GB1569221A - D-homosteroids - Google Patents

D-homosteroids Download PDF

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Publication number
GB1569221A
GB1569221A GB15046/77A GB1504677A GB1569221A GB 1569221 A GB1569221 A GB 1569221A GB 15046/77 A GB15046/77 A GB 15046/77A GB 1504677 A GB1504677 A GB 1504677A GB 1569221 A GB1569221 A GB 1569221A
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homoestra
diene
group
hydroxy
formula
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GB15046/77A
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F Hoffmann La Roche AG
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F Hoffmann La Roche AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
    • C07J63/008—Expansion of ring D by one atom, e.g. D homo steroids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P5/00—Drugs for disorders of the endocrine system

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Diabetes (AREA)
  • Endocrinology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Steroid Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

(54) D-HOMOSTEROIDS (71) We, F. HOFFMANN-LA ROCHE & CO., AKTIENGESELLSCHAFT, a Swiss Company of 124-184 Grenzacherstrasse, Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to Dhomosteroids. More particularly, the invention is concerned with Dhomosteroids, a process for the manufacture thereof and pharmaceutical preparations containing same.
The D-homosteroids provided by the present invention have the following general formula
wherein R13 represents a lower alkyl group, R"46 represents ahydrogen atom or an acyl or lower alkyl group and R'7"" represents a hydrogen atom or a lower alkyl, ethynyl, 1propynyl, vinyl, chloroethynyl, butadiynyl or propadienyl group.
According to the process provided by the present invention, the D-homosteroids of formula I hereinbefore are manufactured by (a) reducing the 3-keto group and any 17a-keto group which may be present in a D-homosteroid of the general formula
wherein X represents a grouping OR17aA and Y represents a grouping R1'aa or X and Y together represent an oxo group and R'3, R'7"B and R17"" have the significance given earlier, to the hydroxy group, or (b) hydrolysing the 3-acyl group in a Dhomosteroid of the general formula
where R'3, R17aP and R17aa have the significance given earlier, or (c) reacting a D-homosteroid of the general formula
wherein R'3 has the significance given earlier.
with a metal-organic compound yielding a grouping R17a.
The term "acyl" used in this Specification denotes acyl groups derived from lower (containing up to 7 carbon atoms) alkanecarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oenanthic acid; or from oxalic acid, succinic acid, citric acid; or from, preferably monocyclic, aromatic carboxylic acids such as benzoic acid, phenylacetic acid or phenoxyacetic acid; or from heterocyclic carboxylic acids such as nicotinic acid; or from cycloaliphatic carboxylic acids, for example, cycloalkylalkanecarboxylic acids such as cyclopentylpropionic acid, cyclohexylacetic acid, cyclopropylacetic acid, or cycloalkanecarboxylic acids such as cyclopropane carboxylic acid, cyclopentane carboxylic acid or cyclohexane carboxylic acid.
The lower alkyl groups referred to in this Specification contain up to 7 carbon atoms and can be straight-chain or branchedchain. Examples of such groups are the methyl, ethyl, propyl, isopropyl and butyl groups and isomers of the latter. Preferably, R'3 represents the methyl or ethyl group.
A preferred group of D-homosteroids of formula I are those in which R'3 represents a methyl or ethyl group, Rl7Ba represents a hydrogen atom or a methyl group and R178P represents a hydrogen atom or a lower alkanoyl group.
Examples of D-homosteroids of formula I are: 3p,17ap - Dihydroxy - D - homoestra 4,16 - diene, l7a - ethynyl - 3p,17ap - dihydroxy - D - homoestra - 4,16 - diene, 17aa - ethynyl - 13 - ethyl - 3p,17ap dihydroxy - D - homogona - 4,16 - diene, 17ap- acetoxy - 17a- ethynyl - 13 ethyl- 3P - hydroxy - D - homogona 4,16 - diene, 3p - hydroxy - 17ass - propionyloxy - D - homoestra - 4,16 - diene, 17a,5- acetoxy - 3p - hydroxy - D - homoestra - 4,16 - diene, 17ap- acetoxy - 17air - ethynyl 3p - hydroxy - D - homoestra - 4,16 - diene, and 17aa - ethynyl - 13 - ethyl - 3 - hydroxy l7a - propionyloxy - D - homogona - 4,16 - diene.
The reduction of a D-homosteroid of formula II according to embodiment (a) of the process can be carried out in a manner known per se using a complex metal hydride; for example, sodium borohydride, a di(lower alkoxy)-aluminium hydride such as diisobutylaluminium hydride, lithium aluminium hydride, sodium aluminium hydride, trimethoxy-lithium aluminium hydride or tributoxy-lithium aluminium hydnde. Suitable solvents for this reduction are hydrocarbons (e.g. cyclohexane, benzene or toluene) and ethers (e.g. diethyl ether or tetrahydrofuran).
The hydrolysis of a D-homosteroid of formula III according to embodiment (b) of the process can be carried out using aqueous-alcoholic bases such as aqueousmethanolic solutions of alkali metal hydroxides or carbonates or alkaline earth metal hydroxides or carbonates, an ester group which may be present in the 17aposition being simultaneously saponified.
As the metal-organic compounds for the reaction with a D-homosteroid of formula IV in accordance with embodiment (c) of the process there come into consideration Grignard compounds (e.g. lower alkyl, ethynyl, propynyl or vinylmagnesium halides) or alkali metal-organic compounds (e.g. sodium, potassium or lithium acetylide or vinyllithium).
The D-homosteroids of formula I have hormonal activity. D-homosteroids of formula I in which R17aa represents a hydrogen atom or a lower alkyl group have androgenic/anabolic activity. They can be administered in daily dosages of 0.0i0.15 mglkg.
D-Homosteroids of formula I in which Rl7a represents an unsaturated group such as the ethynyl group have gestation and ovulation inhibiting activity. They can be used as fertility inhibitors, dosages of 0.01- 0.1 mg/kg coming into consideration.
The D-homosteroids of formula I can be used in ~ the form of pharmaceutical preparations which contain them in association with a compatible pharmaceutical carrier material. This carrier material can be an organic or inorganic inert carrier material which is suitable for enteral or parenteral administration such as, for example, water, gelatine, gum arabic, lactose, starch, magnesium stearate, talc, vegetable oils, polyalkyleneglycols, petroleum jelly etc.
The pharmaceutical preparations can be made up in a solid form (e.g. as tablets, drawees, suppositories or capsules) or in a liquid form (e.g. as solutions, suspensions or emulsions).
The following Examples illustrate the process provided by the present invention: Example 1 A solution of 941 mg of 17ap-hydroxy - D - homoestra - 4,16 - dien - 3 - one in 94 ml of tetrahydrofuran was reacted at 0 C with 104 mg of lithium aluminium hydride for 1.75 hours. After the usual working-up, there were obtained 1.02 g of crude product which was chromatographed on aluminium oxide. 519 mg of 3p,17ap - dihydroxy - D homoestra - 4,16 - diene of melting point l870-l88.50C (from hexane/acelone) could be eluted with hexane/acetone (1923%).
Example 2 A solution of 380 mg of 17ap - hydroxy D - homoestra - 4,16 - dien - 3 - one in 2.3 ml of pyridine and 0.83 ml of propionic acid anhydride was kept at room temperature for 90 hours. Usual working-up and recrystallisation of the crude product gave 410 mg of 17ap- propionyloxy- Dhomoestra - 4,16 - dien - 3 - one of melting point 930-950C.
410 mg of 17a - propionyloxy - D homoestra - 4,16 - diene - 3 - one were dissolved in 17.6 ml of isopropanol and treated with 176 mg of sodium borohydride.
The mixture was stirred for 2 hours at room temperature. Usual working-up and recrystallisation of the crude product from hexane/ether gave 245 mg of 3P - hydroxy 17ap - propionyloxy - D - homoestra - 4,16 - diene of melting point 870-880C.
Example 3 A solution of 0.46 g of 17a - hydroxy D - homo - 19 - nor - l7a - pregna 4,16 - dien - 20 - yn - 3 - one in 20 ml of methanol was treated at 250C whilst stirring with excess solid sodium borohydride. After stirring for 2 hours under argon, the mixture was decomposed carefully with aqueous acetic acid, then made neutral by the addition of aqueous bicarbonate solution and extracted with ether. The crude product obtained after washing with water, drying over sodium sulphate and evaporating on a rotary evaporator was adsorbed on 50 g of silica gel (0.060.2 mm).Elution with hexane/ethyl acetate (2:1) yielded 17a(u - ethynyl - 3,B,17ass - dihydroxy - D - homoestra - 4,16 - diene of melting point 176.50--177.50C (from ether/hexane).
Example 4 500 mg of 17ap - hydroxy - D homoestra - 4,16 - dien - 3 - one were left to stand in 3 ml of pyridine and 0.75 ml of valeric acid anhydride for 25 hours at room temperature. After the usual working-up and -chromatography, there were obtained 566 mg of 17a- valeryloxy - D - homoestra - 4,16 - dien - 3 - one in the form of an oil.
500 mg of the aforementioned valerate were dissolved in 50 ml of tetrahydrofuran, treated with 1.185 mg of lithium aluminium tri(tert.butoxy)hydride and stirred at 200C under nitrogen for 4 hours. After working up and chromatography, there were obtained 280 mg of oily 3P - hydroxy 17ap - valeryloxy - D - homoestra - 4,16 *diene.
Example 5 g g of 3P,17ap-diacetoxy - D homoestra - 4,16 - diene were stirred at room temperature for 1 hour under argon with 16 ml of methanol and a solution of 250 mg of potassium carbonate in 3.5 ml of water. The mixture was then poured into sodium chloride solution and extracted with methylene chloride. After washing, drying and evaporation of the extract, there was obtained 3p,17ap - dihydroxy - D homoestra - 4,16 - diene.
Example 6 A solution of 2.9 g of 3P - hydroxy - D homoestra - 4,16 - dien - 17a - one in 20 ml of tetrahydrofuran was treated under argon with 7.5 ml of a 1.5 - M solution of lithium methyl in diethyl ether. The mixture was stirred overnight at room temperature, poured into ice-water and extracted with diethyl ether. The ethereal extracts were washed with water, dried and evaporated.
The residue was recrystallised from acetone and yielded 3P,17ap - dihydroxy - 17aa - methyl - D - homoestra - 4,16 - diene.
The following Example illustrates a typical pharamaceutical preparation containing one of the D - homosteroids provided by the present invention: Example A A tablet for oral adiminstration can contain the following ingredients: 17aa - Ethynyl - 3A,17a dihydroxy - D - homoestra - 4,16 - diene 1 mg Lactose 60 mg Maize starch 37 mg Talc 1.8 mg Magnesium stearate 0.2 mg Total weight 100 mg WHAT WE CLAIM IS: 1) D-Homosteroids of the general formula
wherein R'3 represents a lower alkyl group, R17 represents a hydrogen atom or an acyl or lower alkyl group and Rl7a represents a hydrogen atom or a lower alkyl, ethynyl, 1 propynyl, vinyl, chloroethynyl, butadiynyl or propadienyl group.
2) D-Homosteroids according to claim 1, wherein R'3 represents a methyl or ethyl group, R1'aa represents a hydrogen atom or a methyl group and R17 represents a hydrogen atom or a lower alkanoyl group.
3) 3P,17ap - Dihydroxy - D homoestra - 4,16 - diene.
4) 3p - Hydroxy -17ap - propionyloxy D - homoestra - 4,16 - diene.
5) 3 - Hydroxy - 17aA-valeryloxy - D homoestra - 4,16 - diene.
6) 17air - Ethynyl - 3p,17ap dihydroxy - D - homoestra - 4,16 - diene.
7) A process for the manufacture of the D - homosteroids of formula I given in claim 1, which process comprises (a) reducing the 3-keto group and any
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (12)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    homoestra - 4,16 - diene - 3 - one were dissolved in 17.6 ml of isopropanol and treated with 176 mg of sodium borohydride.
    The mixture was stirred for 2 hours at room temperature. Usual working-up and recrystallisation of the crude product from hexane/ether gave 245 mg of 3P - hydroxy 17ap - propionyloxy - D - homoestra - 4,16 - diene of melting point 870-880C.
    Example 3 A solution of 0.46 g of 17a - hydroxy D - homo - 19 - nor - l7a - pregna 4,16 - dien - 20 - yn - 3 - one in 20 ml of methanol was treated at 250C whilst stirring with excess solid sodium borohydride. After stirring for 2 hours under argon, the mixture was decomposed carefully with aqueous acetic acid, then made neutral by the addition of aqueous bicarbonate solution and extracted with ether. The crude product obtained after washing with water, drying over sodium sulphate and evaporating on a rotary evaporator was adsorbed on 50 g of silica gel (0.060.2 mm).Elution with hexane/ethyl acetate (2:1) yielded 17a(u - ethynyl - 3,B,17ass - dihydroxy - D - homoestra - 4,16 - diene of melting point 176.50--177.50C (from ether/hexane).
    Example 4
    500 mg of 17ap - hydroxy - D homoestra - 4,16 - dien - 3 - one were left to stand in 3 ml of pyridine and 0.75 ml of valeric acid anhydride for 25 hours at room temperature. After the usual working-up and -chromatography, there were obtained
    566 mg of 17a- valeryloxy - D - homoestra - 4,16 - dien - 3 - one in the form of an oil.
    500 mg of the aforementioned valerate were dissolved in 50 ml of tetrahydrofuran, treated with 1.185 mg of lithium aluminium tri(tert.butoxy)hydride and stirred at 200C under nitrogen for 4 hours. After working up and chromatography, there were obtained 280 mg of oily 3P - hydroxy 17ap - valeryloxy - D - homoestra - 4,16 *diene.
    Example 5 g g of 3P,17ap-diacetoxy - D homoestra - 4,16 - diene were stirred at room temperature for 1 hour under argon with 16 ml of methanol and a solution of 250 mg of potassium carbonate in 3.5 ml of water. The mixture was then poured into sodium chloride solution and extracted with methylene chloride. After washing, drying and evaporation of the extract, there was obtained 3p,17ap - dihydroxy - D homoestra - 4,16 - diene.
    Example 6 A solution of 2.9 g of 3P - hydroxy - D homoestra - 4,16 - dien - 17a - one in 20 ml of tetrahydrofuran was treated under argon with 7.5 ml of a 1.5 - M solution of lithium methyl in diethyl ether. The mixture was stirred overnight at room temperature, poured into ice-water and extracted with diethyl ether. The ethereal extracts were washed with water, dried and evaporated.
    The residue was recrystallised from acetone and yielded 3P,17ap - dihydroxy - 17aa - methyl - D - homoestra - 4,16 - diene.
    The following Example illustrates a typical pharamaceutical preparation containing one of the D - homosteroids provided by the present invention: Example A A tablet for oral adiminstration can contain the following ingredients: 17aa - Ethynyl - 3A,17a dihydroxy - D - homoestra - 4,16 - diene 1 mg Lactose 60 mg Maize starch 37 mg Talc 1.8 mg Magnesium stearate 0.2 mg Total weight 100 mg WHAT WE CLAIM IS: 1) D-Homosteroids of the general formula
    wherein R'3 represents a lower alkyl group, R17 represents a hydrogen atom or an acyl or lower alkyl group and Rl7a represents a hydrogen atom or a lower alkyl, ethynyl, 1 propynyl, vinyl, chloroethynyl, butadiynyl or propadienyl group.
  2. 2) D-Homosteroids according to claim 1, wherein R'3 represents a methyl or ethyl group, R1'aa represents a hydrogen atom or a methyl group and R17 represents a hydrogen atom or a lower alkanoyl group.
  3. 3) 3P,17ap - Dihydroxy - D homoestra - 4,16 - diene.
  4. 4) 3p - Hydroxy -17ap - propionyloxy D - homoestra - 4,16 - diene.
  5. 5) 3 - Hydroxy - 17aA-valeryloxy - D homoestra - 4,16 - diene.
  6. 6) 17air - Ethynyl - 3p,17ap dihydroxy - D - homoestra - 4,16 - diene.
  7. 7) A process for the manufacture of the D - homosteroids of formula I given in claim 1, which process comprises (a) reducing the 3-keto group and any
    17a-keto group which may be present in a D-homosteroid of the general formula
    wherein X represents a grouping OR1'aP and Y represents a grouping R17aa or X and Y together represent an oxo group and R'3, R'7"P and R17"" have the significance given in claim 1, to the hydroxy group, or (b) hydrolysing the 3-acyl group in a homosteroid of the general formula
    wherein R'3, R17aCI and Rl7acr have the significance given in claim 1, or (c) reacting a D-homosteroid of the general formula
    with a metal-organic compound yielding a grouping R178lt.
  8. 8) A process according to claim 7, wherein the 3-keto group in a Dhomosteroid of formula II in which X represents a grouping OR17aP and Y represents a grouping Rl7a is reduced to the hydroxy group or the 3-acyl group in a Dhomosteroid of formula III is hydrolysed.
  9. 9) A process according to claim 7 or claim 8, wherein there is manufactured a Dhomosteroid of formula I in which R'3 represents a methyl or ethyl group, R178 represents a hydrogen atom or a methyl group and Rl7atL represents a hydrogen atom or a lower alkanoyl group.
  10. 10) A process for the manufacture of the D-homosteroids of formula I given in claim 1, substantially as hereinbefore described with reference to any one of Examples 1 to 6.
  11. 11) D-Homosteroids of formula I given in claim 1, when manufactured by the process claimed in any one of claims 7 to 10 or by an obvious chemical equivalent thereof.
  12. 12) A pharmaceutical preparation containing a D-homosteroid of formula I given in claim 1 in association with a compatible pharmaceutical carrier material.
GB15046/77A 1976-04-13 1977-04-12 D-homosteroids Expired GB1569221A (en)

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CH463876 1976-04-13
CH138277 1977-02-04

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JP (1) JPS52125155A (en)
AU (1) AU2404877A (en)
DE (1) DE2715775A1 (en)
ES (1) ES457731A1 (en)
FR (1) FR2348225A1 (en)
GB (1) GB1569221A (en)
GR (1) GR62720B (en)
IL (1) IL51833A0 (en)
LU (1) LU77102A1 (en)
NL (1) NL7703448A (en)
NZ (1) NZ183817A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4788218A (en) * 1984-05-21 1988-11-29 Sri International 17 a β-hydroxy-7 α-methyl-d-homo-19-norandrost-4,16-diene-3-one and the 17-esters thereof: methods of preparation and uses
WO2005021573A1 (en) * 2003-08-21 2005-03-10 Schering Ag Δ15-d-homosteroids having an androgenic effect

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3242892C1 (en) * 1982-11-16 1984-07-12 Schering AG, 1000 Berlin und 4709 Bergkamen Process for the preparation of 17alpha- (Br or J) -ethynyl-17ss-hydroxysteroids

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4788218A (en) * 1984-05-21 1988-11-29 Sri International 17 a β-hydroxy-7 α-methyl-d-homo-19-norandrost-4,16-diene-3-one and the 17-esters thereof: methods of preparation and uses
WO2005021573A1 (en) * 2003-08-21 2005-03-10 Schering Ag Δ15-d-homosteroids having an androgenic effect
US7388003B2 (en) 2003-08-21 2008-06-17 Bayer Schering Pharma Ag Δ15-D-Homosteroids with androgenic action

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NL7703448A (en) 1977-10-17
NZ183817A (en) 1979-03-28
AU2404877A (en) 1978-10-12
LU77102A1 (en) 1978-06-01
IL51833A0 (en) 1977-06-30
ES457731A1 (en) 1978-08-01
FR2348225B1 (en) 1979-03-23
DE2715775A1 (en) 1977-10-27
GR62720B (en) 1979-05-28
JPS52125155A (en) 1977-10-20
FR2348225A1 (en) 1977-11-10

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