GB788784A - Derivatives of 2-keto-2, 3, 4, 5, 6, 7 , 8, 10-octahydronaphthyl-(7)-methane and a process for preparing the same - Google Patents

Derivatives of 2-keto-2, 3, 4, 5, 6, 7 , 8, 10-octahydronaphthyl-(7)-methane and a process for preparing the same

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Publication number
GB788784A
GB788784A GB12375/54A GB1237554A GB788784A GB 788784 A GB788784 A GB 788784A GB 12375/54 A GB12375/54 A GB 12375/54A GB 1237554 A GB1237554 A GB 1237554A GB 788784 A GB788784 A GB 788784A
Authority
GB
United Kingdom
Prior art keywords
keto
octahydronaphthyl
dimethyl
give
diethyl
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
GB12375/54A
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.)
Takeda Pharmaceutical Co Ltd
Original Assignee
Takeda Pharmaceutical Co Ltd
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 Takeda Pharmaceutical Co Ltd filed Critical Takeda Pharmaceutical Co Ltd
Publication of GB788784A publication Critical patent/GB788784A/en
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/19—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same saturated acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • 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
    • C07B2200/07—Optical isomers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention comprises derivatives of 2-keto - 2,3,4,5,6,7,8,10 - octahydronaphthyl - (7) - methane of the formula: <FORM:0788784/IV (b)/1> wherein R1, R2 and R3 each represents hydrogen or alkyl of not more than four carbon atoms, Y is carboxy, carbomethoxy, carboethoxy, cyano, or carbamido, and Z is hydrogen, carboxy, carbomethoxy, carboethoxy, or acyl, and a process of preparing them by reacting a compound of the formula: <FORM:0788784/IV (b)/2> where Q is halogen, with a compound of the formula: <FORM:0788784/IV (b)/3> where Y1 and Z1 correspond to Y and Z except that they do not represent hydrogen, carboxy, or carbamido, or a metal compund thereof, R2, Y1 and Z1 being such as to retain the activity of the hydrogen marked with an asterisk, and then saponifying or decarboxylating the condensation product, if desired. The reaction may be performed in an organic solvent, e.g. alcohol, ether, benzene, toluene, pyridine) in presence of an alkaline condensing agent, a metal, or an anion-exchange resin (e.g. an alkali metal alcoholate, trimethylbenzylammonium hydroxide, an alkali or alkaline earth carbonate or hydroxide, metallic sodium, potassium, or magnesium. Reaction temperature may be room temperature or 60-100 DEG C. In examples: (1) 2-keto-1,10-dimethyl - 2,3,4,5,6,10 - hexahydronaphthalene is reacted with (a) diethyl malonate, to give diethyl - 2 - keto - 1,10 - dimethyl - 2,3,4,5,6,7, 8,10 - octahydronaphthyl - (7) - malonate, (b) diethyl methylmalonate, to give diethyl 2-keto - 1,10 - dimethyl - 2,3,4,5,6,7,8,10 - octahydronaphthyl - (7) - methylmalonate, (c) methyl a -methylcyanoacetate, to give methyl a - cyano - a - [2 - keto - 1,10 - dimethyl - 2,3,4,5,6,7,8,10 - octahydronaphthyl - (7)]-propionate, (d) ethyl acetoacetate, to give ethyl 2 - keto - 1,10 - dimethyl - 2,3,4,5,6,7,8,10-octahydronaphthyl - (7) - acetoacetate, (e) ethyl a -methylacetoacetate, to give ethyl a -[2-keto - 1,10 - dimethyl - 2,3,4,5,6,7,8,10 - octahydronaphthyl - (7)] - a - acetopropionate, (f) diethyl methylmalonate to give diethyl 2-keto-1,10 - dimethyl - 2,3,4,5,6,7,8,10 - octahydronaphthyl - (7) - methylmalonate, (g) methyl cyanoacetate, to give methyl-2-keto-1,10-dimethyl - 2,3,4,5,6,7,8,10 - octahydronaphthyl-(7)-cyanoacetate. Also in examples, (2) 2-keto-10 - methyl - 2,3,4,5,6,10 - hexahydronaphthalene is reacted with ethyl methylmalonate, to give ethyl-2-keto-10-methyl-2,3,4,5,6,7,8,10-octahydronaphthyl - (7) - methylmalonate, (3) 2 - keto - 1,10 - dimethyl - 8 - bromo - 2,3,4,5,6,7,8,10 - octahydronaphthalene is reacted with diethyl methyl malonate to give diethyl 2 - keto - 1,10 - dimethyl - 2,3,4,5,6,7, 8,10 - octahydronaphthyl - (7) - methylmalonate. In further examples, (4) diethyl-2-keto-1,10-dimethyl - 2,3,4,5,6,7,8,10 - octahydronaphthyl - (7) - malonate is partially hydrolysed with hydrochloric acid in dioxane to give the monoethyl ester, which last is (5) decarboxylated by melting under reduced pressure to give ethyl 2 - keto - 1,10 - dimethyl - 2,3,4,5,6,7,8,10-octahydronaphthyl-(7)-acetate, or (6) the diethyl or monoethyl ester is completely hydrolysed to give 2-keto-1,10-dimethyl-2,3,4,5,6,7, 8,10 - octahydronaphthyl - (7) - malonic acid, which (7) is decarboxylated by heating under pressure, to give 2-keto-1,10-dimethyl-2,3,4,5, 6,7,8,10 - octahydronaphthyl - (7) - acetic acid; (8) diethyl - 2 - keto - 1,10 - dimethyl - 2,3,4,5,6, 7,8,10 - octahydronaphthyl - (7) - methyl malonate is partially hydrolysed with alcoholic potash to give the monoethyl ester, or completely hydrolysed to give the acid, or the monoethyl ester is hydrolysed to the acid, and the acid and monoethyl ester are each decarboxylated by heating in pyridine to give a -[2-keto - 1,10 - dimethyl - 2,3,4,5,6,7,8,10 - octahydronaphthyl - (7)] - propionic acid and its ethyl ester; (9) 2-keto-1,10-dimethyl-2,3,4,5,6, 7,8,10 - octahydronaphthyl - (7) - methyl malonic acid is esterified with methanol in presence of sulphuric acid to give the dimethyl ester; (10) methyl a -cyano-a -[2-keto-1,10-dimethyl - 2,3,4,5,6,7,8,10 - octahydronaphthyl-(7)]-propionate is saponified to the acid, which is decarboxylated by heating in collidine to give a - [2 - keto - 1,10 - dimethyl - 2,3,4,5,6,7,8,10-octahydronaphthyl - (7)] - propionitrile, which is saponified by heating with sulphuric acid to give a - [2 - keto - 1,10 - dimethyl - 2,3,4,5,6,7 8,10 - octahydronaphthyl - (7)] - propionamide, which is further saponified to the acid by heating with caustic soda solution in dioxane; (11) methyl - 2 - keto - 1,10 - dimethyl - 2,3,4,5, 6,7,8,10 - octahydronaphthyl - (7) - cyanoacetate is saponified to the acid; (12) diethyl 2-keto-10-methyl - 2,3,4,5,6,7,8,10 - octahydronaphthyl-(7)-methylmalonate is saponified to the acid.
GB12375/54A 1953-04-28 1954-04-28 Derivatives of 2-keto-2, 3, 4, 5, 6, 7 , 8, 10-octahydronaphthyl-(7)-methane and a process for preparing the same Expired GB788784A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP788784X 1953-04-28

Publications (1)

Publication Number Publication Date
GB788784A true GB788784A (en) 1958-01-08

Family

ID=13674055

Family Applications (1)

Application Number Title Priority Date Filing Date
GB12375/54A Expired GB788784A (en) 1953-04-28 1954-04-28 Derivatives of 2-keto-2, 3, 4, 5, 6, 7 , 8, 10-octahydronaphthyl-(7)-methane and a process for preparing the same

Country Status (1)

Country Link
GB (1) GB788784A (en)

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