DK145573B - PROCEDURE FOR THE PREPARATION OF 1-ALKYL-2-AMINOMETHYLPYRROLIDINES - Google Patents
PROCEDURE FOR THE PREPARATION OF 1-ALKYL-2-AMINOMETHYLPYRROLIDINES Download PDFInfo
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- DK145573B DK145573B DK548871AA DK548871A DK145573B DK 145573 B DK145573 B DK 145573B DK 548871A A DK548871A A DK 548871AA DK 548871 A DK548871 A DK 548871A DK 145573 B DK145573 B DK 145573B
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- alkyl
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- aminomethylpyrrolidines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/12—Oxygen or sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
- C07D207/09—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrrole Compounds (AREA)
Description
β (12) FREMLÆGGELSESSKRIFT ου 145573Bβ (12) PUBLICATION WRITING ου 145573B
(13) DANMARK(13) DENMARK
DIREKTORATET FOR PATENT- OG VAREMÆRKEVÆSENETDIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM
(21) Ansøgning nr. 5^88/71 (51) IntCI.3 C 07 D 207/09 (22) Indleveringsdag 9· nov. 1971 (24) Løbedag 9· nov. 1971 (41) Aim. tilgængelig 11 · raaJ 1972 (44) Fremlagt 13· dec. 1982 (86) International ansøgning nr.(21) Application No. 5 ^ 88/71 (51) IntCI.3 C 07 D 207/09 (22) Filing date 9 · Nov. 1971 (24) Race day 9 · Nov. 1971 (41) Aim. available 11 · raaJ 1972 (44) Submitted 13 · dec. 1982 (86) International application no.
(86) International indleveringsdag (85) Videreførelsesdag ~ (62) Stamansøgning nr. “(86) International Filing Day (85) Continuation Day ~ (62) Stock Application No. "
(30) Prioritet 10. nov. 1970, 16628/70, CH(30) Priority 10 Nov. 1970, 16628/70, CH
(71) Ansøger FRATMANN 5.A., Chene-Bougeries (Genf), CH.(71) Applicant FRATMANN 5.A., Chene-Bougeries (Geneva), CH.
(72) Opfinder Fred Kuenzy, CH.(72) Inventor Fred Kuenzy, CH.
(74) Fuldmægtig Ingeniørfirmaet Budde, Schou & Co.(74) Associate Engineering Company Budde, Schou & Co.
(54) Fremgangsmåde til fremstilling af 1-alkyl-2-aminomethylpyrro* lidiner.(54) Process for the preparation of 1-alkyl-2-aminomethylpyrrolidines.
Den foreliggende opfindelse angår en særlig fremgangsmåde til fremstilling af l-alkyl-2-aminomethylpyrrolidiner, ved hvilken en l-alkyl-2-pyrrolidon via et kvaterniseret mellemprodukt først omsættes med et alkalimetalalkoholat og derpå med nitromethan, hvorefter den i 2-stillingen fremkomne nitromethylengruppe reduceres til en aminomethylgruppe.The present invention relates to a particular process for the preparation of 1-alkyl-2-aminomethylpyrrolidines in which a 1-alkyl-2-pyrrolidone is first reacted with an alkali metal alcoholate and then with nitromethane, then the nitromethylene group obtained in the 2-position is reduced to an aminomethyl group.
0 Den omhandlede fremgangsmåde er ejendommelig ved, at ^ det kvaterniserede mellemprodukt dannes ved omsætning af 1- V«, 0 -alkyl-2-pyrrolidonen med phosgen i et opløsningsmiddel ved en 2 temperatur, der ligger mellem -5°C og +10°C.The process of the invention is characterized in that ^ the quaternized intermediate is formed by reacting the 1- V ', 0-alkyl-2-pyrrolidone with phosgene in a solvent at a temperature of 2 to 5 ° C and + 10 ° C.
— Den her omhandlede fremgangsmåde adskiller sig fra ^ den relevante kendte teknik, som er beskrevet i DE-offent- § 145573 2 liggørelsesskrift nr. 1.941.536, ved, at der anvendes et særlig kvaterniseringsmiddel, nemlig phosgen, der ikke uden videre kan indordnes i rækken af de i denne sammenhæng allerede anvendte kvaterniseringsmidler, di-(lavere alkyl)-sulfater og tri-(ligekædet lavere alkyl)-oxonium-fluoroborater, og hvis egnethed til den her omhandlede fremgangsmåde således ikke kunne forudses. Den her omhandlede fremgangsmåde fører derudover, som det fremgår af en sammenligning med angivelserne i det nævnte offentliggørelsesskrift, til renere nitro-methylenforbindelser, der efter reduktionen giver kvalitativt bedre aminomethylforbindelser. Udbyttemæssigt er den her omhandlede fremgangsmåde overlegen i forhold den omtalte kendte fremgangsmåde i det tilfælde, hvor der anvendes dimethyl-sulfat som kvaterniseringsmiddel, og svagt underlegen i det tilfælde, hvor der anvendes triethyloxoniumfluoroborat. Ved den sidstnævnte kendte fremgangsmåde skal det dog ud over, at den fremstillede nitromethylenforbindelse har en ringe renhed, tages i betragtning, at fluoroboratet skal fremstilles i et særligt ekstra trin, medens phosgen, der anvendes som kvaterniseringsmiddel ved fremgangsmåden ifølge opfindelsen, kan fås billigt i enten flydende form under tryk eller opløst i toluen.The method at issue here differs from the relevant prior art described in DE Public Procurement Specification No. 1,941,536 in that a particular quaternizing agent, phosgene, cannot be readily disposed of. in the series of quaternizing agents already used in this context, di- (lower alkyl) sulfates and tri- (straight-chain lower alkyl) oxonium fluoroborates, and whose suitability for the process of the present invention could thus not be foreseen. In addition, the process of this invention, as is evident from a comparison with the disclosures in the aforementioned publication, results in purer nitromethylene compounds which, after reduction, provide qualitatively better aminomethyl compounds. In yield, the present process is superior to the known process in the case where dimethyl sulfate is used as quaternizing agent and slightly inferior in the case where triethyloxonium fluoroborate is used. However, in the latter known process, in addition to the low purity of the nitromethylene compound produced, it must be taken into account that the fluoroborate must be prepared in a special additional step, while phosgene used as a quaternizing agent in the process of the invention can be obtained cheaply. either liquid form under pressure or dissolved in toluene.
Fremgangsmåden ifølge opfindelsen illustreres ved følgende formelskema: -- (1) +coci2 (1)The process according to the invention is illustrated by the following formula: - (1) + coci2 (1)
Lo (2) +2MeOR2 (2)Lo (2) + 2MeOR2 (2)
_N_N
I / R1 (I) O) + ch3no2 (30 metal + syre eller . J^CHNO. _V L 1-ch2nh5 I H2 (katalytisk hydrogenering) | R1 (II) R1 (III) 1 2 hvor R og R betyder alkylgrupper, medens Me betyder et alkalimetal, såsom natrium, kalium osv.I / R1 (I) O) + ch3no2 (30 metal + acid or. J ^ CHNO. _V L 1 -ch2nh5 I H2 (catalytic hydrogenation) | R1 (II) R1 (III) 1 while Me means an alkali metal such as sodium, potassium, etc.
145573 3145573 3
Ved fremgangsmåden ifølge opfindelsen omsættes en l-alkyl-2--pyrrolidon (I) med phosgen, et alkalimetalalkoholat og nitromethan, hvorved man får forbindelsen (II).In the process of the invention, a 1-alkyl-2-pyrrolidone (I) is reacted with phosgene, an alkali metal alcoholate and nitromethane to give the compound (II).
Som eksempel på alkylgruppen (R1) i l-alkyl-2-pyrrolidonerne kan nævnes en methyl-, ethyl-, propyl-, isopropyl-, butyl- eller isobutylgruppe.As an example of the alkyl group (R 1) in the 1-alkyl-2-pyrrolidones may be mentioned a methyl, ethyl, propyl, isopropyl, butyl or isobutyl group.
Omsætningen af l-alkyl-2-pyrrolidonen med phosgen gennemføres i et opløsningsmiddel, fortrinsvis benzen, toluen eller xylen. Omsætningen gennemføres ved en temperatur, der ligger mellem -5°C og +10°C. Det fremkomne produkt har følgende kemiske struktur: CH2-CH2The reaction of the 1-alkyl-2-pyrrolidone with phosgene is carried out in a solvent, preferably benzene, toluene or xylene. The reaction is carried out at a temperature between -5 ° C and + 10 ° C. The resulting product has the following chemical structure: CH2-CH2
I 01 OI 01 O.
CH .C-Cl 11 Θ R1 hvor R1 har den ovenfor angivne betydning. Det kan isoleres og renses. Det kan under alle omstændigheder benyttes til den påfølgende omsætning med alkalimetalalkoholat og nitromethan uden isolering og uden rensning. Sædvanligvis beholdes det i det foregående trin benyttede opløsningsmiddel. Behandlingen med alkalimetalalkoholat bør gennemføres ved lav temperatur, fortrinsvis ved temperaturer mellem 0°C og -20°C. Det fremkomne reaktionsprodukt: CH2-CH2 .-OR2 i1 1 2 hvor R og R har den ovenfor angivne betydning, omsættes med nitromethan ved stuetemperatur.CH .C-Cl 11 Θ R1 where R1 has the meaning given above. It can be insulated and cleaned. It can in any case be used for the subsequent reaction with alkali metal alcoholate and nitromethane without isolation and without purification. Usually, the solvent used in the previous step is retained. The treatment with alkali metal alcoholate should be carried out at low temperature, preferably at temperatures between 0 ° C and -20 ° C. The resulting reaction product: CH 2 -CH 2.-OR 2 in which R and R have the meaning given above, are reacted with nitromethane at room temperature.
l-Alkyl-2-nitromethylenpyrrolidinerne (II) kan isoleres og renses, men de kan ligeledes benyttes til den følgende reaktion, som de er, uden isolering og uden rensning.The 1-alkyl-2-nitromethylene pyrrolidines (II) can be isolated and purified, but they can also be used for the following reaction as they are, without isolation and without purification.
145573 4145573 4
Reduktionen af l-alkyl-2-nitromethylenpyrrolidinerne (II) gennemføres under indvirkning af en syre på et metal eller ved hydrogenering i nærværelse af en metallisk hydrogenerings-katalysator. Som metal ved syre/metal-behandling anvendes hovedsageligt jern og zink sammen med saltsyre eller eddikesyre. Reaktionen gennemføres i et opløsningsmiddel, idet den benyttede syre anvendes som opløsningsmiddel. Dette trin gennemføres under opvarmning. Når der anvendes katalytisk hydrogenering, benyttes sorte metaloxider, metaller, ‘kolloidalei metaller samt metaller på egnede bærere som hydrogenerings--katalysatorer. De oftest anvendte katalysatorer er: platinsort, rhodium på aluminiumoxid, palladium på kul og Raney-nikkel. Den katalytiske hydrogenering gennemføres i et opløsningsmiddel, såsom vand, methanol, ethanol, isopropanol, butanol, tetrahydrofuran, di-oxan eller andre indifferente opløsningsmidler. Disse opløsningsmidler kan benyttes ublandet eller i kombination. Hydrogentrykket kan variere fra atmosfæretryk til høje tryk. Sædvanligvis benyttes tryk fra atmosfæretryk til nogle atmosfærers tryk. Omsætningen bringes fortrinsvis til standsning, når den beregnede hydrogenmængde er blevet absorberet. Reaktionsproduktet (ill) isoleres efter frafil-trering af katalysatoren efterfulgt af afdampning af opløsningsmidlet.The reduction of the 1-alkyl-2-nitromethylene pyrrolidines (II) is effected under the action of an acid on a metal or by hydrogenation in the presence of a metallic hydrogenation catalyst. As metal by acid / metal treatment, mainly iron and zinc are used together with hydrochloric acid or acetic acid. The reaction is carried out in a solvent, using the acid used as the solvent. This step is carried out during heating. When using catalytic hydrogenation, black metal oxides, metals, colloidal alloys and metals on suitable supports are used as hydrogenation catalysts. The most commonly used catalysts are: platinum black, rhodium on alumina, palladium on coal and Raney nickel. The catalytic hydrogenation is carried out in a solvent such as water, methanol, ethanol, isopropanol, butanol, tetrahydrofuran, dioxane or other inert solvents. These solvents can be used unmixed or in combination. Hydrogen pressure can vary from atmospheric pressure to high pressure. Usually, pressure from atmospheric pressure to some atmospheric pressure is used. The reaction is preferably stopped when the calculated amount of hydrogen has been absorbed. The reaction product (III) is isolated after filtration of the catalyst followed by evaporation of the solvent.
I det følgende belyses fremgangsmåden ifølge opfindelsen nærmere ved et eksempel.In the following, the method according to the invention is further illustrated by an example.
a) Fremstilling af l-ethyl-2-nitromethylenpyrrolidin.a) Preparation of 1-ethyl-2-nitromethylene pyrrolidine.
I en trehalset kolbe forsynet med en mekanisk omrører, en tildrypningstragt og et termometer anbringes 23 g 1-ethylpyrrolidon opløst i 100 ml vandfri toluen. Der afkøles til 0°C, og medens temperaturen holdes mellem 0 og 5°C, tilføres 90 Kil af en 21$' s opløsning af phosgen i benzen. For hver tilsat dråbe udfælder der et hvidt produkt, og der observeres en frigørelse af carbondioxid-gas. Tilsætningen foregår i løbet af ca. 1 time. Når phosgentilsætningen er afsluttet^ opretholdes omrøringen i 3 timer ved 0°C, hvorefter der afkøles til -15°C, hvorpå der ved en temperatur mellem -5 og -15°C dråbevis tilføres en opløsning af 170 ml absolut ethanol, i hvilken der er opløst 9*5 g natrium. Tilføringen varer ca. 1 time, eftersom reaktionen er meget eksoterm. 10 minutter efter tilsætningen af natriumethylatet begynder der at udfælde natriumchlorid. Når omsætningen er færdigj henstår blandingen under omrøring, indtil den har antaget stuetemperatur. Derpå tilføres 18 g nitromethan uden af- 145573 5 køling i løbet af 10 minutter. Blandingen omrøres i 2 timer og henstår derpå i ca. 12 timer. Derefter fortyndes blandingen med 1 liter vand. Det organiske lag dekanteres og fraskilles. Vandfasen eks-traheres 3 gange, hver gang med 150 ml chloroform. De organiske faser forenes, tørres over natriumsulfat, filtreres og inddampes til tørhed i vakuum. Den velkrystalliserede remanens tages op med 100 ml diethylether. Produktet befries for væske og tørres ved 40°C. Der fås 25 g l-ethyl-2-nitromethylenpyrrolidin med smeltepunkt 131°C. Udbytte: 78% af det teoretiske.In a three-neck flask equipped with a mechanical stirrer, a dropping funnel and a thermometer, place 23 g of 1-ethylpyrrolidone dissolved in 100 ml of anhydrous toluene. It is cooled to 0 ° C and while the temperature is maintained between 0 and 5 ° C, 90 Kg of a 21 $ solution of phosgene in benzene is added. For each drop added a white product precipitates and a release of carbon dioxide gas is observed. The addition takes place over approx. 1 hour. When the phosgene addition is complete, stirring is maintained for 3 hours at 0 ° C, then cooled to -15 ° C, then a solution of 170 ml of absolute ethanol is added dropwise at a temperature of between -5 and -15 ° C. is dissolved 9 * 5 g of sodium. The supply lasts approx. 1 hour since the reaction is very exothermic. 10 minutes after the addition of the sodium ethylate, sodium chloride begins to precipitate. When the reaction is complete, the mixture is left stirring until it has reached room temperature. Then, 18 g of nitromethane without cooling is added over 10 minutes. The mixture is stirred for 2 hours and then left for approx. 12 hours. The mixture is then diluted with 1 liter of water. The organic layer is decanted and separated. The aqueous phase is extracted 3 times, each time with 150 ml of chloroform. The organic phases are combined, dried over sodium sulfate, filtered and evaporated to dryness in vacuo. The well-crystallized residue is taken up with 100 ml of diethyl ether. The product is freed from liquid and dried at 40 ° C. 25 g of 1-ethyl-2-nitromethylene pyrrolidine are obtained, mp 131 ° C. Yield: 78% of theory.
AnalyseAnalysis
Beregnet: C-%: 53,84 H-%: 7,69 N-$: 17,95Calculated: C%: 53.84 H%: 7.69 N- $: 17.95
Fundet: C-?6: 53,60 E-%: 7,39 N-JÉ: 18,04 b) Fremstilling af i-ethyl-2-aminomethylpyrrolidinFound: C-6: 53.60 E%: 7.39 N-JÉ: 18.04 b) Preparation of i-ethyl-2-aminomethylpyrrolidine
Til en opløsning af 25 g l-ethyl-2-nitromethylenpyrrolidin i 500 mlmethanol sættes ca. 5 g Raney-nikkel, og reaktionsblandingen hydrogeneres ved atmosfæretryk og stuetemperatur, indtil der er absorberet 4 molækvivalenter hydrogen, hvilket varer ca. 5 timer. Det benyttede Raney-nikkel fraskilles ved filtrering, og opløsningsmidlet afdampes under reduceret tryk. Ved destillation af remanensen fås 17 g l-ethyl-2-aminomethylpyrrolidin i form af en olie (koge-punkt/20 mm: 60-6l°C).To a solution of 25 g of 1-ethyl-2-nitromethylene pyrrolidine in 500 ml of methanol is added approx. 5 g of Raney nickel and the reaction mixture is hydrogenated at atmospheric pressure and room temperature until 4 molar equivalents of hydrogen is absorbed, 5 hours. The Raney nickel used is separated by filtration and the solvent is evaporated under reduced pressure. Distillation of the residue gives 17 g of 1-ethyl-2-aminomethylpyrrolidine in the form of an oil (boiling point / 20 mm: 60-6 ° C).
Udbytte: 65# af det teoretiske.Yield: 65 # of theoretical.
De ved fremgangsmåden ifølge opfindelsen fremstillede forbindelser finder anvendelse som mellemprodukter, ud fra hvilke der ved omsætning med forskellige substituerede benzoesyrer kan fremstilles benzamider, som er virksomme psykofarmaka.The compounds prepared by the process according to the invention find use as intermediates from which, by reaction with various substituted benzoic acids, benzamides which are effective psychopharmaceuticals can be prepared.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1662870 | 1970-11-10 | ||
| CH1662870A CH532035A (en) | 1970-11-10 | 1970-11-10 | New process for the preparation of 1-alkyl-2-amino-methylpyrrolidines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK145573B true DK145573B (en) | 1982-12-13 |
| DK145573C DK145573C (en) | 1983-05-30 |
Family
ID=4418871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK548871A DK145573C (en) | 1970-11-10 | 1971-11-09 | PROCEDURE FOR THE PREPARATION OF 1-ALKYL-2-AMINOMETHYLPYRROLIDINES |
Country Status (27)
| Country | Link |
|---|---|
| AT (1) | AT311952B (en) |
| AU (1) | AU464960B2 (en) |
| BE (1) | BE773979A (en) |
| BG (1) | BG21605A3 (en) |
| CA (1) | CA940533A (en) |
| CH (1) | CH532035A (en) |
| CS (1) | CS186206B2 (en) |
| DE (1) | DE2152371A1 (en) |
| DK (1) | DK145573C (en) |
| ES (1) | ES396293A1 (en) |
| FI (1) | FI54471C (en) |
| FR (1) | FR2111371A5 (en) |
| GB (1) | GB1374818A (en) |
| HU (1) | HU162787B (en) |
| IE (1) | IE35775B1 (en) |
| IL (1) | IL37994A (en) |
| IT (1) | IT1043845B (en) |
| LU (1) | LU64227A1 (en) |
| MC (1) | MC896A1 (en) |
| NL (1) | NL7114901A (en) |
| OA (1) | OA03823A (en) |
| PH (1) | PH12022A (en) |
| PL (1) | PL81412B1 (en) |
| SE (1) | SE376415B (en) |
| YU (1) | YU34672B (en) |
| ZA (1) | ZA716998B (en) |
| ZM (1) | ZM15171A1 (en) |
-
1970
- 1970-11-10 CH CH1662870A patent/CH532035A/en not_active IP Right Cessation
-
1971
- 1971-10-14 FR FR7136940A patent/FR2111371A5/fr not_active Expired
- 1971-10-15 BE BE773979A patent/BE773979A/en not_active IP Right Cessation
- 1971-10-19 ZA ZA716998A patent/ZA716998B/en unknown
- 1971-10-20 AU AU34790/71A patent/AU464960B2/en not_active Expired
- 1971-10-21 DE DE19712152371 patent/DE2152371A1/en active Pending
- 1971-10-22 IL IL37994A patent/IL37994A/en unknown
- 1971-10-22 ES ES396293A patent/ES396293A1/en not_active Expired
- 1971-10-26 MC MC953A patent/MC896A1/en unknown
- 1971-10-26 BG BG18861A patent/BG21605A3/xx unknown
- 1971-10-26 CA CA126,128A patent/CA940533A/en not_active Expired
- 1971-10-26 IE IE1354/71A patent/IE35775B1/en unknown
- 1971-10-27 ZM ZM151/71A patent/ZM15171A1/en unknown
- 1971-10-28 NL NL7114901A patent/NL7114901A/xx unknown
- 1971-10-29 IT IT30520/71A patent/IT1043845B/en active
- 1971-11-04 GB GB5122571A patent/GB1374818A/en not_active Expired
- 1971-11-04 CS CS7100007753A patent/CS186206B2/en unknown
- 1971-11-05 OA OA54406A patent/OA03823A/en unknown
- 1971-11-08 PL PL1971151433A patent/PL81412B1/pl unknown
- 1971-11-08 FI FI3193/71A patent/FI54471C/en active
- 1971-11-08 LU LU64227D patent/LU64227A1/xx unknown
- 1971-11-09 DK DK548871A patent/DK145573C/en not_active IP Right Cessation
- 1971-11-09 SE SE7114274A patent/SE376415B/xx unknown
- 1971-11-09 YU YU2823/71A patent/YU34672B/en unknown
- 1971-11-09 HU HUFA897A patent/HU162787B/hu unknown
- 1971-11-10 PH PH13000A patent/PH12022A/en unknown
- 1971-11-10 AT AT969071A patent/AT311952B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| PH12022A (en) | 1978-10-06 |
| MC896A1 (en) | 1972-06-22 |
| NL7114901A (en) | 1972-05-15 |
| IL37994A (en) | 1974-10-22 |
| GB1374818A (en) | 1974-11-20 |
| AU464960B2 (en) | 1975-09-11 |
| IE35775B1 (en) | 1976-05-12 |
| OA03823A (en) | 1971-12-24 |
| FI54471C (en) | 1978-12-11 |
| SE376415B (en) | 1975-05-26 |
| BG21605A3 (en) | 1976-07-20 |
| ES396293A1 (en) | 1974-05-01 |
| IE35775L (en) | 1972-05-10 |
| IT1043845B (en) | 1980-02-29 |
| HU162787B (en) | 1973-04-28 |
| DE2152371A1 (en) | 1972-06-22 |
| DK145573C (en) | 1983-05-30 |
| CH532035A (en) | 1972-12-31 |
| CS186206B2 (en) | 1978-11-30 |
| BE773979A (en) | 1972-04-17 |
| YU34672B (en) | 1979-12-31 |
| PL81412B1 (en) | 1975-08-30 |
| AT311952B (en) | 1973-12-10 |
| IL37994A0 (en) | 1971-12-29 |
| ZA716998B (en) | 1972-07-26 |
| CA940533A (en) | 1974-01-22 |
| AU3479071A (en) | 1973-05-03 |
| YU282371A (en) | 1979-07-10 |
| LU64227A1 (en) | 1972-05-29 |
| ZM15171A1 (en) | 1972-07-21 |
| FR2111371A5 (en) | 1972-06-02 |
| FI54471B (en) | 1978-08-31 |
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