NO125273B - - Google Patents
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- Publication number
- NO125273B NO125273B NO157467A NO15746765A NO125273B NO 125273 B NO125273 B NO 125273B NO 157467 A NO157467 A NO 157467A NO 15746765 A NO15746765 A NO 15746765A NO 125273 B NO125273 B NO 125273B
- Authority
- NO
- Norway
- Prior art keywords
- group
- dioxy
- free
- aldehyde
- formula
- Prior art date
Links
- 238000000034 method Methods 0.000 claims description 9
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 4
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000004043 oxo group Chemical group O=* 0.000 claims description 4
- 150000003431 steroids Chemical class 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000003470 adrenal cortex hormone Substances 0.000 claims 1
- 150000002373 hemiacetals Chemical class 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- 230000001766 physiological effect Effects 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QSKWJTXWJJOJFP-UHFFFAOYSA-N chloroform;ethoxyethane Chemical compound ClC(Cl)Cl.CCOCC QSKWJTXWJJOJFP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- PQSUYGKTWSAVDQ-ZVIOFETBSA-N Aldosterone Chemical compound C([C@@]1([C@@H](C(=O)CO)CC[C@H]1[C@@H]1CC2)C=O)[C@H](O)[C@@H]1[C@]1(C)C2=CC(=O)CC1 PQSUYGKTWSAVDQ-ZVIOFETBSA-N 0.000 description 3
- PQSUYGKTWSAVDQ-UHFFFAOYSA-N Aldosterone Natural products C1CC2C3CCC(C(=O)CO)C3(C=O)CC(O)C2C2(C)C1=CC(=O)CC2 PQSUYGKTWSAVDQ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229960002478 aldosterone Drugs 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HCJKXXMOOMBBPY-IEJDVFFQSA-N [2-[(8s,9s,10r,11s,13r,14s,17s)-13-formyl-11-hydroxy-10-methyl-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl]-2-oxoethyl] acetate Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)COC(=O)C)[C@@]1(C=O)C[C@@H]2O HCJKXXMOOMBBPY-IEJDVFFQSA-N 0.000 description 1
- 210000004100 adrenal gland Anatomy 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006567 deketalization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000001976 hemiacetal group Chemical group 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
- C07C59/215—Saturated compounds having only one carboxyl group and containing keto groups containing singly bound oxygen containing groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
- C07C309/66—Methanesulfonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/14—Benz[f]indenes; Hydrogenated benz[f]indenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/16—Benz[e]indenes; Hydrogenated benz[e]indenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Steroid Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Fremgangsmåte til fremstilling av oksygenerte steroider.
I patent nr. 95 012 og patent nr. 95 014 stilling av mettede og umettede oksygen-er det beskrevet fremgangsmåte til frem- erte steroider med formelen
hvor Ri og R.2betyr fri eller funksjonelt av- | ledete oksy- eller oksogrupper, R.jbetyr en fri eller funksjonelt avledet oksygenert me-tylgruppe og Ri betyr en fri eller forestret oksygruppe. Foreliggende oppfinnelse til-later, i slike steroider som fåes ifølge disse fremgangsmåter, hvori R:! betyr en kar-boksylgruppe og R2en hydroksylgruppe, idet begge disse grupper er laktonisert med hverandre, å erstatte karboksylgruppen med en aldehyd- eller karbinolgruppe. Fremgangsmåten ifølge foreliggende oppfinnelse angår fremstilling av forbindelser med formelen hvor R betyr en aldehyd- eller karbinolgruppe, idet en aldehydgruppe i 13-stilling også kan være acetalisert med den 11-stående oksygruppe og karakteriseres ved at man behandler forbindelser med formelen
hvor R' og R" betyr ketaliserte oksygrupper og R'" betyr en fri eller forestret oksygruppe, med alkalialuminiumhydrider og setter de ketaliserte oksogrupper R' og R" i frihet.
Utgangsstoffene kan fremstilles ifølge patent nr. 95 012 og patent nr. 95 014 eller også ved oksydasjon av aldosteron, det f. eks. i Experentia 9 333 beskrevne høyvirk- somme hormon av binyrer. Aldosteron selv er syntetisk tilgjengelig ifølge foreliggende fremgangsmåte. Fremgangsmåteproduk-tene er dermed fysiologisk virksomme forbindelser eller mellomprodukter til deres fremstilling.
Reduksjonen av laktongruppen i 13-stilling i de karakteriserte utgangsmateri-aler ifølge foreliggende fremgangsmåte skjer fordelaktig med komplekse lettme-tallhydrider, særlig med litiumaluminiumhydrid. Som oppløsningsmiddel anvendes f. eks. tetrahydrofuran.
Oppfinnelsen beskrives nærmere i det følgende eksempel.
Eksempel 1:
1,12 mg 18,11-laktonet av A<4->3,20-di-okso-ll(3,21-dioksypregnen-18-syre opplø-ses i 5 cm<3>etylendiklorid. Etter tilsetning av en liten krystall p-toluolsulfosyre og en dråpe ren etylenglykol avdestilleres etylendiklorid langsomt. Ved dråpevis tilsetning
av nytt oppløsningsmiddel holder man vo-lumet for reaksjonsoppløsningen konstant. Etter 4 timer vaskes kolbeinnholdet to ganger med hver gang 1 cm<3>av en 1 %'s soda-oppløsning og to ganger med hver gang 1 cm<3>vann, oppløsningsmidlet tørkes og inndampes i vakuum. Resten er 18,11-laktonet av A<5->3,20-dietylen-dioksy-lip,21-dioksypregnen-18-syre, som uten rensning oppløses i 5 cm<3>tetrahydrofuran. Etter av-kjøling til — 10° C til — 15° C tilsetter man under omrøring dråpevis en tetrahydrofu-ranoppløsning av litiumaluminiumhydrid, som under hensyntagen til 21-oksygruppen er beregnet for reduksjon av lakton- til halvacetalgruppe. Deretter fjerner man kldebadet og lar temperaturen stige til ca. 20° C. Tetrahydrofuranoppløsningen for-tynnes med 50 cm<3>eter og vaskes i rekke-følge med 0,1-N. svovelsyre og vann, tør-kes og inndampes i vakuum. Det rå A<5->3,20-dietylen-dioksy-lip,21-dioksy-18-okso-
pregnen med formelen
oppløses uten rensning i 50 % eddiksyre og står natten over ved ca. 20° C. Reaksjons-blandingen ekstraheres to ganger med hver gang 5 cm<3>kloroform-eter (1:3), ekstraktene vaskes to ganger med hver gang 1 cm<3>vann, tørkes over natriumsul-fat og inndampes i vakuum. Fra det således erholdte råprodukt lar aldosteron seg utvinne ved hjelp av kromatografi. Anvendes det ved ovenstående reduksjon et overskudd av litiumaluminiumhydrid, får man etter ketalspaltningen A<+->3,20-diokso-lip,18,21-trioksy-pregnen med formelen
Utgangsmaterialet kan fremstilles f. eks. som følger: 1,267 mg aldosteron-monoacetat med sm.p. 190—192° C oppløses i 0,12 cm<3>is-eddik og tilsettes 0,01 cm<3>2 %'s kromtri-oksyd-iseddikoppløsning. Etter 15 minut-ter er kromtrioksydet forbrukt og man tilsetter nok en gang 0,01 cm<3>av den samme oppløsning. Etter 3,5 time tilsetter man re-aksjonsoppløsningen litt metanol, lar stå enda en time og inndamper deretter ved 30° C i vakuum. Resten opptar man i kloroform-eter (1:3), vasker ved 0° C to ganger med hver gang 0,15 cm<3>IN. sodaopp-løsning og to ganger med hver gang 0,1 cm<3>vann, tørker kloroform-eteroppløsnin-gen og inndamper den i vakuum. Nøytral-delen omkrystalliseres to ganger fra ace-ton-eter og vaskes med eter og pentan. Smeltepunktet av de således erholdte far-geløse små blader (delvis også klaser) som er 18,11-laktonet av A<4->3,20-diokso-lip-oksy-21-acetoksy-pregnen-18-syre med formelen
løsning av 7 mg kaliumbikarbonat i '■ 0,24 cm<3>vann og lar stå i 48 timer ved 18° C. Etter ansyring med fortynnet saltsyre ekstraheres med kloroform-eter (1 : 3), eks-traktet vaskes med vann, natriumbikarbo-natoppløsning og nok en gang med vann og oppløsningsmidlet fordampes i vakuum etter tørking. Den således erholdte nøy-traldel utgjør 3,5 mg og er 18,11-laktonet av A<4->3,20-diokso-lip,21-dioksy-pregnen-18-syre. Etter omkrystallisasjon fra aceton-eter danner det små korn som smelter ved 203 til 218° C.
Claims (3)
1. Fremgangsmåte til fremstilling av oksygenerte steroider med den generelle formel
hvori R betyr en aldehyd- eller karbinolgruppe, idet en aldehydgruppe i 13-stilling også kan danne et hemiacetal med den 11-stående oksygruppe, og som har fysiolo-giske virkninger av typen binyrebarkhor-moner eller er mellomprodukter til fremstilling av slike,karakterisert vedat man behandler forbindelser med formelen
hvor R' og R" betyr ketaliserte oksogrupper og R'" betyr en fri eller forestret oksygruppe med alkalialuminiumhydrider og setter de ketaliserte oksogrupper R' og R" i frihet.
2. Fremgangsmåte ifølge påstand 1,karakterisert vedat man anvender litiumaluminiumhydrid.
3. Fremgangsmåte ifølge påstand 1 og 2,karakterisert vedat man anvender 18,11-lakton av A<5->3,20-dietylen-dioksy-ll|3-21-dioksy-pregnen-18-syre som utgangsmate-riale.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO16594066A NO124596B (no) | 1964-09-29 | 1966-12-09 | |
| NO16594166A NO124595B (no) | 1964-09-29 | 1966-12-09 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US400206A US3412107A (en) | 1964-09-29 | 1964-09-29 | 11-hydroxy-5-oxo-3, 5-seco-a-nor-androstan-3-oic acid 3, 11-lactones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO125273B true NO125273B (no) | 1972-08-14 |
Family
ID=23582655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO157467A NO125273B (no) | 1964-09-29 | 1965-03-30 |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US3412107A (no) |
| AT (1) | AT280489B (no) |
| BE (1) | BE663197A (no) |
| CH (1) | CH577446A5 (no) |
| DE (3) | DE1618508A1 (no) |
| DK (3) | DK123235B (no) |
| ES (1) | ES311225A1 (no) |
| FI (6) | FI42552B (no) |
| GB (8) | GB1103987A (no) |
| IL (3) | IL31353A (no) |
| MY (8) | MY6900076A (no) |
| NL (2) | NL6901813A (no) |
| NO (1) | NO125273B (no) |
| SE (3) | SE317968B (no) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3761503A (en) * | 1964-09-29 | 1973-09-25 | Hoffmann La Roche | Substituted-3,5-seco-a-nor-pregnan-3-oic-acids |
| DE2331997A1 (de) * | 1973-06-21 | 1975-01-16 | Schering Ag | Verfahren zur herstellung von bicycloalkan-derivaten |
| CA1195997A (en) * | 1979-02-23 | 1985-10-29 | Andor Furst | Dea-steroids |
| FR2500441A1 (fr) * | 1981-02-23 | 1982-08-27 | Roussel Uclaf | Nouveaux medicaments derives de la 3-hydroxy dodecahydro benz (e) inden-7-one, produits derives de la 3-hydroxy dodecahydro benz (e) inden-7-one et leur procede de preparation |
| DE3434451A1 (de) * | 1984-09-20 | 1986-03-27 | Austgen, René, 6625 Püttlingen | Dieselkraftstoff-filter |
-
1964
- 1964-09-29 US US400206A patent/US3412107A/en not_active Expired - Lifetime
-
1965
- 1965-03-18 IL IL31353A patent/IL31353A/en unknown
- 1965-03-18 IL IL31354A patent/IL31354A/en unknown
- 1965-03-18 IL IL23180A patent/IL23180A/en unknown
- 1965-03-25 CH CH760568A patent/CH577446A5/de not_active IP Right Cessation
- 1965-03-27 DE DE19651618508 patent/DE1618508A1/de active Pending
- 1965-03-27 DE DE1618507A patent/DE1618507C3/de not_active Expired
- 1965-03-27 DE DE1518980A patent/DE1518980C3/de not_active Expired
- 1965-03-29 GB GB36705/67A patent/GB1103987A/en not_active Expired
- 1965-03-29 GB GB13173/65A patent/GB1103574A/en not_active Expired
- 1965-03-29 SE SE4026/65A patent/SE317968B/xx unknown
- 1965-03-29 SE SE10752/69A patent/SE353904B/xx unknown
- 1965-03-29 GB GB36702/67A patent/GB1103984A/en not_active Expired
- 1965-03-29 GB GB36701/67A patent/GB1103983A/en not_active Expired
- 1965-03-29 GB GB36703/67A patent/GB1103985A/en not_active Expired
- 1965-03-29 SE SE10751/69A patent/SE353905B/xx unknown
- 1965-03-29 GB GB36700/67A patent/GB1103982A/en not_active Expired
- 1965-03-29 AT AT282365A patent/AT280489B/de active
- 1965-03-29 GB GB36706/67A patent/GB1103988A/en not_active Expired
- 1965-03-29 GB GB36704/67A patent/GB1103986A/en not_active Expired
- 1965-03-30 NO NO157467A patent/NO125273B/no unknown
- 1965-03-30 FI FI0765/65A patent/FI42552B/fi active
- 1965-03-30 ES ES0311225A patent/ES311225A1/es not_active Expired
- 1965-04-29 BE BE663197A patent/BE663197A/fr unknown
-
1968
- 1968-12-13 DK DK610268AA patent/DK123235B/da unknown
- 1968-12-13 DK DK609968AA patent/DK126031B/da unknown
- 1968-12-13 DK DK610168AA patent/DK123234B/da unknown
-
1969
- 1969-02-05 NL NL6901813A patent/NL6901813A/xx unknown
- 1969-02-05 NL NL6901812A patent/NL6901812A/xx unknown
- 1969-03-24 FI FI0856/69A patent/FI43591B/fi active
- 1969-03-24 FI FI0859/69A patent/FI43594B/fi active
- 1969-03-24 FI FI0858/69A patent/FI43593B/fi active
- 1969-03-24 FI FI0857/69A patent/FI43592B/fi active
- 1969-03-24 FI FI0854/69A patent/FI43590B/fi active
- 1969-12-31 MY MY196976A patent/MY6900076A/xx unknown
- 1969-12-31 MY MY196980A patent/MY6900080A/xx unknown
- 1969-12-31 MY MY196979A patent/MY6900079A/xx unknown
- 1969-12-31 MY MY196982A patent/MY6900082A/xx unknown
- 1969-12-31 MY MY196978A patent/MY6900078A/xx unknown
- 1969-12-31 MY MY196983A patent/MY6900083A/xx unknown
- 1969-12-31 MY MY196977A patent/MY6900077A/xx unknown
- 1969-12-31 MY MY196981A patent/MY6900081A/xx unknown
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