DK149195B - METHOD FOR PREPARING TRIMETHYL-PYRODRUIC ACIDAMIDE - Google Patents
METHOD FOR PREPARING TRIMETHYL-PYRODRUIC ACIDAMIDE Download PDFInfo
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- DK149195B DK149195B DK041981AA DK41981A DK149195B DK 149195 B DK149195 B DK 149195B DK 041981A A DK041981A A DK 041981AA DK 41981 A DK41981 A DK 41981A DK 149195 B DK149195 B DK 149195B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three 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
- C07D253/075—Two hetero atoms, in positions 3 and 5
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
o 149195o 149195
Den foreliggende opfindelse angår en særlig fremgangsmåde af den i indledningen til krav 1 angivne art til frem-' stilling af det hidtil ukendte trimethyl-pyrodruesyreamid, der kan anvendes som mellemprodukt til syntesen af kendte, 5 herbicidt virksomme forbindelser.The present invention relates to a particular process of the kind set forth in the preamble of claim 1 for the preparation of the novel trimethyl-pyruvic acid amide which can be used as an intermediate for the synthesis of known, herbicidal active compounds.
Fremgangsmåden ifølge opfindelsen er ejendommelig ved det i krav l's kendetegnende del angivne.The process according to the invention is characterized by the characterizing part of claim 1.
Det er kendt fra litteraturen, at fremstillingen af o-ketocarboxylsyrer eller deres amider ved forsæbning af til- 10 svarende acylcyanider principielt er forbundet med betydelige vanskeligheder, fordi det ikke er lykkedes i praksis helt at undertrykke en spaltning af acylcyaniderne i hydrogencyanid og carboxylsyrer, der indeholder ét carbonatom mindre end de anvendte acylcyanider, jfr. Angew. Chem. 68, s. 430 (1956).It is known from the literature that the preparation of o-ketocarboxylic acids or their amides by the saponification of corresponding acyl cyanides is, in principle, associated with considerable difficulties because it has not been practically succeeded in completely suppressing a cleavage of the acyl cyanides in hydrogen cyanide and carboxylic acids which contains one carbon atom less than the acyl cyanides used, cf. Angew. Chem. 68, pp. 430 (1956).
15 Det er dog allerede kendt, at pyrodruesyreamid kan fås i godt udbytte (indtil 79%) ved partiel hydrolyse af pyrodrue-syrenitril, idet pyrodruesyrenitrilen i etheropløsning ved ca.However, it is already known that pyruvic acid amide can be obtained in good yield (up to 79%) by partial hydrolysis of pyruvic acid nitrile, the pyruvic acid nitrile in ether solution at ca.
0°C først behandles med tørt, gasformigt hydrogenchlorid og derpå med vand, hvorefter amidet isoleres på gængs måde, jfr. J.0 ° C is first treated with dry gaseous hydrogen chloride and then with water, after which the amide is isolated in the usual manner, cf. J.
20 Amer. Chem. Soc. T3, s. 5914 (1951).20 Amer. Chem. Soc. T3, pp. 5914 (1951).
Det er ligeledes kendt, at visse C-substituerede pyro-druesyreamider, nemlig amider med den almene formel R1 R2-C-CO-CO-NH_ (I) '3 ^It is also known that certain C-substituted pyruvic acid amides, namely amides of the general formula R1 R2-C-CO-CO-NH_ (I) '3
25 R25 R
hvori R·*" betyder hydrogen, og 2 3 R og R er ens eller forskellige og betyder eventuelt med ha- 2 logen substitueret alkyl, og R desuden kan betyde hydrogen, 2 3 30 eller R og R tilsammen betyder en 3- til 8-leddet cyclo- alkyl-ring, der eventuelt er substitueret med alkyl eller halogen, idet R1 i dette tilfælde også kan betyde alkyl, kan fås på tilsvarende måde i højt udbytte (indtil 91%), når tilsvarende acylcyanider med den almene formel 35 ? <*wherein R 2 is hydrogen and 2 3 R and R are the same or different and may optionally be substituted with the halo, and R may also mean hydrogen, 2 3 30 or R and R taken together represent a 3- to 8 -substituted cycloalkyl ring optionally substituted by alkyl or halogen, in which case R1 may also mean alkyl can be similarly obtained in high yield (up to 91%) when corresponding acyl cyanides of the general formula 35? <*
OISLAND
2 149195 R1 R2-C-C0-CN (II) k3 12 3 5 hvori R , R og R har de tidligere angivne betydninger, i nærværelse af et indifferent organisk opløsningsmiddel, såsom især ethere,omsættes først med gasformigt hydrogenchlorid og derpå med vand ved temperaturer mellem -70 og +70°C, fortrinsvis mellem -40 og +20°C, hvorefter slutproduktet isoleres på 10 i og for sig kendt måde, jfr. DE-OS 2.708.184.Wherein R, R and R have the meanings previously defined, in the presence of an inert organic solvent such as, in particular, ethers, are first reacted with gaseous hydrogen chloride and then with water at temperatures between -70 and + 70 ° C, preferably between -40 and + 20 ° C, after which the final product is isolated in a manner known per se, cf. DE-OS 2,708,184.
Ved de fra teknikkens stade kendte fremgangsmåder er det derimod ikke, hvilket egne forsøg har vist, muligt at fremstille det hidtil ukendte trimethyl-pyrodruesyreamid med formlen (III) på tilsvarende måde ud fra pivaloylcyanid (med form-15 len (II) , hvori R·** = R2 = R3 = methyl, eller formlen (IV) i nævneværdigt udbytte.By the methods known in the art, on the other hand, it is not possible, as one's own experiments have shown, to prepare the novel trimethyl-pyruvic acid amide of formula (III) from pivaloyl cyanide (of formula (II)) wherein R · ** = R2 = R3 = methyl, or formula (IV) in appreciable yield.
Det har nu vist sig, at det hidtil ukendte trimethyl--pyrodruesyreamid med formlen (ch3)3C-co-c°-NH2 (III) 20 fås i højt udbytte, når pivaloylcyanid med formlen (ch3)3c-co-cn (IV) eventuelt i nærværelse af en ved reaktionsbetingelserne flydende, lavere aliphatisk carboxylsyre som opløsningsmiddel og eventuelt under tryk, først omsættes med en vandfri stærk, u-25 organisk syre og derefter eventuelt med vand, hver gang ved temperaturer mellem -50 og +50°C, hvorhos der til 1 mol pivaloylcyanid anvendes 1 til 10 mol uorganisk syre og 0 til 10 mol vand.It has now been found that the novel trimethyl-pyruvic acid amide of formula (ch3) 3C-co-c ° -NH2 (III) 20 is obtained in high yield when pivaloyl cyanide of formula (ch3) 3c-co-cn (IV ) optionally in the presence of a lower aliphatic carboxylic acid liquid under the reaction conditions as solvent and optionally under pressure, first reacted with anhydrous strong, inorganic acid and then optionally with water, each time at temperatures between -50 and + 50 ° C. wherein 1 to 10 moles of inorganic acid and 0 to 10 moles of water are used for 1 mole of pivaloyl cyanide.
Det må med henblik på teknikkens stade betegnes som over-30 ordentligt overraskende, at det ved betingelserne ved fremgangsmåden ifølge opfindelsen lykkes at få trimethyl-pyrodruesyreamid i godt udbytte. Det var især ikke at forvente på baggrund af teknikkens stade, at fremgangsmåden ifølge opfindelsen forløber med godt udbytte enten uden opløsningsmiddel eller i nærværelse 35 af en lavere aliphatisk carboxylsyre som opløsningsmiddel, især o 149195 3 da disse organiske syrer ikke anses som. indifferente ved reaktionsbetingelserne, især ikke over for hydrogenhalogenider.For the state of the art, it must be considered quite surprising that, under the conditions of the process of the invention, it is possible to obtain trimethyl-pyruvic acid amide in good yield. In particular, it was not to be expected from the state of the art that the process of the invention proceeds with good yield either without solvent or in the presence of a lower aliphatic carboxylic acid as solvent, especially since these organic acids are not considered. inert to the reaction conditions, especially not to hydrogen halides.
Anvendes der pivaloylcyanid og vand som udgangsforbindelser samt iseddike som opløsningsmiddel og saltsyre som uorganisk 5 syre, kan reaktionsforløbet illustreres ved følgende reaktionsskema:If pivaloyl cyanide and water are used as starting compounds as well as glacial acetic acid as solvent and hydrochloric acid as inorganic acid, the course of the reaction can be illustrated by the following reaction scheme:
1. HC1/CH-COOH1. HCl / CH-COOH
(CH,) ,C-CO-CN — ---- (CH3) 3C-CO-CO-NH2 33 2. H20(CH3), C-CO-CN - ---- (CH3) 3C-CO-CO-NH2 33 2. H2 O
Det som udgangsforbindelse anvendte pivaloylcyanid er kendt og kan f.eks. fremstilles ved omsætning af pivaloyl-chlorid med kobber(I)-cyanid, jfr. f.eks. J. Amer. Chem. Soc.The pivaloyl cyanide used as a starting compound is known and can e.g. is prepared by reacting pivaloyl chloride with copper (I) cyanide, cf. eg. J. Amer. Chem. Soc.
72, s. 2793 (1950).72, pp. 2793 (1950).
Reaktionstemperaturerne kan ved gennemførelse af fremgangsmåden ifølge opfindelsen varieres i et større område, o idet der som tidligere anført arbejdes mellem -50 og +50 C, fortrinsvis ved -20 til +30°C.The reaction temperatures can be varied in a larger range by carrying out the process according to the invention, since, as previously stated, between -50 and + 50 ° C, preferably at -20 to + 30 ° C.
Omsætningen ifølge opfindelsen kan gennemføres under normaltryk, men også ved forhøjet tryk, fortrinsvis i området 20 mellem 1 og 10 bar.The reaction according to the invention can be carried out under normal pressure, but also at elevated pressure, preferably in the range 20 between 1 and 10 bar.
Omsætningen ifølge opfindelsen gennemføres ved hjælp af en stærk, uorganisk syre. Hertil hører fortrinsvis hydrogen-halogenid-syrerne, såsom vandfrit hydrogenchlorid eller -bromid, samt koncentreret svovlsyre.The reaction according to the invention is carried out by means of a strong inorganic acid. Preferably, these include the hydrogen halide acids, such as anhydrous hydrogen chloride or bromide, as well as concentrated sulfuric acid.
25 Omsætningen ifølge opfindelsen kan gennemføres i fra vær eller i nærværelse af en ved reaktionsbetingelserne flydende, lavere aliphatisk carboxylsyre som opløsningsmiddel. Som et sådant opløsningsmiddel kommer især carboxylsyrer med 1 til 6 carbonatomer på tale, f.eks. vandfri eddikesyre, propionsyre 30 eller myresyre. Iseddike foretrækkes særligt.The reaction of the invention may be carried out in weather or in the presence of a lower aliphatic carboxylic acid liquid as a solvent under the reaction conditions. As such, in particular, carboxylic acids having 1 to 6 carbon atoms are discussed, e.g. anhydrous acetic acid, propionic acid 30 or formic acid. Glacial vinegar is particularly preferred.
Et opløsningsmiddel anvendes fortrinsvis, når der som uorganisk syre anvendes et hydrogenhalogenid, mens der ved anvendelse af en uorganisk oxygenholdig syre, såsom især svovlsyre, fortrinsvis arbejdes uden opløsningsmiddel.A solvent is preferably used when an inorganic acid is used as a hydrogen halide, while the use of an inorganic oxygen-containing acid, such as sulfuric acid in particular, is preferably worked without a solvent.
35 Ved anvendelse af en uorganisk oxygenholdig syre kan35 Using an inorganic oxygen-containing acid can
OISLAND
4 149195 det desuden være hensigtsmæssigt at sætte en katalytisk mængde chloridioner som alkalimetal- eller ammoniumchlorid til reaktionsblandingen, fortrinsvis 0,01 til 0,1 mol pr. mol oxygenhol-dig syre. En tilsætning af ammoniumchlorid er særligt egnet, 5 f.eks. ved anvendelse af svovlsyre.In addition, it is convenient to add a catalytic amount of chloride ions such as alkali metal or ammonium chloride to the reaction mixture, preferably 0.01 to 0.1 mole per liter. moles of oxygen-containing acid. An addition of ammonium chloride is particularly suitable, e.g. using sulfuric acid.
En tilsætning af vand til reaktionsblandingen til dannelse af amidet med formlen (III) er i tilfælde, hvor der anvendes en carboxylsyre som opløsningsmiddel og et hydrogenhalogenid som uorganisk syre, ikke tvingende nødvendig: ved indvirkning af 10 hydrogenhalogenidet på carboxylsyren dannes der foruden en vis mængde carboxylsyrehalogenid den tilsvarende‘mængde vand (idet mængden afhænger af de faktisk anvendte reagenser og de faktiske reaktionsbetingelser), hvilken mængde kan være tilstrækkelig til kvantitativ hydrolyse af det anvendte pivaloylcyanid el-15 ler mulige intermediære reaktionstrin. I sådanne tilfælde fungerer den anvendte carboxylsyre ikke kun som opløsningsmiddel, men også delvis som reaktionsdeltager (idet andre reaktionsmekanismer ganske vist også er tænkelige). Det er i alle tilfælde ved denne udførelsesform for opfindelsen ikke nødvendigt at 20 anvende støkiometriske vandmængder.An addition of water to the reaction mixture to form the amide of formula (III) is not imperative in cases where a carboxylic acid is used as a solvent and a hydrogen halide as inorganic acid: in addition to the effect of the hydrogen halide on the carboxylic acid, a certain amount is formed. carboxylic acid halide the corresponding amount of water (the amount being dependent on the reagents actually used and the actual reaction conditions) which may be sufficient for quantitative hydrolysis of the pivaloyl cyanide used or possible intermediate reaction steps. In such cases, the carboxylic acid used not only acts as a solvent, but also partly as a reaction participant (although other reaction mechanisms are also conceivable). In all cases in this embodiment of the invention, it is not necessary to use stoichiometric amounts of water.
Ved gennemførelsen af fremgangsmåden ifølge opfindelsen anvendes der til 1 mol pivaloylcyanid med formlen (IV) som nævnt 1 til 10 mol uorganisk syre og 0 til 10 mol vand, fortrinsvis 1 til 8 mol uorganisk syre og 0 til 2,5 mol vand.In carrying out the process of the invention, 1 mole of pivaloyl cyanide of formula (IV) as mentioned is used for 1 to 10 moles of inorganic acid and 0 to 10 moles of water, preferably 1 to 8 moles of inorganic acid and 0 to 2.5 moles of water.
25 Til isoleringen af trimethyl-pyrodruesyreamidet med formlen (III) neutraliseres reaktionsblandingen, og der oparbejdes på gængs måde.For the isolation of the trimethyl-pyruvic acid amide of formula (III), the reaction mixture is neutralized and worked up in the usual manner.
Trimethyl-pyrodruesyreamidet kan forsæbes på i og for sig kendt måde ved sur eller alkalisk hydrolyse til den frie 30 trimethyl-pyrodruesyre (3,3-dimethyl-2-oxo-smørsyre).The trimethylpyruvic acid amide can be saponified in a manner known per se by acidic or alkaline hydrolysis to the free trimethylpyruvic acid (3,3-dimethyl-2-oxo-butyric acid).
Trimethyl-pyrodruesyreamid med formlen (III) er et værdifuldt mellemprodukt til fremstilling af visse herbicidt virksomme forbindelser i rækken af asymmetriske triazinoner, f.eks. af 4-amino-6-tert.butyl-3-methylthio-l,2,4-triazin-5-(4H)-on 35 med formlen (VII), jfr. DE-PS 1.795.784, DE-AS 2.648.300, DE-Trimethylpyruvic acid amide of formula (III) is a valuable intermediate for the preparation of certain herbicidal active compounds in the series of asymmetric triazinones, e.g. of 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazine-5- (4H) -one of formula (VII), cf. DE-PS 1,795,784, DE-AS 2,648,300, DE-
OISLAND
5 149195 -OS 2.460.889 og DE-OS 2.165.554.5 149195 -OS 2,460,889 and DE-OS 2,165,554.
De følgende fremstillingseksempler skal belyse fremgangsmåden ifølge opfindelsen nærmere.The following manufacturing examples are intended to illustrate in detail the process of the invention.
5 Fremstillingseksempler5 Preparation Examples
Fremstilling af trimethyl-pyrodruesyreamid med formlen (CH3)3C-CO-CO-NH2 10 Eksempel 1Preparation of trimethylpyruvic acid amide of formula (CH3) 3C-CO-CO-NH2 Example 1
Til 800 g af en 36%'s opløsning af hydrogenbromid i iseddike dryppes der ved stuetemperatur under omrøring 111,0 g (1 mol) pivaloylcyanid. Efter afsluttet tilsætning efteromrø-res der i tre timer ved stuetemperatur. Derpå tildryppes der 15 ved 20 til 25°C 9 ml (0,5 mol) vand, og der efteromrøres i én time ved stuetemperatur. Derefter hældes reaktionsopløsningen ud i et overskud af mættet natriumhydrogencarbonat-opløsning.To 800 g of a 36% solution of hydrogen bromide in glacial acetic acid is added dropwise 111.0 g (1 mole) of pivaloyl cyanide at room temperature with stirring. After completion of the addition, stir for three hours at room temperature. Then, at 20 to 25 ° C, 9 ml (0.5 mole) of water is added dropwise and stirred for one hour at room temperature. Then, the reaction solution is poured into an excess of saturated sodium hydrogen carbonate solution.
Der ekstraheres tre gange med hver gang 200 ml methylenchlorid.Extract three times with 200 ml of methylene chloride each time.
De samlede organiske faser vaskes med 200 ml vand, tørres over 20 natriumsulfat, og volumenet reduceres ved afdestillation af opløsningsmidlet i vakuum. Den tilbageblevne olie gennemkrystal-liserer efter nogen tid. Efter omkrystallisation fra petro-leumsether fås der 113,5 g, svarende til 88% af det teoretiske udbytte, trimethyl-pyrodruesyreamid med smeltepunkt 69-70°C.The combined organic phases are washed with 200 ml of water, dried over 20 sodium sulfate and the volume reduced by distillation of the solvent in vacuo. The residual oil crystallizes after some time. After recrystallization from petrochemical ether, 113.5 g, corresponding to 88% of the theoretical yield, is obtained trimethyl-pyruvic acid amide, mp 69-70 ° C.
2525
Eksempel 2Example 2
Til en blanding af 60 g (1 mol) iseddike og 111,0 g (1.mol) pivaloylcyanid ledes der hydrogenchlorid i 5 timer ved 20^25°C/8 bar. Derefter afbrydes tilledningen, og reaktionsblan-30 dingen hældes ud i et overskud af en mættet natriumhydrogencar-bonat-opløsning. Der ekstraheres tre gange med hver gang 200 ml methylenchlorid. De samlede organiske faser vaskes med 200 ml vand, tørres over natriumsulfat, og volumenet reduceres ved afdestillation af opløsningsmidlet i vakuum. Remanensen krystalli-35 serer i løbet af kort tid. Efter omkrystallisation fra petro- 6 o 149195 leumsether fås der 97 g, svarende til 75,2% af det teoretiske udbytte, trimethyl-pyrodruesyreamid med smeltepunkt 68-69°C.To a mixture of 60 g (1 mol) of glacial acetic acid and 111.0 g (1 mol) of pivaloyl cyanide, hydrogen chloride is passed for 5 hours at 20 ^ 25 ° C / 8 bar. Then the feed is discontinued and the reaction mixture poured into an excess of a saturated sodium hydrogen carbonate solution. Extract three times with 200 ml of methylene chloride each time. The combined organic phases are washed with 200 ml of water, dried over sodium sulfate and the volume reduced by distillation of the solvent in vacuo. The residue crystallizes in a short time. After recrystallization from petro-leum ether, 97 g, corresponding to 75.2% of theoretical yield, is obtained trimethyl-pyruvic acid amide, mp 68-69 ° C.
Eksempel 3 5 55,5 g (0,5 mol) pivaloylcyanid og 2 g ammoniumchlorid anbringes i en 500 ml trehalset kolbe. Der afkøles til -5 til 0°C og tildryppes ved denne temperatur 100 ml koncentreret svovlsyre. Derpå tildryppes der, ligeledes ved -5 til 0°C, 18 ml (1 mol) vand. Der efteromrøres i 12 timer ved -5 til 0°C, 10 og derefter hældes reaktionsblandingen ud i en opløsning af 350 g natriumcarbonat i 600 ml vand. Der ekstraheres to gange med hver gang 300 ml methylenchlorid. De samlede organiske faser vaskes med 300 ml vand, tørres over natriumsulfat, og volumenet reduceres ved afdestillation af opløsningsmidlet i va-15 kuum. Efter omkrystallisation fra petroleumsether fås der 66 g, svarende til 51,2% af det teoretiske udbytte, trimethyl-pyrodruesyreamid med smeltepunkt 67-69°C.EXAMPLE 3 55.5 g (0.5 mole) of pivaloyl cyanide and 2 g of ammonium chloride are placed in a 500 ml three-neck flask. Cool to -5 to 0 ° C and drop at 100 ml of concentrated sulfuric acid at this temperature. Then, at -5 to 0 ° C, 18 ml (1 mole) of water is also added dropwise. Stir for 12 hours at -5 to 0 ° C, 10 and then pour the reaction mixture into a solution of 350 g of sodium carbonate in 600 ml of water. Extract twice with 300 ml of methylene chloride each time. The combined organic phases are washed with 300 ml of water, dried over sodium sulfate and the volume reduced by distillation of the solvent in vacuo. After recrystallization from petroleum ether, 66 g, corresponding to 51.2% of the theoretical yield, is obtained trimethyl-pyruvic acid amide, mp 67-69 ° C.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803003542 DE3003542A1 (en) | 1980-01-31 | 1980-01-31 | METHOD FOR THE PRODUCTION OF TRIMETHYLBRAXIC ACID AMIDE |
| DE3003542 | 1980-01-31 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK41981A DK41981A (en) | 1981-08-01 |
| DK149195B true DK149195B (en) | 1986-03-10 |
| DK149195C DK149195C (en) | 1986-08-04 |
Family
ID=6093410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK41981A DK149195C (en) | 1980-01-31 | 1981-01-30 | METHOD FOR PREPARING TRIMETHYL-PYRODRUIC ACIDAMIDE |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0034703B1 (en) |
| JP (1) | JPS56120653A (en) |
| BR (1) | BR8100567A (en) |
| DE (2) | DE3003542A1 (en) |
| DK (1) | DK149195C (en) |
| IL (1) | IL62013A (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2459686A (en) * | 1947-06-13 | 1949-01-18 | American Cyanamid Co | Acetoxy-aliphatic amides |
| DE2708184C3 (en) * | 1977-02-25 | 1980-02-07 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the preparation of a -ketocarboxamides !! (A) |
| DE2733181B2 (en) * | 1977-07-22 | 1979-08-30 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the preparation of N-substituted α-ketocarboxamides |
-
1980
- 1980-01-31 DE DE19803003542 patent/DE3003542A1/en not_active Withdrawn
-
1981
- 1981-01-21 EP EP81100406A patent/EP0034703B1/en not_active Expired
- 1981-01-21 DE DE8181100406T patent/DE3160978D1/en not_active Expired
- 1981-01-29 JP JP1092581A patent/JPS56120653A/en active Granted
- 1981-01-29 IL IL62013A patent/IL62013A/en unknown
- 1981-01-30 DK DK41981A patent/DK149195C/en not_active IP Right Cessation
- 1981-01-30 BR BR8100567A patent/BR8100567A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0034703A2 (en) | 1981-09-02 |
| JPS56120653A (en) | 1981-09-22 |
| EP0034703A3 (en) | 1981-09-16 |
| DK149195C (en) | 1986-08-04 |
| EP0034703B1 (en) | 1983-09-28 |
| BR8100567A (en) | 1981-08-18 |
| DK41981A (en) | 1981-08-01 |
| IL62013A0 (en) | 1981-02-27 |
| JPS64943B2 (en) | 1989-01-10 |
| DE3003542A1 (en) | 1981-08-06 |
| DE3160978D1 (en) | 1983-11-03 |
| IL62013A (en) | 1984-04-30 |
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