DK158977B - PROCEDURE FOR MANUFACTURING SUBSTITUTED GUANIDINES OR SALTS THEREOF - Google Patents
PROCEDURE FOR MANUFACTURING SUBSTITUTED GUANIDINES OR SALTS THEREOF Download PDFInfo
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- DK158977B DK158977B DK265978A DK265978A DK158977B DK 158977 B DK158977 B DK 158977B DK 265978 A DK265978 A DK 265978A DK 265978 A DK265978 A DK 265978A DK 158977 B DK158977 B DK 158977B
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
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Description
DK 158977 BDK 158977 B
Opfindelsen angår en særlig fremgangsmåde til fremstilling af mono-, di- eller trisubstituerede guani-diner med den i indledningen til krav 1 viste almene formel 12 3 I, hvor R , R og R har de sammestedt angivne betydnm- 5 ger, eller salte deraf.The invention relates to a particular process for the preparation of mono-, di- or tri-substituted guanidines of the general formula 12 3 I shown in the preamble of claim 1, wherein R, R and R have the same meanings stated, or salts thereof. .
Især forbindelser med formel I, hvor en af sub-, 1 2 3 stituenterne R , R og R er en benzylgruppe eller en fenætylgruppe er kendte og terapeutisk anvendte, idet de selektivt undertrykker den sympatiske nervefunktion og 10 har ringe eller ingen indflydelse på parasympatiske eller centralenervefunktioner, jf. beskrivelsen til britisk patent nr. 973.882.Particularly, compounds of formula I, wherein one of the sub-, 2, 3-substituents R, R and R is a benzyl group or a phenethyl group are known and therapeutically used, selectively suppressing sympathetic nerve function and having little or no influence on parasympathetic or central nerve functions, as described in British Patent No. 973,882.
Ifølge denne patentbeskrivelse kan forbindelserne fremstilles ved omsætning af ammoniak, et ammonium-15 derivat eller et salt deraf med et S-substitueret iso-thiourinstof eller et salt deraf, fx som følgerAccording to this patent specification, the compounds can be prepared by reacting ammonia, an ammonium derivative or a salt thereof with an S-substituted isothiourea or a salt thereof, e.g.
R1-NH R1NHR1-NH R1NH
C-SR + R NH„-^ ^ C-NHR + RSHC-SR + R NH + - ^ C-NHR + RSH
xSh2 ^ xSh2^ 1 2 20 I dette reaktionsskema er R og R som defineret ovenfor, R er en alkylgruppe, almindeligvis en metylgruppe, og X er en anion.xSh2 ^ xSh2 ^ 1 2 20 In this reaction scheme, R and R are as defined above, R is an alkyl group, usually a methyl group, and X is an anion.
De ildelugtende merkaptaner der dannes ved denne fremgangsmåde må fjernes fuldstændigt hvilket kan være 25 vanskeligt og i hvert fald kræver en separat rensningsproces .The smelly mercaptans formed by this process must be completely removed which can be difficult and at least requires a separate purification process.
Ved den foreliggende fremgangsmåde kan forbindelser med ovennævnte formel I let og i godt udbytte fremstilles af substituerede thiourinstoffer eller isothio-30 urinstoffer uden at der derved som ved den kendte fremgangsmåde dannes ildelugtende merkaptaner.In the present process, compounds of the above Formula I can be readily and in good yield prepared from substituted thioureas or isothioureas without producing, as in the known process, smelly mercaptans.
Fremgangsmåden ifølge opfindelsen er ejendommelig ved det i krav l's kendetegnende del angivne. Der henvi- 12 3 ses til nedenstående reaktionsskema, hvor R , R og R 35 er som defineret i krav 1The process according to the invention is characterized by the characterizing part of claim 1. Reference is made to the following reaction scheme, wherein R, R and R 35 are as defined in claim 1.
DK 158977 BDK 158977 B
22
R1-NH R1-NHR1-NH R1-NH
— ^CS + 3 H000-* , X-SO.H + 3 H~0- ^ CS + 3 H000- *, X-SO.H + 3 H ~ 0
R -NH^ 1 Å R -N ^ ZR -NH 1 R R -N 2 Z
R1-NH 9 R1-NH 9 5 _ ^C-S0oH + R wH0-> 0 ^C-NH-R + H0SO.R1-NH 9 R1-NH 9 5 _ ^ C-SOOH + R wH0-> 0 ^ C-NH-R + HOSO.
r3-n^ 3 2 R3-N^ 2 3r3-n ^ 3 2 R3-n ^ 2 3
Det vil bemærkes, at der i afhængighed af betyd-ningen af R , R og R fås mono-, di- eller trisubsti-tuerede guanidiner.It will be noted that, depending on the meaning of R, R and R, mono-, di- or trisubstituted guanidines are obtained.
10 Som belyst af reaktionsskemaet er hydrogenperoxyd det foretrukne oxydationsmiddel fordi det danner vand ved reaktionen; men andre peroxyder kan anvendes.As illustrated by the reaction scheme, hydrogen peroxide is the preferred oxidizing agent because it forms water in the reaction; but other peroxides may be used.
Ifølge opfindelsen er det, på grund af den derved dannede forbindelses art, særlig hensigtmæssigt at oxy-15 dere N,N'-dimetylthiourinstof til N,N'-dimetylformami- dinsulfonsyre, der derefter omsættes med benzylamin.According to the invention, due to the nature of the compound thus formed, it is particularly convenient to oxidize N, N'-dimethylthiourea to N, N'-dimethylformamide sulfonic acid, which is then reacted with benzylamine.
Følgende eksempler belyser den foreliggende fremgangsmåde .The following examples illustrate the present method.
20 Eksempel 1 A. N-Benzyl-N'-metylformamidinsulfonsyreExample 1 A. N-Benzyl-N'-methylformamidine sulfonic acid
Til en blanding af 100 g 34,6%'s hydrogenperoxyd (1 mol) og 200 ml vand sattes 45 g (0,25 mol) N-benzyl-25 N'-metylthiourinstof i små portioner i løbet af to timer. Eftersom reaktionen er exoterm, holdtes reaktionsblandingens temperatur under 18°C ved køling af reaktionsbeholderen i en blanding af is og vand.To a mixture of 100 g of 34.6% hydrogen peroxide (1 mole) and 200 ml of water was added 45 g (0.25 mole) of N-benzyl-25 N'-methylthiourea in small portions over two hours. Since the reaction is exothermic, the temperature of the reaction mixture was kept below 18 ° C by cooling the reaction vessel in a mixture of ice and water.
Efter tilsætningen af thiourinstofderivatet hen-30 stod reaktionsblandingen i to timer uden køling, hvorved den langsomt antog stuetemperatur.After the addition of the thiourea derivative, the reaction mixture was allowed to stand for two hours without cooling, slowly increasing to room temperature.
Derefter køledes den igen i isvand, hvorved titelforbindelsen udfældede som hvide krystaller. Disse fra-filtreredes og vaskedes med en lille mængde koldt vand og 35 til sidst med æter. Udbyttet var 44 g (0,19 mol), svarende til 76% af det teoretiske udbytte. Forbindelsen smeltede ved 120-125°C under sønderdeling.It was then cooled again in ice water, whereby the title compound precipitated as white crystals. These were filtered off and washed with a small amount of cold water and finally with ether. The yield was 44 g (0.19 mol), corresponding to 76% of the theoretical yield. The compound melted at 120-125 ° C with decomposition.
DK 158977 BDK 158977 B
3 B. N-Benzyl-N* ,N'‘-dimetylguanidiniumiodid 4,56 g (0,020 mol) N-benzyl-N*-metylformamidinsul-fonsyre blandedes med en 24%'s opløsning af 15 ml metyl-amin i vand og 50 ml vand, og blandingen kogtes under 5 tilbagesvaling i 6 timer. Overskud af metylamin blev suget fra i vakuum, hvorefter reaktionsblandingens rumfang var 50 ml. Blandingen syrnedes med koncentreret saltsyre til en pH-værdi mellem 1 og 2, hvorefter der tilsattes 10 ml af en mættet vandig opløsning af Nal og 5 g fast 10 NaCl. Blandingen henstod til næste dag under omrøring og gav et flødefarvet bundfald af titelforbindelsen, der frafiltreredes og omkrystalliseredes fra ætanol. Udbyttet var 3,5 g (0,01148 mol), svarende til 57,4% af det teoretiske udbytte. Smeltepunktet var 192-194°C.3 B. N-Benzyl-N *, N '- dimethylguanidinium iodide 4.56 g (0.020 mol) of N-benzyl-N * -methylformamidine sulfonic acid were mixed with a 24% solution of 15 ml of methylamine in water and 50 ml of water and the mixture was refluxed for 6 hours. Excess methylamine was aspirated in vacuo, after which the volume of the reaction mixture was 50 ml. The mixture was acidified with concentrated hydrochloric acid to a pH between 1 and 2, then 10 ml of a saturated aqueous solution of NaI and 5 g of solid 10 NaCl were added. The mixture was left to stir the next day to give a cream colored precipitate of the title compound which was filtered off and recrystallized from ethanol. The yield was 3.5 g (0.01148 mol), corresponding to 57.4% of the theoretical yield. The melting point was 192-194 ° C.
1515
Eksempel 2 N-Benzyl-N1,N"-dimetylguanidiniumiodidExample 2 N-Benzyl-N1, N "-dimethylguanidinium iodide
En blanding af 3,0 g (0,0197 mol) Ν,Ν'-dimetyl-20 formamidinsulfonsyre (fremstillet af N,N'-dimetylthio-urinstof på samme måde som beskrevet i eksempel 1A), 10 ml (0,092 mol) benzylamin og 60 ml vand kogtes under tilbagesvaling i time. Derefter tilsattes koncentreret saltsyre til en pH-værdi mellem 1 og 2, og så tilsattes 25 10 ml af en mætet vandig opløsning af Nal. Efter kort tids henstand dannedes et næsten hvidt bundfald. Reaktionsblandingen køledes i omkring to timer i en blanding af is og vand, hvorefter bundfaldet, der bestod af titelforbindelsen, frafiltreredes og omkrystalliseredes fra 30 ætanol i et udbytte på 4,7 g (0,0154 mol, 78%) med smeltepunkt 192-194°C.A mixture of 3.0 g (0.0197 mol) of Ν, Ν'-dimethyl-formamidine sulfonic acid (prepared from N, N'-dimethylthiourea in the same manner as described in Example 1A), 10 ml (0.092 mol) of benzylamine and 60 ml of water was refluxed for one hour. Then concentrated hydrochloric acid was added to a pH between 1 and 2 and then 10 ml of a saturated aqueous solution of NaI was added. After a short delay, an almost white precipitate formed. The reaction mixture was cooled for about two hours in a mixture of ice and water, then the precipitate consisting of the title compound was filtered off and recrystallized from ethanol in 4.7 g (0.0154 mol, 78%), m.p. 192-194 ° C.
nedenstående eksempler 3-8 var udgangsmaterialet, N^'-dimetylformamidinsulfonsyre, fremstillet på den måde 35 der er beskrevet i eksempel 1A.Examples 3 to 8 below were the starting material, N 2 '- dimethylformamidine sulfonic acid, prepared in the manner described in Example 1A.
'DK 158977 BDK 158977 B
Eksempel 3 4 N-Benzyl-N1,N"-dimetylguanidiniumiodidExample 3 4 N-Benzyl-N1, N "-dimethylguanidinium iodide
En blanding af 12 g N,N'-dimetylformamidinsulfon-syre, 20 ml benzylamin og 120 ml vand ved stuetemperatur 5 henstilledes under omrøring til næste dag. Blandingen syr-nedes med saltsyre til en pH-værdi på 1, og der tilsattes en mættet, vandig opløsning af Nal. Efter omrøring og køling i omkring en time frafiltreredes det af titelforbindelsen bestående bundfald og vaskedes først med vand og 10 derefter med æter, hvorefter det til slut tørredes ved 30°C. Smeltepunktet var 195°C, og udbyttet var 19 g (79%).A mixture of 12 g of N, N'-dimethylformamidine sulfonic acid, 20 ml of benzylamine and 120 ml of water at room temperature was left stirring until the next day. The mixture was acidified with hydrochloric acid to a pH of 1 and a saturated aqueous solution of NaI was added. After stirring and cooling for about an hour, the precipitate of the title compound was filtered off and washed first with water and then with ether, then finally dried at 30 ° C. The melting point was 195 ° C and the yield was 19 g (79%).
Eksempel 4 15 Ν,Ν1,N"-Trimetylguanidiniumiodid 15,2 g (0,10 mol) N,N'-dimetylformamidinsulfonsyre og 75 ml af en 24%'s vandig opløsning af metylamin opløstes i 250 ml vand. Blandingen kogtes under tilbagesvaling i 3 timer. Overskuddet af metylamin frasugedes i va-20 kuum, hvorefter der tilsattes koncentreret saltsyre til en pH-værdi mellem 1 og 2. Så tilsattes en mættet vandig opløsning af natriumiodid, hvorved et hvidt bundfald af titelforbindelsen dannedes. Bundfaldet frafiltreredes og omkrystalliseredes fra vand som skinnende hvide, nålefor-25 mede krystaller. Udbyttet var 18,0 g (0,0786 mol, 78,6%) med smeltepunkt over 320°C.Example 4 15 Ν, Ν1, N "-trimethylguanidinium iodide 15.2 g (0.10 mol) of N, N'-dimethylformamidine sulfonic acid and 75 ml of a 24% aqueous solution of methylamine were dissolved in 250 ml of water. The mixture was refluxed. The excess methylamine was suctioned off in vacuo and then concentrated hydrochloric acid was added to a pH between 1 and 2. Then a saturated aqueous solution of sodium iodide was added to give a white precipitate of the title compound. from water as shiny white, needle-shaped crystals The yield was 18.0 g (0.0786 mol, 78.6%), m.p. over 320 ° C.
Eksempel 5Example 5
DK 158977 BDK 158977 B
5 U^TSI1 -Dimetyl-N"- (3,4-metylendioxybenzyl) -guanidiniumiodid 4.56 g (0,030 mol) N,N'-dimetylformamidinsulfon-syre og 18,1 g (0,12 mol) 3,4-metylendioxybenzylamin op- 5 løstes i 60 ml vand, og opløsningen kogtes under tilbagesvaling i 4| time. Derefter inddampedes reaktionsblandingen til et rumfang på 40 ml, hvorefter der først tilsattes koncentreret saltsyre til en pH-værdi mellem 1 og 3 og derefter 25 ml af en mættet vandig opløsning af na-10 triumiodid. Et hvidt, krystallinsk bundfald af titelforbindelsen dannedes, frafiltreredes og vaskedes med vand. Udbyttet var 8,4 g (0,0241 mol), svarende til 80,3% af det teoretiske udbytte, og smeltepunktet var 211,0-2l2r0°C.5 U 3 TSI 1 -Dimethyl-N "- (3,4-methylenedioxybenzyl) -guanidinium iodide 4.56 g (0.030 mole) of N, N'-dimethylformamidine sulfonic acid and 18.1 g (0.12 mole) of 3,4-methylenedioxybenzylamine on - 5 was dissolved in 60 ml of water and the solution was refluxed for 4 hours, then the reaction mixture was evaporated to a volume of 40 ml and then concentrated hydrochloric acid was added to a pH between 1 and 3 and then 25 ml of a saturated A white crystalline precipitate of the title compound formed, filtered and washed with water The yield was 8.4 g (0.0241 mol), corresponding to 80.3% of the theoretical yield, and the melting point was 211,0-2l2r0 ° C.
1515
Eksempel 6 N-(2-Klorbenzyl)-N',N"-dimetylguanidiniumiodid 4.56 g (0,030 mol) N,N'-dimetylformamidinsulfon-syre og 17,0 g (0,12 mol) 2-klorbenzylamin opløstes i 60 £» v ml vand, og opløsningen kogtes under tilbagesvaling i 5| time. Opløsningen syrnedes med koncentreret saltsyre til en pH-værdi på 1-3, og så tilsattes 25 ml af en mættet, vandig opløsning af natriumiodid, hvorved der udskiltes et gult, olielignende stof. Reaktionsblandingen henstod un-25 der omrøring til næste dag, hvorved den udskilte olie blev halvkrystallinsk. Moderluden fradekanteredes, og den tilbageblivende rest vaskedes. gentagne gange med æter, til alt blev krystallinsk. Stoffet omkrystalliseredes fra vand, idet opløsningen rensedes med aktivt kul, og titelforbindelsen udskiltes igen som en olie, der imidlertid hurtigt blev krystallinsk ved skrabning. Udbyttet af det flødefarvede stof var 6,7 g (0,0197 mol, 65,7%) med smeltepunkt 157,5-158,5°C.Example 6 N- (2-Chlorobenzyl) -N ', N "-dimethylguanidinium iodide 4.56 g (0.030 mol) of N, N'-dimethylformamidine sulfonic acid and 17.0 g (0.12 mol) of 2-chlorobenzylamine were dissolved in 60 µl. The solution was acidified with concentrated hydrochloric acid to a pH of 1-3 and then 25 ml of a saturated aqueous solution of sodium iodide was separated to give a yellow, oil-like solution. The reaction mixture was allowed to stir until the next day, the separated oil becoming semi-crystalline, the mother liquor was decanted off and the residue was washed repeatedly with ether, until everything became crystalline The substance was recrystallized from water as the solution was purified with activated carbon and the title compound is again separated as an oil which, however, quickly became crystalline by scraping The yield of the cream colored was 6.7 g (0.0197 mol, 65.7%), mp 157.5-158.5 ° C.
3535
Eksempel 7Example 7
DK 158977 BDK 158977 B
6 N, N1-dimetyl-N"-(4-metoxybenzyl)-guanidiniumiodid6 N, N1-dimethyl-N "- (4-methoxybenzyl) -guanidinium iodide
Fremgangsmåden i eksempel 6 gentoges under anvendelse af 16,44 g (0,12 mol) 4-metoxybenzylamin i stedet 5 for 2-klorbenzylamin. Titelforbindelsen, der også først udskiltes som en olie, vandtes til slut som et hvidt stof i et udbytte på 5,8 g (0,0173 mol, 57,7%) med smeltepunkt 162,0-162,5°C.The procedure of Example 6 was repeated using 16.44 g (0.12 mol) of 4-methoxybenzylamine instead of 2-chlorobenzylamine. The title compound, which was also first excreted as an oil, was finally obtained as a white substance in a yield of 5.8 g (0.0173 mol, 57.7%), mp 162.0-162.5 ° C.
10 Eksempel 8 N-Cyklohexyl-N',N"-dimetylguanidiniumiodid 4,56 g (0,030 mol) N,N'-dimetylformamidinsulfon-syre og 12,0 g (0,12 mol) cyklohexylamin opløstes i 60 ml vand. Blandingen henstod under omrøring til næste dag og inddampedes da til et rumfang på omkring 30 ml. Reaktionsblandingen syrnedes derefter med saltsyre til en pH-værdi på 2, hvorefter der tilsattes 10 ml af en mættet, vandig opløsning af natriumiodid. Der udskiltes et olie-2q lignende stof, som hurtigt krystalliserede fra vand.Example 8 N-Cyclohexyl-N ', N "-dimethylguanidinium iodide 4.56 g (0.030 mole) of N, N'-dimethylformamidine sulfonic acid and 12.0 g (0.12 mole) of cyclohexylamine were dissolved in 60 ml of water. with stirring until the next day and then evaporated to a volume of about 30 ml. The reaction mixture was then acidified with hydrochloric acid to a pH of 2, then 10 ml of a saturated aqueous solution of sodium iodide was added. substance which quickly crystallized from water.
Det faste stof, bestående af titelforbindelsen, vandtes i et udbytte på 3,70 g (0,0125 ml, 41,7%) med smeltepunkt 195,5-196,9°C.The solid, consisting of the title compound, was obtained in a yield of 3.70 g (0.0125 ml, 41.7%), mp 195.5-196.9 ° C.
25 1 nærværende beskrivelse skal udtrykkene alkyl- gruppe, herunder cykloalkylgruppe, og fenylalkylgruppe forstås som de pågældende grupper som defineret i krav 1.In this specification, the terms alkyl group, including cycloalkyl group, and phenylalkyl group are to be understood as the groups concerned as defined in claim 1.
30 3530 35
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2553377A GB1587258A (en) | 1977-06-17 | 1977-06-17 | Production of substituted guanidines |
| GB2553377 | 1977-06-17 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK265978A DK265978A (en) | 1978-12-18 |
| DK158977B true DK158977B (en) | 1990-08-13 |
| DK158977C DK158977C (en) | 1991-01-21 |
Family
ID=10229222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK265978A DK158977C (en) | 1977-06-17 | 1978-06-14 | PROCEDURE FOR MANUFACTURING SUBSTITUTED GUANIDINES OR SALTS THEREOF |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5448714A (en) |
| AU (1) | AU520839B2 (en) |
| CA (1) | CA1083603A (en) |
| DE (1) | DE2826452A1 (en) |
| DK (1) | DK158977C (en) |
| GB (1) | GB1587258A (en) |
| NL (1) | NL187856C (en) |
| NZ (1) | NZ187557A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6043414U (en) * | 1983-08-29 | 1985-03-27 | 本田技研工業株式会社 | Heater devices for motorcycles, etc. |
| US4851094A (en) * | 1985-03-15 | 1989-07-25 | Mcneilab, Inc. | Process for producing amidine sulfonic acid intermediates for guanidines |
| US4693850A (en) * | 1985-03-15 | 1987-09-15 | Mcneilab, Inc. | Methane sulfonic acid derivatives |
| US4656270A (en) * | 1985-03-15 | 1987-04-07 | Mcneilab, Inc. | Process for producing guanidines such as linogliride |
| US4781866A (en) * | 1985-03-15 | 1988-11-01 | Mcneilab, Inc. | Process for producing amidine sulfonic acid intermediates for guanidines |
| US4656291A (en) * | 1985-03-15 | 1987-04-07 | Mcneilab, Inc. | Process for producing amidine sulfonic acids |
| US5948939A (en) * | 1986-09-10 | 1999-09-07 | Syntex (U.S.A.) Inc. | Selective amidination of diamines |
| DE3774975D1 (en) * | 1986-09-10 | 1992-01-16 | Syntex Inc | SELECTIVE AMIDINATION OF DIAMINES. |
| KR970002877B1 (en) * | 1987-07-17 | 1997-03-12 | 더 누트라스웨트 캄파니 | High potency sweetening agents |
| WO1990000552A1 (en) * | 1988-07-12 | 1990-01-25 | The Nutrasweet Company | High potency sweetening agents |
| GB9309321D0 (en) * | 1993-05-06 | 1993-06-16 | Wellcome Found | Process for the preparation of ng-monoalkyl-l-arginine derivatives |
| CN102363601A (en) * | 2011-09-20 | 2012-02-29 | 科迈化工股份有限公司 | Method for producing rubber accelerator DGP by using hydrogen peroxide as oxidant |
| CN102363602A (en) * | 2011-09-20 | 2012-02-29 | 科迈化工股份有限公司 | Method for producing vulcanization accelerator DPG with hydrogen peroxide as oxidant |
| CN110407720B (en) * | 2019-08-20 | 2021-07-27 | 西安近代化学研究所 | Synthetic method for preparing substituted guanidine by desulfurizing thiourea under catalysis of iodine |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB973882A (en) * | 1959-12-23 | 1964-10-28 | Wellcome Found | Benzyl-guanidines,their preparation and pharmaceutical compositions containing them |
-
1977
- 1977-06-17 GB GB2553377A patent/GB1587258A/en not_active Expired
-
1978
- 1978-06-13 NZ NZ18755778A patent/NZ187557A/en unknown
- 1978-06-14 DK DK265978A patent/DK158977C/en active
- 1978-06-15 JP JP7157778A patent/JPS5448714A/en active Granted
- 1978-06-15 AU AU37154/78A patent/AU520839B2/en not_active Expired
- 1978-06-16 DE DE19782826452 patent/DE2826452A1/en active Granted
- 1978-06-16 NL NL7806526A patent/NL187856C/en not_active IP Right Cessation
- 1978-06-16 CA CA305,594A patent/CA1083603A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL7806526A (en) | 1978-12-19 |
| JPS5748106B2 (en) | 1982-10-14 |
| DK158977C (en) | 1991-01-21 |
| DE2826452C2 (en) | 1987-01-22 |
| JPS5448714A (en) | 1979-04-17 |
| AU3715478A (en) | 1979-12-20 |
| GB1587258A (en) | 1981-04-01 |
| NL187856C (en) | 1992-02-03 |
| AU520839B2 (en) | 1982-03-04 |
| NZ187557A (en) | 1980-08-26 |
| CA1083603A (en) | 1980-08-12 |
| NL187856B (en) | 1991-09-02 |
| DK265978A (en) | 1978-12-18 |
| DE2826452A1 (en) | 1979-01-11 |
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