5a-androstane-17P-ol-3-one

Synonyms 5a-Androstan-17p-ol-3-one benzoate dihydrotestosterone benzoate stanolone benzoate Trade Names ... 

The phase-I-metabolism of testosterone leads primarily to 5a-androstan-17P-ol-3-one (dihydrotestosterone), 5a-androstan-3a-ol-17-one (androsterone), and 5P-androstan-3a-ol-17-one (etiocholanolone) (Fig. 3.6,2-4, respectively), which represent important parameters of the so-called urinary steroid profile in sports drug testing (see Chapter 6). 

Steroidal agents such as 5a-androstan-17P-ol-3-one (Fig. 4.5,1) and selected analogues (Fig. 4.5, 2-4) dissociate efficiently upon ESI and CID as shown exemplarily for 5a-androstan-17P-ol-3-one (Fig. 4.6a). Commonly, the saturated scaffold of cyclopenta[a]phenanthrene-derived compounds results in product ion mass spectra predominantly containing ions of low specificity, which are separated by methylene units (14 Da). Although a,P-unsaturated 3-keto-steroids also yield such product ions, the presence of double bonds commonly directs the dissociation pathway to specific and more characteristic fragments vide infra). 

Figure 4.5 Structures of selected steroidal analytes 5a-androstan-17P-ol-3-one (1), 5P-androstan-17P-ol-3-one (2), 17a-methyl-5a-androstan-17P-ol-3-one (3), la-methyl-5a-androstan-17P-ol-3-one (4), testosterone (5), nandrolone (6), 1-testosterone (7), metenolone (8), 5a-androst-l-ene-3,17-dione (9), metandienone (10), 18-nor-17P-hydroxymethyl,17a-methyl-androst-l,4,13-trien-3-one (metandienone metabolite) (11), androsta-4,6-dien-17P-ol-3-one (12), androsta-4,9-dien-17P-ol-3-one (13), trenbo-lone (14), methyltrienolone (15), tetrahydrogestrinone (THG, 16), and stanozolol (17).

Figure 46 ESI product ion mass spectra of protonated molecules [M+H] of (a) 5a-androstan-17P-ol-3-one (mol wt = 290), (b) testosterone (mol wt = 288), and (c) nan-drolone (mol wt = 274) recorded on a QTrap 2000 system.

A solution of 2a,3a,16a,17a-diepoxy-17p-acetoxy-5a-androstane (25 grams), prepared from 3,17-diacetoxy-5a-androstane-2,16-diene (Chem. Abs. 1960, 54, 8908) by treatment with m-chlor-perbenzoic acid, in piperidine (120 ml) and water (40 ml) was boiled under reflux for 5 days, the solution was concentrated and the product precipitated by the addition of water. The solid was collected, dissolved in dilute hydrochloric acid, filtered to give a clear solution and precipitated by the addition of sodium hydroxide solution. Crystallization from acetone gave 2p,16p-bis-piperidino-5a-androstan-3a-ol-17-one (18.9 grams), MP 179-185°C. 

Methyltestosterone 17a-methyl-5a-androstane-3a,17P-diol 17a-methyl-5P-androstane-3a,17P-diol 17P-methyl-androst-4,6-dien-17a-ol-3-one... 

A fascinating application of these principles has been reported by GUnter Neef and his colleagues at Schering in Berlin. They converted two diastereomeric but-3-yn-l-ols prepared from 17P-methoxymethoxy-5a-androstan-3-one with benzenesulfenyl chloride into the diastereomeric sulfoxides 92. These reacted with methyllithium stereospecifically, the chiral (R) [or (P)] sulfoxide giving the (/ ) allene 93 and the (5) [or (A/)] sulfoxide the (S) allene exclusively. The lithium intermediate was instantaneously quenched by the acidic by-product methyl phenyl sulfoxide (Scheme 1-64). ... 

---