Some Steroid Mercaptols

Organic chemistry

“…per mole, it seems possible that perfluoro-heterocyclic nitrogen compounds might be obtainable by the milder method of fluorination using CoF,. That the -CN group appears to be able to withstand fluorination is supported by the observation that treatment of AgNC with fluorine yields several isomeric nitrogen-containing ~ubstances,~, including (I), (11) be of interest to examine the fluorination of 1 : 3 : 5-tristrifluoromethyl-2 : 4 : 6-triazine which is obtainable by a substitution method (see The aromatic ether linkage also appears to be stable under certain conditions, for fluorination of diphenyl ether furnishes perfluorocyclohexyl ether (470,/,), the rest of the material undergoing cleavage and fluorination with the formation of perfluorocyclohexane (30 Aliphatic compounds containing a carbonyl group appear to be prone to cleavage when treated with fluorine as shown by the fact that acetone gives a complicated mixture of substances among which the following have been identified : CH,F*CO*CH,, CF,.CO*CF,, CF,*COF, (COF),, COF,, and CF4.,0…”

“…Isomerisation with aluminium chloride in hexane solution converted the perhydroanthracene, m. p. 61" (I), into a mixture from which the isomer, m. p. 39" (11), was isolated. This in turn gave a small yield of the perhydroanthracene, m. p. 90" (111).…”

“…L. Ruzicka, P. A. Plattner, and their collaborators 87, from a study of the stepwise degradation of cedrene, consider that the reactive ring is formulated better as a cyclopentene than a cyclohexene ring, 80 that w partial formula, for cedrene is (I). Ozonisation of cedrene gives the keto-carboxylic acid (11), oxidised by sodium hypobromite to cedrenedicarboxylic acid (111),89 which as L. Ruzicka and J. A. van Melsen90 showed does not form a cyclic ketone, but with acetic anhydride gives the anhydride.87 Chromic acid oxidation of cedrene gives cedrenone (formerly cedrone) (IV), ozonised to the keto-carboxylic acid (V), which gives with reduced by sodium and alcohol back to cedrsne, and t'his transformation is therefore analogous to the auto-oxidation of a-pinene to verbenol, and dehydration to verbenene.87 W. Treibs 93 has shown that cedrene is oxidised by selenium dioxide to the isomeric primary cedrenol (IX), further oxidised by potassium permanganate followed by nitric acid to norcedrenedicarboxylic acid (VI).…”

Addition of Thiols or Hydrogen Sulfide to Carbonyl Compounds

“…Autenrieth and Geyer 13 had already shown that the principal product of the reaction of acetone with pentamethylene dithiol was the sixteen-membered ring compound (XI, JZ=5), while Marvel et al 14t showed that hexamethylene dithiol gave linear polymercaptals with aldehydes. Hauptmann 16 showed that this reaction is particularly valuable in the steroid series, where its selectivity has received much attention in recent work. This was first applied to simple aldehydes and ketones by Wolfrom and Karabinos, 15 who also showed that the diethyl mercaptals of sugars could be readily desulfurized.…”

“…The cyclic hemithioketals (XIV) have been shown to be useful compounds for synthetic work, since they are more readily decomposed in dilute acid. 16 Campaigne and Leal 28 studied the products of the acid catalyzed reaction of thiophenol with certain phenyl ketones (XXI) under conditions which usually lead to mercaptal formation. Djerassi and co-workers 22 have shown that the cyclic hemithioketals are useful for protecting a carbonyl group, since Raney nickel desulfurization regenerates the ketone.…”