GB1211697A - Method for preparing acetylenic compounds - Google Patents

Method for preparing acetylenic compounds

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GB1211697A
GB1211697A GB49203/67A GB4920367A GB1211697A GB 1211697 A GB1211697 A GB 1211697A GB 49203/67 A GB49203/67 A GB 49203/67A GB 4920367 A GB4920367 A GB 4920367A GB 1211697 A GB1211697 A GB 1211697A
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oxo
yne
seco
bicyclo
pentadec
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GB49203/67A
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Albert Eschenmoser
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • 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
    • C07C29/145—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 with hydrogen or hydrogen-containing gases
    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
    • 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
    • C07C35/23—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 hydroxy on a condensed ring system having two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/516—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of nitrogen-containing compounds to >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
    • C07J71/0005—Oxygen-containing hetero ring
    • C07J71/001—Oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/32—All rings being cycloaliphatic the ring system containing at least eleven carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

1,211,697. Acetylenic compounds. A. ESCHENMOSER. 30 Oct., 1967 [1 Nov., 1966; 23 Dec., 1966; 10 Feb., 1967 (2); 9 March, 1967], No. 49203/67. Headings C2C and C2U. [Also in Division C5] Acetylenic compounds of the Formula (I) are prepared by fragmentation of compounds of the Formula (II) with loss of molecular nitrogen (R 1 and R 2 and/or R 3 and R 4 are directly bonded to each other, and, if desired, R 2 and R 3 and/or R 1 and R 4 are also directly bonded to each other; R 1 , R 2 , R 3 and R 4 are each organic radicals, mono-, di- or tri-valent, or, when singly bonded, may also be H; X<SP>1</SP> is N = R 5 in which R 5 is ethyleneimino, free, esterified or etherified hydroxy, or amino substituted by a nucleofuge, particularly tosyl; and X is a reactive esterified hydroxyl group and Y is a free hydroxyl group, or X and Y together are an oxido group). Fragmentation can occur under the very conditions under which the starting oximes and hydrazones are formed, e.g. when the corresponding carbonyl compounds are reacted with a substituted hydrazine or with a reactive ether or ester of hydroxylamine. Preferred starting compounds include (a) carbocyclic or heterocyclic compounds with the double bond in a ring but not having either of its carbon atoms common to 2 rings and the conjugated carbonyl group in a side-chain, e.g. 1 - propionyl - cyclohexa - 1,4 - diene; (b) carbocyclic or heterocyclic compounds with both the keto group and the double bond in the same ring, the carbon atoms belonging to the double bond not being involved in any other ring, e.g. 2,3 - dimethyl - cyclopent - 2 - en - 1 - one; (c) an at least bicyclic carbocyclic or heterocyclic compound with the double bond forming the fusion face of 2 rings and the keto group being in one of these rings, e.g. bicyclo [10.3.0] pentadec - 1(12) - en - 13 - one; (d) cyclic ketones with a double bond between a carbon atom alpha to the keto group and a carbon atom common to two rings, e.g. 6-methyl-bicyclo [4-4-0] dec-1(2)-en-3-one; and (e) as (a) but having the carbon atom of the double bond more remote from the side chain common to 2 rings, e.g. 10,10-dimethyl-4-acetyl-tricyclo [7.1.1.0<SP>3.8</SP>] undec-3(4)-ene; and these lead respectively to (a) open chain compounds with a carbonyl group and a triple bond or cyclic compounds with the carbonyl group and the triple bond in 2 different side-chains; (b) as (a), but when cyclic having the carbonyl group and triple bond not necessarily in different sidechains; (c) mono or poly-cyclic compounds with the carbonyl group and triple bond in the same ring; (d) substituted cyclic compounds in which the carbonyl group is in a ring and the triple bond is in a side-chain to this ring; and (e) similar to (d). Steroids with a nuclear double bond and a nuclear or side-chain, e.g. 20, keto group are especially preferred starting materials. Hydrazones carrying a nucleofuge may be fragmented by acidic reagents, inorganic or organic bases, or sodium hydride in DMS, or thermally or photochemically, or by contact with polar adsorption agents, e.g. silica gel, or ion exchange resins. In the spontaneous decomposition of hydrazones referred to above the product may itself be converted to a hydrazone if excess of hydrazine reagent is present; these hydrazones may then be cleaved to the free ketones. Aldehyde products formed in the presence of alcohols may be isolated as acetals or hemi-acetals. The oximes are fragmented in a basic medium with reactive esters of hydroxylamine. The products of the process, many of which are new, may be converted to known odiferous compounds and flavours, e.g. by catalytic hydrogenation or partial hydrogenation. The seco-steroid products may be converted to biologically active steroids. Examples describe the preparation of the following starting materials and intermediates, products of the process of the invention and compounds into which these products are converted: 1,12 - epoxy - bicyclo [10.3.0] pentadecan - 13 - one and its tosyl hydrazone, cyclopentadec - 4 - yn - 1 - one, cyclopentadec - 4 - en- 1 - one, cyclopentadecanone, 3 - methyl - cyclopentadec - 4 - yn - 1 - one, 3 - methylcyclopentadec - cis - 4 - en - 1 - one, 3 - methyl - cyclopentadecan - 1 - one, 2 - ethyl - 2,3 - epoxy - cyclopentanone, hept - 4 - yn - 1 - al, cis - hept - 4 - en- 1 - al, epoxy -jasmone, undec - 8 - en - 5 - yn-2- one, undecan - 2 - one, 2 - methyl - 2,3 - oxidocyclohexan - 1 - one, hept - 5 - yn - 1 - al, cis - hept- 5 - en - 1 - al, the tosyl hydrazone of epoxy-isophorone, 4,4 - dimethylhept - 6 - yn - 2 - one, 4,4 - dimethylhept - 6 - en - 2 - one, 4,4 - dimethyl heptan - 2 - one, 2,3 - dihydroxy - 3,5,5- trimethyl - cyclohexanone - (1) and its 3-mesylate and the oxime of the last-named, the epoxide of cedranal, 1 - formylmethyl - 3 - ethynyl - 4,4,8- trimethyl - bicyclo [3.3.0] octane, 4 - acetoxy-4- cyano - 10,10 - dimethyl - tricyclo [7.1.1.0<SP>3.8</SP>]- undec - 7 - ene, 10,10 - dimethyl - tricyclo [7.1.1.0<SP>3.8</SP>] undec - 3(8) - en - 4 - one and its epoxide, 10,10 - dimethyl - bicyclo [7.1.1]- undec - 6 - yn - 2 - one, the epoxide of piperitone, 3 - isopropylhept - 1 - yn - 6 - one, 3 - isopropylheptan - 6 - one, the epoxide of 2 - n - pentylcyclopent - 2 - en - 1 - one, dec - 4 - yn - 1 - al, 3 - methyl - 2,3 - oxido - cyclohexan - 1 - one, hept - 6 - yn - 2 - one, hept - 6 - en - 2 - one, heptan - 2 - one, 1,2 - epoxy - 6 - methylbicyclo [4.4.0] decan - 3 - one, 2 - methyl - 2 - (but - 3 - yn - 1 - yl) - cyclohexan - 1 - one, 1 - propionylcyclohexa - 1,4 - diene, 1,2 - epoxy - 1 - propionylcyclohex - 4 - ene and its tosyl hydrazone, cisnon - 3 - en - 6 - yn - 1 - al, cis,cis - nona - 3 6 - dien - 1 - al, the tosyl hydrazone of 14 - methylbicyclo [10.3.0] pentadec - 1(12) - en - 13 - one, 1,7 - epoxybicyclo [5.3.0] decan - 2 - one, cyclodec - 5 - yn - 1 - one, 1,6 - epoxy - bicyclo [4.4.0]- decan - 2 - one, cyclodec - 5 - yn - 1 - one, 7,7- dimethyl - 1 - hydroxyticyclo [4.4.0] decan - 3 - one and its epoxide, 3,3-dimethyl-2-(but-3-yn-1-yl)- cyclohexan - 1 - one, bicyclo [9.4.0] pentadec- 1(11)-en- 12-one and its epoxide, cyclopentadec-5- yn - 1 - one, cyclopentadec - 5 - en - 1 - one, 14- methylbicyclo [10.3.0] pentadec - 13 - ol, 14- methyl - bicyclo [10.3.0] pentadec - 1(12) - ene, 3- methyl - cyclopentadecane - 1,5 - dione, 14- methylbicyclo [9.4.0] pentadec - 1(11) - en - 12-one and its epoxide, 3 - methylcyclopentadec - 5 - yn - 1 - one, 3 - methylcyclopentadec - 5 - en-l-one, bicyclo [9.4.0] pentadec - 1(11) - en - 12 - one and its tosyl hydrazone, bicyclo [9.4.0] pentadecan- 12 - ol, bicyclo [9.4.0] pentadec - 1(11) - ene, cyclopentadecane - 1,6 - d 7 one, bicyclo [10.3.0] pentadec - 1(12) - en - 2 - one and its epoxide, cyclopentadec - 5 - yn - 1 - one, bicyclo [10.4.0] hexadec - 1(12) - en - 13 - one and its epoxide, cyclohexadec - 5 - yn - 1 - one, cis - cyclohexadec- 5 - en - 1 - one, cyclohexadecanone; cycloheptadec - 4 - yn - 1 - one, cycloheptadec-5-yn-1-one, cycloheptadec - 6 - yn - 1 - one, and the corresponding cycloheptadecenones; undec-5-yn-2- one, undec - 5 - en - 2 - one, 1,2 - epoxy - 2 - hexylcyclopentanone, undec - 4 - yn - 1 - al, cis-undec- 4 - en - 1 - al, 2 - butyl - 2,3 - epoxycyclopentan-1- one, non - 4 - yn - 1 - al, cis - non - 4 - en - 1 - al, 2 - heptyl - 2,3 - epoxycyclopentan - 1 - one, dodec- 4 - yn - 1 - al, cis - dodec - 4 - en - 1 - al, 2-decyl- 2,3 - epoxycyclopentan - 1 - one, pentadec - 4 - yn- 1 - al, cis - pentadec - 4 - en - 1 - al, 2,3 - epoxy-2- ethyl - cyclopentan - 1 - one, hept - 4 - yn - 1 - al, undeca - 4,8 - dien - 2 - one, dec - 4 - yn - 1 - al, cis - dec - 4 - en - 1 - al, 1,2 - epoxy - 1 - propionylcyclopentane, hept - 5 - yn - 1 - al, 1 - oxo - 17#- acetoxy - 1,2 - seco - 5α - androst - 2 - yne, 5-oxo- 11# - hydroxy - 17α,20; 20,21 - bismethylenedioxy-4,5-seco-pregn-3-yne and the corresponding 19 - nor - compound, 5,20 - dioxo-11#, 17α - 21 - trihydroxy - 4,5 - secopregn - 3 - yne, 3# - acetoxy - 16 - oxo - 16,17 - seco - #<SP>5</SP>-pregnen - 17(20) - yne and its diethyl acetal, 5- oxo - 17# - acetoxy - 4,5 - seco - androst - 3 - yne and the corresponding 19-nor compound, 5,20- dioxo - 21 - hydroxy - 4,5 - seco - pregn - 3 - yne and its 21-acetate and 20-ethylene ketal, the tosyl hydrazone of 3#-acetoxy-16-oxo- 16,17- seco - #<SP>5</SP> - pregnen - 17(20) - yne, 3 - methoxy- 16 - oxo - 16,17 - seco - #<SP>1,3,5(10)</SP> - 19 - norpregnatrien - 17(20) - yne and its dimethyl and diethyl acetals, 5-oxo-17α-ethynyl-17#-hydroxy- 4,5 - seco - 19 - norandrost - 3 - yne, 3#,17#- diacetoxy - 5 - oxo - 5,6 - seco - androst - 6 - yne, 5,17 - dioxo - 4,5 - seco - estr - 3 - yne, 5,20- dioxo - 4,5 - seco - pregn - 3 - yne, 3# - hydroxy- 9 - oxo - 9,11 - seco - 5α - spirost - 11 - yne, 4- methyl - 5 - oxo - 17# - acetoxy - 4,5 - secoandrost - 3 - yne, 3# - acetoxy - 16 - oxo - 16- methyl - 16,17 - seco - #<SP>5</SP> pregn -17(20) - yne, 3 - oxo 17# - acetoxy - 2,3 - seco - 5α - androst- 1 - yne, 3,3,17,17 - bisethylenedioxy - 10 - oxo- 5,10 - seco - estr - 5(6) - yne and the corresponding 17-one, 5 - oxo - 17# - carbomethoxy- 4,5 - seco - androst - 3 - yne and 5 - oxo - 4,5- seco-cholest-3-yne. Steroid starting materials prepared are 3-oxo- 4,5 - oxido - 20,20 - ethylenedioxy - 21 - hydroxypregnane (by ketalizing 3,21-dihydroxy-20-oxo- #<SP>5</SP> - pregnane, Oppenauer oxidation and epoxidation of the #<SP>4</SP> double bond); 3-oxo-4#,5-oxido- 17# - hydroxy - 17α - ethynyl - 19 - nor - androstane; 3 - methoxy - 16α,17α - oxido - 20 - oxo- #<SP>1,3,5(10)</SP> - 19 - norpregnatriene; 3#,17# - diacetoxy - 5,6 - oxido - 7 - oxo - androstane (mixture of epimers) and its tosyl hydrazone; the oximes of 17α,20,20,21 - bismethylenedioxy - 3 - oxo - 4#,5#- and 4α,5α - epoxy - 11# - hydroxypregnanes, 3 - oxo
GB49203/67A 1966-11-01 1967-10-30 Method for preparing acetylenic compounds Expired GB1211697A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CH1581566A CH482637A (en) 1966-11-01 1966-11-01 Process for the production of acetylene compounds
CH1847766A CH495348A (en) 1966-11-01 1966-12-23 Process for the preparation of a-oxo-a, B-seco-steroid-B (y) -ynes
CH202667A CH542193A (en) 1966-11-01 1967-02-10 Process for the manufacture of secosteroids
CH202567A CH521297A (en) 1966-11-01 1967-02-10 Process for the production of acetylene compounds
CH342467 1967-03-09

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GB1211697A true GB1211697A (en) 1970-11-11

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GB49203/67A Expired GB1211697A (en) 1966-11-01 1967-10-30 Method for preparing acetylenic compounds

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JP (1) JPS4818214B1 (en)
BE (1) BE705698A (en)
CH (4) CH482637A (en)
DE (1) DE1643948A1 (en)
FR (1) FR1577241A (en)
GB (1) GB1211697A (en)
NL (1) NL6714663A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052422A (en) * 1974-11-08 1977-10-04 E. R. Squibb & Sons, Inc. 4,5-secopregnane derivatives
US4127589A (en) 1974-11-08 1978-11-28 E. R. Squibb & Sons, Inc. 4,5-Seco-steroids
US4235824A (en) * 1976-07-27 1980-11-25 Naarden International N.V. Method for the preparation of fragrances, and method for the preparation of perfume compositions
WO2005077875A1 (en) * 2004-02-16 2005-08-25 Firmenich Sa A process for the preparation of optically active cyclohexenones
WO2016193330A1 (en) * 2015-06-03 2016-12-08 Basf Se Process for preparing 3-methylcyclopentadecane-1,5-dione

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50140727U (en) * 1974-05-08 1975-11-19
JPS5175340U (en) * 1974-12-10 1976-06-14
US4328383A (en) * 1980-01-18 1982-05-04 S. A. Firmenich Process for preparing unsaturated bicyclic hydrocarbons

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052422A (en) * 1974-11-08 1977-10-04 E. R. Squibb & Sons, Inc. 4,5-secopregnane derivatives
US4127589A (en) 1974-11-08 1978-11-28 E. R. Squibb & Sons, Inc. 4,5-Seco-steroids
US4235824A (en) * 1976-07-27 1980-11-25 Naarden International N.V. Method for the preparation of fragrances, and method for the preparation of perfume compositions
WO2005077875A1 (en) * 2004-02-16 2005-08-25 Firmenich Sa A process for the preparation of optically active cyclohexenones
US7332633B2 (en) 2004-02-16 2008-02-19 Firmenich Sa Process for the preparation of optically active cyclohexenones
WO2016193330A1 (en) * 2015-06-03 2016-12-08 Basf Se Process for preparing 3-methylcyclopentadecane-1,5-dione
US10053409B2 (en) 2015-06-03 2018-08-21 Basf Se Process for preparing 3-methylcyclopentadecane-1,5-dione

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DE1643948A1 (en) 1972-06-08
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CH482637A (en) 1969-12-15
BE705698A (en) 1968-03-01
CH542193A (en) 1973-11-15
JPS4818214B1 (en) 1973-06-04
FR1577241A (en) 1969-08-08
CH495348A (en) 1970-08-31

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