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United States Patent Office Patented Jan 3,164,611 United States Patent Office Patented Jan. 5, 1965 1. 2 reaction, care must be taken in applying this method 3,164,611 to the oxidation of heat sensitive compounds. OXDATION OF PRIMARY AND SECONDARY AL COHOLS TO THE CORRESPONDING CARBONY These organic base-chromium trioxide complexes are CSCMPOUNDS (USNG A TERTARY AMENE particularly useful oxidizing agents for effecting the oxida (CERORySSJR, TROXDE COMPLEX tion of alcohols having at least one hydrogen atom at Lewis H. Sarett, Friscetos, N.J., assigaor to Merck & Co., tached to the carbon atom bearing the hydroxyl sub Inc., Rahway, N.J., a corporatioia of New Jersey Stituent, i.e., primary and secondary alcohols, to the No Drawing. Fied any 26, 1956, Ser. No. 686,463 corresponding carbonyl compounds. Thus, primary al 13 Caias. (C. 260-349.9) cohols are oxidized to aldehydes, and secondary alcohols IO are converted to ketones. This invention relates to a novel process for the oxida This method of oxidizing alcohols to the corresponding tion of chemical compounds, and more particularly to carbonyl compounds is generally applicable to all pri an improved method for the oxidation of primary and mary and secondary alcohols. Examples of such al Secondary alcohols to the corresponding carbonyl com cohols that might be mentioned are aliphatic alcohols pounds. 5 such as alkanals, alkenols, alkinois, polyhydric alkanols, This application is a continuation-in-part application polyhydric alkenols and polyhydric alkinols; aralkyl al of my application Serial No. 263,016, filed December cohols; aralkenyl alcohols; aralkinyl alcohols; alicyclic 22, 1951, now abandoned, and my copending application alcohols such as cycloalkyl, cycloalkenyl, cycloalkinyl, Serial No. 292,985, filed June 11, 1952, now abandoned. spiran, terpene, polyterpene, steroid and carotenoid al While various methods are known for effecting the 20 cohols; alicyclic alkyl alcohols; allicyclic alkenyl alcohols; oxidation of chemical compounds, these methods suffer alicyclic atkinyl alcohols; heterocyclic alcohols; hetero from the serious disadvantage in that they very often cause cyclic alkyl alcohols; heterocyclic alkenyl alcohols; undesirable side reactions. For example, in oxidizing heterocyclic alkinyl alcohols; and the like. primary and secondary alcohols to the corresponding The primary and secondary alcohols reduced by the carbonyl compounds, frequently the oxidizing agents will 25 methods of the present invention can be unsubstituted attack unsaturated bonds, or oxidize the compound be alcohols or alcohols containing substituents such as halo, yond the desired stage. Further, many of the known amino, nitro carbonyl, sulfonic acid groups, and the like. processes employ acid reagents which attack acid-sensi Specific examples of such alcohols that might be men tive portions of compounds being oxidized. ... tioned are ethanol, propanol, butanol, farnesol, cit It is an object of my present invention to provide 30 ronellol, geraniol, glycol, propylene glycol, glycerol, novel process for effecting chemical oxidations. It is (3-phenylethanol, cyclopropanol, cyclobutanol, cyclopen another object to provide a method of oxidizing chemical tanol, cyclohexanol, cyclooctanol, benzylalcohol, menthol, compounds under alkaline conditions. It is a further carnomenthol, cyclohexylethanol, p-nitrobenzyl alcohol, object to provide an improved method of oxidizing pri 1,2-diphenyl ethanol, 4,4'-dimethoxydiphenyl carbonol, mary and secondary alcohols to the corresponding car 35 3-hydroxy-1,3-diphenyl propene, trichlorenthanol, 4,4' bonyl compounds. Other objects will be apparent from dihydroxy diphenyl carbinol, methyl 3-pyridylcarbinol, the detailed description hereinafter provided. furfuryl alcohol, codeine, biotin, scopolamine, atropine, In accordance with my invention, I have found that hydroxy proline and cyclopentanol. The process of the complexes formed by reacting an organic base with present invention is particularly useful in oxidizing chromium trioxide may be employed as agents in the 40 cyclopentanopolyhydrophenanthrene alcohols such as steroids to the corresponding carbonyl compounds. Thus, oxidation of chemical compounds having an oxidizable sterols such as cholesterol, cholestanol, epicholesterol, functional group. Thus, the complexes formed by react coprostanol, epicoprostanol, ergosterol, stigmasterol, and ing chromium trioxide with organic bases such as pyridine, lumisterol, bile acids such as cholic acid, desoxycholic y-picoline, (3-picoline, lutidines, quinoline, diethyl form acid, lithocholic acid, 3-epidesoxycholic acid, bisnor amide and the like, function as mild oxidizing agents and cholic acid, cholanic acid, allocholanic acid and bufo are conveniently employed in oxidizing chemical com choianic acid, heart poisons such as strophanthidin, iso pounds. strophanthidin, periplogenin, 17-isoperiplogenin, di In carrying out oxidations with these complexes, the gitoxigenin, sarmentogenin, Scillariden and bufotalin, organic compound being oxidized is intimately contacted 50 sapogenins such as tigogenin, sarsasapogenin, similogenin, with the complex for sufficient time to effect the de neotigogenin, Samogenin and hecogenin, sex hormones sired oxidation. Usually, I prefer to carry out the oxida such as estriol, estrane, equilenin, equilin, androsterone tion by dissolving the organic compound in a suitable and epiandrosterone, can be oxidized by the base-chro inert non-acidic solvent, such as benzene, toluene, pyridine mium trioxide complexes to produce the corresponding and the like, adding thereto the organic base-chromium 5 5 carbonyl compounds. In addition to these steroids other trioxide complex, agitating the reaction mixture to effect saturated or unsaturated derivatives of such steroids such intimate contact of the reactants, and permitting the re as primary and secondary alcohols of estranes, andro stanes, etiocholanes, pregnanes, cholanes, cholestanes, action mixture to stand for sufficient time at room tem spirostanes, isoaillospirostanes, and the like, can be oxi perature to complete the oxidation. Alternatively, as 60 dized by the processes of the present invention. Also, al will be readily apparent to those skilled in the art, the cohols of the dodecahydrophenanthrene series are con compound to be oxidized may be dissolved in an organic veniently oxidized by the processes of the present inven base, and the chromium trioxide may then be added form tion. ing the organic base-chromium trioxide complex in situ. in accordance with a preferred embodiment of my in Since the formation of the complex is an exothermic 65 vention, i have found that complexes prepared by re 3,164,611 3. 4. acting chromium trioxide with tertiary amines are espe be utilized as oxidizing agents since chromium trioxide cially valuable oxidizing agents. In particular, I have had always been employed as an oxidizing agent under found the pyridine-chromium trioxide complex, which acid conditions. - has been described by Sisler et al. in the Journal of the The following examples are presented to illustrate spe American Chemical Society, 70, 3828, (1948) to be of cific embodiments of my invention: outstanding value in effecting the oxidation of primary EXAMPLE 1. and secondary alcohols to the corresponding carbonyl compounds. Preparation of 3-acetoxy-11,20-diketo pregnane by the The pyridine-chromium trioxide complex is readily oxidation of 3-acetoxy-11-keto-20-hydroxy pregnane prepared by reacting chromium trioxide with pyridine. 10 Since this complex is relatvely insoluble in pyridine, it can CH3 (H, be obtained in solid form by reacting chromium trioxide (Hot CO with a moderate excess of pyridine. Thus, by reacting about one gram of chromium trioxide with 10 cc. of pyr idine, the solid complex is precipitated and, if desired, or ?h may be separated in accordance with conventional pro cedures. By reacting chromium trioxide with a large excess of pyridine, for example, by adding about one gram of chromium trioxide to 75 cc. of pyridine, a solution of pyridine-chromium trioxide complex in pyridine is ob 20 To aC.C. solution of 17 mg. of 3-acetoxy-11-keto-20-hydroxy taned. Although the complex which may be prepared in solid form as indicated above, may be employed as the pregnane in 0.3 cc. of dry pyridine was added 75 mg. of oxidizing agent, I have usually found it most convenient pyridine-chromium trioxide complex. The mixture, after to utilize it in the form of a suspension or solution in standing 36 hours at room temperature, was poured into pyridine. 25 ether and water, and the ether layer was washed with In carrying out the oxidation of alcohols pursuant to dilute aqueous hydrochloric acid. Concentration of the the preferred embodiment of my invention, the alcohol is ethereal solution and crystallization of the residue from dissolved in a suitable inert non-acidic solvent and the ether gave 3-acetoxy-11,20-diketo-pregnane, M.P. 131 C. pyridine-chromium trioxide complex added as a suspen EXAMPLE 2 sion or solution in pyridine. Various solvents such as 30. Preparation of 3,21-diacetoxy-17-hydroxy-11,20-diketo benzene, toluene, picoline and the like are suitable as sol pregnane from 3,21-diacetoxy-11-keto-17,20-dihydroxy vents for the alcohol, although I usually find that pyri dine is most satisfactory. After intimately contacting the pregnane resulting reaction mixture of the alcohol with the pyridine CHOAC CHO Ac chromium trioxide complex, it is permitted to stand, pref 35 s erably at room temperature, for sufficient time to insure
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