Steroids, periodic acid oxidation

Most of the compounds that had been reported (before March, 1942) to show cleavage oxidation by periodic acid are recorded in the table the substances are listed alphabetically in the following groups of related compounds (1) carbocyclic compounds (2) carbohydrates (3) a-diketones and a-ketols (4) hydroxyamino compounds (5) polyhydroxy and hydroxyketo acids (6) polyhydroxy alcohols (7) steroids (8) miscellaneous compounds. French journals after May, 1940, and the majority of other foreign publications after June, 1941, were unavailable for the survey. 

Allylic alcohols in steroids are oxidized by 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), either alone (equation 258) [975] or as a catalyst with periodic acid as a reoxidant [974]. Saturated alcohols and other func-... 

Acetaldehydogenic and formaldehydogenic steroids, on the C i hydroxygroups in the side chain, can be determined after oxidation with periodic acid to acetaldehyde or formaldehyde, as with other polyols (p. 132). The aldehydes formed are determined in the oxidized urinary extracts, either after microdistillation or after reducing the excess of periodic acid with lithium bisulphite. 

Plasma has been treated in various ways in attempts to identify and remove the interfering component. Dialysis, heat treatment (80° for 20 min), and oxidation with periodate have had no effect. Precipitation of plasma proteins with trichloroacetic acid or perchlorate, and subsequent dialysis, produced a dialyzate that had no appreciable effect on hydroxyapatite. This approach is impractical, however, because it cannot easily be applied to plasma immediately prior to assay. So far, we have not managed to find a simple solution to this problem that will enable hydroxyapatite to be used to separate free and antibody-bound steroid in the presence of significant concentrations of nonextracted plasma. 

This statement too may cause raised eyebrows but an objective assessment of errors and costs can support it. Thus, De Courcy s trichloroacetic acid reagent (D2) is capable of convenient application to the detection of pregnanetriol in the nonketonic fraction from one-sixteenth of a 24-hour collection from men (100-150 ml) on simple LLC paper chromatograms (a TLC method could no doubt also be devised for this). As she pointed out, the same quantity can be obtained from one-thousandth of a 24-hour collection (1.5-2 ml) of urine from some patients with adrenal hyperplasia. Quantitative estimation by the same reaction after elution from the paper or TLC chromatogram could also be used either by one of the many variations of the micro-17-ketogenic steroid methods or by the same fluorescence reaction (e.g., W7). Further confirmation of identity could be obtained by using a small fraction of the latter after the periodate oxidation for a paper LLC, or TLC, chromatogram and application of the Zimmerman reaction to demonstrate the formation of etiocholanolone (B32). 

Deoxycholic acid was an important starting material for the early synthesis of cortisone and other cortical steroids. It was obtained principally from cholic acid by selective oxidation and subsequent Wolff-Kishner reduction. Cholic acid was obtained from beef bile which also contains substantial amounts of deoxycholic acid. The history of this period of steroid investigation is reviewed by Fieser and Fieser (1). 

Digoxin is a steroidal glycoside of the P-l,4-linked trimer of 2,6-dideoxy-D-ribo-hexose. Periodate oxidation and reaction of the product with oo-aminocar-boxylic acids led to compounds 15 which were assessed in enzymic and immunological studies. ... 

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