GB969083A - Novel polyhydro-phenanthrene derivatives and a process for the manufacture thereof - Google Patents

Novel polyhydro-phenanthrene derivatives and a process for the manufacture thereof

Info

Publication number
GB969083A
GB969083A GB18413/62A GB1841362A GB969083A GB 969083 A GB969083 A GB 969083A GB 18413/62 A GB18413/62 A GB 18413/62A GB 1841362 A GB1841362 A GB 1841362A GB 969083 A GB969083 A GB 969083A
Authority
GB
United Kingdom
Prior art keywords
product
alkyl
group
hydrogen
ethenyl
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
GB18413/62A
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.)
F Hoffmann La Roche AG
Original Assignee
F Hoffmann La Roche AG
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
Application filed by F Hoffmann La Roche AG filed Critical F Hoffmann La Roche AG
Publication of GB969083A publication Critical patent/GB969083A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/30—Unsaturated compounds
    • C07C62/32—Unsaturated compounds containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
    • C07C35/37—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings
    • C07C35/42—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings derived from the phenanthrene skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/20—Preparation of ethers by reactions not forming ether-oxygen bonds by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/29—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with halogen-containing compounds which may be formed in situ
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Steroid Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pyrrole Compounds (AREA)

Abstract

The invention comprises compounds of the formula: <FORM:0969083/C1/1> R2 is hydrogen, C1-7 alkyl, ethynyl or ethenyl and A wherein R1 is hydrogen or C1-7 alkyl; R2 is hydrogen, C1-7 alkyl, ethynyl or ethenyl and A is one of the following groups: <FORM:0969083/C1/2> <FORM:0969083/C1/3> <FORM:0969083/C1/4> <FORM:0969083/C1/5> and their preparation by oxidizing a ketone of the formula: <FORM:0969083/C1/6> to the corresponding acid, esterifying this and reducing the ester with a mixed metal hydride to give a product wherein R1 and R2 are both hydrogen, or by reducing the ketone II with a mixed metal hydride, catalytically activated hydrogen or aluminium isopropoxide to give a product wherein only R1 is hydrogen, or by reacting the ketone II with an alkyl Grignard reagent to give a product wherein R1 and R2 are the same or different alkyl groups, or by reacting the ketone II with an alkali metal acetylide to give a product wherein R1 is alkyl and R2 is ethynyl and then, if desired, reducing the ethynyl group to an ethenyl or ethyl group (any 7-oxo group being protected if desired when organo metallic reagents are being used); and then, if desired, converting the "A" group therein into an "A" group characterized by a higher number by reaction with lithium in liquid ammonia and hydrolysis of the reaction product (A1-->A2), by reduction with lithium in liquid ammonia (A2-->A3) and/or by reduction with a mixed metal hydride or with aluminium isopropoxide (A3-->A4) or by appropriate sequential combination of these reactions. In particular, the keto group of a 2-alkanoyl -7- methoxy-1, 2, 3, 4, 4a, 9, 10, 10a-octa hydrophenanthrene may be acetalized, the product reduced with lithium and an alcohol in liquid ammonia and the reduction product hydrolysed, the hydrolysis product reduced with lithium in liquid ammonia if the tetra deca hydro product is required, the 7-oxo group in the resulting compounds protected by pyrrolidine enamine formation, and the protected compound reduced by one of the processes of the invention for the formation of the C(OH)R1R2 group. Other variants of the process of the invention are also described, some intermediates having 4b-8 and 6-7 double bonds in the "A" ring, and others having a saturated "A" ring, and detailed examples of a number of these are provided. 2-Alkanoyl -7- methoxy-1, 2, 3, 4, 9, 10-hexahydrophenanthrenes are prepared by reacting 1-ethenyl -6- methoxy-3, 4-dihydronaphthalene with alkyl ethenyl ketones to give 2-alkanoyl -7-methoxy-1, 2, 3, 9, 10, 10a-hexahydrophenanthrenes and then isomerizing these. They may be reduced, after acetal formation, to the corresponding octahydro compounds. The phenanthrene derivatives of the invention, which are stated to be useful as hypocholesterolenic or antifertility agents, antiandrogens, estrogens or anabolic agents, may be made up into pharmaceutical compositions with suitable carriers. They may take the form of tablets, dragees, suppositories, capsules, solutions, suspensions or emulsions and may contain preserving, stabilizing, wetting or emulsifying agents, salts for varying the osmotic pressure or buffers. Specifications 667,552 and 825,907 are referred to.
GB18413/62A 1961-05-15 1962-05-14 Novel polyhydro-phenanthrene derivatives and a process for the manufacture thereof Expired GB969083A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10988261A 1961-05-15 1961-05-15

Publications (1)

Publication Number Publication Date
GB969083A true GB969083A (en) 1964-09-09

Family

ID=22330073

Family Applications (1)

Application Number Title Priority Date Filing Date
GB18413/62A Expired GB969083A (en) 1961-05-15 1962-05-14 Novel polyhydro-phenanthrene derivatives and a process for the manufacture thereof

Country Status (7)

Country Link
BE (1) BE617616A (en)
CH (1) CH408910A (en)
DE (2) DE1518983A1 (en)
DK (3) DK103183C (en)
ES (1) ES277295A1 (en)
FR (1) FR2110M (en)
GB (1) GB969083A (en)

Also Published As

Publication number Publication date
BE617616A (en) 1962-11-14
DE1443986A1 (en) 1969-03-20
DE1518983A1 (en) 1969-08-21
ES277295A1 (en) 1962-10-16
CH408910A (en) 1966-03-15
FR2110M (en) 1963-10-28
DK103073C (en) 1965-11-15
DK103183C (en) 1965-11-29
DK104457C (en) 1966-05-23

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