GB757998A - Manufacture of new tricyclic ketones - Google Patents
Manufacture of new tricyclic ketonesInfo
- Publication number
- GB757998A GB757998A GB13156/53A GB1315653A GB757998A GB 757998 A GB757998 A GB 757998A GB 13156/53 A GB13156/53 A GB 13156/53A GB 1315653 A GB1315653 A GB 1315653A GB 757998 A GB757998 A GB 757998A
- Authority
- GB
- United Kingdom
- Prior art keywords
- methyl
- oxo
- prepared
- propionic acid
- dioxo
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/347—Saturated compounds containing more than one carboxyl group containing keto groups
- C07C59/353—Saturated compounds containing more than one carboxyl group containing keto groups containing rings
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention comprises (1) compounds of formula <FORM:0757998/IV(a)/1> wherein n is 1 or 2 and a free or functionally converted oxo (e.g. cyclic ketal) group is present in the a 1-position; (2) the selective reduction thereof to the corresponding a 1-hydroxyl derivatives; (3) the conversion of the a 1-hydroxyl group into a functional derivative thereof (e.g. an esterified hydroxyl group); and (4) the splitting off of a free or functionally converted a 1-hydroxyl group with the formation of a double bond between the a 1 and b 1 carbon atoms. Diketones of the above formula are prepared by treating a compound of formula <FORM:0757998/IV(a)/2> wherein the oxo groups are protected and X represent a carbamyl, preferably an N:N-dialkyl carbamyl, group, with a metal ethyl compound, and treating the product with a hydrolysing agent. The a 1-keto group may be subsequently selectively converted into a cyclic ketal group. The examples describe the preparation of D 8:14-1:7-dioxo-, D 8:14-1-hy droxy - 7 - oxo -, D 8:14 - 1 - benzoyloxy - 7 -oxo -, D 8:14 - 1 - oxo - 7 - ethylenedioxy - and D 1:8:14 - 7 - oxo - 8:11 - dimethyldodecahydrophenanthrenes, and D 8:9-3:8-dimethyl-7-oxo-3:4 - (31 - oxo - cyclopentano - 21:11) - octa hydronaphthalene. 1 - Carbethoxy - 6 - chlorohexane - 4 - one is prepared by treating glutaric acid monoethyl ester chloride with ethylene in presence of aluminium chloride. 1 - Methyl - 1 - (6 - carbethoxy - hex - 31 - oneyl) - cyclohexane - 2:6 - dione is prepared by reacting 1 - methyl - 6 - chlorohexane - 4 - one with 1 - methyl - cyclohexane - 2:6 - dione in presence of triethylamine. b - (1:6 - Dioxo - 9 - methyl - D 5:10 - octalyl-5) - propionic acid ethyl ester is prepared by ring closing 1-methyl-1-(61-carbethoxy-hex-3-one - yl) - cyclohexane - 2:6 - dione with benzoic acid and triethylamine in xylene. b - (1:6 - Dioxo - 9 - methyl - decalyl - 5) - propionic acid ethyl ester is prepared by hydrogenating b - (1:6 - dioxo - 9 - methyl - D 5:10-octyl - 5) - propionic acid ethyl ester in presence of palladium black. b - (1:6 - Dioxo - 9 - methyl - decalyl - 5) - propionic acid is prepared by hydrolysis of the corresponding ethyl ester, and may be converted to the methyl ester by treatment with diazo-methane. b - (1:6 - Di - ethylenedioxy - 9 - methyldecalyl - 5) - propionic acid methyl ester is prepared by boiling a benzene solution of b -(1:6-dioxo - 9 - methyl - decalyl - 5) - propionic acid methyl ester with ethylene glycol in presence of para-toluene sulphonic acid, hydrolysing the carboxylic ester group and re-esterifying with diazo-methane in ether. b - (1:6 - Di - ethylenedioxy - 9 - methyldecalyl - 5) - N - diethyl - and N - dimethyl - propionamide are prepared by treating b -1:6-diethylenedioxy - 9 - methyl - decalyl - 5) - propionic acid methyl ester with methyl magnesium iodide and diethylamine or dimethylamine respectively, and decomposing the product with saturated ammonium chloride solution. The former compound may also be prepared by heating a toluene solution of b -(1:6-dioxo - 9 - methyl - decalyl - 5) - propionic acid with diethylamine in a closed vessel and boiling a benzene solution of the resulting b -(1:6-di-oxo - 9 - methyl - decalyl - 5) - N - diethyl - propionamide with ethylene glycol in presence of para-toluene sulphonic acid.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH757998X | 1952-07-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB757998A true GB757998A (en) | 1956-09-26 |
Family
ID=4534444
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB13156/53A Expired GB757998A (en) | 1952-07-18 | 1953-05-11 | Manufacture of new tricyclic ketones |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB757998A (en) |
-
1953
- 1953-05-11 GB GB13156/53A patent/GB757998A/en not_active Expired
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