GB1055353A - Process for the preparation of 3-hydroxy-and 3-alkoxy-estratrienes and intermediates therefor - Google Patents

Process for the preparation of 3-hydroxy-and 3-alkoxy-estratrienes and intermediates therefor

Info

Publication number
GB1055353A
GB1055353A GB50273/63A GB5027363A GB1055353A GB 1055353 A GB1055353 A GB 1055353A GB 50273/63 A GB50273/63 A GB 50273/63A GB 5027363 A GB5027363 A GB 5027363A GB 1055353 A GB1055353 A GB 1055353A
Authority
GB
United Kingdom
Prior art keywords
cyano
androstene
give
formula
dione
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
GB50273/63A
Inventor
Alberto Ercoli
Rinaldo Gardi
Cesare Pedrali
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Francesco Vismara SpA
Original Assignee
Francesco Vismara SpA
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 claimed from IT1999363A external-priority patent/IT1051710B/en
Application filed by Francesco Vismara SpA filed Critical Francesco Vismara SpA
Publication of GB1055353A publication Critical patent/GB1055353A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
    • 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
    • C07J21/00—Normal steroids containing carbon, hydrogen, halogen or oxygen having an oxygen-containing hetero ring spiro-condensed with the cyclopenta(a)hydrophenanthrene skeleton
    • 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
    • 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
    • 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)

Abstract

The invention comprises compounds of the Formulae I and II, wherein X2 represents a group of the Formula III or IV and a process for preparing compounds of the Formula V or VI, wherein X represents one of the groups of the Formula VII, lower alkyl and acyl radicals having 1 to 4 carbon atoms and the term lower alkynyl denotes ethynyl, and R represents an unsubstituted or hydroxy substituted saturated or unsaturated, straight or branched aliphatic hydrocarbon radical of 1 to 18 carbon atoms by reacting a compound of the Formula VIII or a compound of the Formula IX or a mixture thereof, when X1 represents one of the groups of the Formula X, wherein Z represents a ketonic oxygen atom or a C1- 14 alkylene ketal group with a mineral or organic acid having a pK of less than 1.5 m. solution in an inert, non-alcoholic organic solvent (when the 3-substituent of the product is -OH) or in an alcohol of the formula R-OH (when the 3-substituent of the product is -OR) and the preparation of compounds of the Formulae VIII and IX by epoxidation of the corresponding D 5(6) and D 5(10) steroids with a per acid or with hydrogen peroxide. <FORM:1055353/C2/1> <FORM:1055353/C2/2> <FORM:1055353/C2/3> <FORM:1055353/C2/4> <FORM:1055353/C2/5> <FORM:1055353/C2/6> <FORM:1055353/C2/7> <FORM:1055353/C2/8> <FORM:1055353/C2/9> <FORM:1055353/C2/100> 19 - Nor - 5(6) - androstene (and -5(10) - androstene) -3,17 - dione - 3,17 - bis - (ethylene ketal) are prepared by acetylating 3b ,17b -dihydroxy-5a androstan-6-one, to give the 3b ,17b -diacetyloxy derivative reducing the latter with sodium borohydride to give the 3,17-diacetate of 5a -androstane 3b ,6b ,17b -triol which, with nitrosyl chloride gives 5a - androstane - 3b ,17b - diacetoxy - 6b - yl nitrite, irradiating the latter with ultra-violet radiation to give the nitroso dimer corresponding to 19-oximino - 5a - androstane - 3b ,6b ,17b - triol,3,17-diacetate which is treated with phosphorus oxychloride to give 10b -cyano-19-nor-5-androstene-3b ,17b -diol, diacetate followed by hydrolysis to give 10b - cyano - 19 - nor - 5 - androstene - 3b ,17b -diol which on treatment with chromic acid gives 10b - cyano - 19 - nor - 5 - androstene - 3,17 - dione, converting the latter its 3,17-bis-(ethylene ketal) and treating with sodium metal in absolute ethanol. In a similar manner to the above, 19-nor-5(6) (and 5(10)) - pregnene - 3,20 - dione, 3,20 - bis - (ethylene ketal) are prepared from the 3,20-diacetate of 5a -pregnane-3b ,20b -diol-6-one, via 5a -pregnane - 3b ,6b ,20b - triol, 3,20 - diacetate; 3b , 20b - diacetoxy - 5a - pregnan - 6b - yl - nitrite; the 3b ,20b - diacetoxy - 19 - nitroso - 5a - pregnan - 6b -ol dimer, together with 3b ,20b -diacetoxy-19-oximino -5a - pregnan - 6b - ol; 10b - cyano - 19 - nor - 5 - pregnene - 3b ,20b - diol - diacetate; 10b -cyano-19 - nor - 5 - pregnene - 3b ,20b - diol; 10b - cyano-19 - nor - 5 - pregnene - 3,20 - dione and 10b -cyano - 19 - nor - 5 - pregnene-3,20 -dione. The D 5(6) and D 5(10) isomers of 17a -ethynyl-19-nor - androsten - 17b - ol - 3 - one - 3 - ethylene ketal may be prepared from 10b -cyano-19-nor-5-androstene-3b ,17b -diol by reduction with cyclohexonone aluminium isopropoxide to give 10b -cyano - 19 - nor - D 4 - androstene - 3,17 - dione, conversion to the 3-ethylene ketal treatment with acetylene to give 10b -cyano-17a -ethynyl-19-nor-5-androsten - 17b - ol - 3 - one - 3 - ethylene ketal followed by treatment with lithium in liquid ammonia.
GB50273/63A 1962-12-19 1963-12-19 Process for the preparation of 3-hydroxy-and 3-alkoxy-estratrienes and intermediates therefor Expired GB1055353A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2485662 1962-12-19
IT1999363A IT1051710B (en) 1963-09-30 1963-09-30 PROCEDURE FOR THE PREPARATION OF 3 BONES AND 3 EXTRATRIENAL ALCOSS

Publications (1)

Publication Number Publication Date
GB1055353A true GB1055353A (en) 1967-01-18

Family

ID=26327365

Family Applications (1)

Application Number Title Priority Date Filing Date
GB50273/63A Expired GB1055353A (en) 1962-12-19 1963-12-19 Process for the preparation of 3-hydroxy-and 3-alkoxy-estratrienes and intermediates therefor

Country Status (6)

Country Link
US (1) US3231567A (en)
BE (1) BE641351A (en)
CH (1) CH441304A (en)
DE (1) DE1223379B (en)
DK (1) DK104301C (en)
GB (1) GB1055353A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689512A (en) * 1970-10-06 1972-09-05 American Home Prod Novel 3-etherified-1,3,5(10)-triene-steroids and process thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3381003A (en) * 1965-06-01 1968-04-30 Merck & Co Inc 3-keto-13beta-alkyl-17beta-acetyl-gona-4-ene-17alpha-ol compounds and processes of preparing them
US3487155A (en) * 1968-02-19 1969-12-30 Sandoz Ag Substituted estradiol alkyl ethers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2378918A (en) * 1941-08-19 1945-06-26 Squibb & Sons Inc Cyclic ketals of keto-cyclopentanoperhydrophenanthrenes and methods of preparing them
US2729654A (en) * 1954-05-19 1956-01-03 Searle & Co 10-hydroxy-3-ketosteroids

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689512A (en) * 1970-10-06 1972-09-05 American Home Prod Novel 3-etherified-1,3,5(10)-triene-steroids and process thereof

Also Published As

Publication number Publication date
US3231567A (en) 1966-01-25
CH441304A (en) 1967-08-15
DK104301C (en) 1966-05-02
BE641351A (en)
DE1223379B (en) 1966-08-25

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