and application thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU193199B (en) * | 1984-03-01 | 1987-08-28 | Budapesti Mueszaki Egyetem | Process for preparing optically active alpha-amino-beta-phenyl-propionic acids |
| US4642205A (en) * | 1984-03-01 | 1987-02-10 | Alkaloida Vegyeszeti Gyar | Diastereomer salts of phenylalanine and N-acyl derivatives thereof and process for the separation of optically active phenylalanine and N-acyl derivatives thereof |
| JPH01155119A (en) * | 1987-12-14 | 1989-06-19 | Rinnai Corp | Combustion control device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2107926A1 (en) * | 1970-09-24 | 1972-05-12 | Beecham Group Ltd | |
| AT334345B (en) * | 1973-06-07 | 1976-01-10 | Pliva Pharm & Chem Works | PROCESS FOR THE PRODUCTION OF L- (-) -ALPHA- METHYL -BETA- (3,4-DIHYDROXYPHENYL) -ALANINE |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL268416A (en) * | 1960-08-19 | |||
| US3904681A (en) * | 1971-03-30 | 1975-09-09 | Ciba Geigy Corp | Propionic acid |
| US3796748A (en) * | 1972-08-16 | 1974-03-12 | Bristol Myers Co | Dehydroabietylammonium d-(-)-2-chloroacetylamino-2-(p-hydroxyphenyl)-acetate |
| JPS5069039A (en) * | 1973-10-23 | 1975-06-09 | ||
| JPS50116434A (en) * | 1974-03-01 | 1975-09-11 | ||
| JPS5152154A (en) * | 1974-10-26 | 1976-05-08 | Sankyo Co | nn karubometokishifuenirugurishinno kogakubunkatsuho |
-
1977
- 1977-08-09 DE DE19772735834 patent/DE2735834A1/en not_active Withdrawn
-
1978
- 1978-07-28 DE DE7878100531T patent/DE2860839D1/en not_active Expired
- 1978-07-28 EP EP78100531A patent/EP0000745B1/en not_active Expired
- 1978-08-04 DD DD78207128A patent/DD137580A5/en unknown
- 1978-08-04 BG BG040601A patent/BG35593A3/en unknown
- 1978-08-07 HU HU78HO2093A patent/HU178248B/en unknown
- 1978-08-07 CS CS785160A patent/CS203200B2/en unknown
- 1978-08-07 IT IT26559/78A patent/IT1098014B/en active
- 1978-08-07 IL IL55293A patent/IL55293A/en unknown
- 1978-08-07 US US05/931,529 patent/US4182899A/en not_active Expired - Lifetime
- 1978-08-08 CA CA308,911A patent/CA1110653A/en not_active Expired
- 1978-08-08 SU SU782645702A patent/SU913937A3/en active
- 1978-08-08 IE IE1611/78A patent/IE47236B1/en unknown
- 1978-08-08 AT AT577278A patent/AT359997B/en not_active IP Right Cessation
- 1978-08-09 JP JP9628578A patent/JPS5430132A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2107926A1 (en) * | 1970-09-24 | 1972-05-12 | Beecham Group Ltd | |
| AT334345B (en) * | 1973-06-07 | 1976-01-10 | Pliva Pharm & Chem Works | PROCESS FOR THE PRODUCTION OF L- (-) -ALPHA- METHYL -BETA- (3,4-DIHYDROXYPHENYL) -ALANINE |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041637A (en) * | 1988-07-12 | 1991-08-20 | Presidenza Del Consiglio Del Ministri-Ufficio Del Ministro Per Il Coordinamento Delle Iniziatjvo Per La Ricerca Scientifica E. Technologica | Process for the synthesis of optically active aminoacids |
| FR2672593A1 (en) * | 1991-02-08 | 1992-08-14 | Beecham Sa Laboratoires | NEW COMPOUNDS USEFUL FOR THE RESOLUTION OF DL-N-ACETYL OR DL-N-HALOACETYL-HYDROXYPHENYLGLYCINE. |
| WO1992013823A1 (en) * | 1991-02-08 | 1992-08-20 | Les Laboratoires Beecham S.A. | Aminoalcohols useful as optical resolving agents |
| US5583259A (en) * | 1991-02-08 | 1996-12-10 | Les Laboratoires Beecham S.A. | 2-(RO)-1-(R) ethylamines |
| CN102887836A (en) * | 2011-07-18 | 2013-01-23 | 西南大学 | L-phenylglycine derivative and application thereof |
| CN102887836B (en) * | 2011-07-18 | 2014-03-26 | 西南大学 | L-phenylglycine derivative and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| IE781611L (en) | 1979-02-09 |
| IT7826559A0 (en) | 1978-08-07 |
| US4182899A (en) | 1980-01-08 |
| DE2735834A1 (en) | 1979-02-22 |
| IE47236B1 (en) | 1984-01-25 |
| SU913937A3 (en) | 1982-03-15 |
| IT1098014B (en) | 1985-08-31 |
| DD137580A5 (en) | 1979-09-12 |
| EP0000745B1 (en) | 1981-07-15 |
| ATA577278A (en) | 1980-05-15 |
| CA1110653A (en) | 1981-10-13 |
| CS203200B2 (en) | 1981-02-27 |
| AT359997B (en) | 1980-12-10 |
| DE2860839D1 (en) | 1981-10-22 |
| BG35593A3 (en) | 1984-05-15 |
| JPS5430132A (en) | 1979-03-06 |
| HU178248B (en) | 1982-04-28 |
| IL55293A (en) | 1982-09-30 |
| IL55293A0 (en) | 1978-10-31 |
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