Steroid sulphates, hydrolysis

In those cases where a suitable antibody for radioimmunoassay is not available, a full multi-component screening procedure is necessary, and also needs to be undertaken as a confirmatory test in cases where the nature of the anabolic steroid is not known. The full analysis involves the separation of the glucuronic acid and sulphate conjugate fractions and their separate hydrolysis followed by GC-MS of their silyl or methoxime-silyl derivatives. It should be noted that the sulphatase in Helix pomatia will not hydrolyse the sulphate conjugates of the 1713-hydroxy steroids, which require mild acid hydrolysis. 

The hydrolysis of steroid hydrogen sulphates, important to biochemists in view of the excretion of many steroid hormone metabolites as water soluble salts of hydrogen sulphates, has been studied in some detail [20,21]. It had been known for some years that ether extraction of the steroid hydrogen sulphate from acidified solutions is accompanied by hydrolysis of the sulphate in the ether phase, with liberation of the steroid alcohol. This hydrolysis was shown to follow first-order kinetics, but to be dependent in a remarkable way on the solvent. Ethers are the most effective solvents, followed by others of low polarity including benzene, esters and ketones, while water and alcohols have a strong retarding effect on hydrolysis. Neither acids nor bases produce significant catalysis, and the presence of did not result in incorporation of isotopic... 

The reactions of bromohydrins in the cholestane series with Ag20 have been shown to depend markedly on the conformation of the bromine. Thus, for example, the 6a-bromo-7 -hydroxy-compounds (107) and (108), which have the equatorial bromine, gave the B-nor-aldehyde (110) whereas the 6/8-bromo-7/S-hydroxy-compound (109) gave the 7-oxo-compound (111) via a hydride shift. Hydrolysis of the dipotassium 5)3-pregnane-3a,20a-diyl sulphate in 3N-HC1 gave the D-homo-steroids (112) and (113) in addition to the expected... 

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