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United States Patent Office Patented May 14, 1974

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United States Patent Office Patented May 14, 1974 3,810,931 United States Patent Office Patented May 14, 1974 1. 2 3,810,931 trated in Reaction Scheme A. The structural formulas CTRICACD DERVATIVES Robert William Guthrie, Fairfield, James Guthrie Hamil depicted herein as drawn do not illustrate the relative or ton, Nutley, Richard Wightman Kierstead, North Cald absolute stereochemistry of the particular molecules. It well, and O. Neal Miller, Montclair, N.J., and Ann Clare should be understood, however, that all of the compounds Sullivan, New York, N.Y., assignors to Hoffmann-La described herein exist in two relative stereochemical forms: Roche Inc., Nutley, N.J. a cis and trans form for compounds of formula II and No Drawing. Filed Dec. 2, 1971, Ser. No. 204,334 a threo and erythro form for the remainder of the com nt. C. C07c. 143/68; C07d 1/20, 1/22 pounds. To facilitate the description of stereochemical U.S. C. 260-456 R 7 Claims transformations reported herein, the threo and erythro 10 nomenclature as defined by Cram et al., J. Almer. Chem. Soc., vol. 74, p. 5828 (1952) and by Prelog et al., Ex ABSTRACT OF THE DISCLOSURE perientia, vol. 12, p. 81 (1956) has been adopted. Each of Epoxyaconitic acid and esters thereof are useful for the these relative stereochemical forms exists as a racemate control of lipogenesis. and as two optical antipodes, and the formulas shown 15 herein are meant to include all of the isomeric and anti podal forms of the compounds depicted. BRIEF DESCRIPTION OF THE INVENTION Epoxyaconitic acid, compound Ia, may be prepared by The present invention relates to novel epoxides of the epoxidation of aconitic acid. Trans-aconitic acid affords formula threo-epoxide and cis-aconitic acid affords erythro epoxide. The epoxidation is suitably performed utilizing Icoir 20 an epoxidizing agent. Representative epoxidizing agents o useful for this reaction include hydrogen peroxide and per C-CHCOR acids. Suitable peracids include persulfuric acid, per bor I acetic acid, trifluoroperacetic acid, mono perphthalic acid, 25 perbenzoic acid, metachloroperbenzoic acid, and so forth. wherein all R groups are either hydrogen or the same When hydrogen peroxide is used as the epoxidizing agent, lower alkyl; and the stereoisomers, optical antipodes and it is preferred to use an epoxidation catalyst in conjunc pharmaceutically acceptable salts thereof, which com tion therewith. A particularly effective epoxidation pounds inhibit fatty acid synthesis in biological systems catalyst is tungstic acid or a salt thereof, particularly an and are thus useful in the treatment of obesity and in cor 30 alkali metal salt. The epoxidation is preferably carried recting conditions of lipid abnormalities. out in an aqueous medium, but an organic solvent such As used throughout the specification and the appended as an alcohol or ether may be employed as a diluent if claims, the term "lower alkyl" shall mean a straight or desired. Alternatively, the epoxidation may be performed branched chain hydrocarbon group containing no un in an inert organic solvent such as a hydrocarbon, a halo saturation and having up to and including 8 carbon atoms, 35 genated hydrocarbon or an ether. The reaction tempera such as methyl, ethyl, hexyl, isopropyl, tert-butyl and so ture is suitably in the range of from about 0° C. to about forth. The term “aryl' shall mean phenyl or naphthyl 100° C. To avoid rearrangement of cis-aconitic acid to which may be substituted with one of the following groups: trans-aconitic acid prior to epoxidation, it is generally halogen (i.e. chlorine, bromine, iodine or fluorine), lower preferred to epoxidize the cis-acid between about 20 and alkyl, hydroxy, lower alkoxy or nitro. 40 50. Cis-aconitic acid anhydride may be suitably em The preparation of compounds of Formula I is illus ployed in place of the acid. REACTION SCHEMEA CHCOH CHCOH OE 2-CHCOH -> O bHcott (bo, H (Ia) Yé-CHCOH (Ia)OE rootsH (IIIa) N N Y OX(Hoor o? CHCOR mead Y-CHCOR Roc? tion OR” (Ib) H (W) y / N / / CHCOR CO2H to HCOR." acO Roc? YCH, coir run) domina i. (Ib) Roc/TYCH, coir HO a" OH (IIIb) 3,810,931 3 4 w wherein R' is lower alkyl and X is lower alkylsulfonyl or sodium hydroxide; alkali metal carbonates, for example, arylsulfonyl. sodium carbonate; alkali metal hydrides, for example The epoxidation of aconic esters of Formula IIb to sodium hydride; and so forth. Choice of solvents and epoxy esters of Formula Ib may be accomplished in the reaction temperatures are not critical and will vary de same manner as described above for the conversion of IIa 5 pending upon the nature of the base utilized. Suitable to Ia. solvents include lower alkanols, e.g. methanol or ethanol; . The interconversion of epoxides Ia and Ib may be ac hydrocarbons, e.g. benzene or toluene; and the like. When complished according to standard chemical procedures. an alkanol is utilized as solvent, it is preferred to utilize For example, the epoxy triacid of formula Ia may be the alkanol corresponding to the R' portion of the com esterified to epoxy triester of Formula Ib by contacting O pound of formula V so that no trans-esterification occurs. said acid with a diazo, alkylene such as diazomethane or When utilizing a base stronger than an alkoxide, it is diazoethane according to well-known procedures. Con preferred to use an aprotic solvent such as benzene or versely, the triester of Formula Ib may be hydrolyzed to toluene so that reaction between the base and the solvent the triacid of formula Ia by treatment with base. Suitable does not occur. Suitable combinations of bases and sol bases include for example alkali metal hydroxides, e.g. vents include, for example, sodium hydride in benzene, sodium hydroxide; and alkali metal carbonates or bicar sodium acetate in methanol, and so forth. The reaction bonates, e.g. sodium carbonate or sodium bicarbonate. temperature may be in the range from about 20 to The hydrolysis may be carried out in an aqueous alcoholic about 150° C. A lower reaction temperature may be medium at temperatures ranging from about 0 to about employed where a stronger base is utilized and vice 50° C. 20 versa. This elimination reaction takes place with inver . It is generally not preferred to hydrolyze the erythro sion of configuration. Thus, threo-mesylate affords ery epoxy ester of Formula Ib to the corresponding erythro thro-epoxide and erythro-mesylate affords threo-epoxide. epoxy acid of Formula Ia due to the relative liability of the Epoxy triacids of formula Ia are readily converted to erythro-epoxides as compared with the corresponding hydroxy citric acids of formula IIIa which, in turn, form threo-epoxides. 25 the corresponding ?y-lactones of formula IV. Compounds An alternative method for the preparation of epoxides of formulas IIIa and IV. are known useful compounds of formula Ib involve, as a first step, cis-hydroxylation of for the control of lipogenesis. See, for example, Belgian aconitic ester IIb. The cis-hydroxylation reaction may be Pat. 758,122. The conversion of Ia to IIIa may be ac accomplished by utilizing a peroxide in the presence of complished by aqueous cleavage of the epoxide in the a hydroxylation catalyst. An especially preferred peroxide 30 presence of either acid or base. Generally, the hydroxy is hydrogen peroxide. An especially preferred hydroxy citric acid IIIa is converted to the y-lactone IV in the lation catalyst is osmium tetroxide. The catalyst may be reaction mixture during work up. - employed in small quantities as compared with the sub Suitable bases include alkali metal hydroxides, e.g. strate to be hydroxylated, for example from about 0.01 sodium hydroxide. As mentioned above, the hydrolysis to about 25 mole percent. Approximately 0.1 mole per 35 reaction is carried out in an aqueous medium. The re cent of hydroxylation catalyst is preferred. The hydroxy action temperature can vary from about 20 to about lation is suitably performed in any aqueous solvent or 150. Generally, a reaction temperature of from about solvent mixture. When osmium tetroxide is utilized as a 50 to about 100 is preferred. hydroxylation catalyst, it is generally preferred to treat An epoxide of formula Ia may also be cleaved by the reaction mixture with a reducing agent before work 40 heating alone in an aqueous medium; that is, the epoxy up. Suitable reducing agents include sodium sulfite, sodium acid itself serves as the acid catalyst. The reaction tem bisulfite, sodium thiosulfate, and so forth. The reaction perature for this autocatalyzed cleavage can be in the temperature of the hydroxylation reaction can be in the range from about 20 to about 150', although a tempera range from about 0 to about 100° C. For example, if ture of from about 50 to about 100 is generally pre one utilizes a trans-aconitic ester of Formula IIb, then a 45 ferred. It is preferred to carry out the cleavage of the threo-diol of formula IIIb is produced. he secondary hydroxyl group of the diol of formula threo-epoxide under basic conditions and the cleavage of IIIb can then be selectively functionalized to a suitable the erythro-epoxide. under acidic conditions. leaving group OX, wherein X is lower alkyl sulfonyl or In another variation, diol IIIb may be prepared di aryl sulfonyl, by reaction with the appropriate sulfonyl rectly from hydroxy citric acid y-lactone of formula halide. Suitable sulfonyl halides include methanesulfonyl IV by alkanolysis of the lactone ring and concomitant chloride, p-toluenesulfonyl chloride, p-bromobenzenesul esterification of the carboxyl groups. In this reaction, the fonyl chloride, p-nitrobenzenesulfonyl chloride, and so ?y-lactone is treated with the desired alcohol, ROH, forth Methanesulfonyl chloride is particularly preferred, wherein R is as above, in the presence of an acid.
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