Pregn

PEROXIDES AND PEROXIDE COMPOUNDS - ORGANIC PEROXIDES] (Vol 18) llb,21-Dihydroxy-17-(l-oxobutoxy)-pregn-4-ene-3,20-dione. See Hydrocortisone butyrate. 

Methylation of hydrocortisone/prednisolone ia positions C-4, C-7, C-12, and C-21 failed to give useful products. Methylation at C-16, ia contrast, led to 16a- and 16P-methyl-9a- uoroprednisolones which were exceptionally useful. Both series were prepared usiag 3a-acetoxy-5a-pregn-16-ene-ll,20-dione derived from desoxychoHc acid (80). A much shorter route was subsequentiy developed from... 

A partial explanation of the above findings must lie in the known ease of addition of nucleophilic reagents to the conjugated double bond of pregn-16-en-20-ones. The amide ion that is a by-product of the reduction probably adds to a portion of the unreduced pregn-16-en-20-one giving the lithium enolate of amino ketone (74). This enolate may well be relatively stable at — 33° and would be protonated to the free 16-amino-20-one during work-up... 

Aside from pregn-16-en-20-ones, no other conjugated steroidal enones that are known to undergo facile nucleophilic addition to the carbon-carbon... 

Ethyleneketal of 20 -hydroxypregn-5-ene-3,11-dione from the 3-ethyIeneketal of pregn-5-ene-3,1 i,20-trione ... 

A solution of 0.3 of 3j9-acetoxy-21-ethoxy-17a-pregn-5-en-20-yn-17/3-ol in 7 ml of pure pyridine is hydrogenated over 90 mg of 2.5% palladium-on-calcium carbonate at room temperature and atmospheric pressure. The reaction mixture is filtered and evaporated and the residue recrystallized to give 80 % of the 17a-vinyl product. 

Deuteration of 5a.-Pregn-9-en-12-one at C-8 and C-11 by Exchange with Deuterium Oxide-20% Sodium Deuterioxide in Methanol- OD... 

A solution of 5a-pregn-9-en-12-one (36, 29 mg) in methanol-OD (5 ml) is saturated with 20% sodium deuterioxide in deuterium oxide and heated under reflux for 3 days. After cooling, the reaction mixture is diluted with ether... 

In contrast to this, hydrolysis of 17a,20 20,21-bismethylenedioxy-19-nor-9y ,10a-pregn-4-en-3-one using aqueous 90% formic acid at reflux temperature for 3 min gives an overall yield of 17a,21-dihydroxy-19-nor-9, 10a-pregn-4-ene-3,20-dione 21-formate of 12%. 

---