Steroid Acids and their Transformation Products. VI. Some New Aldehydes and Their Derived Cyanohydrins

Attempted Syntheses of Pelletierine

“…Phenyl j3-(2piperidyl)thiolpropionate hydrochloride (23 g., 0.08 mole) was dissolved in 95% alcohol (150 cc.) and to the hot stirred solution there was added 12 teaspoons of Raney nickel; the mixture was stirred and refluxed for 1.5 hours, after which time a small portion of the mixture gave no odor of thiophenol on treatment with hydrochloric acid. After removal of the nickel the filtrate was evaporated to dryness under a vacuum and the resultant residue was leached with ether to remove organic material.…”

“…Because both Wibaut and Beets and Spielman and co-workers had been unable to prepare pelletierine by acidic treatment of one of its most logical chemical precursors, there was devised a reaction scheme which had as its ultimate step a reaction carried out under essentially neutral conditions, namely, the Raney nickel desulfurization of a thiol ester group to an aldehyde group (9)(10)(11)(12). To this end, the following sequence of reactions was carried out: In the hydrolysis and dehydration of the trichlorocarbinol VII to ß-(2-pyridyl)-acrylic acid (VIII) a variety of conditions wras tried in addition to those reported by Einhorn and Liebrecht (14).…”

The Action of Raney Nickel on Organic Sulfur Compounds.

“…When the original procedure (369,370,371) or those of Mozingo and his group (336,337) or of Ruggli and Preiswerk (389) was used or when no special mention of the method employed was made, the term "Raney nickel" will be used throughout this review. When, however, Raney nickel of special activity (W-l to W-7) (4,5,59), deactivated (327,328,413) or degassed (248,251,252) Raney nickel was employed, this will be stated in the text.…”

Bile acids. XXVI. Metabolism of 12α-hydroxycholanoic acid-24-14C in the rat

“…Purification by preparative thin-layer chromatography and crystallization from a mixture of acetone and water provided needles: mp 208-209°, [a]25 +61.5 ± 0.1°( CHC1,, c 0.5%); lit. (McIntosh et al, 1949) mp 214-215°, [a]"+71°.…”