CH376909A - Verfahren zur Herstellung von 6a,6a-Dichlor-6,7-methylen- und 6a,6a-Dibrom-6,7-methylenverbindungen von 4-3-Ketosteroiden - Google Patents

Verfahren zur Herstellung von 6a,6a-Dichlor-6,7-methylen- und 6a,6a-Dibrom-6,7-methylenverbindungen von 4-3-Ketosteroiden

Info

Publication number: CH376909A
Authority: CH; Switzerland
Prior art keywords: sep; ether; dibromo; methylene; solution
Prior art date: 1958-06-13

Application number

CH7441259A

Other languages

German (de)

English (en)

Inventor

Ole Godtfredsen Wagn

Liisberg Sven

Original Assignee

Leo Pharm Prod Ltd

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1958-06-13

Filing date

1959-06-13

Publication date

1964-04-30

1958-06-13 Priority claimed from GB1906758A external-priority patent/GB862235A/en

1959-06-13 Application filed by Leo Pharm Prod Ltd filed Critical Leo Pharm Prod Ltd

1964-04-30 Publication of CH376909A publication Critical patent/CH376909A/de

Links

238000000034 method Methods 0.000 title claims description 12
238000002360 preparation method Methods 0.000 title description 10
150000001875 compounds Chemical class 0.000 claims description 18
238000006243 chemical reaction Methods 0.000 claims description 10
238000004519 manufacturing process Methods 0.000 claims description 10
239000000460 chlorine Substances 0.000 claims description 9
WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
229910052794 bromium Inorganic materials 0.000 claims description 5
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
229910052801 chlorine Inorganic materials 0.000 claims description 4
150000002084 enol ethers Chemical class 0.000 claims description 4
QZLYKIGBANMMBK-UGCZWRCOSA-N 5α-Androstane Chemical compound C([C@@H]1CC2)CCC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CCC[C@@]2(C)CC1 QZLYKIGBANMMBK-UGCZWRCOSA-N 0.000 claims description 3
239000002253 acid Substances 0.000 claims description 3
239000003054 catalyst Substances 0.000 claims description 3
150000003128 pregnanes Chemical class 0.000 claims description 3
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
229910052736 halogen Inorganic materials 0.000 claims description 2
150000002367 halogens Chemical class 0.000 claims description 2
239000011777 magnesium Substances 0.000 claims description 2
229910052749 magnesium Inorganic materials 0.000 claims description 2
150000001451 organic peroxides Chemical class 0.000 claims description 2
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 46
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 35
HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 28
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 28
MUMGGOZAMZWBJJ-DYKIIFRCSA-N Testosterone Natural products O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 MUMGGOZAMZWBJJ-DYKIIFRCSA-N 0.000 description 18
239000000126 substance Substances 0.000 description 18
238000002844 melting Methods 0.000 description 17
230000008018 melting Effects 0.000 description 17
238000001953 recrystallisation Methods 0.000 description 16
229960001701 chloroform Drugs 0.000 description 14
UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 14
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
239000000706 filtrate Substances 0.000 description 12
239000000203 mixture Substances 0.000 description 12
229960003604 testosterone Drugs 0.000 description 11
RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 10
238000001816 cooling Methods 0.000 description 10
239000002244 precipitate Substances 0.000 description 10
239000011541 reaction mixture Substances 0.000 description 10
WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
239000000047 product Substances 0.000 description 9
239000013078 crystal Substances 0.000 description 8
XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 6
229960003290 cortisone acetate Drugs 0.000 description 6
ITRJWOMZKQRYTA-RFZYENFJSA-N Cortisone acetate Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)COC(=O)C)(O)[C@@]1(C)CC2=O ITRJWOMZKQRYTA-RFZYENFJSA-N 0.000 description 5
125000004432 carbon atom Chemical group C* 0.000 description 5
-1 dibromomethylene group Chemical group 0.000 description 5
BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 5
238000010992 reflux Methods 0.000 description 5
XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
238000009835 boiling Methods 0.000 description 4
238000002329 infrared spectrum Methods 0.000 description 4
LQFCAMBNXSGPLG-DXNWCKCOSA-N (8R,9S,10R,13S,14S,17S)-17-hydroxy-10,13-dimethyl-6-(tribromomethyl)-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one Chemical compound BrC(C1C[C@@H]2[C@H](CC[C@@]3([C@H](CC[C@H]32)O)C)[C@]3(CCC(C=C13)=O)C)(Br)Br LQFCAMBNXSGPLG-DXNWCKCOSA-N 0.000 description 3
CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 description 3
238000004587 chromatography analysis Methods 0.000 description 3
238000001914 filtration Methods 0.000 description 3
125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
239000012442 inert solvent Substances 0.000 description 3
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
229960003387 progesterone Drugs 0.000 description 3
239000000186 progesterone Substances 0.000 description 3
239000002904 solvent Substances 0.000 description 3
GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 3
BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
VPGRYOFKCNULNK-ACXQXYJUSA-N Deoxycorticosterone 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)CC2 VPGRYOFKCNULNK-ACXQXYJUSA-N 0.000 description 2
239000005977 Ethylene Substances 0.000 description 2
229930194542 Keto Natural products 0.000 description 2
239000000370 acceptor Substances 0.000 description 2
BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
229910052921 ammonium sulfate Inorganic materials 0.000 description 2
235000011130 ammonium sulphate Nutrition 0.000 description 2
HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 2
229910052799 carbon Inorganic materials 0.000 description 2
125000001309 chloro group Chemical group Cl* 0.000 description 2
UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 2
239000012043 crude product Substances 0.000 description 2
IHUREIPXVFKEDT-UHFFFAOYSA-N dibromo(dichloro)methane Chemical compound ClC(Cl)(Br)Br IHUREIPXVFKEDT-UHFFFAOYSA-N 0.000 description 2
238000001035 drying Methods 0.000 description 2
238000010438 heat treatment Methods 0.000 description 2
239000012535 impurity Substances 0.000 description 2
230000001678 irradiating effect Effects 0.000 description 2
229910052943 magnesium sulfate Inorganic materials 0.000 description 2
235000019341 magnesium sulphate Nutrition 0.000 description 2
239000012452 mother liquor Substances 0.000 description 2
239000003208 petroleum Substances 0.000 description 2
238000000746 purification Methods 0.000 description 2
238000003756 stirring Methods 0.000 description 2
VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
PEOZOGKIOIMGCE-DXNWCKCOSA-N (8R,9S,10R,13S,14S,17S)-17-hydroxy-10,13-dimethyl-6-(trichloromethyl)-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one Chemical compound ClC(C1C[C@@H]2[C@H](CC[C@@]3([C@H](CC[C@H]32)O)C)[C@]2(CCC(C=C12)=O)C)(Cl)Cl PEOZOGKIOIMGCE-DXNWCKCOSA-N 0.000 description 1
AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
FOYWCEUVVIHJKD-UHFFFAOYSA-N 2-methyl-5-(1h-pyrazol-5-yl)pyridine Chemical compound C1=NC(C)=CC=C1C1=CC=NN1 FOYWCEUVVIHJKD-UHFFFAOYSA-N 0.000 description 1
239000004342 Benzoyl peroxide Substances 0.000 description 1
OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
238000003747 Grignard reaction Methods 0.000 description 1
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
GCKMFJBGXUYNAG-HLXURNFRSA-N Methyltestosterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@](C)(O)[C@@]1(C)CC2 GCKMFJBGXUYNAG-HLXURNFRSA-N 0.000 description 1
GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
238000010521 absorption reaction Methods 0.000 description 1
229960000583 acetic acid Drugs 0.000 description 1
SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
235000019400 benzoyl peroxide Nutrition 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
229960004486 desoxycorticosterone acetate Drugs 0.000 description 1
125000003963 dichloro group Chemical group Cl* 0.000 description 1
MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
238000010828 elution Methods 0.000 description 1
239000012259 ether extract Substances 0.000 description 1
238000001704 evaporation Methods 0.000 description 1
230000008020 evaporation Effects 0.000 description 1
238000011049 filling Methods 0.000 description 1
229910052731 fluorine Inorganic materials 0.000 description 1
239000011737 fluorine Substances 0.000 description 1
239000012362 glacial acetic acid Substances 0.000 description 1
239000011521 glass Substances 0.000 description 1
229910000042 hydrogen bromide Inorganic materials 0.000 description 1
125000000468 ketone group Chemical group 0.000 description 1
229910052753 mercury Inorganic materials 0.000 description 1
230000004048 modification Effects 0.000 description 1
238000012986 modification Methods 0.000 description 1
DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
230000001766 physiological effect Effects 0.000 description 1
239000000741 silica gel Substances 0.000 description 1
229910002027 silica gel Inorganic materials 0.000 description 1
229910052938 sodium sulfate Inorganic materials 0.000 description 1
235000011152 sodium sulphate Nutrition 0.000 description 1
239000007787 solid Substances 0.000 description 1
239000011343 solid material Substances 0.000 description 1
238000001179 sorption measurement Methods 0.000 description 1
238000001228 spectrum Methods 0.000 description 1
239000007858 starting material Substances 0.000 description 1
150000003431 steroids Chemical class 0.000 description 1
125000001424 substituent group Chemical group 0.000 description 1
239000006188 syrup Substances 0.000 description 1
235000020357 syrup Nutrition 0.000 description 1
238000002211 ultraviolet spectrum Methods 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
- 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
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Health & Medical Sciences (AREA)
General Health & Medical Sciences (AREA)
Steroid Compounds (AREA)

CH7441259A 1958-06-13 1959-06-13 Verfahren zur Herstellung von 6a,6a-Dichlor-6,7-methylen- und 6a,6a-Dibrom-6,7-methylenverbindungen von 4-3-Ketosteroiden CH376909A (de)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
GB1906758A GB862235A (en)	1958-06-13	1958-06-13	Dihalogen derivatives of steroids and methods for their production
GB2933958		1958-09-12

Publications (1)

Publication Number	Publication Date
CH376909A true CH376909A (de)	1964-04-30

Family

ID=26253818

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
CH7441259A CH376909A (de)	1958-06-13	1959-06-13	Verfahren zur Herstellung von 6a,6a-Dichlor-6,7-methylen- und 6a,6a-Dibrom-6,7-methylenverbindungen von 4-3-Ketosteroiden

Country Status (2)

Country	Link
BE (1)	BE579663A (fr)
CH (1)	CH376909A (fr)

1959
- 1959-06-13 CH CH7441259A patent/CH376909A/de unknown
- 1959-06-13 BE BE579663A patent/BE579663A/fr unknown

Also Published As

Publication number	Publication date
BE579663A (fr)	1959-10-01

Publication	Publication Date	Title
DE1493080C3 (de)	1974-11-28	Spiro(steroid-6,l'-cyclopropane) und Verfahren zu deren Herstellung
DE1253708B (de)	1967-11-09	Verfahren zur Herstellung von delta 16-20-Ketosteroiden
DE1921778A1 (de)	1969-11-20	Neue Steriode und Verfahren zu ihrer Herstellung
DE1232138B (de)	1967-01-12	Verfahren zur Herstellung von delta 5-6-Methylsteroiden
US3047566A (en)	1962-07-31	6a, 6a-dihalo-6, 7-methylene steroids and method
DE1793633C3 (de)	1973-10-04	Verfahren zur Herstellung von Gona 4(5),9(10)dien3 onen Ausscheidung aus 1468642
CH376909A (de)	1964-04-30	Verfahren zur Herstellung von 6a,6a-Dichlor-6,7-methylen- und 6a,6a-Dibrom-6,7-methylenverbindungen von 4-3-Ketosteroiden
DE1114487B (de)	1961-10-05	Verfahren zur Herstellung von 6a, 6a-Dichlor-6,7-methylen- und 6a, 6a-Dibrom-6,7-methylenverbindungen von í¸-3-Ketosteroiden der Androstan- und Pregnanreihe
DE1593052C3 (de)	1975-04-17	Verfahren zur Herstellung von 16-Methylen-19-norprogesteron-derivaten
DE1468988B1 (de)	1971-11-25	17alpha-Chloraethinyl-13beta-aethyl-4- oder -5(10)-gonen-3-ketone
DE2403985C2 (de)	1984-03-01	Verfahren zur Herstellung von racemischem 13&beta;-Äthyl-3-methoxy-8,14-secogona-1,3,5(10),8-tetraen-17&beta;-ol-14-on
DE1643010A1 (de)	1971-04-15	Verfahren zur Herstellung von 17alpha-Alkinyl-17ss-alkanoyloxy-Steroiden der Andostran- und Oestranreihe
DE1468642C (de)	1971-10-28	Gona-4(5), 9(10>dien-3-one
DE1468988C (de)	1972-07-06	nalpha-Chloräthinyl-lSbeta-äthyl-4-oder-5( 10)- gonen-3 -ketone.'
DE1493313C (de)	1971-08-12	16b, 17 Cycloenolather des 17alpha Hydroxy öalpha methyl 3,20 dioxo 4 pregnen 16alpha acetaldehyds und des 1 lbeta, 17alpha Dihydroxy 9alpha fluor 6alpha methyl 3,20 dioxo 1,4 pregnadien 16alpha acetaldehyds und Verfahren zu ihrer Herstellung
DE1568971C3 (de)	1974-03-14	Steroidoxazoline und Verfahren zu ihrer Herstellung
DE1593348C3 (de)	1975-03-06	Verfahren zur Herstellung von 19-Fluorsteroidepoxyden und 19-Fluor-11,19epoxysteroide
AT235477B (de)	1964-08-25	Verfahren zur Herstellung von neuen, mit einem Isoxazolring kondensierten Steroidverbindungen
AT249865B (de)	1966-10-10	Verfahren zur Herstellung neuer Pyrazolverbindungen der Pregnanreihe
DE909935C (de)	1954-04-26	Verfahren zur Herstellung von í¸-3-Oxysteroiden oder ihren Derivaten
DE1081888B (de)	1960-05-19	Verfahren zur Herstellung von ?-3-Keto-9 ª‡-halogensteroiden
DE1121610B (de)	1962-01-11	Verfahren zur Herstellung von Alkanoylthiosteroiden
DE1159939B (de)	1963-12-27	Verfahren zur Herstellung von í¸-bzw. í¸-3-Keto-6ª‡-trifluormethylsteroiden der Androstan-, 19-Norandrostan- und Pregnanreihe bzw. von 3-Enolaethern entsprechender í¸-3-Keto-6ª‡-trifluormethylsteroide
CH518918A (de)	1972-02-15	Verfahren zur Herstellung von Gona-4,9-dien-3-onen
DE1241825B (de)	1975-10-16	Ver fahren zur Herstellung von 6 Chlor 4 6diLirverbindungen der Pregnan-, Androstan oder Cholestanreihe