DE2615594C3 - Process for the preparation of aminocarboxylic acids - Google Patents
Process for the preparation of aminocarboxylic acidsInfo
- Publication number
- DE2615594C3 DE2615594C3 DE2615594A DE2615594A DE2615594C3 DE 2615594 C3 DE2615594 C3 DE 2615594C3 DE 2615594 A DE2615594 A DE 2615594A DE 2615594 A DE2615594 A DE 2615594A DE 2615594 C3 DE2615594 C3 DE 2615594C3
- Authority
- DE
- Germany
- Prior art keywords
- acid
- carbamoyl
- preparation
- amino acid
- mol
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 229940024606 amino acid Drugs 0.000 description 12
- 150000001413 amino acids Chemical class 0.000 description 12
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZGUNAGUHMKGQNY-SSDOTTSWSA-N D-alpha-phenylglycine Chemical compound OC(=O)[C@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-SSDOTTSWSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229930195722 L-methionine Natural products 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- GIOUOHDKHHZWIQ-SSDOTTSWSA-N N-carbamoyl-D-phenylglycine Chemical compound NC(=O)N[C@@H](C(O)=O)C1=CC=CC=C1 GIOUOHDKHHZWIQ-SSDOTTSWSA-N 0.000 description 1
- DEWDMTSMCKXBNP-BYPYZUCNSA-N N-carbamoyl-L-methionine Chemical compound CSCC[C@@H](C(O)=O)NC(N)=O DEWDMTSMCKXBNP-BYPYZUCNSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
- C07C227/20—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters by hydrolysis of N-acylated amino-acids or derivatives thereof, e.g. hydrolysis of carbamates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Es ist bekannt daß optisch aktive Carbamoylderivate von Aminosäuren aus den entsprechenden racemischen Hydantoinen durch stereo-selektive enzymatische Hydrolyse gemäß der DE-OS 24 22 737 erhalten werden können.It is known that optically active carbamoyl derivatives of amino acids from the corresponding racemic Hydantoins can be obtained by stereoselective enzymatic hydrolysis according to DE-OS 24 22 737 can.
Das auf diese Weise erhaltene Carbamoylderivat wurde anschließend in die entsprechende Aminosäure durch bloßes Sieden in wäßriger Lösung übergeführt.The carbamoyl derivative thus obtained was then converted into the corresponding amino acid converted into aqueous solution by mere boiling.
Jedoch war die Hydrolyse des Carbamoylderivats in die Aminosäure, die unter derartigen Bedingungen hervorgerufen wurde, sehr langsam, erforderte eine strenge Kontrolle der Arbeitsbedingungen und gab zuweilen Anlaß zur Bildung von Nebenprodukten unter Herabsetzung der Ausbeute und sogar unter teilweiser Racemisierung.However, hydrolysis of the carbamoyl derivative to the amino acid was possible under such conditions elicited very slowly, required strict control of working conditions, and gave occasionally give rise to the formation of by-products with a reduction in the yield and even in part Racemization.
Es wurde nun ein neuer und einfacher Weg für die Überführung von Carbamoylderivaten in die entsprechenden Aminosäuren gefunden, der unter milden Bedingungen abläuft, derart, daß die auf diese Weise gebildete Aminosäure die optische Reinheit der Ausgangscarbamoylderivate beibehält.A new and easier way of converting carbamoyl derivatives into the corresponding ones has now been found Amino acids found that expires under mild conditions, such that the in this way The amino acid formed maintains the optical purity of the starting carbamoyl derivatives.
Die Erfindung betrifft daher ein Verfahren zur Herstellung von Aminocarbonsäuren, das dadurch gekennzeichnet ist, daß man das der herzustellenden Aminocarbonsäure entsprechende N-Carbamoylderivat oder ein Salz dieses Derivates mit 1 bis 1,5 Äquivalenten salpetriger Säure oder eines ihrer Salze in Gegenwart eines saure Gruppen enthaltenden lonenaustauschharzes bei einer Temperatur von 0 bis 40° C umsetzt.The invention therefore relates to a process for the preparation of aminocarboxylic acids, which thereby is characterized in that the N-carbamoyl derivative corresponding to the aminocarboxylic acid to be prepared is used or a salt of this derivative with 1 to 1.5 equivalents of nitrous acid or one of its salts in the presence an ion exchange resin containing acidic groups at a temperature of 0 to 40 ° C.
Die Durchführbarkeit des erfindungsgemäßen Verfahrens ist insofern äußerst überraschend, als bisher bekannt war, daß derartige Reaktanten auf die Aminogruppe der Aminosäure unter Bildung der entsprechenden Hydroxysäure einwirken und es dann unmöglich war, das Carbamoylderivat in die entsprechende Aminosäure überzuführen, da wie gesagt die letztere sogleich in c*se Hydroxysäure übergeführt wurde (vgl. Fieser und Fieser, Chimica Organica, Seite 254, italienische Ausgabe; Merck Index, 9. Ausgabe; Organic Name Reaction-Van Slyke Determination [ON R-9 O] und Beyer, Lehrbuch der Organischen Chemie, Hirzel-Verlag, Leipzig, 1967, Seite 128). Im Gegensatz hierzu wurde neu gefunden, daß bei einer Arbeitsweise in Gegenwart von kationischen Harzen bei einem geeigneten pH-Wert und bei geeigneten Temperaturbedingungen überraschenderweise hohe Ausbeuten erreicht werden können, da die Aminosäure von einem Angriff durch die oxydierende Reaktante vollständig ausgenommen ist.The feasibility of the method according to the invention is extremely surprising to that extent than before it was known that such reactants act on the amino group of the amino acid to form the corresponding hydroxy acid act and it was then impossible to convert the carbamoyl derivative into the corresponding Amino acid to be converted, since, as I said, the latter is immediately converted into a hydroxy acid (see Fieser and Fieser, Chimica Organica, Page 254, Italian edition; Merck Index, 9th Edition; Organic Name Reaction-Van Slyke Determination [ON R-9 O] and Beyer, Textbook of Organic Chemistry, Hirzel-Verlag, Leipzig, 1967, page 128). In contrast, it was newly found that in one Operation in the presence of cationic resins at a suitable pH and at suitable Temperature conditions surprisingly high yields can be achieved because the amino acid is completely exempt from attack by the oxidizing reactant.
Das erfindungsgemäße Verfahren wird durchgeführt, indem man das Carbamoylderivat oder ein Salz desselben in Wasser bei einer variierbaren Konzentration, vorzugsweise nahe der Sättigung, löstThe inventive method is carried out by adding the carbamoyl derivative or a salt it dissolves in water at a variable concentration, preferably close to saturation
Die Lösung wird durch eine Menge an kationischem Harz in der Säureform bzw. sauren Form, das eine derartige Austauscherkapazität besitzt daß 1 bis 5 Mol Produkt gebunden werden, ergänzt Während dieser Stufe wird der pH erniedrigt und das Carbamoylderivat in einer Menge, die dessen Löslichkeit übersteigtThe solution is through an amount of cationic resin in the acid form or acid form, the one has such an exchange capacity that 1 to 5 moles of product are bound, supplements during this Step the pH is lowered and the carbamoyl derivative in an amount that exceeds its solubility
ίο ausgefällt Es wird die salpetrige Säure oder eines ihrer Salze hinzugefügt wobei die gesamte Stufe bei der angegebenen Temperatur durchgeführt wird.ίο precipitated It will be the nitrous acid or one of its Salts added, the entire stage being carried out at the specified temperature.
Als kationische Harze können Harze mit verschiedenen sauren Gruppen bzw. Säuregruppen verwendet werden, obgleich Harze vom Sulfon- bzw. Sulfonsäuretyp bevorzugt verwendet werden.Resins having various acidic groups or acidic groups can be used as the cationic resins although sulfonic acid type resins are preferably used.
Nach vollständiger Reaktion wird die Aminosäure aus dem Harz mit einer Base eluiert wohingegen das Harz erneut in seine saure Form übergeführt werden kann. Aus dem Eluat wird die Aminosäure durch einfache Konzentrierungs- und Kristallisationsverfahren gewonnen.When the reaction is complete, the amino acid is eluted from the resin with a base whereas the Resin can be converted back into its acidic form. The amino acid is made from the eluate simple concentration and crystallization processes obtained.
Die vorstehend erläuterte Verfahrensweise und weitere Einzelheiten werden anhand der folgenden Beispiele näher veranschaulichtThe above procedure and other details are illustrated by the following Examples illustrated in more detail
VergleichsversuchComparative experiment
50 ml einer 25-mM-Lösung von N-Carbamoyl-a-alanin werden bei 0°C mit 5 ml einer 50-mM-Lösung von NaNO2 in Wasser behandelt Man mißt gelegentlich die Konzentration der Aminosäure in der Lösung. Die Konzentration nimmt langsam ab, nachdem in der ersten Stunde der Umsetzung ein Maximum von 5 mM erreicht worden war und fällt nach 5 Std. auf 3,2 mM.50 ml of a 25 mM solution of N-carbamoyl-a-alanine are treated at 0 ° C with 5 ml of a 50 mM solution of NaNO2 in water. The Concentration of the amino acid in the solution. The concentration slowly decreases after being in the A maximum of 5 mM had been reached in the first hour of the reaction and fell to 3.2 mM after 5 hours.
Die chromatographische Analyse der Mischung zeigt die Anwesenheit einer beträchtlichen Menge an Milchsäure.Chromatographic analysis of the mixture indicates the presence of a substantial amount Lactic acid.
■to Man schlämmte 195 g (1 Mol) D-N-Carbamoyl-phenylglycin mit einer optischen Reinheit von 99% in 10 I entionisiertem Wasser in Gegenwart von 8 I Kationenaustauscher mit vernetztem Polystyrolgerüst mit —SO2—OH -Gruppen auf. Unter Weiterrühren der Lösung bei Raumtemperatur fügte man 83 g (1,2MoI) Natriumnitrit hinzu. Nach ca. 2 Std. wurde das Harz abfiltriert, zweimal mit 101 entmineralisiertem Wasser gewaschen und dann auf eine Säule (Durchmesser 11 cm, Höhe 1 m) übergeführt. Das Harz wurde dannTo man slurried 195 g (1 mol) of D-N-carbamoyl-phenylglycine with an optical purity of 99% in 10 l of deionized water in the presence of 8 l of cation exchanger with a cross-linked polystyrene structure with —SO2 — OH groups. While continuing to stir the Solution at room temperature was added 83 g (1.2MoI) Add sodium nitrite. After about 2 hours, the resin was filtered off, twice with 101% of demineralized water washed and then transferred to a column (diameter 11 cm, height 1 m). The resin was then
w mit 2-m Ammoniak eluiert: Die Aminosäure liegt in ihrer Gesamtheit in der Fraktion von 10 bis 15 1 Eluat vor.w eluted with 2-m ammonia: the amino acid is in its entirety in the fraction of 10 to 15 l of eluate before.
Die Lösung des Ammoniumsalzes des D-Phenylglycins (5 1) wird unter vermindertem Druck zur Trockne eingedampft. Es werden 150 g (99% d. Th.) D(-)-Phenylglycin mit einem Wert für [<x]7S von 157° (c=0,5; HCI 1 n), d. h. einer optischen Reinheit von mehr als 98%, wenn man für den [oc] f-Wert die Daten der technischen Literatur (Org. Synth., 22, 23, 1942) zugrunde legt, erhalten.The solution of the ammonium salt of D-phenylglycine (5 l) is evaporated to dryness under reduced pressure. 150 g (99% of theory) of D (-) - phenylglycine with a value for [<x] 7 S of 157 ° (c = 0.5; HCl 1 n), ie an optical purity of more than 98% if the data from the technical literature (Org. Synth., 22, 23, 1942) is used as a basis for the [oc] f value.
Wenn man die in Beispiel 1 angegebene Verfahrensweise befolgt und von 132 g (1 Mol) L-N-Carbamoyl-aalanin mit einer optischen Reinheit von 98% ausgeht, werden 87 g (0,98 Mol) L-a-Alanin mit einem Wert für [λ] "von +14,3° (C= 2; HCI In) (Literaturwert für [λ]"= + 14,7, J. Chem.Soc, 113,526,1918) erhalten.If the procedure given in Example 1 is followed and starting from 132 g (1 mol) of LN-carbamoyl-aalanine with an optical purity of 98%, 87 g (0.98 mol) of La-alanine with a value for [λ] "of + 14.3 ° (C = 2; HCI In) (literature value for [λ]" = + 14.7, J. Chem. Soc, 113,526,1918).
Wenn man das Verfahren der Beispiele 1 und 2 befolgt und von 16Og(I Mol) L-N-Carbamoyl-valin mit einer optischen Reinheit von 97% ausgeht, erhält man HOg (0,94MoI) L-Valin; [a]g>=28,2o (c= 3; HCI 6 n), Literaturwert für[«] S1= 28.8° (Ber, 39,2320,1906).If the procedure of Examples 1 and 2 is followed and starting from 160 g (1 mol) LN-carbamoyl-valine with an optical purity of 97%, one receives HOg (0.94 mol) L-valine; [a] g> = 28.2 o (c = 3; HCI 6 n), literature value for [«] S 1 = 28.8 ° (Ber, 39.2320.1906).
Wenn man die Verfahrensweise der Beispiele 1 und 3 befolgt und von 192 g (1 Mol) L-N-Carbamoyl-methionin mit einer hohen optischen Reinheit von 99%If the procedure of Examples 1 and 3 is followed and 192 g (1 mol) of L-N-carbamoyl-methionine with a high optical purity of 99% ausgeht, erhält man 145 g (0,97 Mol) L-Methionin; [α] »=-8,01° (c= 0,8 Wasser) (Literaturwert für [Ot]0= -8(11°;J. Am.Chem.Soc,53,3490,1931).goes out, 145 g (0.97 mol) of L-methionine are obtained; [α] »= -8.01 ° (c = 0.8 water) (literature value for [Ot] 0 = -8 ( 11 °; J. Am. Chem. Soc, 53.3490, 1931).
Wenn man die in den Beispielen 2 und 4 beschriebenen Verfahrensweisen befolgt und von 190 g (1 Mol) L-N-Carbamoyl-glutaminsäure mit einer optischen Reinheit von 98% ausgeht, erhält man 183 g ίο (0,96 Mol) L-Glutaminsäure; [α]? = 31° (c= 1; HCl 6 n) (Literaturwert für [α]'/= + 31,2°; Ber, 40,3717.1907).If the procedures described in Examples 2 and 4 are followed and starting from 190 g (1 mol) of LN-carbamoylglutamic acid with an optical purity of 98%, 183 g of ίο (0.96 mol) of L-glutamic acid are obtained; [α]? = 31 ° (c = 1; HCl 6 n) (literature value for [α] '/ = + 31.2 °; Ber, 40.3717.1907).
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT22144/75A IT1037176B (en) | 1975-04-09 | 1975-04-09 | PROCEDURE FOR THE PREPARATION OF AMINDACIDS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2615594A1 DE2615594A1 (en) | 1976-10-14 |
| DE2615594B2 DE2615594B2 (en) | 1978-07-20 |
| DE2615594C3 true DE2615594C3 (en) | 1979-03-15 |
Family
ID=11192138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2615594A Expired DE2615594C3 (en) | 1975-04-09 | 1976-04-09 | Process for the preparation of aminocarboxylic acids |
Country Status (38)
| Country | Link |
|---|---|
| JP (1) | JPS5940823B2 (en) |
| AR (1) | AR217052A1 (en) |
| AT (1) | AT343092B (en) |
| AU (1) | AU503651B2 (en) |
| BE (1) | BE840527A (en) |
| BG (1) | BG24664A3 (en) |
| BR (1) | BR7602173A (en) |
| CA (1) | CA1058213A (en) |
| CH (1) | CH620421A5 (en) |
| CS (1) | CS194756B2 (en) |
| DD (1) | DD123599A5 (en) |
| DE (1) | DE2615594C3 (en) |
| DK (1) | DK146622C (en) |
| EG (1) | EG12543A (en) |
| ES (1) | ES447176A1 (en) |
| FR (1) | FR2306976A1 (en) |
| GB (1) | GB1490054A (en) |
| HU (1) | HU176009B (en) |
| IE (1) | IE42673B1 (en) |
| IL (1) | IL49372A (en) |
| IN (1) | IN144346B (en) |
| IT (1) | IT1037176B (en) |
| LU (1) | LU74714A1 (en) |
| MW (1) | MW1076A1 (en) |
| MX (1) | MX3304E (en) |
| MY (1) | MY7900100A (en) |
| NL (1) | NL7603816A (en) |
| NO (1) | NO143901C (en) |
| PH (1) | PH12101A (en) |
| PL (1) | PL104015B1 (en) |
| PT (1) | PT64983B (en) |
| RO (1) | RO70427A (en) |
| SE (1) | SE409701B (en) |
| SU (1) | SU670213A3 (en) |
| TR (1) | TR18877A (en) |
| YU (1) | YU90376A (en) |
| ZA (1) | ZA761941B (en) |
| ZM (1) | ZM4476A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS584707B2 (en) * | 1977-02-21 | 1983-01-27 | 鐘淵化学工業株式会社 | Method for producing optically active phenylglycines |
| IT1204979B (en) * | 1987-04-28 | 1989-03-10 | Eniricerche Spa | SUMMARY OF OPTICALLY ACTIVE ALPHA AMINO ACIDS |
| FR2725991B1 (en) * | 1994-10-24 | 1997-01-17 | Univ Montpellier Ii | PROCESS FOR PEPTIDE SYNTHESIS FROM N- (N '- (R') - N '-NITROSOCARBAMOYLS) AMINOACIDS |
| CN1057518C (en) * | 1995-09-29 | 2000-10-18 | 中国科学院微生物研究所 | Process for preparation of optically active amino-acid by hot- hydrolysis of nitrogen-ammonia formyl-amino acid |
| US6087136A (en) * | 1997-03-31 | 2000-07-11 | Council Of Scientific & Industrial Research | Microbial process for the production of D(-)-N-carbamoylphenylglycine |
| CN105601542B (en) * | 2016-01-08 | 2017-10-24 | 南京工业大学 | Method for crystallizing N-carbamylglutamic acid by using mixed acid |
-
1975
- 1975-04-09 IT IT22144/75A patent/IT1037176B/en active
-
1976
- 1976-03-31 DK DK154676A patent/DK146622C/en not_active IP Right Cessation
- 1976-03-31 ZA ZA761941A patent/ZA761941B/en unknown
- 1976-04-01 MW MW10/76A patent/MW1076A1/en unknown
- 1976-04-02 CA CA249,437A patent/CA1058213A/en not_active Expired
- 1976-04-05 AU AU12648/76A patent/AU503651B2/en not_active Expired
- 1976-04-05 ZM ZM44/76A patent/ZM4476A1/en unknown
- 1976-04-05 EG EG196/76A patent/EG12543A/en active
- 1976-04-05 CH CH423676A patent/CH620421A5/en not_active IP Right Cessation
- 1976-04-06 TR TR18877A patent/TR18877A/en unknown
- 1976-04-06 GB GB13783/76A patent/GB1490054A/en not_active Expired
- 1976-04-07 LU LU74714A patent/LU74714A1/xx unknown
- 1976-04-07 DD DD192242A patent/DD123599A5/xx unknown
- 1976-04-07 PT PT64983A patent/PT64983B/en unknown
- 1976-04-07 NO NO761189A patent/NO143901C/en unknown
- 1976-04-07 FR FR7610087A patent/FR2306976A1/en active Granted
- 1976-04-08 BE BE165963A patent/BE840527A/en not_active IP Right Cessation
- 1976-04-08 IE IE737/76A patent/IE42673B1/en unknown
- 1976-04-08 IL IL49372A patent/IL49372A/en unknown
- 1976-04-08 HU HU76SA2914A patent/HU176009B/en unknown
- 1976-04-08 PH PH18315A patent/PH12101A/en unknown
- 1976-04-08 IN IN611/CAL/76A patent/IN144346B/en unknown
- 1976-04-08 BR BR7602173A patent/BR7602173A/en unknown
- 1976-04-08 AT AT258276A patent/AT343092B/en not_active IP Right Cessation
- 1976-04-08 YU YU00903/76A patent/YU90376A/en unknown
- 1976-04-08 CS CS762334A patent/CS194756B2/en unknown
- 1976-04-09 MX MX000157U patent/MX3304E/en unknown
- 1976-04-09 BG BG032860A patent/BG24664A3/en unknown
- 1976-04-09 RO RO7685571A patent/RO70427A/en unknown
- 1976-04-09 JP JP51039420A patent/JPS5940823B2/en not_active Expired
- 1976-04-09 SU SU762343157A patent/SU670213A3/en active
- 1976-04-09 ES ES447176A patent/ES447176A1/en not_active Expired
- 1976-04-09 AR AR262843A patent/AR217052A1/en active
- 1976-04-09 DE DE2615594A patent/DE2615594C3/en not_active Expired
- 1976-04-09 SE SE7604237A patent/SE409701B/en unknown
- 1976-04-09 PL PL1976188626A patent/PL104015B1/en unknown
- 1976-04-09 NL NL7603816A patent/NL7603816A/en active Search and Examination
-
1979
- 1979-12-30 MY MY100/79A patent/MY7900100A/en unknown
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