NO152598B - TRACTOR WEIGHT. - Google Patents
TRACTOR WEIGHT. Download PDFInfo
- Publication number
- NO152598B NO152598B NO782314A NO782314A NO152598B NO 152598 B NO152598 B NO 152598B NO 782314 A NO782314 A NO 782314A NO 782314 A NO782314 A NO 782314A NO 152598 B NO152598 B NO 152598B
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- Norway
- Prior art keywords
- aluminum
- acetone
- solution
- water
- chromium trioxide
- Prior art date
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 claims description 11
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 claims description 11
- 229960003399 estrone Drugs 0.000 claims description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 9
- 229940117975 chromium trioxide Drugs 0.000 claims description 8
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007868 Raney catalyst Substances 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000003333 secondary alcohols Chemical class 0.000 claims description 4
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 2
- VTHIKKVKIVQWHV-UHFFFAOYSA-N chromium(6+) oxygen(2-) pyridine Chemical compound [O-2].[O-2].[O-2].[Cr+6].C1=CC=NC=C1 VTHIKKVKIVQWHV-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims 1
- 239000004927 clay Substances 0.000 claims 1
- 229960005309 estradiol Drugs 0.000 claims 1
- 229930182833 estradiol Natural products 0.000 claims 1
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 claims 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- KDCIHNCMPUBDKT-UHFFFAOYSA-N hexane;propan-2-one Chemical compound CC(C)=O.CCCCCC KDCIHNCMPUBDKT-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- VBTQNRFWXBXZQR-UHFFFAOYSA-N n-bromoacetamide Chemical compound CC(=O)NBr VBTQNRFWXBXZQR-UHFFFAOYSA-N 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- -1 steroid compounds Chemical class 0.000 description 3
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- XHJMDTAEPZXEKG-SLHNCBLASA-N (8r,9s,13s,14s,17r)-17-ethenyl-13-methyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthrene-3,17-diol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C=C)[C@@H]4[C@@H]3CCC2=C1 XHJMDTAEPZXEKG-SLHNCBLASA-N 0.000 description 1
- GQHYKMYMSVJXJM-SLHNCBLASA-N (8r,9s,13s,14s,17s)-17-ethyl-13-methyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthrene-3,17-diol Chemical compound C1CC2=CC(O)=CC=C2[C@@H]2[C@@H]1[C@@H]1CC[C@](CC)(O)[C@@]1(C)CC2 GQHYKMYMSVJXJM-SLHNCBLASA-N 0.000 description 1
- JXQJDYXWHSVOEF-GFEQUFNTSA-N 17alpha-Methylestradiol Chemical compound C1CC2=CC(O)=CC=C2[C@@H]2[C@@H]1[C@@H]1CC[C@](C)(O)[C@@]1(C)CC2 JXQJDYXWHSVOEF-GFEQUFNTSA-N 0.000 description 1
- BFPYWIDHMRZLRN-UHFFFAOYSA-N 17alpha-ethynyl estradiol Natural products OC1=CC=C2C3CCC(C)(C(CC4)(O)C#C)C4C3CCC2=C1 BFPYWIDHMRZLRN-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- FOSCDBCOYQJHPN-UHFFFAOYSA-M Cl[Mg] Chemical compound Cl[Mg] FOSCDBCOYQJHPN-UHFFFAOYSA-M 0.000 description 1
- BFPYWIDHMRZLRN-SLHNCBLASA-N Ethinyl estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 BFPYWIDHMRZLRN-SLHNCBLASA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000003810 Jones reagent Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000006036 Oppenauer oxidation reaction Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BYNPVFHVZRNRQD-UHFFFAOYSA-N acetic acid;benzene Chemical compound CC(O)=O.C1=CC=CC=C1 BYNPVFHVZRNRQD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 229940090961 chromium dioxide Drugs 0.000 description 1
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 description 1
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- AXDDJHKBOYNJPY-UHFFFAOYSA-L dipotassium;carboxylato carbonate Chemical compound [K+].[K+].[O-]C(=O)OC([O-])=O AXDDJHKBOYNJPY-UHFFFAOYSA-L 0.000 description 1
- 150000002159 estradiols Chemical class 0.000 description 1
- 150000002167 estrones Chemical class 0.000 description 1
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D49/00—Tractors
- B62D49/08—Tractors having means for preventing overturning or tipping
- B62D49/085—Counterweight
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Transportation (AREA)
- Mechanical Engineering (AREA)
- Agricultural Machines (AREA)
- Body Structure For Vehicles (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
Description
Fremgangsmåte til fremstilling av østronderivater. Process for the production of estrone derivatives.
Oppfinnelsen vedrører en ny fremgangsmåte til å fremstille østron og 17a-substituerte derivater av østradiol, idet det gåes ut fra tilsvarende Ai(|())>5-3-hydrok-sylforbindelser. The invention relates to a new process for preparing estrone and 17a-substituted derivatives of estradiol, starting from corresponding Ai(|())>5-3-hydroxyl compounds.
Det er i litteraturen beskrevet flere metoder for fremstilling av ring-A-aroma-tiske steroider hvor det gåes ut fra A1>4>6-3-keto eller Ai^,c-3-keto-forbindelse ved termisk nedbrytning (H.H. Inhoffen An-gew. Chem. 53, 471 (1940)), ved pyrolyse i en mineralolje — [C. Djerassi et al. Journal Am. Chem. Soc. 72, 4534 (1950) og ibid. 73, 1523 (1951) og E.B. Hershberb. et al., Journal Org. Chem. 15, 292 (1950)] —. På grunn av de drastiske betingelser er an-vendelsen av disse metoder meget begren-set på grunn av at de ikke kan anvendes for steroidforbindelser med varmeustabile substituenter, spesielt ved temperaturer omkring 600°C. Dessuten fåes meget lavere utbytter. .Aromatiseringen av ring A i steroidforbindelser med syre er også beskrevet av \ C. Djerassi et al., Journal Am. Chem. Soc. 72, side'4540 (1950). Vandring av vinkel-metylgruppen til ring A inntreffer i dette tilfelle. There are several methods described in the literature for the production of ring-A-aromatic steroids where the starting point is A1>4>6-3-keto or Ai^,c-3-keto compound by thermal decomposition (H.H. Inhoffen An -gew. Chem. 53, 471 (1940)), by pyrolysis in a mineral oil — [C. Djerassi et al. Journal Am. Chem. Soc. 72, 4534 (1950) and ibid. 73, 1523 (1951) and E.B. Hershberb. et al., Journal Org. Chem. 15, 292 (1950)] —. Due to the drastic conditions, the use of these methods is very limited because they cannot be used for steroid compounds with heat-unstable substituents, especially at temperatures around 600°C. In addition, much lower yields are obtained. .The aromatization of ring A in steroid compounds with acid has also been described by \ C. Djerassi et al., Journal Am. Chem. Soc. 72, pp'4540 (1950). Migration of the angular methyl group to ring A occurs in this case.
I henhold til oppfinnelsen er det nå funnet at hvis et 3-hydroksy-AK1°).5-l9-nor-steroid behandles med et oksydasjonsmiddel som kan oksydere sekundære alkoholer til.ketoner, fåes tilsvarende Ai^.sdo)-østratrien-forbindelser med meget gode utbytter som yises av følgende likning der bare ringene A og B i steroidmolekylet re-presenteres: In accordance with the invention, it has now been found that if a 3-hydroxy-AK1°).5-19-nor-steroid is treated with an oxidizing agent which can oxidize secondary alcohols to ketones, corresponding Ai^.sdo)-estratriene compounds are obtained with very good yields as shown by the following equation where only rings A and B in the steroid molecule are represented:
Utgangsmaterialene som anvendes ved fremgangsmåten ifølge oppfinnelsen er Ai (i o),5-i9-rtor-androstadien-3|3-ol-17-on, Ai(io),5-i9-nor-androstadien-'|3, 17|3-diol og dets 17a-alkyl, -alkenyl eller -alkinylsub-stituerte derivat som fåes ved reaksjon, av en 3-acyloksy-19-hydroksy-17-etylendiok-sy-A5-androsten eller en 3-acyloksy-17,19-dihydroksy-A5-androstenforbindelse med kromtioksyd i pyridin under dannelse av 3-acyloksy-A5(10)-19-nor-6-ketoderivat etterfulgt av en reduksjon med litiumalu-minium-hydrid og syrebehandling av således dannede 3,6-dihydroksyforbindelser. The starting materials used in the method according to the invention are Ai (i o),5-i9-rtor-androstadien-3|3-ol-17-one, Ai(io),5-i9-nor-androstadien-'|3, 17| 3-diol and its 17α-alkyl, -alkenyl or -alkynyl substituted derivative obtained by reaction of a 3-acyloxy-19-hydroxy-17-ethylenedioxy-A5-androstene or a 3-acyloxy-17,19 -dihydroxy-A5-androstene compound with chromium dioxide in pyridine to form 3-acyloxy-A5(10)-19-nor-6-keto derivative followed by a reduction with lithium aluminum hydride and acid treatment of thus formed 3,6-dihydroxy compounds.
Som angitt ovenfor kan ethvert oksydasjonsmiddel som kan oksydere sekundære alkoholer til ketoner, anvendes ved utførelsen av fremgangsmåten ifølge oppfinnelsen. Reaksjonsbetingelsene (kvanti-tet, reaksjonskomponenter, oppløsnings-midler, temperatur, reaksjonstid etc.) av-henger av det anvendte oksydasjonsmiddel, men er vanligvis ikke forskjellig fra de som vanligvis anvendes for oksydasjon av sekundære alkoholer til ketoner. Blant hensiktsmessige reagenser som anvendes ved denne fremgangsmåte er Oppenauer-reagens som aluminium-isopropy-lat, aluminium-t-butylat og aluminiumfe-nylat, aktivert aluminiumoksyd eller Raney-nikkel i nærvær av en hydrogen-ak-septor, kromtrioksyd i vannholdig eddiksyre, komplekset av kromtrioksyd i pyridin, en oppløsning av kromtrioksyd i aceton, hensiktsmessig omkring 8-normal og i nærvær av svovelsyre, natrium- eller kaliumdikarbonat i vannholdig eddiksyre, N-halogenamider, N-halogenimider og liknende. As stated above, any oxidizing agent which can oxidize secondary alcohols to ketones can be used in carrying out the method according to the invention. The reaction conditions (quantity, reaction components, solvents, temperature, reaction time, etc.) depend on the oxidizing agent used, but usually do not differ from those usually used for oxidizing secondary alcohols to ketones. Among suitable reagents used in this method are Oppenauer reagents such as aluminum isopropylate, aluminum t-butylate and aluminum phenylate, activated alumina or Raney nickel in the presence of a hydrogen acceptor, chromium trioxide in aqueous acetic acid, the complex of chromium trioxide in pyridine, a solution of chromium trioxide in acetone, suitably about 8-normal and in the presence of sulfuric acid, sodium or potassium dicarbonate in aqueous acetic acid, N-halogenamides, N-halogenimides and the like.
Hvis Oppenhauer-betingelser anvendes behandles 3-hydroksy-A1 (1 o),5-i9-nor-steroider med et overskudd av et aluminiumalkoholat i et organisk oppløsningsmiddel eller i nærvær av hydrogenakseptor. Reaksjonen gjennomføres vanligvis under til-bakeløpstemperatur i en tidsperiode på størrelsesorden 1—12 timer, men kan imid-lertid utføres ved lavere temperatur i lø-pet av lengre tid. If Oppenhauer conditions are used, 3-hydroxy-A1 (1 o),5-i9-nor-steroids are treated with an excess of an aluminum alcoholate in an organic solvent or in the presence of a hydrogen acceptor. The reaction is usually carried out under reflux temperature for a time period of the order of 1-12 hours, but can, however, be carried out at a lower temperature over a longer period of time.
Blant aluminiumalkoholater som kan anvendes ved fremgangsmåten ifølge oppfinnelsen kan nevnes: aluminiumisopropylat, aluminium-t-butylat, aluminium-fenylat eller et annet alkoholat som fin-nes tilgjengelig i handelen. Klormagne-siumalkoholater eller kalium-t-butylat kan også anvendes som katalysatorer. Foretrukne hydrogen-akseptorer er cykloheksanon. Andre ketoner kan imid-lertid anvendes som aceton, metyletylke-ton, dietylketon, benzolkinon etc. Organiske oppløsningsmidler utgjøres hensiktsmessig av upolare oppløsningsmidler, som toluol, xylol, benzol og liknende. Among the aluminum alcoholates that can be used in the method according to the invention can be mentioned: aluminum isopropylate, aluminum t-butylate, aluminum phenylate or another alcoholate that is available in the trade. Chloromagnesium alcoholates or potassium t-butylate can also be used as catalysts. Preferred hydrogen acceptors are cyclohexanone. Other ketones can, however, be used such as acetone, methyl ethyl ketone, diethyl ketone, benzolquinone, etc. Organic solvents are conveniently made up of non-polar solvents, such as toluene, xylol, benzene and the like.
Som nevnt "ovenfor kan man isteden-, for aluminiumalkoholat anvende aktivert aluminiumoksyd eller Raney-nikkel. Be-tingelsene for Oppenauer-oksydasjon er generelt de som er beskrevet av C. Djerassi i Organic Reactions, vol. VI, side 207 (John Wiley and Sons, Inc.). As mentioned above, instead of aluminum alcoholate, activated alumina or Raney nickel can be used. The conditions for Oppenauer oxidation are generally those described by C. Djerassi in Organic Reactions, vol. VI, page 207 (John Wiley and Sons, Inc.).
Omdannelsen av AK^-s-^-nor-an-drostadien i tilsvarende ring-A-aroma-tiske forbindelser under anvendelse av kromtrioksyd som oksydasjonsmiddel ut-føres under vanlige reaksjonsbetingelser. Man kan således eksempelvis anvende fra 1—2 mol kromtrioksyd i vannholdig ed-diksyreoppløsning ved en temperatur mellom 15 og 18°C i en tidsperiode på 1—3 timer. En 8-normal oppløsning av kromsyre i aceton og i nærvær av svovelsyre (Jones reagens) kan også anvendes. The conversion of the AK^-s-^-nor-androstage into corresponding ring-A-aromatic compounds using chromium trioxide as oxidizing agent is carried out under normal reaction conditions. One can thus, for example, use from 1-2 mol of chromium trioxide in an aqueous acetic acid solution at a temperature between 15 and 18°C for a period of 1-3 hours. An 8-normal solution of chromic acid in acetone and in the presence of sulfuric acid (Jones reagent) can also be used.
Oksydasjonen med kromtrioksyd-pyridin-komplekset utføres vanligvis ved værelsetemperatur i en periode mellom 6—24 timer. Kalium- eller natriumdikromat anvendes i eddiksyre-benzol-oppløsning ved værelsetemperatur og i løpet av 15—24 timer. The oxidation with the chromium trioxide-pyridine complex is usually carried out at room temperature for a period between 6-24 hours. Potassium or sodium dichromate is used in acetic acid-benzene solution at room temperature and within 15-24 hours.
Hvis reagenser anvendes ifølge oppfinnelsen i form av N-halogenamider eller N-halogenimider, som N-bromacetamid el- If reagents are used according to the invention in the form of N-halogenamides or N-halogenimides, such as N-bromoacetamide or
ler N-bromosuccinimid, utføres reaksjonen hensiktsmessig i t-butanoloppløsning og i ler N-bromosuccinimide, the reaction is conveniently carried out in t-butanol solution and i
nærvær av pyridin ved lav temperatur i presence of pyridine at low temperature i
en periode på' 12—24-timer. a period of 12-24 hours.
Følgende eksempler illustrerer fremgangsmåten ifølge oppfinnelsen uten å be-grense den. The following examples illustrate the method according to the invention without limiting it.
Eksempel 1. Example 1.
En oppløsning av 5 g A1<1°)'5-19-nor-androstadien-3|3-ol-17-on i 80 ems tørr toluol og 15 ems cykloheksanon ble tørket ved avdestillering av 10 ems av oppløs-ningsmidlet. En oppløsning av 5 g aluminiumisopropylat oppløst i 35 cm» vann- A solution of 5 g of A1<1°)'5-19-nor-androstadien-3|3-ol-17-one in 80 ems of dry toluene and 15 ems of cyclohexanone was dried by distilling off 10 ems of the solvent. A solution of 5 g of aluminum isopropylate dissolved in 35 cm" of water-
fri toluol ble deretter tilsatt og blandingen kokt under ^tilbakeløp, 10 ems eddiksyre ble tilsatt og oppløsningsmidlet fjernet ved dampdestillering. Produktet ble ekstrahert flere ganger med etylacetat og de organiske ekstrakter vasket med 5 pst. klorhydrogensyreoppløsning, vann, 10 pst. natriumkarbonatoppløsning og vann til nøytral reaksjon, tørket over vannfritt natriumsulfat og inndampet til tørrhet. Resten ble krystallisert fra aceton-heksan under dannelse av 4,1 g østron som var identisk med en autentisk prøve. free toluene was then added and the mixture refluxed, 10 ems of acetic acid was added and the solvent removed by steam distillation. The product was extracted several times with ethyl acetate and the organic extracts washed with 5% hydrochloric acid solution, water, 10% sodium carbonate solution and water to neutral reaction, dried over anhydrous sodium sulfate and evaporated to dryness. The residue was crystallized from acetone-hexane to give 4.1 g of estrone identical to an authentic sample.
Eksempel 2. Example 2.
Eksempel 1 ble gjentatt under anvendelse av aluminium-t-butylat i stedet for aluminiumisopropylat under dannelse av østron med liknende utbytter. Example 1 was repeated using aluminum t-butylate instead of aluminum isopropylate to form estrone in similar yields.
Eksempel 3. Example 3.
Aluminiumisopropylat i henhold til eksempel 1 ble erstattet med aluminium-fenoksylat med samme resultat. Aluminum isopropylate according to Example 1 was replaced with aluminum phenoxylate with the same result.
Eksempel 4. Example 4.
Fra en blanding av 1 g A1<10>'5-19-nor-androstadien-3(3, 17(5-diol, 60 ems vannfri toluol og 6 g benzolkinon ble det avdestil-lert 10 cm3 for å fjerne fuktighet. 1 g aluminium-t-butylat oppløst i 10 cm<8> vann- From a mixture of 1 g of A1<10>'5-19-nor-androstadien-3(3,17(5-diol, 60 ems of anhydrous toluene and 6 g of benzolquinone) 10 cm 3 were distilled off to remove moisture. 1 g of aluminum t-butylate dissolved in 10 cm<8> of water
fri toluol ble deretter tilsatt og blandingen kokt under tilbakeløp i en time under vannfrie betingelser. 5 cm.3 eddiksyre ble deretter tilsatt og toluolen fjernet ved dampdestillering, hvoretter det ble ekstrahert med etylacetat og det organiske ekstrakt ble vasket med kalium-hydroksyd-oppløsning og vann til nøytral reaksjon samt tørket over vannfritt natrium-sulfat og inndampet til tørrhet. Krystallisering free toluene was then added and the mixture refluxed for one hour under anhydrous conditions. 5 cm.3 of acetic acid was then added and the toluene removed by steam distillation, after which it was extracted with ethyl acetate and the organic extract was washed with potassium hydroxide solution and water to a neutral reaction and dried over anhydrous sodium sulfate and evaporated to dryness. Crystallization
av residuet fra aceton-heksan ga også østron med et utbytte på 75 pst. of the residue from acetone-hexane also gave estrone with a yield of 75 per cent.
Eksempel 5. Example 5.
Fremgangsmåten i henhold til eksempel 1 ble gjentatt under anvendelse av 100 cm<3> aceton i stedet for cykloheksanon og tilbakeløpskokningsperioden ble forlen-get til 8 timer etterfulgt av den ovenfor be-skrevne teknikk for isolering av produktet. Man fikk østron med et utbytte av 78 pst. The procedure of Example 1 was repeated using 100 cm<3> of acetone instead of cyclohexanone and the refluxing period was extended to 8 hours followed by the above described technique for isolating the product. Estrone was obtained with a yield of 78 per cent.
Eksempel 6. Example 6.
En oppløsning av 2 g 17a-metyl-Aid°)-5-19-nor-androstadien-3|3, 17(3-diol i 100 ems benzol og 50 ems aceton ble tørket ved azeotrop destillering av 15 cm» oppløs-ningsmiddel. 2 g aluminiumisopropylat oppløst i 40 cm3 vannfri benzol ble tilsatt og blandingen kokt under tilbakeløp i 12 timer. Den ble deretter avkjølt, vasket med fortynnet klorhydrogensyreoppløsning og vann til nøytral reaksjon, tørket og inndampet til tørrhet. Resten ble krystallisert fra aceton-eter under dannelse av: 17«-metyløstradiol. i Eksempel 7. A solution of 2 g of 17α-methyl-Aid°)-5-19-nor-androstadien-3|3,17(3-diol in 100 ems benzene and 50 ems acetone was dried by azeotropic distillation of 15 cm» of solvent 2 g of aluminum isopropylate dissolved in 40 cm3 of anhydrous benzene was added and the mixture was refluxed for 12 hours. It was then cooled, washed with dilute hydrochloric acid solution and water until neutral reaction, dried and evaporated to dryness. The residue was crystallized from acetone-ether under formation of: 17"-methylestradiol. in Example 7.
Til en oppløsning av 10 g A'(in)>5-19-' nor-androstadien-3'P-ol-17-on i 80 cm3 av: en blanding av toluol og cykloheksanon 1:11 ble det satt 40 g aktivert aluminiumoksyd, j 10 cm3 av oppløsningsmidlet ble avdestil-j lert for å fjerne fuktighet og reaksjons-; blandingen ble deretter kokt under tilba-' keløp i 7 timer under vannfrie betingelser. Aluminiumoksydet ble skilt fra den varme oppløsning ved filtrering og vasket grun-; dig med varm etylacetat. Etylacetatet fra! filtratet ble inndampet under nedsatt j trykk og toluolet og cykloheksanonet ble<1 >fjernet ved dampdestillering. Det faste produkt ble avfiltrert, vasket med vann og tørket i luft. To a solution of 10 g of A'(in)>5-19-'nor-androstadien-3'P-ol-17-one in 80 cm3 of: a mixture of toluene and cyclohexanone 1:11 was added 40 g activated alumina, j 10 cm3 of the solvent was distilled off to remove moisture and reaction; the mixture was then refluxed for 7 hours under anhydrous conditions. The aluminum oxide was separated from the hot solution by filtration and washed thoroughly; with warm ethyl acetate. The ethyl acetate from! the filtrate was evaporated under reduced j pressure and the toluene and cyclohexanone were<1 >removed by steam distillation. The solid product was filtered off, washed with water and dried in air.
Etter krystallisering fra aceton-heksan fåes østron med utbytte på 82 pst. After crystallization from acetone-hexane, estrone is obtained with a yield of 82 per cent.
På samme måte omdannes 17a-vinyl AKio),5-i9-androstadien-3|3, 17(3-diol og 17-a-etinyl A1 <1 o).5-l9-nor-androstadien-2[3, 17p-diol til 17a-vinyl-østradiol og 17a-etinyl-østradiol, som er identiske med au-tentiske prøver. In the same way, 17a-vinyl AKio),5-i9-androstadien-3|3, 17(3-diol and 17-a-ethynyl A1 <1 o).5-l9-nor-androstadien-2[3, 17p -diol to 17α-vinyl-estradiol and 17α-ethynyl-estradiol, which are identical to authentic samples.
Eksempel 8. Example 8.
En suspensjon av 16 g Raney-nikkel i vann ble vasket flere ganger med vann til pH 7. Den ble avdekantert, 200 g toluol sattes til nikkelet og oppløsningsmidlet av-destillert for å fjerne vann ved azeotropisk destillering til et sluttvolum på omtrent 50 ems. Deretter ble det tilsatt 10 g AKi°)>5-19-nor-androstadien-3p-ol-17-on og 50 cm<>>> cykloheksanon og reaksjonsblandingen ble kokt under tilbakeløp under vannfri betingelser i 6 timer. Katalysatoren ble filtrert fra og vasket med 150 cm» toluol. Filtratet ble dampdestillert og det faste produkt ble skilt fra ved filtrering, vasket og lufttørket, hvorved man fikk 'østron med ovennevnte utbytte. A suspension of 16 g of Raney nickel in water was washed several times with water to pH 7. It was decanted, 200 g of toluene was added to the nickel and the solvent distilled off to remove water by azeotropic distillation to a final volume of about 50 ems. Then 10 g of AKi°)>5-19-nor-androstadien-3p-ol-17-one and 50 cm<>>> cyclohexanone were added and the reaction mixture was refluxed under anhydrous conditions for 6 hours. The catalyst was filtered off and washed with 150 cc of toluene. The filtrate was steam-distilled and the solid product was separated by filtration, washed and air-dried, whereby estrone was obtained with the above-mentioned yield.
Eksempel 9. Example 9.
En oppløsning av 2 g A1*10) 5-19-nor-androstadien-3p-ol-17-on i 40 cm<3> pyridin ble satt til en blanding av 2 g kromtrioksyd i 40 cm3 pyridin. Reaksjonsblandingen var holdt ved værelsetemperatur natten over. Det ble deretter fortynnet med etylacetat, filtrert gjennom celit og filtratet vasket godt med vann, tørket og inndampet til tørrhet. Resten ble krystallisert fra aceton-heksan under dannelse av østron som var identisk med en autentisk prøve. A solution of 2 g of A1*10) 5-19-nor-androstadien-3p-ol-17-one in 40 cm<3> of pyridine was added to a mixture of 2 g of chromium trioxide in 40 cm3 of pyridine. The reaction mixture was kept at room temperature overnight. It was then diluted with ethyl acetate, filtered through celite and the filtrate washed well with water, dried and evaporated to dryness. The residue was crystallized from acetone-hexane to give estrone identical to an authentic sample.
Eksempel 10. Example 10.
En oppløsning av 500 mg kromsyre i 5 ems 80 pst.-ig eddiksyre ble tilsatt dråpevis til en omrørt oppløsning av 1 g 17a-etyl A^i^s-lQ-nor-androstadien-Sp.np-diol i 20 cm3 iseddik mens temperaturen ble holdt på omkring 20°C. Etter 2 timer ved værelsetemperatur ble blandingen holdt i isvann og den dannede utfelling oppsamlet, vasket med vann og omkrystal-lisert fra metanol, idet man fikk 17a-etyl-østradiol. A solution of 500 mg of chromic acid in 5 ml of 80% acetic acid was added dropwise to a stirred solution of 1 g of 17a-ethyl A^i^s-lQ-nor-androstadiene-Sp.np-diol in 20 cm3 of glacial acetic acid while the temperature was kept at about 20°C. After 2 hours at room temperature, the mixture was kept in ice water and the precipitate formed was collected, washed with water and recrystallized from methanol to give 17α-ethyl estradiol.
Eksempel 11. Example 11.
En oppløsning av 1 g Ai(10)>5-19-nor-androstadien-3|3-ol-17-on i 10 cm» aceton, ble avkjølt til 0°C og behandlet under en atmosfære av nitrogen under omrøring med en oppløsning av 8-normal kromsyre (fremstilt ved blanding av 26 g kromtrioksyd og 23 ems konsentrert svovelsyre og fortynning med vann til 100 cm»), inntil reagensets farge ble tilbake i blandingen. Den ble omrørt i ytterligere 4 timer ved 0—5°C og fortynnet med vann. Utfellingen ble oppsamlet og vasket med vann og tørket under vakuum under dannelse av østron som ble renset ved krystallisering fra aceton-heksan. A solution of 1 g of Ai(10)>5-19-nor-androstadien-3|3-ol-17-one in 10 cm» of acetone was cooled to 0°C and treated under an atmosphere of nitrogen while stirring with a solution of 8-normal chromic acid (prepared by mixing 26 g of chromic trioxide and 23 ems of concentrated sulfuric acid and diluting with water to 100 cm"), until the color of the reagent returned to the mixture. It was stirred for a further 4 hours at 0-5°C and diluted with water. The precipitate was collected and washed with water and dried under vacuum to give estrone which was purified by crystallization from acetone-hexane.
Eksempel 12. Example 12.
Til en omrørt oppløsning av 1,5 g 17a-metyl-A<1>(i»).fi-19-nor-androstadien-3(3,17p-diol i 60 cm3 benzol ble det dråpevis satt en oppløsning av 2 g natriumdikromatdi-hydrat oppløst i 50 cm» eddiksyre som ble A solution of 2 g sodium dichromate dihydrate dissolved in 50 cm» of acetic acid which became
holdt ved en temperatur mellom 15 og kept at a temperature between 15 and
18°C. Reaksjonsblandingen ble holdt ved 18°C. The reaction mixture was maintained
værelsetemperatur i 24 timer, fortynnet room temperature for 24 hours, diluted
med eter, og det organiske sjikt vasket med with ether, and the organic layer washed with
vann, natriumkarbonatoppløsning og vann water, sodium carbonate solution and water
til nøytral reaksjon, tørket over vannfritt to neutral reaction, dried over anhydrous
natriumsulfat og inndampet til tørrhet sodium sulfate and evaporated to dryness
ved nedsatt trykk. Resten ble krystallisert at reduced pressure. The residue was crystallized
fra aceon-heksan under dannelse av 17a-metyløstradiol som var identisk med den from aceone-hexane to form 17α-methylestradiol which was identical to it
prøve som ble dannet i henhold til eksempel 6. sample which was formed according to Example 6.
Eksempel 13. Example 13.
Til en kald oppløsning av 1 g A'(10^5-19-nor-androstadien-3(3-ol-17.-on i 10 cm<3>To a cold solution of 1 g of A'(10^5-19-nor-androstadien-3(3-ol-17.-one in 10 cm<3>
t-butyl-alkohol, 1 cm<8> vann og 1 ems pyridin ble det satt 2 mol N-bromacetamid t-butyl alcohol, 1 cm<8> water and 1 ems pyridine, 2 mol of N-bromoacetamide were added
og reaksjonsblandingen ble holdt ved 0°C and the reaction mixture was kept at 0°C
natten over. Den ble fortynnet med vann, overnight. It was diluted with water,
ekstrahert med metylen-klorid og det organiske ekstrakt vasket med fortynnet extracted with methylene chloride and the organic extract washed with dil
klorhydrogensyre og vann til nøytral reaksjon, tørket over vannfritt natriumsulfat hydrochloric acid and water to neutral reaction, dried over anhydrous sodium sulfate
og inndampet til tørrhet. Resten ble krystallisert fra aceton-heksan under dannelse and evaporated to dryness. The residue was crystallized from acetone-hexane under formation
også av østron med ovennevnte utbytter. also of estrone with the above-mentioned yields.
Eksempel 14. Example 14.
Eksempel 13 ble gjentatt med anvendelse av N-bromsuccinimid i stedet for N-bromacetamid med samme resultat. Example 13 was repeated using N-bromosuccinimide instead of N-bromoacetamide with the same result.
Claims (7)
Applications Claiming Priority (1)
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|---|---|---|---|
| GB2845777 | 1977-07-07 |
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|---|---|
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| NO152598B true NO152598B (en) | 1985-07-15 |
| NO152598C NO152598C (en) | 1985-10-23 |
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| NO782314A NO152598C (en) | 1977-07-07 | 1978-07-03 | TRACTOR WEIGHT. |
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| DE (1) | DE2829193C2 (en) |
| DK (1) | DK144998C (en) |
| FI (1) | FI78267C (en) |
| NO (1) | NO152598C (en) |
| SE (1) | SE437685B (en) |
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| US3492019A (en) * | 1969-02-03 | 1970-01-27 | Folkert Inc | Tractor weights |
| DE2059208C3 (en) * | 1970-12-02 | 1981-02-12 | Kloeckner-Humboldt-Deutz Ag, 5000 Koeln | Device for connecting a ballast weight to a tractor that can be used in agriculture and / or construction |
| FR2290321A1 (en) * | 1974-11-05 | 1976-06-04 | Rigaux Roger | Compensator weights for agricultural tractors - has weight automatically secured by cone and elongated slot (BE230476) |
-
1978
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- 1978-07-03 DE DE2829193A patent/DE2829193C2/en not_active Expired
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| NO152598C (en) | 1985-10-23 |
| SE7807620L (en) | 1979-01-08 |
| FI782180A (en) | 1979-01-08 |
| DE2829193A1 (en) | 1979-01-18 |
| DK144998C (en) | 1982-12-20 |
| DK144998B (en) | 1982-07-26 |
| DE2829193C2 (en) | 1985-12-19 |
| NO782314L (en) | 1979-01-09 |
| FI78267B (en) | 1989-03-31 |
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