IL28112A - 11beta-alkoxy-estra 1,3,5(10)-trienes and their preparation - Google Patents

11beta-alkoxy-estra 1,3,5(10)-trienes and their preparation

Info

Publication number: IL28112A
Authority: IL; Israel
Prior art keywords: carbon; agent; designates; radical; action
Prior art date: 1966-06-07

Application number

IL28112A

Other languages

English (en)

Original Assignee

Roussel Uclaf

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.)

1966-06-07

Filing date

1967-06-08

Publication date

1973-08-29

1967-06-08 Application filed by Roussel Uclaf filed Critical Roussel Uclaf

1973-08-29 Publication of IL28112A publication Critical patent/IL28112A/en

Links

238000002360 preparation method Methods 0.000 title claims description 17
239000000203 mixture Substances 0.000 claims description 25
150000001875 compounds Chemical class 0.000 claims description 19
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
229910052799 carbon Inorganic materials 0.000 claims description 17
125000000217 alkyl group Chemical group 0.000 claims description 15
239000003795 chemical substances by application Substances 0.000 claims description 11
238000000034 method Methods 0.000 claims description 8
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
125000004432 carbon atom Chemical group C* 0.000 claims description 6
239000003054 catalyst Substances 0.000 claims description 6
150000003431 steroids Chemical class 0.000 claims description 5
238000006243 chemical reaction Methods 0.000 claims description 4
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
229910052700 potassium Inorganic materials 0.000 claims description 3
239000011591 potassium Substances 0.000 claims description 3
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
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 claims description 2
125000002252 acyl group Chemical group 0.000 claims description 2
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
239000001257 hydrogen Substances 0.000 claims description 2
229910052739 hydrogen Inorganic materials 0.000 claims description 2
239000001301 oxygen Substances 0.000 claims description 2
229910052760 oxygen Inorganic materials 0.000 claims description 2
NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical group O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 claims description 2
229910052708 sodium Inorganic materials 0.000 claims description 2
239000011734 sodium Substances 0.000 claims description 2
150000007524 organic acids Chemical class 0.000 claims 2
239000002253 acid Substances 0.000 claims 1
150000008064 anhydrides Chemical class 0.000 claims 1
125000004429 atom Chemical group 0.000 claims 1
239000003638 chemical reducing agent Substances 0.000 claims 1
239000012374 esterification agent Substances 0.000 claims 1
238000006266 etherification reaction Methods 0.000 claims 1
QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
230000001225 therapeutic effect Effects 0.000 claims 1
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
239000011541 reaction mixture Substances 0.000 description 14
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
239000000243 solution Substances 0.000 description 12
238000010992 reflux Methods 0.000 description 11
239000000047 product Substances 0.000 description 10
239000002244 precipitate Substances 0.000 description 9
238000003756 stirring Methods 0.000 description 8
KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
150000005671 trienes Chemical class 0.000 description 5
IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
239000012043 crude product Substances 0.000 description 4
230000000694 effects Effects 0.000 description 4
230000001076 estrogenic effect Effects 0.000 description 4
238000002844 melting Methods 0.000 description 4
230000008018 melting Effects 0.000 description 4
239000012074 organic phase Substances 0.000 description 4
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
239000012298 atmosphere Substances 0.000 description 3
238000001816 cooling Methods 0.000 description 3
INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
239000000155 melt Substances 0.000 description 3
229910052763 palladium Inorganic materials 0.000 description 3
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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 2
KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
125000003118 aryl group Chemical group 0.000 description 2
238000004587 chromatography analysis Methods 0.000 description 2
238000002425 crystallisation Methods 0.000 description 2
230000008025 crystallization Effects 0.000 description 2
229960002568 ethinylestradiol Drugs 0.000 description 2
125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
125000004356 hydroxy functional group Chemical group O* 0.000 description 2
JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
229910052757 nitrogen Inorganic materials 0.000 description 2
VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
235000011118 potassium hydroxide Nutrition 0.000 description 2
238000001953 recrystallisation Methods 0.000 description 2
239000000741 silica gel Substances 0.000 description 2
229910002027 silica gel Inorganic materials 0.000 description 2
239000000377 silicon dioxide Substances 0.000 description 2
239000012312 sodium hydride Substances 0.000 description 2
229910000104 sodium hydride Inorganic materials 0.000 description 2
238000001228 spectrum Methods 0.000 description 2
239000000725 suspension Substances 0.000 description 2
VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 1
QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
206010013786 Dry skin Diseases 0.000 description 1
206010019851 Hepatotoxicity Diseases 0.000 description 1
239000004285 Potassium sulphite Substances 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
238000004458 analytical method Methods 0.000 description 1
239000008346 aqueous phase Substances 0.000 description 1
239000007864 aqueous solution Substances 0.000 description 1
150000001768 cations Chemical class 0.000 description 1
239000013078 crystal Substances 0.000 description 1
150000001993 dienes Chemical class 0.000 description 1
VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
238000001035 drying Methods 0.000 description 1
238000010828 elution Methods 0.000 description 1
229960005309 estradiol Drugs 0.000 description 1
229930182833 estradiol Natural products 0.000 description 1
229940011871 estrogen Drugs 0.000 description 1
239000000262 estrogen Substances 0.000 description 1
125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
229940093499 ethyl acetate Drugs 0.000 description 1
235000019439 ethyl acetate Nutrition 0.000 description 1
238000001704 evaporation Methods 0.000 description 1
230000008020 evaporation Effects 0.000 description 1
239000000284 extract Substances 0.000 description 1
239000000706 filtrate Substances 0.000 description 1
ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
239000007789 gas Substances 0.000 description 1
230000002440 hepatic effect Effects 0.000 description 1
230000007686 hepatotoxicity Effects 0.000 description 1
231100000304 hepatotoxicity Toxicity 0.000 description 1
150000004678 hydrides Chemical class 0.000 description 1
150000002430 hydrocarbons Chemical group 0.000 description 1
125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 1
125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
230000004048 modification Effects 0.000 description 1
238000012986 modification Methods 0.000 description 1
239000012299 nitrogen atmosphere Substances 0.000 description 1
230000002611 ovarian Effects 0.000 description 1
125000004430 oxygen atom Chemical group O* 0.000 description 1
ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
239000012047 saturated solution Substances 0.000 description 1
238000006748 scratching Methods 0.000 description 1
230000002393 scratching effect Effects 0.000 description 1
235000017557 sodium bicarbonate Nutrition 0.000 description 1
229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
229910000033 sodium borohydride Inorganic materials 0.000 description 1
239000012279 sodium borohydride Substances 0.000 description 1
239000011780 sodium chloride Substances 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
239000002904 solvent Substances 0.000 description 1
CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
238000003828 vacuum filtration Methods 0.000 description 1
229940099259 vaseline Drugs 0.000 description 1
238000005406 washing Methods 0.000 description 1
239000003643 water by type Substances 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
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/56—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids
- A61K31/565—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/56—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids
- A61K31/565—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol
- A61K31/566—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol having an oxo group in position 17, e.g. estrone
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/56—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids
- A61K31/565—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol
- A61K31/567—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol substituted in position 17 alpha, e.g. mestranol, norethandrolone
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general

Landscapes

Health & Medical Sciences (AREA)
Chemical & Material Sciences (AREA)
General Health & Medical Sciences (AREA)
Organic Chemistry (AREA)
Animal Behavior & Ethology (AREA)
Life Sciences & Earth Sciences (AREA)
Epidemiology (AREA)
Pharmacology & Pharmacy (AREA)
Public Health (AREA)
Veterinary Medicine (AREA)
Medicinal Chemistry (AREA)
Steroid Compounds (AREA)
Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

IL28112A 1966-06-07 1967-06-08 11beta-alkoxy-estra 1,3,5(10)-trienes and their preparation IL28112A (en)

Applications Claiming Priority (6)

Application Number	Priority Date	Filing Date	Title
FR64481A FR5519M (de)	1966-06-07	1966-06-07
FR75528A FR1514122A (fr)	1966-06-07	1966-09-07	Dérivés stéroïdes substitués en position 11 à noyau a aromatique et procédé de préparation
FR86879A FR6021M (de)	1966-06-07	1966-12-09
FR91611A FR6030M (de)	1966-06-07	1967-01-18
FR96848A FR6182M (de)	1966-06-07	1967-02-28
FR98154A FR1540942A (fr)	1966-06-07	1967-03-09	Dérivés stéroïdes substitués en positions 11 et 17 à noyau a aromatique et procédé de préparation

Publications (1)

Publication Number	Publication Date
IL28112A true IL28112A (en)	1973-08-29

Family

ID=27546052

Family Applications (2)

Application Number	Title	Priority Date	Filing Date
IL28113A IL28113A (en)	1966-06-07	1967-06-08	11beta-alkoxy-17alpha-substituted-gona 1,3,5(10)-trienes and preparation processes
IL28112A IL28112A (en)	1966-06-07	1967-06-08	11beta-alkoxy-estra 1,3,5(10)-trienes and their preparation

Family Applications Before (1)

Application Number	Title	Priority Date	Filing Date
IL28113A IL28113A (en)	1966-06-07	1967-06-08	11beta-alkoxy-17alpha-substituted-gona 1,3,5(10)-trienes and preparation processes

Country Status (14)

Country	Link
US (2)	US3526648A (de)
AT (3)	AT290023B (de)
BE (2)	BE699393A (de)
CH (3)	CH474495A (de)
DE (1)	DE1618830C3 (de)
DK (2)	DK121857B (de)
ES (5)	ES341435A1 (de)
FR (6)	FR5519M (de)
GB (2)	GB1152226A (de)
IL (2)	IL28113A (de)
NL (2)	NL6707906A (de)
SE (2)	SE335979B (de)
SU (2)	SU483828A3 (de)
YU (6)	YU33880B (de)

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
FR2140258B1 (de) *	1971-06-07	1974-08-23	Roussel Uclaf
US3906096A (en) *	1971-11-23	1975-09-16	Roussel Uclaf	Novel 11{62 -alkoxy steroids
FR2183555B1 (de) *	1972-05-10	1975-06-20	Roussel Uclaf
NL7613248A (nl) *	1976-11-26	1978-05-30	Akzo Nv	Werkwijze voor het bereiden van nieuwe steroid- esters.
FR2401173A1 (fr) *	1977-06-27	1979-03-23	Roussel Uclaf	Nouveaux steroides, leur procede de preparation et leur application dans la synthese de steroides marques au tritium
US4636496A (en) *	1984-03-20	1987-01-13	Wayne State University	Compositions inhibiting murine MXT ductal carcinoma
US4668668A (en) *	1984-03-20	1987-05-26	Wayne State University	Compositions inhibiting murine MXT ductal carcinoma
US4568673A (en) *	1984-03-20	1986-02-04	Wayne State University	Compositions inhibiting murine MXT ductal carcinoma
US4705783A (en) *	1985-06-25	1987-11-10	Sri International	9α, 11β-substituted and 11β-substituted estranes
WO2002022645A2 (en) *	2000-09-14	2002-03-21	Accelerated Pharmaceuticals, Inc.	Method of making 7alpha-methyl-11beta-methoxy estradiol and related compounds with estrogenic activity
US9301920B2 (en)	2012-06-18	2016-04-05	Therapeuticsmd, Inc.	Natural combination hormone replacement formulations and therapies
EP3936133A1 (de)	2011-11-23	2022-01-12	TherapeuticsMD, Inc.	Natürliche kombinationshormonersatzformulierungen und therapien
US20130338122A1 (en)	2012-06-18	2013-12-19	Therapeuticsmd, Inc.	Transdermal hormone replacement therapies
US10806740B2 (en)	2012-06-18	2020-10-20	Therapeuticsmd, Inc.	Natural combination hormone replacement formulations and therapies
US20150196640A1 (en)	2012-06-18	2015-07-16	Therapeuticsmd, Inc.	Progesterone formulations having a desirable pk profile
US10806697B2 (en)	2012-12-21	2020-10-20	Therapeuticsmd, Inc.	Vaginal inserted estradiol pharmaceutical compositions and methods
US10471072B2 (en)	2012-12-21	2019-11-12	Therapeuticsmd, Inc.	Vaginal inserted estradiol pharmaceutical compositions and methods
US10568891B2 (en)	2012-12-21	2020-02-25	Therapeuticsmd, Inc.	Vaginal inserted estradiol pharmaceutical compositions and methods
US10537581B2 (en)	2012-12-21	2020-01-21	Therapeuticsmd, Inc.	Vaginal inserted estradiol pharmaceutical compositions and methods
US11246875B2 (en)	2012-12-21	2022-02-15	Therapeuticsmd, Inc.	Vaginal inserted estradiol pharmaceutical compositions and methods
US9180091B2 (en)	2012-12-21	2015-11-10	Therapeuticsmd, Inc.	Soluble estradiol capsule for vaginal insertion
US11266661B2 (en)	2012-12-21	2022-03-08	Therapeuticsmd, Inc.	Vaginal inserted estradiol pharmaceutical compositions and methods
CA2947767A1 (en)	2014-05-22	2015-11-26	Therapeuticsmd, Inc.	Natural combination hormone replacement formulations and therapies
CA3006267C (en) *	2014-11-26	2023-08-29	The Regents Of The University Of California	Estrogen receptor modulators
US10328087B2 (en)	2015-07-23	2019-06-25	Therapeuticsmd, Inc.	Formulations for solubilizing hormones
US10286077B2 (en)	2016-04-01	2019-05-14	Therapeuticsmd, Inc.	Steroid hormone compositions in medium chain oils
BR112018070199A2 (pt)	2016-04-01	2019-01-29	Therapeuticsmd Inc	composição farmacêutica de hormônio esteroide
US11633405B2 (en)	2020-02-07	2023-04-25	Therapeuticsmd, Inc.	Steroid hormone pharmaceutical formulations

1966
- 1966-06-07 FR FR64481A patent/FR5519M/fr not_active Expired
- 1966-09-07 FR FR75528A patent/FR1514122A/fr not_active Expired
- 1966-12-09 FR FR86879A patent/FR6021M/fr not_active Expired
1967
- 1967-01-18 FR FR91611A patent/FR6030M/fr not_active Expired
- 1967-02-28 FR FR96848A patent/FR6182M/fr not_active Expired
- 1967-03-09 FR FR98154A patent/FR1540942A/fr not_active Expired
- 1967-06-01 GB GB25315/67A patent/GB1152226A/en not_active Expired
- 1967-06-01 GB GB25314/67A patent/GB1151404A/en not_active Expired
- 1967-06-02 US US643061A patent/US3526648A/en not_active Expired - Lifetime
- 1967-06-02 BE BE699393D patent/BE699393A/xx unknown
- 1967-06-02 BE BE699394D patent/BE699394A/xx not_active IP Right Cessation
- 1967-06-03 YU YU1125/67A patent/YU33880B/xx unknown
- 1967-06-05 SE SE07862/67A patent/SE335979B/xx unknown
- 1967-06-05 SE SE07863/67A patent/SE335980B/xx unknown
- 1967-06-06 DK DK294467AA patent/DK121857B/da not_active IP Right Cessation
- 1967-06-06 ES ES341435A patent/ES341435A1/es not_active Expired
- 1967-06-06 SU SU1161494A patent/SU483828A3/ru active
- 1967-06-06 DK DK294567AA patent/DK119925B/da not_active IP Right Cessation
- 1967-06-06 SU SU1250885A patent/SU432714A3/ru active
- 1967-06-07 CH CH806367A patent/CH474495A/fr not_active IP Right Cessation
- 1967-06-07 AT AT1252868A patent/AT290023B/de not_active IP Right Cessation
- 1967-06-07 AT AT532367A patent/AT301037B/de not_active IP Right Cessation
- 1967-06-07 DE DE1618830A patent/DE1618830C3/de not_active Expired
- 1967-06-07 AT AT532267A patent/AT279815B/de not_active IP Right Cessation
- 1967-06-07 CH CH806467A patent/CH475965A/fr not_active IP Right Cessation
- 1967-06-07 NL NL6707906A patent/NL6707906A/xx unknown
- 1967-06-07 CH CH450769A patent/CH490361A/fr not_active IP Right Cessation
- 1967-06-07 NL NL6707903A patent/NL6707903A/xx unknown
- 1967-06-08 IL IL28113A patent/IL28113A/en unknown
- 1967-06-08 IL IL28112A patent/IL28112A/en unknown
- 1967-09-06 ES ES344805A patent/ES344805A1/es not_active Expired
- 1967-09-07 YU YU1758/67A patent/YU33882B/xx unknown
- 1967-12-07 ES ES348057A patent/ES348057A1/es not_active Expired
- 1967-12-08 YU YU2408/67A patent/YU33725B/xx unknown
1968
- 1968-01-17 YU YU109/68A patent/YU34050B/xx unknown
- 1968-02-27 ES ES350987A patent/ES350987A1/es not_active Expired
- 1968-02-27 YU YU455/68A patent/YU33883B/xx unknown
- 1968-03-08 ES ES351368A patent/ES351368A1/es not_active Expired
- 1968-03-08 YU YU545/68A patent/YU33972B/xx unknown
1969
- 1969-08-25 US US852905A patent/US3579545A/en not_active Expired - Lifetime

Also Published As

Publication number	Publication date
GB1152226A (en)	1969-05-14
GB1151404A (en)	1969-05-07
BE699394A (de)	1967-12-04
DE1793738B2 (de)	1975-11-27
BE699393A (de)	1967-12-04
DE1793738A1 (de)	1973-01-11
FR1540942A (fr)	1968-10-04
YU54568A (en)	1978-02-28
FR6030M (de)	1968-05-13
FR5519M (de)	1967-11-06
DE1618830C3 (de)	1975-02-20
FR1514122A (fr)	1968-02-23
SE335980B (de)	1971-06-21
DE1618830B2 (de)	1974-07-04
ES351368A1 (es)	1969-06-01
FR6182M (de)	1968-07-15
ES344805A1 (es)	1968-11-01
YU34050B (en)	1978-10-31
YU33880B (en)	1978-06-30
IL28113A (en)	1973-08-29
US3526648A (en)	1970-09-01
YU33883B (en)	1978-06-30
SE335979B (de)	1971-06-21
CH474495A (fr)	1969-06-30
DK119925B (da)	1971-03-15
YU10968A (en)	1978-05-15
YU33882B (en)	1978-06-30
AT290023B (de)	1971-05-10
YU33972B (en)	1978-09-08
DE1618830A1 (de)	1972-04-13
AT279815B (de)	1970-03-25
FR6021M (de)	1968-05-13
YU240867A (en)	1977-08-31
ES341435A1 (es)	1968-07-01
CH490361A (fr)	1970-05-15
YU45568A (en)	1977-12-31
DE1618829A1 (de)	1971-01-14
ES348057A1 (es)	1969-03-01
NL6707903A (de)	1967-12-08
NL6707906A (de)	1968-03-08
DK121857B (da)	1971-12-13
ES350987A1 (es)	1969-05-16
SU483828A3 (ru)	1975-09-05
YU175867A (en)	1977-12-31
US3579545A (en)	1971-05-18
SU432714A3 (de)	1974-06-15
YU33725B (en)	1978-02-28
YU112567A (en)	1977-12-31
AT301037B (de)	1972-08-25
CH475965A (fr)	1969-07-31

Publication	Publication Date	Title
IL28112A (en)	1973-08-29	11beta-alkoxy-estra 1,3,5(10)-trienes and their preparation
Christensen et al.	1960	The Partial Synthesis of 12α-Methyl-11-dehydrocorticosterone
Robinson et al.	1972	Reduction of. alpha.,. beta.-oxido ketones with chromous acetate. Synthesis of 3. beta., 5. beta., 17. beta., 19-tetrahydroxy-5. beta.-androstane, a degradation product of strophanthidin
US3682983A (en)	1972-08-08	Preparation of {66 {11 {11 -17 ethinyl steroids
Wendler et al.	1958	The Faworskii rearrangement in the formation of 17-methyl steroids: The configuration of C-17 bromides
JP2584829B2 (ja)	1997-02-26	９（１１）−デヒドロステロイドの製造方法
US5998639A (en)	1999-12-07	Sulfatation of estrogen mixtures
US2554882A (en)	1951-05-29	3-hydroxy-11-ketoetiocholanic acid and its esters
JPH02500739A (ja)	1990-03-15	１４，１７β―エタノ―１４β―エストラトリエン、その製法及び該化合物を含有するエストロゲン作用医薬調製剤
Paryzek	1979	Tetracyclic triterpenes. Part 2. A synthetic approach to cucurbitacins
Agnello et al.	1963	A Stereospecific Synthesis of C-21-Methylated Corticosteroids1a, d
Zderic et al.	1962	Steroids. CLXXVIII. 1 9a-Aza-C-homo Steroids
Deno et al.	1979	Functionalization of steroid side chains: conversion of cholesterol to chol-5-ene-3. beta., 24-diol
US3252930A (en)	1966-05-24	Intermediates in the synthesis of 1alpha-hydroxy-3-ketosteroids
US4022892A (en)	1977-05-10	17β-Ethynyl-3,17α-estradiol and derivatives thereof
Bolt	1951	O‐hetero‐analogues of steroids
IL23453A (en)	1968-09-26	Process for the preparation of 17alpha-ethynyl-19-nor steroids
Mazur	1960	Azasteroids. II1, 2
EP0875515B1 (de)	2004-09-22	Sulfatierung von Östrogen-Mischungen
US3037021A (en)	1962-05-29	Novel process for the preparation of an 11, 18-oxygenated steroid and products resulting therefrom
Johns	1971	Synthesis and reactions of 5. alpha., 8-epidioxyandrost-6-enes
US3260733A (en)	1966-07-12	1beta-methyl steroids
US3595883A (en)	1971-07-27	Process for the preparation of 14beta-hydroxy - 17 -keto - 15 - androstenes and novel intermediates produced thereby
US3852312A (en)	1974-12-03	Preparation of mannich bases
US3408372A (en)	1968-10-29	Preparation of 3-keto-10beta-methyl-11beta-hydroxy-delta4 steroids