| 摘要 |
<p>The invention comprises compounds of the following formulae:-<FORM:0909261/IV (b)/1> (wherein R represents a free, esterified or etherified hydroxyl group) their 3-ketals, 11b -acetoxy-16,18-dioxoandrostane compounds and their ketals, particularly D 4-11b -acetoxy-13,16,18-trioxo-14-isoandrostene, D 5,14 - 3 - ethylenedioxy - 11b - acetoxy - 16,18 - dioxoandrostadiene, D 5-3-ethylenedioxy-11b -acetoxy-14,15-oxido - 16,18 - dioxoandrostene, also 11b - hydroxy-16,18-dioxoandrostane compounds, their free, esterified or etherified 18,11-cyclohemiacetals and their ketals, particularly D 4-3,16,18-trioxo - 11b - hydroxyandrostene, and 18,11-lactones of 11b -hydroxy-16-oxoandrostan-18-acids and their ketals, particularly the 18,11-lactones of D 5,14-3-ethylene-11b -hydroxy-16-oxo-androstadien-18-acid and D 5-3-ethylenedioxy - 11b - hydroxy-16-oxo-androsten-18-acid, together with a process for the preparation of 11,18-dioxygenated 16-oxo-androstane compounds by subjecting a D 4,18-3,16-dioxo-11b ,18a - oxido - 18a - methyl-18-homoandrostadiene of formula:- <FORM:0909261/IV (b)/2> which may contain a double bond in the 14,15-position, or a 3-ketal derivative, to oxidative cleavage of the 18,18a-double bond, e.g. by ozonisation and reductive cleavage of the ozonide, or hydroxylation and periodate splitting, the 11b -acetoxy group in the resulting 11b -acetoxy-18-oxo compound is hydrolysed in an alkaline medium, and if there is a 14,15-double bond, such bond or the 16-oxo group is temporarily protected and, if desired the resulting 18,11-cyclosemiacetal group is functionally converted and/or the 14,15-double bond is hydrogenated at any stage of the process. Detailed examples illustrate the invention and reference is made to further steps leading to a synthesis of aldosterone. Specifications 814,711, 893,577 and U.S.A. Specification 2,904,545 are referred to.</p> |
