NZ200856A - Preparation of 2-(thien-(2 or 3)-yl)ethylamines - Google Patents
Preparation of 2-(thien-(2 or 3)-yl)ethylaminesInfo
- Publication number
- NZ200856A NZ200856A NZ200856A NZ20085682A NZ200856A NZ 200856 A NZ200856 A NZ 200856A NZ 200856 A NZ200856 A NZ 200856A NZ 20085682 A NZ20085682 A NZ 20085682A NZ 200856 A NZ200856 A NZ 200856A
- Authority
- NZ
- New Zealand
- Prior art keywords
- process according
- thienyl
- general formula
- carried out
- hydrogenation
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
<div class="application article clearfix" id="description">
<p class="printTableText" lang="en">New Zealand Paient Spedficaiion for Paient Number £00856 <br><br>
NO DRAWIfSP <br><br>
Priority Date(s)*. k.*?? <br><br>
Complete Specification Filed: <br><br>
Class: ...££I?-k?v?.3 <br><br>
Publication Data (' P.O. Journal, No: ...... J.Q-i7.~7. <br><br>
Patents Form No. 5 Number <br><br>
PATENTS ACT 1953 Dated <br><br>
COMPLETE SPECIFICATION <br><br>
Process for preparing 2-(thienyl-2)-ethylamines and 2-(thienyl-3)-ethylamines <br><br>
MWe SANOFI a French company of 40, Avenue George V, 75008 Paris, France do hereby declare the invention for which yiwe pray that a Patent may be granted to ros/us, and the method by which it is to be performed, to be particularly described in and by the following statement: <br><br>
2008 56 <br><br>
-2- <br><br>
The present invention is concerned with a new process for preparing 2-(thienyl-2)-ethylamines and 2-(thienyl-3)-ethylamines, a considerable number of which are known and used as intermediates for obtaining derivatives used in the chemical industry as pharmaceuticals. <br><br>
The compounds prepared by the process according to the present invention have the general formula in which and 1*2, which may be the same or different, are hydrogen atoms or straight-chained or branched alkyl radicals or heterocyclic or non-heterocyclic aromatic radicals, such as thienyl, furyl, pyridyl, phenyl or naphthyl, which are optionally mono- or poly-substituted. <br><br>
The aminoethyl radical and the substituent may be in any desired position of the thiophene nucleus. <br><br>
The compounds of general formula (I) have already been prepared by various methods: <br><br>
reduction of 2- or 3-0-nitrovinylthiophenes with the use of lithium aluminium hydride (see R.T. Gilsdorf and F.F. Nord, L. Org. Chem., ljj, 807/1950; E. Campaigne and W.C. McCarthy, J.A.C.S., 7_6# 4466/1954) or electro- <br><br>
4 3 <br><br>
(I) <br><br>
200856 <br><br>
-3- <br><br>
chemically (see British Patent Specification No. <br><br>
2013196): <br><br>
reduction of 2-(thienyl-2)- and 2-(thienyl-3)-aceto-nitriles with lithium aluminium hydride (see B.F. Crowe and F.F. Nord, J. Org. Chem., 15, 81/1950: E. Campaigne and W.C. McCarthy, loc. cit. ) or with sodium amalgam (see F.F. Blicke and J.H. Burckhalter, J.A.C.S., 64, 477/1942); <br><br>
by the Curtius degradation of 3-(thienyl-2)- and 3-(thienyl-3)-propionic acids (see G. Barger and A.P.T. Eassou, J. Chem. Soc., 2100/1938; E. Canpaigne and W.C. McCarthy, loc. cit.); <br><br>
starting from halide or arylsulphonate derivatives of 2-(thienyl-2)- or 2-(thienyl-3)-ethanol by direct amination (see F.F. Blicke and J.H. Burckhalter, loc.cit; British Patent Specification No. 1469226 ) or via a phthalimide intermediate (see BritishPatent Specification No. 1469226 ). <br><br>
However, these various processes, which are difficult to carry out, do not give good yields which are of interest for use on a large scale. <br><br>
It is an object of the present invention to provide a process for obtaining compounds of general formula (X) which is simple and not very laborious. <br><br>
In order to achieve this object, in practice, as starting material there is used a compound of the general formula:- F ; <br><br>
!— <br><br>
200856 <br><br>
ri <br><br>
-4- <br><br>
ch=c(r2)-n02 (iv) <br><br>
in which and R2 have the same meanings as in general formula (I), which may be prepared by various known methods, for example by condensing a compound of the general formula <br><br>
R2~CH2~N02 (I3:) <br><br>
in which R2 has the same meaning as in general formula (I), with a carbonyl derivative of the general formula:- <br><br>
R1 <br><br>
cho (iii) <br><br>
in which R^ has the same meaning as in general formula (i), operating under known conditions, to give a compound of the general formula rich=c(r2)no2 (iv) <br><br>
in which R^ and R2 have the same meanings as in general formula (I). <br><br>
Thus, according to the present invention, there is provided a process for preparing compounds of general formula (I), wherein a) a compound of general formula (IV) is subjected to a <br><br>
200 <br><br>
-5- <br><br>
catalytic hydrogenation Reaction in a non-alkaline solvent, under a hydrogen pressure of from 1 to 100 atomospheres and at a temperature of from 20 to 100°C, to give a compound of the general formula :- <br><br>
*1 \ f.—3^-^ ch2-c=n-°h (v) <br><br>
*2 " <br><br>
s in which Ri and R2 have the same meanings as above; and b) the compound of general formula (V) is, in turn, also converted by catalytic hydrogenation in an alcoholic solvent medium which contains ammonia in a dissolved state, under a hydrogen pressure of from 1 to 100 atmospheres and at a temperature of from 20 to 100°C, into a compound of general formula (I). <br><br>
Generally speaking, obtaining the compounds of the arylethylamino type according to the following equation: <br><br>
R2 <br><br>
Ar-CH=C—NO- > Ar-CH2-CH-NB2 <br><br>
I catalyst ' <br><br>
R * <br><br>
i.e. by the catalytic hydrogenation of ^-nitrovinylaryl compounds, is already known. However, it has never been used in cases in which the aromatic radical is thiophene. Nevertheless, there has previously been described the hydrogenation of 2-^-nitrovinylthiophene but limited to obtaining the oxime of 2-(thienyl-2 )-acetaldehyde and carried out in the; presence of- <br><br>
palladium (see L. Kh. Freidlin, E.F.Litvin and V.M. Chursina, <br><br>
! — :•> <br><br>
Khimiya G. et Soed., 3 22/1967; Chem. Abs., 62 73465 y) but the quantities of catalyst employed (0.200 g. of metallic <br><br>
-6- <br><br>
200856 <br><br>
palladium per 0.775 g. of substrate to be hydrogenated) exclude all reasonable industrial application of the process: the proportion of palladium used is, in effect, more than 25%, referred to the substrate. <br><br>
In contradistinction thereto, by the process according to the present invention, 2-(thienyl-2)- and 2-(thienyl-3)-ethylamines are obtained under conditions which are simple to carry out and which are not expensive because of the small amounts of catalyst employed. <br><br>
The process according to the present invention is, in particular, characterised by carrying out the reduction in two stages using different conditions. <br><br>
In the first stage, a compound of general formula <br><br>
(IV) is hydrogenated in a non-alkaline solvent, which may be an alcohol, such as methanol, <br><br>
above, for example a mixture of methanol or ethanol and acetic acid. The hydrogenation is carried out in the presence of a metal catalyst, for example palladium, platinum, ruthenium, rhodium or iridium. <br><br>
The metal catalyst is advantageously diluted with 10 to 100 times its weight of a support material, for example charcoal, alumina or barium sulphate, and, <br><br>
generally speaking, use is made of a quantity which is from 1 to 10% of the amount of substrate to be hydrogenated. <br><br>
formic acid, acetic acid or propionic acid, or, still more advantageously, in a mixture of two solvents each selected from one of the groups of solvents mentioned ethanol or isopropanol, or an organic acid, such as <br><br>
200856 <br><br>
-7- <br><br>
which corresponds to amounts of 1/10,000 to 1/100 of palladium. The hydrogenation is carried out under a hydrogen pressure which is generally from 1 to 100 atmospheres and preferably from 5 to 25 atmospheres at a temperature Which is generally from 20 to l00°cl and preferably from 30 to 60°C. The duration of the operation is generally from 30 minutes to several hours. <br><br>
In the second stage, the derivative of general formula (V), isolated in appropriate manner from the reaction mixture, is, after removal of the catalyst, hydrogenated in an alcoholic solvent medium, for I <br><br>
example methanol, ethanol or isopropanol, which, in order to avoid the formation of secondary amines, <br><br>
contains ammonia in a dissolved state. <br><br>
The hydrogenation is carried out in the presence of a metal catalyst and particularly of nickel, which may be Raney nickel or nickel deposited on a support, <br><br>
such as silica or alumina, the quantity of metal catalyst used being from 1 to 10% of the substrate to be hydrogenated. The hydrogenation is carried out under a hydrogen pressure of generally from 1 to 100 atmospheres and preferably of from 5 to 25 atmospheres at a temperature which is generally from 20 to 100°C. and preferably from 40 to 80°C. The duration of the operation is generally from 30 minutes to several hours. <br><br>
The compounds thus obtained of general formula (I) may subsequently be isolated and purified according to <br><br>
20085 6 <br><br>
-8- <br><br>
conventional methods. In order to carry out these operations, it may be advantageous to convert the free bases of general formula (I) into their salts, for example their acid addition salts, by reaction with mineral or organic acids. Starting from the salts, the free bases of general formula (I) may be liberated by known methods. <br><br>
The present invention is also concerned with the intermediates obtained at different stages of the synthesis, i.e. the compounds of general formula:- <br><br>
in which and R£ have the same meanings as above. <br><br>
The following Examples are given for the purpose of illustrating the present invention Example 1. <br><br>
Preparation of 2-(thienyl-2)-ethylamine hydrochloride, a) 2-Thienylacetaldehyde oximes. <br><br>
A solution of 100 g. (0.645 mole) 2-(thienyl-2)- <br><br>
(V) <br><br>
in which R^ and R2 have the same meanings as above; and the compounds of the general formula:- <br><br>
(I) <br><br>
2008 56 <br><br>
-9- <br><br>
nitroethylene in 2 litres of a mixture of acetic acid and ethanol (75/25 v/v) is hydrogenated in an autoclave at 35°C. under a pressure of 20 bars in the presence of 5 g. of palladium-charcoal (5%) until absorption of hydrogen ceases (duration: about 2 hours). After filtering off the catalyst and washing it with ethanol, the solution obtained is evaporated in a vacuum at 50°C. The oily residue obtained is taken up in 500 ml. methylene chloride and the solution is successively washed with an approximately IN aqueous solution of sodium carbonate and then with water and finally evaporated to give 97 g. of the oximes (mixture of syn and anti) of 2-thienyl-acetaldehyde in the form of an orange-yellow oil which is used as such in the following step. <br><br>
b) The mixture of oximes obtained above, in solution in 2 litres of methanol saturated with ammonia, is hydrogenated in an autoclave at 60°C. at a pressure of 20 bars in the presence of 10 g. of Raney nickel until absorption ceases (duration about 20 hours). After filtering off the catalyst and washing it with methanol, the solution is evaporated. The oily residue obtained is added to 500 ml. toluene. The organic phase is extracted with approximately IN aqueous hydrochloric acid. The aqueous acid phase is isolated and rendered alkaline with an approximately IN aqueous solution of sodium carbonate and then extracted with toluene. The addition to the isolated organic phase of a solution <br><br>
100856 <br><br>
-10- <br><br>
of gaseous hydrogen chloride in diisopropyl ether brings about the formation of a precipitate which is filtered off and dried. There are thus obtained 68 g. (yield 65% of theory, referred to the 2-(thienyl-2)-nitroethylene used), of the hydrochloride of 2-(thienyl-2)-ethylamine in the form of white crystals; m.p. 202°C. Analysis: <br><br>
C6HgNS.HCl (m.w. 163.67) <br><br>
calc. : C 44.03%: H 6.15%; N 8.55% <br><br>
found : 43.98%; 6.16%; 8.54% <br><br>
Example 2. <br><br>
2-(Thienyl-3)-ethylamine hydrochloride. <br><br>
Operating under the reaction conditions described in Example 1 but using 5% rhodium/charcoal instead of 5% palladium/charcoal, there is obtained the desired hydrochloride in a yield of 66% of theory; m.p. 216°C. Analysis: <br><br>
C6H9NS.HC1 (m.w. 163.67) <br><br>
calc. : C 44.03%; H 6.15%; N 8.55% <br><br>
found : 43.92%; 6.18%; 8.50% <br><br>
Example 3. <br><br>
1-Methyl-2-(thienyl-3)-ethylamine hydrochloride. <br><br>
Operating under the reaction conditions used in Example 1 but using 5% platinum/charcoal instead of 5% palladium/charcoal, there is obtained the desired hydrochloride in a yield of 81% of theory; m.p. 138°C. <br><br></p>
</div>
Claims (10)
1. A process for the preparation of 2-(thienyl-2)- and 2-(thienyl-3)-ethylamines of the general formula:-<br><br> f 4<br><br> ^ s ^<br><br> CH--CH-HH-I ^ R„<br><br> (I)<br><br> in which R^ and R2/ which can be the same or different, are hydrogen atoms, straight-chained or branched alkyl radicals or heterocyclic or non-heterocyclic aromatic radicals, which are optionally mono- or polysubstituted, wherein a compound of the general formula:-<br><br> F'<br><br> O*<br><br> ><br><br> cz<br><br> CD <0<br><br> O<br><br> 35 J i<br><br> CH=C-NO.<br><br> (IV)<br><br> oo ! |? • in which Ri and R2 have the same meanings as above, is subjected to catalytic hydrogenation in a non-alkaline solvent under a hydrogen pressure of from 1 to 100 atmospheres and at a temperature of from 20 to 100°C. to give a compound of the general formula:-<br><br> s<br><br> CH2-C=N-OH<br><br> (V)<br><br> in which R^ and R2 have the same meanings as above, and after<br><br> 2C0E56<br><br> isolation thereof, this is converted into a compound of general formula (I) by catalytic hydrogenation in an alcoholic solvent which contains ammonia in a dissolved state, under a hydrogen pressure of from 1 to 100 atmospheres and at a temperature of from 20 to 100°C.<br><br>
2. A process according to claim 1, wherein the first catalytic hydrogenation phase is carried out in an organic solvent or in an organic acid or in a mixture thereof.<br><br>
3. A process according to claim 2, wherein the organic solvent is methanol, ethanol or isopropanol and the organic acid is formic acid, acetic acid or propionic acid.<br><br>
4. A process according to any one of the preceding claims,<br><br> wherein the catalyst used for the first hydrogenation stage is used on a substrate and in an amount of from 1:10,000 to 1:100 by weight.<br><br>
5. A process according to any one of the preceding claims,<br><br> wherein the alcoholic solvent in which the second catalytic hydrogenation phase is carried out is methanol, ethanol or isopropanol.<br><br>
6. A process according to any one of the preceding claims, wherein one or both of the hydrogenation phases is carried out<br><br> 200856<br><br> -14-<br><br> under a hydrogen pressure of from 5 to 25 atmospheres.<br><br>
7. A process according to any one of the preceding claims, wherein the first hydrogenation phase is carried out at a temperature of from 30 to 60°C.<br><br>
8. A process according to any one of the preceding claims, wherein the second hydrogenation phase is carried out at a temperature of from 40 to 80°C.<br><br>
9. A process according to claim 1 for the preparation of<br><br> 2-(thienyl-2)- and 2-(thienyl-3)-ethylamines substantially as hereinbefore described and exemplified.<br><br>
10. 2-(thienyl-2)- and 2-(thienyl-3)-ethylamines of general formula (I) given in claim,1, whenever prepared by the process according to any one of claims 1 to 9.<br><br> WEST-WALKER, McCABE<br><br> pen<br><br> ATTO<br><br> </p> </div>
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8113066A FR2508456A1 (en) | 1981-06-30 | 1981-06-30 | PROCESS FOR THE PREPARATION OF (THIENYL-2) -2 ETHYLAMINES AND (THIENYL-3) -2 ETHYLAMINES |
Publications (1)
Publication Number | Publication Date |
---|---|
NZ200856A true NZ200856A (en) | 1985-11-08 |
Family
ID=9260133
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NZ200856A NZ200856A (en) | 1981-06-30 | 1982-06-04 | Preparation of 2-(thien-(2 or 3)-yl)ethylamines |
Country Status (24)
Country | Link |
---|---|
EP (1) | EP0069002B1 (en) |
JP (1) | JPS5810575A (en) |
KR (1) | KR840000539A (en) |
AR (1) | AR231444A1 (en) |
AT (1) | ATE15369T1 (en) |
AU (1) | AU556916B2 (en) |
CA (1) | CA1205811A (en) |
CS (1) | CS236482B2 (en) |
DD (1) | DD202711A5 (en) |
DE (1) | DE3266028D1 (en) |
DK (1) | DK153793C (en) |
ES (1) | ES8305348A1 (en) |
FI (1) | FI822318L (en) |
FR (1) | FR2508456A1 (en) |
GR (1) | GR77203B (en) |
HU (1) | HU186867B (en) |
IE (1) | IE53278B1 (en) |
IL (1) | IL65984A (en) |
NO (1) | NO155345C (en) |
NZ (1) | NZ200856A (en) |
PT (1) | PT75156B (en) |
SU (1) | SU1148562A3 (en) |
YU (1) | YU142982A (en) |
ZA (1) | ZA824618B (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NZ214698A (en) * | 1984-12-31 | 1988-08-30 | Merrell Dow Pharma | Thiophene derivatives and pharmaceutical compositions containing such |
FR2608607B1 (en) * | 1986-12-23 | 1989-04-28 | Sanofi Sa | PROCESS FOR THE PREPARATION OF THIENYLETHYLAMINES AND DITHIENYLETHYLAMINES THUS OBTAINED |
CA1309719C (en) * | 1987-02-26 | 1992-11-03 | Thomas M. Bargar | Heterocycly1-2-propyn-1-amines |
FR2622191B1 (en) * | 1987-10-22 | 1991-06-21 | Sanofi Sa | PROCESS FOR THE PREPARATION OF N- (2-CHLORO-BENZYL) -2 ETHYLAMINE AND INTERMEDIATE PRODUCTS IN THIS PREPARATION |
US4906756A (en) * | 1988-05-10 | 1990-03-06 | Syntex (U.S.A.) Inc. | 2-(2-nitrovinyl)thiophene reduction and synthesis of thieno[3,2-c]pyridine derivatives |
US5191090A (en) * | 1990-01-25 | 1993-03-02 | Syntex (U.S.A.) Inc. | Preparation of 2-(2'-thienyl)ethylamine derivatives and synthesis of thieno[3,2-c]pyridine derivatives therefrom |
FR2664276B1 (en) * | 1990-07-04 | 1992-10-23 | Sanofi Sa | GLYCIDIC THIENYL-2 DERIVATIVE, ITS PREPARATION METHOD AND ITS USE AS A SYNTHESIS INTERMEDIATE. |
US5208252A (en) * | 1992-07-24 | 1993-05-04 | Ortho Pharmaceutical Corporation | Aminoethylthiophene derivatives |
GB201818117D0 (en) * | 2018-11-06 | 2018-12-19 | Syngenta Participations Ag | Enantioselective process |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2623174A1 (en) * | 1976-05-22 | 1977-12-01 | Basf Ag | Primary amine prepn. from oximes - by hydrogenation in presence of ammonia with catalysts contg. aluminium and nickel and/or cobalt |
-
1981
- 1981-06-30 FR FR8113066A patent/FR2508456A1/en active Granted
-
1982
- 1982-06-01 IE IE1314/82A patent/IE53278B1/en not_active IP Right Cessation
- 1982-06-04 NZ NZ200856A patent/NZ200856A/en unknown
- 1982-06-06 IL IL65984A patent/IL65984A/en not_active IP Right Cessation
- 1982-06-08 AR AR289630A patent/AR231444A1/en active
- 1982-06-09 ES ES514220A patent/ES8305348A1/en not_active Expired
- 1982-06-09 GR GR68378A patent/GR77203B/el unknown
- 1982-06-10 AU AU84752/82A patent/AU556916B2/en not_active Expired
- 1982-06-21 DE DE8282401132T patent/DE3266028D1/en not_active Expired
- 1982-06-21 EP EP82401132A patent/EP0069002B1/en not_active Expired
- 1982-06-21 AT AT82401132T patent/ATE15369T1/en not_active IP Right Cessation
- 1982-06-25 SU SU823457191A patent/SU1148562A3/en active
- 1982-06-29 FI FI822318A patent/FI822318L/en not_active Application Discontinuation
- 1982-06-29 CA CA000406317A patent/CA1205811A/en not_active Expired
- 1982-06-29 PT PT75156A patent/PT75156B/en unknown
- 1982-06-29 HU HU822110A patent/HU186867B/en unknown
- 1982-06-29 CS CS824901A patent/CS236482B2/en unknown
- 1982-06-29 NO NO822228A patent/NO155345C/en not_active IP Right Cessation
- 1982-06-29 DK DK291782A patent/DK153793C/en not_active IP Right Cessation
- 1982-06-29 ZA ZA824618A patent/ZA824618B/en unknown
- 1982-06-30 YU YU01429/82A patent/YU142982A/en unknown
- 1982-06-30 JP JP57113845A patent/JPS5810575A/en active Granted
- 1982-06-30 DD DD82241258A patent/DD202711A5/en not_active IP Right Cessation
- 1982-06-30 KR KR1019820002916A patent/KR840000539A/en unknown
Also Published As
Publication number | Publication date |
---|---|
NO155345B (en) | 1986-12-08 |
KR840000539A (en) | 1984-02-25 |
FR2508456B1 (en) | 1983-09-09 |
DE3266028D1 (en) | 1985-10-10 |
EP0069002A1 (en) | 1983-01-05 |
PT75156B (en) | 1984-02-21 |
FI822318A0 (en) | 1982-06-29 |
JPS5810575A (en) | 1983-01-21 |
IL65984A0 (en) | 1982-09-30 |
PT75156A (en) | 1982-07-01 |
ZA824618B (en) | 1983-04-27 |
DK153793B (en) | 1988-09-05 |
ES514220A0 (en) | 1983-04-01 |
CS236482B2 (en) | 1985-05-15 |
ATE15369T1 (en) | 1985-09-15 |
AU8475282A (en) | 1983-01-06 |
AU556916B2 (en) | 1986-11-27 |
IL65984A (en) | 1985-09-29 |
JPH039914B2 (en) | 1991-02-12 |
NO155345C (en) | 1987-03-18 |
IE821314L (en) | 1982-12-30 |
CA1205811A (en) | 1986-06-10 |
DD202711A5 (en) | 1983-09-28 |
DK291782A (en) | 1982-12-31 |
HU186867B (en) | 1985-10-28 |
GR77203B (en) | 1984-09-11 |
DK153793C (en) | 1989-01-23 |
IE53278B1 (en) | 1988-09-28 |
YU142982A (en) | 1984-12-31 |
FR2508456A1 (en) | 1982-12-31 |
AR231444A1 (en) | 1984-11-30 |
FI822318L (en) | 1982-12-31 |
ES8305348A1 (en) | 1983-04-01 |
EP0069002B1 (en) | 1985-09-04 |
SU1148562A3 (en) | 1985-03-30 |
NO822228L (en) | 1983-01-03 |
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