OA1429A - Novel unsaturated steroid derivatives and process for their preparation - Google Patents

Novel unsaturated steroid derivatives and process for their preparation Download PDF

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Publication number
OA1429A
OA1429A OA51946A OA51946A OA1429A OA 1429 A OA1429 A OA 1429A OA 51946 A OA51946 A OA 51946A OA 51946 A OA51946 A OA 51946A OA 1429 A OA1429 A OA 1429A
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OA
OAPI
Prior art keywords
hydroxy
oxo
17α
estratriene
a4
Prior art date
Application number
OA51946A
Other languages
French (fr)
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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.)
Filing date
Publication date
Priority to FR925431A priority Critical patent/FR1426077A/en
Priority to FR940549A priority patent/FR1453214A/en
Priority to FR949608 priority
Priority to FR949609 priority
Priority to BE644138A priority patent/BE644138A/xx
Priority to FR974762A priority patent/FR1514075A/en
Priority to FR985285 priority
Application filed by Roussel Uclaf filed Critical Roussel Uclaf
Priority to FR19090A priority patent/FR1492782A/en
Priority to FR29732A priority patent/FR5235M/fr
Publication of OA1429A publication Critical patent/OA1429A/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/56Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives, e.g. steroids
    • A61K31/565Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol
    • A61K31/567Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives, 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
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/10Organic substances
    • A23K20/168Steroids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/56Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives, e.g. steroids
    • A61K31/565Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/56Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives, e.g. steroids
    • A61K31/565Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol
    • A61K31/566Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives, 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J1/00Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J41/00Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J75/00Processes for the preparation of steroids in general
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00Systems containing at least three condensed rings
    • C07C2603/02Ortho- or ortho- and peri-condensed systems
    • C07C2603/04Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12Ortho- 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
    • C07C2603/16Benz[e]indenes; Hydrogenated benz[e]indenes

Abstract

Novel 17a - substituted - gona - 4,9,11triene-3-one derivatives having the general formula <FORM:1048231/C2/1> in which R represents either a hydrogen atom or an acyl group derived from an organic carboxylic acid, R1 represents a hydrocarbon radical having from 1-12 carbon atoms and optionally substituted with a halogen atom and R2 represents a hydrocarbon radical having 1-18 carbon atoms and the corresponding 3-oximido - 17b - hydroxy - 17a - substituted -estra-4,9,11-trienes are obtained by reacting a 17b -hydroxy-gona-4,9,11-trine-3-one having the formula <FORM:1048231/C2/2> with hydroxylamine or an alkyl ether thereof to form the corresponding 3-oximido-17b -hydroxy-gona-4,9,11-triene, oxidizing this compound to form the corresponding 3-oximido-gona-4,9,11triene-17-one, reacting this compound with a metallic derivative of the R1 substituent it is desired to introduce at the 17a -position so as to form the corresponding 17a - substituted - 3 - oximido - 17b - hydroxy - gona - 4,9,11 - triene which is subjected to acid hydrolysis to form the desired corresponding 17a -substituted-17b -hydroxy -gona-4,9,11-triene-3-one. Pharmaceutical compositions of the above compounds, having anabolizing and androgenic actions and also an inhibiting action on the pituitary gland, are administered orally, perlingually, transcutaneously or rectally.

Description

AFRICAN OFFICE AND MALAGASY

OF INDUSTRIAL PROPERTY B. P. 887 YAOUNDE (Cameroon)

PATENT

International Classification: A 61 - C 07 N ° 01429

REQUESTED ON DECEMBER 31, 1964 at 18 h 36 mn at ΙΌ.Α.Μ.Ρ.Ι. (P.V. No. 51.946) by the Society known as: Roussel-Uclaf, resident in France. ISSUED ON 4 JULY 1969, published in Official Bulletin No. 1 of 1969. PRIORITY: Patent application filed in France under No. 940,549 on 5 July 1963 in the name of the plaintiff.

Novel unsaturated steroid derivatives and methods of preparation

The present invention, to the realization of which participated MM. Nomine Gérard, Bucourt Robert and Pierdet André, has for object new unsaturated steroid derivatives, as well as their prepara-tion processes.

In its French patent application of February 20, 1963, entitled "New unsaturated steroid derivative and preparation method", the applicant company adorns 3-oxo 17 (i-hydroxy 17a-methyl A4'9'lx-estra-triene, produced by distinguishing by androgenic, orally active, active.

However, it has now been found that the 4,4'-9,11'-estratrienic derivatives of general formula:

in which R represents a hydro-carbonésaturé or unsaturated radical having at least 2 carbon atoms, and in particular:

3-oxo 17g-hydroxy 17α-ethynyl A4.9'11-estratriene,

3-oxo 178-hydroxy 17a-vinyl A4'9,11-estratriene,

3-Oxo 173-hydroxy 17α-allyl A'4'9,11-estratriene, also exhibit a very interesting pharmacological activity, and especially as progestomimetic agents, androgens, anabolic and hypophysis blocking agents. The present invention targets them as new industrial products.

These products can be prepared according to the invention by reaction of 3-oximido 17-oxo A'1,9,11-estratrien with a corresponding organometallic derivative, followed by cleavage of the oxime in 3.

To prepare 3-oxo-17 (3-hydroxy-17α-ethynyl) -4,8-estratriene or 3-oxo-17β-hydroxy-17α-allyl-4,9-istratriene, a magnesium reagent is advantageously chosen as the organometallic agent. such as bromide or the corresponding alkyl magnesium iodide.

The cleavage of the oxime function in 3-oximido derivatives 170-hydroxy 17a-RA'1'9'11-estratrienic can be carried out for example with the aid of the acidpyruvique.

As an alternative to the general process described above, it is possible, in the particular case of the preparation of 3-oxo-17β-hydroxy-17α-vinyl A4 ', 11-estratriene, to obtain this by catalytic hydrogenation of 3-oxo-173-hydroxy-17α. ethynyl A4 · 911-estratriene. The invention naturally includes:

The 3-oximido 17P-hydroxy 17 "-R A'1'a-11-estratrienes, and in particular:

3-oximido 173-hydroxy 17a-ethynyl A4'9'U-estra-triene,

3-oximido 17g-hydroxy 17 "-vinyl A4'9,11-estra-triene,

3-Oximido 173-hydroxy 17α-allyl A4'9,11-estra-triene, which serve as intermediates in the above processes.

The following examples illustrate the invention without, however, limiting it.

Example I

Preparation of 3-oxo-17-hydroxy-17α-ethynyl-4-estratriene.

Step A: Oxime of 3-oxo-17-hydroxy-17% -ethynyl-3-estratriene.

Preparation of the magnesian:

6 g of magnesium are suspended in a nitrogen atmosphere under anhydrous conditions in anhydrous tetrahydrofuran (300 cc), and demethyl bromide is bubbled through until the magnesium disappears.

The resulting methylmagnesium bromide solution was cooled to about 40 ° C, an anhydrous acetylene stream bubbled for three hours, and a solution of ethynylmagnesium bromide was obtained.

Condensation:

The ethynylmagnesium bromide solution obtained above is refluxed under a nitrogen atmosphere and 0.82 g of 3-oximido 17-oxo A4,9,11-estratriene (obtained according to the French patent application of 20 February 1963, titled: "Novel unsaturated steroid derivative and process of preparation") in 10 cm3 of tetrahydrofuran.

Heating was continued at reflux for two hours, then cooled and slowly added 100 cm3 of

Claims (5)

  1. [01429] 2 saturated solution of ammonium chloride. Extracted with ether, washed with water until neutral washing water, distilled to dryness under vacuum, and obtains0,993 g of product which is chromatographed on magnesium silicate, eluted with methylene chloride 1% methanol and collected 0.784 g of the oxime of 3-oxo-17-hydroxy-17α-ethynyl A4'9'11-estratriene. This product is insoluble in water, diluted aqueous etalcalis acids, soluble in alcohols, ether, acetone, benzene and chloroform. This compound is not described in the literature. Stage B: 3-oxo 17β-hydroxy-7α-ethynyl A4 · 9 · 11-estratriene. 0.77 g of oxime of 3-oxo-173-hydroxy-17α-ethynyl-4'-9'-estratriene is introduced into a mixture of 25 cm 3 of acetic acid, 25 cm 3 of water and 2.5 cm 3 of pyruvic acid and heated. at reflux under a nitrogen atmosphere for one hour. It is cooled, poured into ice water, excess sodium bicarbonate is added, extracted with ether, washed with water until neutral, dried under vacuum, and 0.656 g of product is obtained. The product obtained is dissolved in methylene chloride, chromatographed on magnesium silicate, eluted with methylene chloride and 0.51 g of product is obtained which is recrystallized by heating in ether-isopropyl, cooling and spinning, and obtains 36 g of 3-oxo-173-hydroxy-17α-ethynyl-4'-9'-tri-triene. For analysis, it is recrystallized from isopropyl ether and distilled at ordinary pressure. The product is in the form of pale yellow needles, insoluble in water, dilute aqueous acids and alkalis in alcohols, ether, acetone, benzene and chloroform. Mp = 169 ° C, [, +] - + 63 ° C (c = 0.5%, ethanol) Spectrum TJ.V .: Max, at 342 overnight ε - 29 100. Max at 238 mp ε Analysis: ## STR2 ## Calc'd: C2% H1 7.53 Found: C% 81.6 H% 7.6 This compound is not described in the literature. EXAMPLE II Preparation of 3-oxo-17-hydroxy-17-yl-amino-4 · 9 · 1 1-estratriene 0.429 g of 3-oxo-173-hydroxy-17α-ethyl-nyl β-9,9-estratriene are introduced into A mixture of 16 cm 3 of tetrahydrofuran, 16 cm 3 of anhydrous dimethylformamide and 1.6 cm 3 of pyridine, 0.04 g of 5% palladium catalyst deposited on calcium carbonate is added with stirring at around 20 ° to 25 ° C. In sixteen minutes the absorption reaches a plateau corresponding to 32 cm, ie 1 molecule of hydrogen, the catalyst is filtered off, the filtrate is concentrated to a small volume and poured over a mixture of water and ice. with methylene chloride washed with water, distilled to dryness under vacuum and obtains 0.48 g The product obtained is dissolved in methylene chloride, chromatographed on magnesium silicate, eluted with methylene chloride and crystallizes the product obtained in a mixture of ethyl and isopropyl ethers (1: 1). 0.285 g of 3-oxo-173-hydroxy-17α-vinyl-4'-9'-estratriene are obtained. Mp = 143-144 ° C, [α] 20 = -27 ° C (c = 0.5%, ethanol). The product is in the form of yellow-water prisms insoluble in water, soluble in chloroform. Analysis: CoqHO402 = 296.39. Calculated: C "% 81.04 H% 8.16 Found: C% 80.9 H% 8.4 This compound is not described in the literature.Example III Preparation of 3-oxo 17β-hydroxy 17α Preparation of the allylic magnesium: 10 g of magnesium are slowly suspended in a nitrogen atmosphere and stirred in 40 cm3 of ethyl ether, added in the course of two hours while heating at slight reflux. 20 g of allyl bromide in 160 cm3 of ethyl ether is heated under reflux for 30 minutes after the end of the addition and a solution of 0.7 N allylmagnesium bromide is obtained. the temperature of +3 ° C. and stirring with 0.55 g of 3-oximido-17-oxo-4'-α-1-estratriene in 70 cm 3 of benzene, add in the space of eight minutes 150 cm 3 of the allyl bromide solution. 0.7 N magnesium and stirring for fifty minutes at the starting temperature. ium, wash with water until the washing water is neutral, dry, and distil dry. The product collected is chromatographed on magnesium silicate, eluted with methylene chloride to 1% ethanol and 0.497 g of 3-oximido 173-hydroxy17a-allyl A4'9,11-estratriene. U.V. Spectrum: Max. at 321 mp ε = 35,300 (in ethanol). Maxi. at 333 mp ε - 31,730. This compound is not described in the literature. Pyruvic hydrolysis of the product obtained leads to 3-oxo 173-hydroxy 17α-allyl A4'9,11-estratriene which is not described in the literature. SUMMARY The subject of the invention is: 1 ° As new industrial products, A4,9'11-estratrienic derivatives of general formula:
    in which R represents a hydro-carbonated or unsaturated radical having at least 2 carbon atoms, and in particular: 3-oxo-173-hydroxy-17β-ethynyl-β-ethyltratriene. 3-Oxo 173-hydroxy 17a-vinyl A4> 9'11-estratriene. 3-Oxo 173-hydroxy 17α-allyl A4'9> 11-estratriene.
  2. 2 ° A process for the preparation of the above products, characterized in that a corresponding organometallic derivative-3 is reacted on 3-oximido 17-oxo A4'9'11-estratriene, then cleaves the oximeen 3 and gives the desired 3-oxo-17α-hydroxy 17α-R ^H-estra-triene.
  3. 3 ° Modes of execution of the process according to 2 ° charac-terized by the following points, taken singly or combinations: a. The organometallic derivative used is an Orga-nomagnesian. b. The cleavage of the oxime at 3 "is carried out using pyruvic acid.
  4. 4 ° As intermediates: 3-Oximido 173-hydroxy 17a-R A4'9'11-estratrienes, and in particular: 3-oximido 17β-hydroxy 17α-ethynyl A4'8,11-estra-triene. The 3-oximido 17p-hydroxy 17a-vinyl A4,9,11-estra-triene. 3-oximido 17 [] - hydroxy 17α-allyl A4,9,11estratriene.
  5. As an alternative to the process according to a process for the preparation of 3-oxo-17α-hydroxy-17α-vinyl-9,11-estratriene in which the 3-oxo-173-hydroxy-17α-ethynyl A4'9,11-estratrene is subjected. at the catalytic hydrogenation Society known as ROUSSEL-UCLAF By proxy: Robert Pucheu
OA51946A 1963-02-20 1964-12-31 Novel unsaturated steroid derivatives and process for their preparation OA1429A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
FR925431A FR1426077A (en) 1963-02-20 1963-02-20 New estratriénique derivative and process for preparing
FR940549A FR1453214A (en) 1963-02-20 1963-07-05 Novel unsaturated steroids and methods for preparing
FR949608 1963-10-04
FR949609 1963-10-04
BE644138A BE644138A (en) 1963-02-20 1964-02-20
FR974762A FR1514075A (en) 1964-02-17 1964-05-15 New steroid triene derivative and process for preparing
FR985285 1964-08-14
FR19090A FR1492782A (en) 1963-02-20 1965-06-01 New unsaturated steroid derivative and process for preparing
FR29732A FR5235M (en) 1963-02-20 1965-08-27

Publications (1)

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OA1429A true OA1429A (en) 1969-07-04

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OA51946A OA1429A (en) 1963-02-20 1964-12-31 Novel unsaturated steroid derivatives and process for their preparation

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US (2) US3248294A (en)
BE (1) BE644138A (en)
BR (2) BR6456982D0 (en)
CH (2) CH429713A (en)
DE (2) DE1291337B (en)
DK (1) DK117957B (en)
FR (8) FR1426077A (en)
GB (2) GB1048231A (en)
NL (6) NL6401555A (en)
OA (2) OA1428A (en)
SE (3) SE323073B (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424745A (en) * 1964-05-27 1969-01-28 Roussel Uclaf Novel process for the preparation of trienic steroid derivatives
US3346454A (en) * 1964-11-04 1967-10-10 Roussel Uclaf 17-alkyl-19-nor-delta4, 9, 11-pregnatriene-3, 20-diones, process and intermediates for preparing same and therapeutic compositions thereof
US3422121A (en) * 1965-08-13 1969-01-14 Merck & Co Inc Process for the preparation of 13-lower alkyl-gona-4,8(14),9-triene-3,17-dione
US3424769A (en) * 1966-04-04 1969-01-28 Syntex Corp Process for the preparation of novel 6alpha-methyl-delta4,9(10)- diene steroids
NL129638C (en) * 1966-08-12
US3461118A (en) * 1966-10-17 1969-08-12 Syntex Corp 3beta-tetrahydrofuranyloxy - and 3beta-tetrahydropyranyloxyestra - 4,9(10) - dienes and -4,9(10),11-trienes,their preparation and intermediates thereof
US3760073A (en) * 1971-06-09 1973-09-18 Roussel Uclaf Treatment of wounds
FR2162268B1 (en) * 1971-12-08 1975-02-07 Roussel Uclaf
FR2407940B1 (en) * 1977-11-08 1980-12-05 Roussel Uclaf
HU201091B (en) * 1985-12-26 1990-09-28 Mitsubishi Chem Ind Process for producing gonatriene derivatives and pharmaceutical compositions comprising same
IE60964B1 (en) * 1986-12-11 1994-09-07 Roussel Uclaf Zootechnical compositions containing a beta-adrenergic
DE4232521A1 (en) * 1992-09-22 1994-03-24 Schering Ag Progestin effective 4,5; 11,12-Estradiene, to processes for their preparation, to pharmaceutical compositions containing Estradiene and their use for the preparation of medicaments
FR2696641B1 (en) * 1992-10-13 1997-07-04 Roussel Uclaf New use of Altrenogest.
US6498153B1 (en) 1998-12-31 2002-12-24 Akzo Nobel N.V. Extended release growth promoting two component composition
CN101704871B (en) 2009-12-01 2012-05-23 北京紫竹药业有限公司 Steroid compound and application thereof

Also Published As

Publication number Publication date
CH429713A (en) 1967-02-15
SE319173B (en) 1970-01-12
CH467255A (en) 1969-01-15
NL6607609A (en) 1966-12-02
US3257278A (en) 1966-06-21
BR6680069D0 (en) 1973-12-26
NL126190C (en)
GB1048232A (en) 1966-11-16
FR1492782A (en) 1967-08-25
NL6615432A (en) 1967-01-25
DK117957B (en) 1970-06-22
DE1291337B (en) 1969-03-27
FR1426077A (en) 1966-01-28
FR5235M (en) 1967-07-17
FR3069M (en)
FR3060M (en)
OA1428A (en) 1969-07-04
US3248294A (en) 1966-04-26
NL124135C (en)
FR2713M (en)
SE323071B (en) 1970-04-27
FR1453214A (en) 1966-06-03
DE1593307A1 (en) 1970-07-23
BE644138A (en) 1964-08-20
SE323073B (en) 1970-04-27
BR6456982D0 (en) 1973-08-14
GB1048231A (en) 1966-11-16
NL6401555A (en) 1964-08-21
NL127247C (en)
FR3804M (en)

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