1-Dehydrotestosterone acetate

Photoketone (118) has served as the key intermediate in a relatively simple transformation of 3-keto-10/ -steroids to 3-keto-lOa-isomers without the assistance of other functional groups suitably situated next to the ring junction—a task that appears difficult to attempt by other methods. Optimal yields of (118) are achieved by catalytic hydrogenation of the unsaturated ketone (175), the photoisomer of 1-dehydrotestosterone acetate (see section III-C). In this way, a 6-step conversion of 1-dehydrotestosterone acetate (174) to IOa-testosterone acetate (127 acetate) is achieved in good yield. ° ... 

Dehydrotestosterone acetate (174) in nonprotic solvents (dioxane, benzene) undergoes a rearrangement to the isomer (175). This product is photolabile and isomerizes readily to new cross-conjugated dienones. Thus, ultraviolet irradiation of (174), its 1-, 2- and 4-methyl homologs, and its lOa-stereoisomer (188) in dioxane solution causes, in each case, a series of rearrangements as summarized on page 331 for (174) and (188). ... 

Decomposition of hypoiodites, 247 Deformylation of steroid 19-aldehydes, 273 1-Dehydrotestosterone acetate, 320, 330, 333, 337... 

That solvent incorporation becomes a dominating feature of dienone photochemistry in protic media was again recognized for the first time with santonin (28) which was converted to isophotosantonic lactone (31) in aqueous acetic acid (Chart 4). In addition to 5/7-fused hydroxy-ketones, spirocyclic isomers may be formed as well irradiation of 1-dehydrotestosterone acetate (32a) in aqueous acetic acid gave approxi-... 

H Spectra.—The total analysis of the 1H n.m.r. spectrum of 11 p-hydroxypro-gesterone, reported briefly last year,42 has now been described in full.43 This is a further illustration of the value of computer-controlled use of a 400 MHz spectrometer to obtain two-dimensional J spectra, and n.O.e. difference and decoupling difference spectra, which provided all the XH chemical shifts and virtually all geminal and vicinal coupling constants. Comparisons with the previously reported findings42 for 1-dehydrotestosterone acetate represent the first step in a correlation of detailed n.m.r. and structural parameters which promises to have widespread application in future studies on steroidal and terpenoid compounds. 220 MHz spectra permit quantitative estimation of C-24 epimeric mixtures of 24-alkyl sterols.44... 

Photochemistry of 1-dehydrotestosterone acetate and its methyl derivatives begins with conversion of 2, 5-cyclohexadienones (XVI) into a bicyclo [3.1.0] hexenone (XVII) and then to new cyclohexadienone (XVIII) of assigned... 

When testosterone acetate is refluxed with 2,3-dichloro-5,6-dicyano-p-benzoquinone andp-toluenesulfonic acid in benzene for 5 h, a 60% yield of 6-dehydrotestosterone acetate is obtained [966]. The treatment of an-drost-4-ene-3,17-dione in dioxane with the same quinone and gaseous hydrogen chloride gives a 72% yield of androsta-4,6-diene-3,17-dione [966] (equation 30). 

Dehydrotestosterone acetate adds butadiene under u.v. irradiation, giving as one product the remarkable 4a,5a,6a,7a-adduct (637), containing three fused cyclobutane rings despite very considerable strain, this product was stable to basic hydrolysis and to acetylation at C-17. The major photo-addition product with butadiene was the trans-fused 4a,5)5-adduct (638), which isomerized in a... 

Dehydrotestosterone Derivatives. Irradiation of 1-dehydro-4-methyltestosterone acetate (Formula 57, R=H) in dioxane gives Formula 58 (R=H), an analog of lumisantonin, in 60-70% yield (37). 

Figure 4 Chromatogram of a mixture of eight steroids. Chromatographic systems (A) ODS-2/0.12moll SDS/6% (v/v) 1-pentanol, and (B) ODS-2/52% (v/v) acetonitrile. Compounds (1) dehydrotestosterone, (2) testosterone, (3) methyltestoster-one, (4) medroxyprogesterone acetate, (5) dydrogesterone, (6) progesterone, (7) testosterone propionate, and (8) nandro-ione.

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