Synthesis and Reactions of Chlorinated 3-Ketosteroids

Beereboom, John J.; Djerassi, Carl; Ginsburg, David; Fieser, Louis

doi:10.1021/ja01110a057

Cited by 35 publications

(10 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The following materials were commercial preparations: cholesterol, f-sitosterol (24b-ethylcholest-5-en-3fl-ol), stigmasterol, ergosterol, calciferol, 7-hydroxych,. 3sterol A number of steroids the authors owe to the courtesy of various donors: cholesterol, purified via the dibromide (Professor L. F. Fieser, Harvard University); 'sitosterol' and 2a-chlorocholestan-3,8-ol (see Beerenboom, Djerassi, Ginsburg & Fieser, 1953) (Professor D. Ginsburg, Hebrew Technical College, Haifa); y-sitosterol (24a-ethylcholest-5en-3j3-ol) (Dr W. Graham, Organon Laboratories Ltd., England); diosgenin (Lepetit, Milano, Italy).…”

Section: Methodsmentioning

confidence: 99%

Steroid utilization and fatty acid synthesis by the larva of the housefly Musca vicina Macq

Levinson

Bergmann

1957

Biochemical Journal

View full text Add to dashboard Cite

Section: Methodsmentioning

confidence: 99%

Steroid utilization and fatty acid synthesis by the larva of the housefly Musca vicina Macq

Levinson

Bergmann

1957

Biochemical Journal

View full text Add to dashboard Cite

“…194-196°( dec.) undepressed upon admixture with a sample prepared according to (a). While 2-chlorocholestanone is recovered unchanged (1) to the extent of 50% when treated with chromous chloride, this was not the case with the 2-chloro-4-bromo derivative VI; 1 g. treated with 40 cc. of chromous chloride solution (17) for 30 min.…”

mentioning

confidence: 93%

“…In our hands, the best synthesis of 2a-chlorocholestan-3-one (II) involved chlorination of cholestan-3-one with fert-butyl hypochlorite (1). Only traces of a dichloro derivative could be isolated in this reaction in spite of the use of a large excess of the chlorinating agent, We had assigned earlier (1) the 2,2-dichloro formulation (I) to this compound on the basis of its high positive rotation, analogous to that exhibited by 2,2-dibromo-3-keto alio steroids (3)(4)(5), and of the ultraviolet absorption spectum of its reaction product (VUIb) with 2,4-dinitrophenylhydrazine which resembled closely that of the corresponding A1-2-bromo derivative (6).…”

mentioning

confidence: 99%

See 1 more Smart Citation

SYNTHESIS AND REACTIONS OF MIXED BROMO-CHLORO 3-KETOSTEROIDS¹

Beereboom¹,

Djerassi²

1954

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

Our recently reported study (1) of chlorinated 3-ketosteroids, particularly of the 5a(alio) series, has demonstrated a marked difference in the behavior of these chloro ketones as compared to their bromo and iodo analogs towards reagents such as sodium iodide, collidine, and chromous chloride. It appeared of interest, therefore, to extend this investigation to mixed bromo-chloro 3-ketosteroids which should lend themselves to interesting, selective manipulations and the present paper is concerned with a description of such experiments. Since completion of this manuscript, there has come to our attention a very recent communication by Ellis and Petrow (2) bearing on the same subject. Wherever the work of the British workers parallels that of our past (1) and present papers, the results are in good agreement. SUMMARY 2,2-Dichlorocholestanone (I) can be dehydrochlorinated with collidine or 2,4-dinitrophenylhydrazine to A1-2-chlorocholesten-3-one (VIII) but it cannot be rearranged with hydrogen bromide to a 2,4-isomer. Chlorination of 2abromocholestanone (III) or bromination of 2a-chlorocholestanone (II) leads to

show abstract

“…2a-Bromocholestan-3-one (2, X = Br) was prepared by the method of Butenandt and Wolff,32 and 2a-chlorocholestan-3-one (2, X = Cl) was prepared according to Berreboom, Djerassi, Ginsburg, and Fieser. 33 The methanol-O-rfi was prepared by the method of Streitwieser, Verbit, and Stang34 and was >98.5% di. Baker Analyzed solute methanol was used without further purification.…”

mentioning

confidence: 99%