DK164324B - 11beta-substituerede 5-hydroxy-9-en-steroidforbindelser til anvendelse som udgangsmaterialer ved fremstilling af 11beta-substituerede 4,9-diensteroidforbindelser samt fremgangsmaade til fremstilling af disse udgangsmaterialer - Google Patents
11beta-substituerede 5-hydroxy-9-en-steroidforbindelser til anvendelse som udgangsmaterialer ved fremstilling af 11beta-substituerede 4,9-diensteroidforbindelser samt fremgangsmaade til fremstilling af disse udgangsmaterialer Download PDFInfo
- Publication number
- DK164324B DK164324B DK013778A DK13778A DK164324B DK 164324 B DK164324 B DK 164324B DK 013778 A DK013778 A DK 013778A DK 13778 A DK13778 A DK 13778A DK 164324 B DK164324 B DK 164324B
- Authority
- DK
- Denmark
- Prior art keywords
- 11beta
- compounds
- substituted
- hydroxy
- preparation
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 7
- -1 copper halide Chemical class 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 8
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 5
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000556 agonist Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 208000002874 Acne Vulgaris Diseases 0.000 description 1
- 208000003200 Adenoma Diseases 0.000 description 1
- 206010001233 Adenoma benign Diseases 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 208000005171 Dysmenorrhea Diseases 0.000 description 1
- 206010013935 Dysmenorrhoea Diseases 0.000 description 1
- 201000009273 Endometriosis Diseases 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- 206010020880 Hypertrophy Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- 241000786363 Rhampholeon spectrum Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 239000000051 antiandrogen Substances 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000000938 luteal effect Effects 0.000 description 1
- RMGJCSHZTFKPNO-UHFFFAOYSA-M magnesium;ethene;bromide Chemical compound [Mg+2].[Br-].[CH-]=C RMGJCSHZTFKPNO-UHFFFAOYSA-M 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000000962 progestomimetic effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0051—Estrane derivatives
- C07J1/0081—Substituted in position 17 alfa and 17 beta
- C07J1/0088—Substituted in position 17 alfa and 17 beta the substituent in position 17 alfa being an unsaturated hydrocarbon group
- C07J1/0096—Alkynyl derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0051—Estrane derivatives
- C07J1/0059—Estrane derivatives substituted in position 17 by a keto group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J21/00—Normal steroids containing carbon, hydrogen, halogen or oxygen having an oxygen-containing hetero ring spiro-condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C07J21/005—Ketals
- C07J21/006—Ketals at position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J33/00—Normal steroids having a sulfur-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C07J33/002—Normal steroids having a sulfur-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton not condensed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J51/00—Normal steroids with unmodified cyclopenta(a)hydrophenanthrene skeleton not provided for in groups C07J1/00 - C07J43/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
- C07J71/0005—Oxygen-containing hetero ring
- C07J71/001—Oxiranes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Description
DK 164324B
- i -
Opfindelsen angår hidtil ukendte llbeta-substituerede 5-hy-droxy-9-en-steroidforbindelser til anvendelse som udgangsmaterialer ved fremstilling af terapeutisk aktive llbeta--substituerede 4,9-diensteroidforbindelser med den i krav 5 l's indledning angivne almene formel I, og disse udgangsmaterialer er ejendommelige ved, at de har den i krav l's kendetegnende del anførte almene formel II.
Forbindelserne II egner sig til en særlig enkel omdannelse 10 til de terapeutisk aktive forbindelser I, idet man omsætter dem med et dehydratiseringsmiddel, fortrinsvis en sulfon-harpiks på sur form eller en uorganisk syre, som er i stand til at frigøre ketofunktionen, til fremstilling af den tilsvarende forbindelse med formlen I, hvorpå man eventuelt 15 omdanner en eventuel tilstedeværende hydroxygruppe i 17-stillingen til en acetoxygruppe eller eventuelt hydrolyserer en eventuel tilstedeværende acetoxygruppe i 17beta-stillingen.
20 Forbindelserne med formlen I har interessante farmakologiske egenskaber og navnlig en meget god progestomimetisk aktivitet. Dette gælder navnlig for forbindelserne med formlen I, hvor 17alpha-substituenten er en ethynylgruppe eller en acetoxygruppe, og 17beta-substituenten er en hydroxy-25 gruppe eller en acetylgruppe. Forbindelserne med formlen I kan altså anvendes fx til behandling af menorrhe, hyperme-norrhe, dysmenorrhe og lutealinsufficiens, jf. dansk ' pa-tentans. nr. 138/78 (patent nr. 161333).
30 Desuden har visse produkter med formlen I og navnlig sådanne, hvor 17alpha-substituenten er et hydrogenatom eller en methylgruppe, og 17beta-substituenten er en hydroxygruppe, en aktivitet, som er en androgenantagonist- eller agonist-komposant.
De kan følgelig anvendes fx for antagonisternes vedkommende 35
DK 164324 B
- 2 - i behandlingen af hypertrofi (adenom) og prostatacancer, hyperandrogeni, acne og hirsutisme og, for agonisternes vedkommende, i behandlingen af andropause, det adiposogeni-tale syndrom, funktionel metrorragi, fibrom og endometriose 5 samt i behandlingen af astheni, osteoporose, alderdomsfænomener og metaboliske forstyrrelser efter langvarig cortico-terapi.
Opfindelsen angår ligeledes en særlig fremgangsmåde til 10 fremstilling af forbindelserne II som angivet i krav 2's kendetegnende del. Det skal anføres, at llbeta-stillingen synes udpræget sterisk hindret. Litteratur vedrørende 3,4--epoxy-1-buten har vist, at reaktionen fører til en blanding. I tilfælde af det her foreliggende endnu mere sterisk 15 hindrede molekyle får man imidlertid 100% af den forventede forbindelse. Den omhandlede fremgangsmåde er den første generelle metode til indføring af en substituent i llbeta-stillingen. De tidligere kendte metoder er meget vanskelige at gennemføre, jf. Tet. Let. nr. 22, s. 2051-4 (1979) 20 og.Steroids, Vol. 37, nr. 4, s. 361-382 (1981).
Nedenstående eksempler illustrerer fremgangsmåden ifølge opfindelsen.
25
Eksempel 1 3-(1,2-ethandiyl)-acetal af 5alpha,17beta-dihydroxy--llbeta-methylestr-9-en-3-on (17-benzoat)
Man indfører ved 0°C 4,6 ml af en 2,2 M opløsning af me-30 thyllithium i ethylether i en suspension indeholdende 955 mg cuproiodid i 5 ml ether.
Til den således opnåede opløsning sætter man 436 mg 3-(1,2--ethandiyl)-acetal af 5alpha,10alpha-epoxy-17beta-hydroxy-35 estr-9(ll)-en (17-benzoat) og 2 ml tetrahydrofura. Man omrører reaktionsblandingen i 35 minutter ved 0°C, hælder den i en vandig ammoniumchloridopløsning og ekstraherer
DK 164324 B
- 3 - den med ether. Man tørrer, inddamper til tørhed og får således 460 mg af det ønskede produkt.
N.M.R. spektrum (60 MHz): 5 18 CH3, 37 Hz 11 CH3, 63-71 Hz 11 H, 180 Hz
Eksempel 2 10 3-(1,2-ethandiyl)-acetal af 17-benzoat af 5alpha,17beta- -dihydroxy-llbeta-ethylestr-9-en-3-on
Man indfører ved -20°C 14 ml af en 0,43 M opløsning af ethyllithium i ether i en suspension indeholdende 570 mg cuproiodid i ethylether. Man tilsætter derpå 872 mg 17be-15 ta-benzoat af 3-(1,2-ethandiyl)-acetal af 5alpha,lOalpha--epoxyestr-9(11)-en. Man lader temperaturen stige til 0°C, hælder reaktionsblandingen i en vandig opløsning af ammoni-umchlorid, ekstraherer med ether, tørrer og afdamper opløsningsmidlet under formindsket tryk. Der fås således 966 mg 20 af det ønskede produkt.
Eksempel 3 3-(1,2-ethandiyl)-acetal af 5alpha-hydroxy-lIbeta-vinyl--17alpha-methyl-17beta-acetylestr-9-en-3-on 25 Ved -40°C sætter man 150 mg cuprochlorid til 17,6 ml af en opløsning af vinylmagnesiumbromid. Man tilsætter derpå 4 g 3-(1,2-ethandiyl)-acetal af Salpha,10alpha-epoxy-17alpha--methyl-17beta-acetylestr-9(11)-en-3-on opløst i 15 ml te-trahydrofuran. Efter 2 timer ved -40°C hælder man reak-30 tionsblandingen i en vandig opløsning af ammoniumchlorid og ekstraherer med ether, tørrer, inddamper til tørhed, krystalliserer af isopropylether og får således 2,68 g af det ønskede produkt.
35 3-(1,2-ethandiyl)-acetal af 5alpha,10alpha-epoxy-17alpha- -methyl-17beta-acetylestr-9(11)-en-3-on fås på følgende måde: - 4 -
DK 164324 B
Man indfører 10 g 3-(1,2-ethandiyl)-acetal af 17alpha-me-thyl-17beta-acetylestra-5(10),9. (11)-dien-3-on fremstillet efter fremgangsmåden ifølge fransk patentskrift 2.149.302 i en opløsning af 0,5 ml pyridin i 240 ml methylenchlorid.
5 Man afkøler til 0°C og tilsætter 40 ml opløsning af hexa-fluoracetone (30 mmol). Efter 10 minutters forløb hælder man i en vandig opløsning af natriumthiosulfat og natrium-bicarbonat. Man ekstraherer med methylenchlorid, tørrer, inddamper til tørhed, krystalliserer af isopropylether og 10 får 8,2 g af det ønskede produkt.
15 20 25 30 35
Claims (3)
- 2. Fremgangsmåde til fremstilling af forbindelserne med formlen II ifølge krav 1, .kendetegnet ved, at man bringer en forbindelse med formlen III 10 p2 fl - 111 i hvilken L, R^, R^ og betegner det samme som i krav 1, til at reagere med en forbindelse, som udgøres af (R^^
- 20 CuLi, R^MgHal eller R^Li, hvor R^ betegner det samme som i krav 1, og Hal betegner et halogenatom, eventuelt i nærværelse af en katalytisk mængde kobberhalogenid, til fremstilling af den tilsvarende forbindelse med formlen II. 25
- 30 I 35
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7700857A FR2377417A1 (fr) | 1977-01-13 | 1977-01-13 | Nouveaux derives steroides substitues en 11b, ainsi que leur procede de preparation |
| FR7700857 | 1977-01-13 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK13778A DK13778A (da) | 1978-07-14 |
| DK164324B true DK164324B (da) | 1992-06-09 |
| DK164324C DK164324C (da) | 1992-11-02 |
Family
ID=9185436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK013778A DK164324C (da) | 1977-01-13 | 1978-01-12 | 11beta-substituerede 5-hydroxy-9-en-steroidforbindelser til anvendelse som udgangsmaterialer ved fremstilling af 11beta-substituerede 4,9-diensteroidforbindelser samt fremgangsmaade til fremstilling af disse udgangsmaterialer |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US4147695A (da) |
| JP (1) | JPS5390253A (da) |
| BE (1) | BE862868A (da) |
| CA (1) | CA1122971A (da) |
| CH (1) | CH629823A5 (da) |
| DE (1) | DE2801415A1 (da) |
| DK (1) | DK164324C (da) |
| FR (1) | FR2377417A1 (da) |
| GB (1) | GB1595131A (da) |
| HU (1) | HU175290B (da) |
| IE (1) | IE46300B1 (da) |
| LU (1) | LU78860A1 (da) |
| NL (1) | NL7800365A (da) |
| SE (1) | SE440780B (da) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0110434B1 (fr) * | 1981-01-09 | 1986-10-29 | Roussel-Uclaf | Nouveaux produits intermédiaires stéroides substitués en 11-beta et procédé de préparation de ces produits |
| ZA8231B (en) * | 1981-01-09 | 1982-11-24 | Roussel Uclaf | New 11 -substituted steroid derivatives, their preparation, their use as medicaments, the compositions containing them and the new intermediates thus obtained |
| FR2522328B1 (fr) * | 1982-03-01 | 1986-02-14 | Roussel Uclaf | Nouveaux produits derives de la structure 3-ceto 4,9 19-nor steroides, leur procede de preparation et leur application comme medicaments |
| FR2586021B1 (fr) * | 1985-08-09 | 1988-10-14 | Roussel Uclaf | Nouveaux produits derives de la structure 5a-oh d 9(10) 19-nor steroides |
| US5929262A (en) * | 1995-03-30 | 1999-07-27 | The United States Of America As Represented By The Department Of Health And Human Services | Method for preparing 17α-acetoxy-11β-(4-N, N-dimethylaminophyl)-19-Norpregna-4,9-diene-3, 20-dione, intermediates useful in the method, and methods for the preparation of such intermediates |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2880233A (en) * | 1956-01-05 | 1959-03-31 | Sterling Drug Inc | Compounds of the perhydrochrysene and related series and preparation thereof |
| US3299108A (en) * | 1965-10-18 | 1967-01-17 | Searle & Co | 17alpha-alkynyl/alkenyl-13beta-alkyl-11-alkylgona-1, 3, 5 (10)-triene-3, 17beta-diols, ethers and esters thereof and intermediates thereto |
| US3346602A (en) * | 1966-10-12 | 1967-10-10 | Searle & Co | 13beta-alkyl-11-alkylgona-1, 3, 5 (10)-trien-17-ones, ethers and esters thereof |
| FR2235949B1 (da) * | 1973-06-18 | 1978-03-17 | Roussel Uclaf | |
| FR2237906A1 (en) * | 1973-06-26 | 1975-02-14 | Roussel Uclaf | 11-oxo estr-9-ene derivs. - intermediates in the synthesis of steroids |
-
1977
- 1977-01-13 FR FR7700857A patent/FR2377417A1/fr active Granted
- 1977-12-21 SE SE7714612A patent/SE440780B/sv not_active IP Right Cessation
-
1978
- 1978-01-06 US US05/867,484 patent/US4147695A/en not_active Expired - Lifetime
- 1978-01-12 NL NL7800365A patent/NL7800365A/xx not_active Application Discontinuation
- 1978-01-12 BE BE184283A patent/BE862868A/xx not_active IP Right Cessation
- 1978-01-12 DK DK013778A patent/DK164324C/da not_active IP Right Cessation
- 1978-01-12 CA CA294,843A patent/CA1122971A/fr not_active Expired
- 1978-01-12 HU HU78RO953A patent/HU175290B/hu not_active IP Right Cessation
- 1978-01-12 LU LU78860A patent/LU78860A1/xx unknown
- 1978-01-13 DE DE19782801415 patent/DE2801415A1/de not_active Withdrawn
- 1978-01-13 JP JP206578A patent/JPS5390253A/ja active Granted
- 1978-01-13 GB GB1375/78A patent/GB1595131A/en not_active Expired
- 1978-01-13 CH CH38978A patent/CH629823A5/fr not_active IP Right Cessation
- 1978-01-13 IE IE77/78A patent/IE46300B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BE862868A (fr) | 1978-07-12 |
| LU78860A1 (da) | 1978-09-18 |
| DK13778A (da) | 1978-07-14 |
| HU175290B (hu) | 1980-06-28 |
| NL7800365A (nl) | 1978-07-17 |
| SE7714612L (sv) | 1978-07-14 |
| GB1595131A (en) | 1981-08-05 |
| IE46300B1 (en) | 1983-04-20 |
| CA1122971A (fr) | 1982-05-04 |
| FR2377417A1 (fr) | 1978-08-11 |
| IE780077L (en) | 1978-07-13 |
| JPS631320B2 (da) | 1988-01-12 |
| US4147695A (en) | 1979-04-03 |
| DK164324C (da) | 1992-11-02 |
| CH629823A5 (fr) | 1982-05-14 |
| JPS5390253A (en) | 1978-08-08 |
| DE2801415A1 (de) | 1978-07-20 |
| FR2377417B1 (da) | 1979-04-20 |
| SE440780B (sv) | 1985-08-19 |
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