NO143901B - PROCEDURE FOR THE PREPARATION OF AMINO ACIDS. - Google Patents
PROCEDURE FOR THE PREPARATION OF AMINO ACIDS. Download PDFInfo
- Publication number
- NO143901B NO143901B NO761189A NO761189A NO143901B NO 143901 B NO143901 B NO 143901B NO 761189 A NO761189 A NO 761189A NO 761189 A NO761189 A NO 761189A NO 143901 B NO143901 B NO 143901B
- Authority
- NO
- Norway
- Prior art keywords
- carbamyl
- amino acids
- amino acid
- procedure
- preparation
- Prior art date
Links
- 150000001413 amino acids Chemical class 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 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 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229940024606 amino acid Drugs 0.000 description 14
- 235000001014 amino acid Nutrition 0.000 description 14
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 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
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis 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
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 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
- 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
- JDXMIYHOSFNZKO-BYPYZUCNSA-N N-carbamoyl-L-valine Chemical compound CC(C)[C@@H](C(O)=O)NC(N)=O JDXMIYHOSFNZKO-BYPYZUCNSA-N 0.000 description 1
- 235000004279 alanine Nutrition 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
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 150000001469 hydantoins Chemical class 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
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 229960004295 valine Drugs 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
Foreliggende oppfinnelse vedrører en fremgangsmåte for fremstilling av aminosyrer, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at N-karbamylderivatet som tilsvarer den angjeldende amino-syre, eller et salt derav, i nærvær av en ionebytter-harpiks som inneholder sure grupper, omsettes med 1-1,5 ekvivalenter salpetersyrling eller et av dens salter ved en temperatur på 0-40°C. The present invention relates to a method for the production of amino acids, and the distinctive feature of the method according to the invention is that the N-carbamyl derivative corresponding to the amino acid in question, or a salt thereof, in the presence of an ion exchange resin containing acidic groups, is reacted with 1-1.5 equivalents of nitric acid or one of its salts at a temperature of 0-40°C.
Disse trekk ved oppfinnelsen fremgår av patentkravet. These features of the invention appear in the patent claim.
Det er kjent at optisk aktive karbamylderivater av amino-syrer kan fremstilles fra de tilsvarende racemiske hydantoiner ved stereoselektiv enzymhydrolyse, se f.eks. tysk off. skrift 242 27 37. It is known that optically active carbamyl derivatives of amino acids can be prepared from the corresponding racemic hydantoins by stereoselective enzyme hydrolysis, see e.g. german off. script 242 27 37.
Det således oppnådde karbamylderivat ble deretter omdannet til den tilsvarende aminosyre ved enkel koking i en vandig, løsning. The carbamyl derivative thus obtained was then converted into the corresponding amino acid by simple boiling in an aqueous solution.
Hydrolysen av karbamylderivatet til aminosyre, bevirket til å foregå under disse betingelser, var imidlertid meget langsom og krevet en nøyaktig kontroll av arbeidsbeting-elsene og ga enkelte ganger anledning til dannelse av biprodukter med en nedsettelse av utbyttet og endog en delvis racemisering. The hydrolysis of the carbamyl derivative to amino acid, caused to take place under these conditions, was, however, very slow and required a precise control of the working conditions and sometimes gave rise to the formation of by-products with a reduction in the yield and even a partial racemization.
Et formål for den foreliggende oppfinnelsen er å tilveie-bringe en fremgangsmåte for en særegen og enkel omdannelse av karbamylderivatene til de tilsvarende aminosyrer, som foregår under milde betingelser slik at den derved frem-stilte aminosyre fremdeles bibeholder den optiske renhet av utgangs-karbamylderivatet. Dette resultat er ytterst overraskende, da det tidligere var kjent at den anvendte type oksydasjonsmidler virket på aminogruppen i aminosyren til å gi den tilsvarende hydroksysyre og at det da var umulig å omdanne karbamylderivatet til dets aminosyre, An object of the present invention is to provide a method for a distinctive and simple conversion of the carbamyl derivatives into the corresponding amino acids, which takes place under mild conditions so that the thereby produced amino acid still retains the optical purity of the starting carbamyl derivative. This result is extremely surprising, as it was previously known that the type of oxidizing agents used acted on the amino group in the amino acid to give it the corresponding hydroxy acid and that it was then impossible to convert the carbamyl derivative into its amino acid,
da den siste øyeblikkelig ble omdannet til hydroksysyre. when the latter was instantly converted into hydroxy acid.
I motsetning hertil er det ved den foreliggende oppfinnelse erkjent at når man arbeider under passende betingelser for pH og temperatur, oppnås overraskende høye utbytter i og med at aminosyren er fullstendig skånet for angrep av den oksyderende reaksjonskomponent. In contrast to this, it is recognized in the present invention that when working under suitable conditions for pH and temperature, surprisingly high yields are achieved in that the amino acid is completely spared from attack by the oxidizing reaction component.
Den ovenfor angitte fremgangsmåte gjennomføres ved å opp-løse karbamylderivatet, eller et salt derav, i vann i ønsket konsentrasjon, foretrukket nær metningskonsentra-sjon. Oppløsningen tilsettes en mengde av en sur ione-veksler-harpiks med en utvekslingskapasitet slik at den kan binde fra 1,1 til 5 mol produkt. Under dette trinn nedsettes pH og karbamylderivatet, i overskuddsmengde i forhold til dets oppløselighet, utfelles. The above-mentioned method is carried out by dissolving the carbamyl derivative, or a salt thereof, in water in the desired concentration, preferably close to saturation concentration. To the solution is added a quantity of an acidic ion-exchange resin with an exchange capacity such that it can bind from 1.1 to 5 moles of product. During this step, the pH is lowered and the carbamyl derivative, in excess of its solubility, is precipitated.
Som sure ionebytter-harpikser kan det anvendes harpikser med forskjellige sure grupper, men harpikser av sulfon-' syretypen foretrekkes. As acidic ion exchange resins, resins with various acidic groups can be used, but resins of the sulfonic acid type are preferred.
Etter fullført omsetning elueres aminosyren fra After completion of the reaction, the amino acid is eluted from
harpiksen med en base. Harpiksen kan bringes tilbake til sin sure form. Fra eluatet isoleres aminosyren med enkle operasjoner for konsentrering og krystallisering. the resin with a base. The resin can be brought back to its acidic form. From the eluate, the amino acid is isolated with simple operations for concentration and crystallization.
Arbeidsmåten som angitt ovenfor og ytterligere detaljer vil fremgå klarere fra de følgende utførelseseksempler. The way of working as stated above and further details will appear more clearly from the following examples of execution.
SAMMENLIGNINGSEKSEMPEL COMPARISON EXAMPLE
50 ml av en 25 mM løsning av N-karbamyl-(X.-alanin behandles ved 0°C ved 5 ml av en 50 mM løsning av NaNC^ i vann. Konsentrasjonen av aminosyren i løsningen måles fra tid til annen. Konsentrasjonen var maksimalt 5mM etter den første times reaksjon, men sank sakte og falt etter 5 timer til 3,2 mM. 50 ml of a 25 mM solution of N-carbamyl-(X.-alanine) is treated at 0°C with 5 ml of a 50 mM solution of NaNC^ in water. The concentration of the amino acid in the solution is measured from time to time. The concentration was maximum 5mM after the first hour of reaction, but decreased slowly and fell after 5 hours to 3.2mM.
Kromatografisk analyse av blandingen viser nærværet av en betraktelig mengde melkesyre. Chromatographic analysis of the mixture shows the presence of a considerable amount of lactic acid.
EKSEMPEL 1 EXAMPLE 1
194 g (1 mol) D-N-karbamyl-fenylglycin med en optisk renhet på 99% oppslemmes i 10 1 av deionisert vann, i nærvær av 8 liter "Amberlite" I.R. 120 (H<+>). Ved å holde opp-løsningen omrørt ved romtemperatur tilsettes 83 g (1,2 mol) natriumnitritt. Etter omtrent 2 timer frafiltreres harpiksen, vaskes to ganger med 10 liter demineralisert vann og overføres deretter til en kolonne (diameter 11 cm, 194 g (1 mole) of D-N-carbamyl-phenylglycine with an optical purity of 99% is slurried in 10 1 of deionized water, in the presence of 8 liters of "Amberlite" I.R. 120 (H<+>). By keeping the solution stirred at room temperature, 83 g (1.2 mol) of sodium nitrite are added. After about 2 hours, the resin is filtered off, washed twice with 10 liters of demineralized water and then transferred to a column (diameter 11 cm,
høyde 1 meter). Harpiksen elueres så med 2 m ammoniakk. Aminosyren er i sin helhet tilstede i fraksjonen fra 10 height 1 meter). The resin is then eluted with 2 m ammonia. The amino acid is present in its entirety in the fraction from 10
til 15 liter eluat. to 15 liters of eluate.
Oppløsningen av ammoniumsaltet av D-fenylglycin, 5 liter, inndampes under redusert trykk til tørrhet. Det oppnås på denne måte 150 g (99% av teoretisk utbytte) D(-)fenylglycin med (°0D<2>° = 150° (c = 0,5, HC1, ln), det vil si en optisk renhet på mer enn 98% på bakgrunn av verdien for The solution of the ammonium salt of D-phenylglycine, 5 liters, is evaporated under reduced pressure to dryness. 150 g (99% of theoretical yield) of D(-)phenylglycine with (°0D<2>° = 150° (c = 0.5, HC1, ln) is obtained in this way, i.e. an optical purity of more than 98% on the basis of the value for
20 20
(ot)D tatt fra den tekniske litteratur (Org. Synth. 22, (ot)D taken from the technical literature (Org. Synth. 22,
23, 1942). 23, 1942).
EKSEMPEL 2 EXAMPLE 2
Ved å anvende den samme fremgangsmåte som angitt i eksempel 2, ved å gå ut fra 112 g (1 mol) L-N-karbamyl-a- alanin med en optisk renhet på 98% oppnås 87 g (0,98 mol) L-ct-alanin med (cOp20 = + 14,4°, (c = 2, HC1, ln)' (fra litteraturen (°0D15 = + 14,7°, J. Chem. Soc 113, 526 , 1918). Using the same procedure as stated in example 2, starting from 112 g (1 mol) of L-N-carbamyl-α-alanine with an optical purity of 98%, 87 g (0.98 mol) of L-ct- alanine with (cOp20 = + 14.4°, (c = 2, HC1, ln)' (from the literature (°0D15 = + 14.7°, J. Chem. Soc 113, 526 , 1918).
EKSEMPEL 3 EXAMPLE 3
Med den samme fremgangsmåte som angitt i eksemplene 1 og 2 og ved å gå ut fra 160 g (1 mol) L-N-karbamyl-valin med en optisk renhet på 97%, ble det oppnådd 110 g (0,94 mol) L-valin (a) <20> = 28,2° (c =3,HC1, 6n). Verdi fra litteraturen: (a)D = 28,8°, Ber. 39, 2320, 9106). Using the same procedure as stated in examples 1 and 2 and starting from 160 g (1 mol) of L-N-carbamyl-valine with an optical purity of 97%, 110 g (0.94 mol) of L-valine were obtained (a) <20> = 28.2° (c = 3.HCl, 6n). Value from the literature: (a)D = 28.8°, Ber. 39, 2320, 9106).
EKSEMPEL 4 EXAMPLE 4
Ved å anvende samme fremgangsmåte som i eksempel 1 og 3, ble det fra 192 g (1 mol) L-N-karbamyl-metionin med en optisk renhet så høy som 99%, oppnådd 145 g (0,97 mol) L-metionin. { a) = 8,01° (c = 0,8 vann) (litteraturen angir (a) = - 8,11°, J. Am. Chem. Soc., 53, 3490, 1931). Using the same procedure as in examples 1 and 3, 145 g (0.97 mol) of L-methionine was obtained from 192 g (1 mol) of L-N-carbamyl-methionine with an optical purity as high as 99%. { a) = 8.01° (c = 0.8 water) (the literature states (a) = - 8.11°, J. Am. Chem. Soc., 53, 3490, 1931).
EKSEMPEL 5 EXAMPLE 5
Med samme fremgangsmåte som beskrevet i eksempel 1 og 3 ble det fra 190 g (1 mol) N-L-karbamyl-glutaminsyre med en optisk renhet på 98% oppnådd 183 g (0,96 mol) L-glutamin-syre (a) <2>^ = + 31° (c = 1; HC1, 6n) (litteraturen angir (a) = + 31,2°, Ber., 40,3717, 1907). Using the same method as described in examples 1 and 3, 183 g (0.96 mol) of L-glutamic acid (a) <2 were obtained from 190 g (1 mol) of N-L-carbamyl-glutamic acid with an optical purity of 98% >^ = + 31° (c = 1; HC1, 6n) (the literature states (a) = + 31.2°, Ber., 40.3717, 1907).
Claims (1)
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 |
|---|---|
| NO761189L NO761189L (en) | 1976-10-12 |
| NO143901B true NO143901B (en) | 1981-01-26 |
| NO143901C NO143901C (en) | 1981-05-06 |
Family
ID=11192138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO761189A NO143901C (en) | 1975-04-09 | 1976-04-07 | PROCEDURE FOR THE PREPARATION OF AMINO 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 | A kind of method that nitration mixture crystallizes N carbamylglutamic acids |
-
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 EG EG196/76A patent/EG12543A/en active
- 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 CH CH423676A patent/CH620421A5/en not_active IP Right Cessation
- 1976-04-06 GB GB13783/76A patent/GB1490054A/en not_active Expired
- 1976-04-06 TR TR18877A patent/TR18877A/en unknown
- 1976-04-07 DD DD192242A patent/DD123599A5/xx unknown
- 1976-04-07 FR FR7610087A patent/FR2306976A1/en active Granted
- 1976-04-07 PT PT64983A patent/PT64983B/en unknown
- 1976-04-07 LU LU74714A patent/LU74714A1/xx unknown
- 1976-04-07 NO NO761189A patent/NO143901C/en unknown
- 1976-04-08 HU HU76SA2914A patent/HU176009B/en unknown
- 1976-04-08 BE BE165963A patent/BE840527A/en not_active IP Right Cessation
- 1976-04-08 PH PH18315A patent/PH12101A/en unknown
- 1976-04-08 IN IN611/CAL/76A patent/IN144346B/en unknown
- 1976-04-08 YU YU00903/76A patent/YU90376A/en unknown
- 1976-04-08 IL IL49372A patent/IL49372A/en unknown
- 1976-04-08 IE IE737/76A patent/IE42673B1/en unknown
- 1976-04-08 CS CS762334A patent/CS194756B2/en unknown
- 1976-04-08 AT AT258276A patent/AT343092B/en not_active IP Right Cessation
- 1976-04-08 BR BR7602173A patent/BR7602173A/en unknown
- 1976-04-09 PL PL1976188626A patent/PL104015B1/en unknown
- 1976-04-09 BG BG7600032860A patent/BG24664A3/en unknown
- 1976-04-09 RO RO7685571A patent/RO70427A/en unknown
- 1976-04-09 AR AR262843A patent/AR217052A1/en active
- 1976-04-09 SU SU762343157A patent/SU670213A3/en active
- 1976-04-09 JP JP51039420A patent/JPS5940823B2/en not_active Expired
- 1976-04-09 NL NL7603816A patent/NL7603816A/en active Search and Examination
- 1976-04-09 MX MX000157U patent/MX3304E/en unknown
- 1976-04-09 SE SE7604237A patent/SE409701B/en unknown
- 1976-04-09 ES ES447176A patent/ES447176A1/en not_active Expired
- 1976-04-09 DE DE2615594A patent/DE2615594C3/en not_active Expired
-
1979
- 1979-12-30 MY MY100/79A patent/MY7900100A/en unknown
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