DK146622B - PROCEDURE FOR PREPARING AMINO ACIDS FROM THE SIMILAR N-CARBAMYLAMINOS ACIDS - Google Patents
PROCEDURE FOR PREPARING AMINO ACIDS FROM THE SIMILAR N-CARBAMYLAMINOS ACIDS Download PDFInfo
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- DK146622B DK146622B DK154676AA DK154676A DK146622B DK 146622 B DK146622 B DK 146622B DK 154676A A DK154676A A DK 154676AA DK 154676 A DK154676 A DK 154676A DK 146622 B DK146622 B DK 146622B
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- Prior art keywords
- acids
- carbamylaminos
- procedure
- similar
- amino acids
- Prior art date
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- 150000001413 amino acids Chemical class 0.000 title description 17
- 238000000034 method Methods 0.000 title description 10
- 239000002253 acid Substances 0.000 title description 7
- 150000007513 acids Chemical class 0.000 title 1
- 229940024606 amino acid Drugs 0.000 description 16
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- -1 N-carbamylamino acids Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 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
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 229960004295 valine Drugs 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
- 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
- 230000002378 acidificating effect Effects 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
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 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
- 230000003467 diminishing effect Effects 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000000376 reactant Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003756 stirring Methods 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
/ Λ ' (19) DANMARK \PEy/ Λ '(19) DENMARK \ PEy
f,i2) FREMLÆGGELSESSKRIFT (n) 146622 Bf, i2) PUBLICATION MANUAL (n) 146622 B
DIREKTORATET FOR PATENT- OG VAREMÆRKEVÆSENETDIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM
(21) Patentansøgning nr.: 1546/76 (51) Int.CI.3: C 07 C 99/00 (22) Indleveringsdag: 31 mar 1976 (41) Aim. tilgængelig: 10 old 1976 (44) Fremlagt: 21 nov 1983 (86) International ansøgning nr.: - (30) Prioritet: 09 apr1975IT22144/75 (71) Ansøger: *ANIC S.P.A.; Palermo, IT.(21) Patent Application No. 1546/76 (51) Int.CI.3: C 07 C 99/00 (22) Filing Date: 31 Mar 1976 (41) Aim. available: 10 old 1976 (44) Submitted: 21 Nov 1983 (86) International Application No: - (30) Priority: 09 Apr1975IT22144 / 75 (71) Applicant: * ANIC S.P.A.; Palermo, IT.
(72) Opfinder: Francesco ‘Cecere; IT, Walter 'Marconi; IT, Franco 'Morisi; IT, Bruno 'Rappuoli; IT.(72) Inventor: Francesco 'Cecere; IT, Walter 'Marconi; IT, Franco 'Morisi; IT, Bruno 'Rappuoli; IT.
(74) Fuldmægtig: Internationalt Patent-Bureau_ (54) Fremgangsmåde til fremstilling af aminosyrer ud fra de tilsvarende N-carbamylaminosyrer(74) Plenipotentiary: International Patent Bureau_ (54) Process for the preparation of amino acids from the corresponding N-carbamylamino acids
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af aminosyrer ud fra de tilsvarende N-carbamylaminosyrer.The present invention relates to a process for preparing amino acids from the corresponding N-carbamylamino acids.
Det er kendt, at optisk aktive N-carbamylderivater af aminosyrer kan vindes ud fra de tilsvarende racemiske hydantoiner ved stereo-selektiv enzym-hydrolyse, ® således som beskrevet i DE patentskrift nr. 24 22 737.It is known that optically active N-carbamyl derivatives of amino acids can be recovered from the corresponding racemic hydantoins by stereo-selective enzyme hydrolysis, as described in DE Patent No. 24,227,377.
Det saledes vundne N-carbamylderivat blev derefter omdannet til den til-® svarende aminosyre ved blot at koge det i en vandig opløsning.The N-carbamyl derivative thus obtained was then converted to the corresponding amino acid by simply boiling it in an aqueous solution.
Ϊ Den hydrolyse af N-carbamylderivattil aminosyre, der bevirkes under sådan- ^ ne betingelser, er imidlertid meget langsom og kræver en nøje kontrol af arbejds- 2 betingelserne og giver undertiden anledning til biprodukter med deraf følgende formindskelse af udbyttet og endog partiel racemisering.Imidlertid However, the hydrolysis of N-carbamyl derivative to amino acid produced under such conditions is very slow and requires close control of the working conditions and sometimes gives rise to by-products resulting in diminishing yield and even partial racemization.
2 1A 6 6 2 22 1A 6 6 2 2
Den foreliggende opfindelse tilvejebringer en hidtil ukendt og simpel fremgangsmåde til fremstilling af aminosyrer ud fra de tilsvarende N-carbamylaminosyrer, hvilken fremstilling finder sted under milde betingelser, således at den frembragte aminosyre stadig har·samme optiske renhed som det som udgangsmateriale andvendte N-carbamylderivat.The present invention provides a novel and simple method for preparing amino acids from the corresponding N-carbamylamino acids, which preparation takes place under mild conditions such that the produced amino acid still has the same optical purity as the starting material used as N-carbamyl derivative.
Fremgangsmåden ifølge opfindelsen er ejendommelig ved, at N-carbamylderi-vatet eller et salt af dette derivat i vandig opløsning omsættes med 1 til 1,5 ækvivalenter salpetersyrling eller et salt deraf i nærværelse af en syregruppe-holdig, kationisk ionbytterharpiks, der anvendes i en sådan mængde, at den kan binde 1-5 mol produkt pr.mol N-carbamylaminosyre, ved en temperatur på fra 0 til 40°C, hvorefter den dannede forbindelse elueres fra harpiksen med en base.The process of the invention is characterized in that the N-carbamyl derivative or a salt of this derivative in aqueous solution is reacted with 1 to 1.5 equivalents of nitric acid or a salt thereof in the presence of an acid group-containing cationic ion exchange resin used in an aqueous solution. such that it can bind 1-5 moles of product per mole of N-carbamylamino acid, at a temperature of from 0 to 40 ° C, after which the compound formed is eluted from the resin with a base.
Forløbet af denne fremgangsmåde var meget overraskende, idet det er kendt, at oxiderende midler indvirker på aminosyrens aminogruppe under øjeblikkelig omdannelse af aminosyren til den tilsvarende hydroxysyre og således umuliggør udvinding af aminosyren.The course of this process was very surprising in that it is known that oxidizing agents act on the amino acid of the amino acid during immediate conversion of the amino acid to the corresponding hydroxy acid, thus making it impossible to recover the amino acid.
Det har imidlertid vist sig, at når der arbejdes ved de til fremgangsmåden ifølge opfindelsen foreskrevne temperaturbetingelser og de som følge af ioribytter-harpiksens tilstedeværelse foreliggendepH-betingelser, er aminogruppen fuldstændigt fri for angreb fra den oxiderende reaktant, og der kan overraskende opnås høje udbytter af aminosyren.However, it has been found that when employed at the temperature conditions prescribed for the process of the invention and the pH conditions of the ioribylate resin present, the amino group is completely free from attack by the oxidizing reactant and surprisingly high yields of the amino acid.
Den ovenfor beskrevne fremgangsmåde gennemføres ved at opløse N-carbamyl-derivatet, eller et salt deraf, i vand i variabel koncentration, fortrinsvis nær mætning. Til opløsningen sættes en syregruppeholdig, kationisk ionbytterharpiks med ovennævnte bindingsevne. Under dette trin falder pH-værdien, og N-carbamyl-derivatet, der som følge heraf foreligger i overskud i forhold til dets opløselighed, udfældes. Der tilsættes fra 1 til 1,5 ækvivalenter salpetersyrling eller et salt deraf, hvorhos hele omsætningen gennemføres ved en temperatur i området fra 0°C til 40°C.The above-described process is carried out by dissolving the N-carbamyl derivative, or a salt thereof, in variable concentration water, preferably near saturation. To the solution is added an acid group-containing cationic ion exchange resin having the above-mentioned binding ability. During this step, the pH decreases and the N-carbamyl derivative which, as a result, is in excess of its solubility is precipitated. Add from 1 to 1.5 equivalents of nitric acid or a salt thereof, the whole reaction being carried out at a temperature in the range of 0 ° C to 40 ° C.
Som kationiske harpikser kan anvendes harpikser med forskellige sure grupper, men den anvendte harpiks er ifølge opfindelsen fortrinsvis af sulfonsyrety-pen.As cationic resins, resins having different acidic groups can be used, but the resin used according to the invention is preferably of the sulfonic acid type.
Ved endt reaktion bliver aminosyren elueret fra harpiksen med en base, og harpiksen kan atter bringes i syreform. Fra eluatet isoleres aminosyren ved simple koncentrerings- og krystallisations-operationer.Upon completion of the reaction, the amino acid is eluted from the resin with a base and the resin can again be acidified. From the eluate, the amino acid is isolated by simple concentration and crystallization operations.
Fremgangsmåden ifølge opfindelsen beskrives nærmere gennem følgende eksempler.The process according to the invention is further described by the following examples.
3 1466223 146622
Eksempel 1 (Sammenligning) 50 ml af en 25 mM opløsning af N-carbamyl-a-alanin blev behandlet ved 0°C med 5 ml af en 50 mM opløsning af NalW^ i vand. Koncentrationen af aminosyren i opløsningen blev lejlighedsvis målt. Efter at koncentrationen i løbet af den første times reaktion havde nået et loft på 5mM, sank den langsomt og var efter 5 timer faldet til 3,2 mM.Example 1 (Comparison) 50 ml of a 25 mM solution of N-carbamyl-α-alanine was treated at 0 ° C with 5 ml of a 50 mM solution of NalW 2 in water. The concentration of the amino acid in the solution was occasionally measured. After the concentration reached a ceiling of 5mM during the first hour of reaction, it slowly decreased and after 5 hours dropped to 3.2mM.
Chromatografi-analyse af blandingen viste tilstedeværelse af en betydelig mængde mælkesyre.Chromatography analysis of the mixture showed the presence of a significant amount of lactic acid.
Eksempel 2 194 g (1 mol) D-N-carbamyl-phenylglycin med en optisk renhed på 99% blev opslemmet i 10 liter deioniseret vand i nærværelse af 8 literVAmberlite'^I.R. 120 (H+). Under omrøring af opløsningen ved stuetemperatur blev der tilsat 83 g (1,2 mol) natriumnitrit. Efter ca. 2 timer blev harpiksen frafiltreret, vasket to gange med 10 liter demineraliseret vand og derefter overført til en søjle (diameter 11 cm, højde 1 m). Harpiksen blev derefter elueret med 2M ammoniak. Al aminosyren var tilstede i fraktionen fra 10 til 15 liter af eluat.Example 2 194 g (1 mole) of D-N-carbamyl-phenylglycine with an optical purity of 99% were slurried in 10 liters of deionized water in the presence of 8 liters of VAmberlite 120 (H +). While stirring the solution at room temperature, 83 g (1.2 mol) of sodium nitrite was added. After approx. For 2 hours, the resin was filtered off, washed twice with 10 liters of demineralized water and then transferred to a column (diameter 11 cm, height 1 m). The resin was then eluted with 2M ammonia. All the amino acid was present in the fraction of 10 to 15 liters of eluate.
Opløsningen af ammoniumsaltet af D-phenylglycin, 5 liter, blev inddampet til tørhed under reduceret tryk. Herved vandtes 150 g (99% af det teoretiske) D(-)-phenylglycin med [of]_ =-157° (c = 0,5, HC1 IN), hvilket er en optisk renhed højere end 987° ved som [a]^ at tage værdien fra den tekniske litteratur (Org.The 5-liter solution of the ammonium salt of D-phenylglycine was evaporated to dryness under reduced pressure. This yielded 150 g (99% of theory) of D (-) - phenylglycine with [of] _ = -157 ° (c = 0.5, HCl 1N), which is an optical purity higher than 987 ° at as [a ] ^ to take the value from the technical literature (Org.
Synth. 22, 23, 1942).Synth. 22, 23, 1942).
Eksempel 3Example 3
Ved at anvende samme fremgangsmåde som i Eksempel 2, men gå ud fra 132 g (1 mol) L-N-carbamyl-a-alanin med en optisk renhed på 98%,»vandtes 87 g (0,98 mol) L-a-alanin med [a]^° = +14,3° (c = 2,HC1 IN) (fra litteraturen [a]^ = 14,7°, J. Chem. Soc. 113, 526, 1918).Using the same procedure as in Example 2, but starting from 132 g (1 mole) of LN-carbamyl-α-alanine with an optical purity of 98%, 87 g (0.98 mole) of La-alanine were obtained with [ a] + = 14.3 ° (c = 2, HCl IN) (from the literature [a] + = 14.7 °, J. Chem. Soc. 113, 526, 1918).
Eksempel 4Example 4
Ved anvendelse af samme fremgangsmåde som i eksemplerne 2 og 3 og ud fra 160 g (1 mol) L-N-carbamyl-valin med en optisk renhed på 97% vandtes 110 g (0,94 mol) L-valin, [«1^° = 28,2° (c = 3, HC1 6N), (fra litteraturen [a]^ ” 28,8°,Using the same procedure as in Examples 2 and 3 and from 160 g (1 mole) of LN-carbamyl-valine with an optical purity of 97%, 110 g (0.94 mole) of L-valine was obtained, [ = 28.2 ° (c = 3, HCl 6N), (from the literature [a]
Ber. 39, 2320, 1906).Ber. 39, 2320, 1906).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2214475 | 1975-04-09 | ||
| IT22144/75A IT1037176B (en) | 1975-04-09 | 1975-04-09 | PROCEDURE FOR THE PREPARATION OF AMINDACIDS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK154676A DK154676A (en) | 1976-10-10 |
| DK146622B true DK146622B (en) | 1983-11-21 |
| DK146622C DK146622C (en) | 1984-04-30 |
Family
ID=11192138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK154676A DK146622C (en) | 1975-04-09 | 1976-03-31 | PROCEDURE FOR PREPARING AMINO ACIDS FROM THE SIMILAR N-CARBAMYLAMINOS 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 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 PT PT64983A patent/PT64983B/en unknown
- 1976-04-07 DD DD192242A patent/DD123599A5/xx unknown
- 1976-04-07 FR FR7610087A patent/FR2306976A1/en active Granted
- 1976-04-07 LU LU74714A patent/LU74714A1/xx unknown
- 1976-04-07 NO NO761189A patent/NO143901C/en unknown
- 1976-04-08 IE IE737/76A patent/IE42673B1/en unknown
- 1976-04-08 YU YU00903/76A patent/YU90376A/en unknown
- 1976-04-08 IN IN611/CAL/76A patent/IN144346B/en unknown
- 1976-04-08 HU HU76SA2914A patent/HU176009B/en unknown
- 1976-04-08 BR BR7602173A patent/BR7602173A/en unknown
- 1976-04-08 IL IL49372A patent/IL49372A/en unknown
- 1976-04-08 CS CS762334A patent/CS194756B2/en unknown
- 1976-04-08 PH PH18315A patent/PH12101A/en unknown
- 1976-04-08 BE BE165963A patent/BE840527A/en not_active IP Right Cessation
- 1976-04-08 AT AT258276A patent/AT343092B/en not_active IP Right Cessation
- 1976-04-09 DE DE2615594A patent/DE2615594C3/en not_active Expired
- 1976-04-09 RO RO7685571A patent/RO70427A/en unknown
- 1976-04-09 JP JP51039420A patent/JPS5940823B2/en not_active Expired
- 1976-04-09 BG BG032860A patent/BG24664A3/en unknown
- 1976-04-09 SE SE7604237A patent/SE409701B/en unknown
- 1976-04-09 SU SU762343157A patent/SU670213A3/en active
- 1976-04-09 MX MX000157U patent/MX3304E/en unknown
- 1976-04-09 ES ES447176A patent/ES447176A1/en not_active Expired
- 1976-04-09 NL NL7603816A patent/NL7603816A/en active Search and Examination
- 1976-04-09 AR AR262843A patent/AR217052A1/en active
- 1976-04-09 PL PL1976188626A patent/PL104015B1/en unknown
-
1979
- 1979-12-30 MY MY100/79A patent/MY7900100A/en unknown
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