@article{db79dfebd1bd48258d25ae6f0d3a733d,
title = "Steroids and related natural products. Part XLI. 14α-Methyl {\OE}stranes",
abstract = "{\OE}strone has been converted into 14α-methyl{\oe}str-4-ene-3, 15-dione (V) in 14 steps. Direct alkylation at position 14 (activated by a 15-oxo-group) proved convenient for introducing the angular methyl group. Configuration of the 14-methyl substituent was established by o.r.d. measurements.",
author = "George Pettit and Brown, {Thomas H.}",
note = "Funding Information: 6 1.06 (CH,), 1-25 (CH,), 3.76 (CH,O), 6-5-7-2 p.p.m. complex (3 aromatic protons) (Found : C, 80-1; H, 8.6; 0, 11.1. C20H2802 requires C, 80-5; H, 8.8; 0, 10.7%). 140c-Methyl~?stra-5-ene-3,15-dione (V) .-Ether (IV) (0.050 g.) in tetrahydrofuran (5 ml.) and t-butyl alcohol (3 ml.) was slowly added to liquid ammonia (10 ml.) maintained at approximately -30{"}. Freshly cut lithium (0.10 g.) was added in 10 equal quantities during 0-5 hr. Stirring was continued for an additional 1.5 hr. while allowing the ammonia to evaporate. The residue was treated with ab- solute ethanol (5 ml.) followed by cautious addition of saturated aqueous sodium chloride. The resulting mixture was extracted with ether and the extract concentrated to a colourless crystalline solid (0.048 g.). The enol ether 3-Methoxy-l4a-methyZ~?stra-l, 3,5( 10) , 16-tetraen-1 &one [a1400 +156{"}~ [a1310 +lSs{"}, [.I335 O{"}J La1328 -1180~ [a1324 lo K. Bowden, I. M. Heilbron, E. R. H. Jones, and B. C. L. Weedon, J. Chem. SOL, 1946, 39.2026 intermediate displayed one spot on t.1.c. A solution of this intermediate in methanol ( 5 ml.) and hydrochloric acid (2 ml., 8%) was heated on a steam-bath for 20 min. Following dilution with saturated aqueous sodium chloride and extraction with ether, the combined extract was washed with water and concentrated (iut vacuo) to dryness. The oily residue was subjected to Jones oxidation as described above for the preparation of ketone (IId) to give the product (V) as needles (0.025 g.), m. p. 149-150{"} (from J. Chem. SOC. (C), 1967 ethanol), t.l.c., RF 0.11 (CHCL,); vmx. 1730 and 1670 cm.-l; [a]58e - 38{"}, [alas,, - 265{"}, [a]34o - 1000°, [ ~ t ] , ~ ~ Oo (c 0.065) (Found: C, 79.5; H, 9.0. C,eH,60, requires C, 79.7; H, 9.15%). This investigation was supported by Public Health Service Research Grants from the National Cancer In- stitute and in part by the National Science Foundation. [7/344 Received, March 20th, 19671 Copyright: Copyright 2007 Elsevier B.V., All rights reserved.",
year = "1967",
doi = "10.1039/J39670002024",
language = "English (US)",
pages = "2024--2026",
journal = "Journal of the Chemical Society C: Organic Chemistry",
issn = "0022-4952",
publisher = "Chemical Society",
}