178. the use of aprotic solvents for nucleophilic substitution reactions at C(3) and C(17) in steroids

H. B. Henbest, W. R. Jackson

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Cholestanes containing 3α-substituents (cyano, azido, bromo, fluoro, acetoxy) have been obtained in good yields (>70%) from reactions of cholestan-3β-yl toluene-9-sulphonate with nucleophiles in aprotic solvents. In comparison, reactions of cholestan-3α-yl toluene-p-sulphonate with cyanide and acetate ions gave more elimination, but the 3β-cyanide and 3β-acetate were obtained in 40% and 57% yields, respectively. Use of aprotic solvents inhibits structural rearrangement in nucleophilic replacement reactions at C(17), and good yields of 17α-azido-, -bromo-, -chloro-, and -fluoro-compounds were obtained from testosterone toluene-p-sulphonate. Reaction of this ester with acetate anion in N-methylpyrrolidone gave the 17α-acetate (34%) and 3-oxoandrosta-4,16- diene (57%).

Original languageEnglish
Pages (from-to)954-959
Number of pages6
JournalJournal of the Chemical Society (Resumed)
Publication statusPublished - 1 Dec 1962
Externally publishedYes

Cite this

@article{4e18369767854e26945249fbea93a68a,
title = "178. the use of aprotic solvents for nucleophilic substitution reactions at C(3) and C(17) in steroids",
abstract = "Cholestanes containing 3α-substituents (cyano, azido, bromo, fluoro, acetoxy) have been obtained in good yields (>70{\%}) from reactions of cholestan-3β-yl toluene-9-sulphonate with nucleophiles in aprotic solvents. In comparison, reactions of cholestan-3α-yl toluene-p-sulphonate with cyanide and acetate ions gave more elimination, but the 3β-cyanide and 3β-acetate were obtained in 40{\%} and 57{\%} yields, respectively. Use of aprotic solvents inhibits structural rearrangement in nucleophilic replacement reactions at C(17), and good yields of 17α-azido-, -bromo-, -chloro-, and -fluoro-compounds were obtained from testosterone toluene-p-sulphonate. Reaction of this ester with acetate anion in N-methylpyrrolidone gave the 17α-acetate (34{\%}) and 3-oxoandrosta-4,16- diene (57{\%}).",
author = "Henbest, {H. B.} and Jackson, {W. R.}",
year = "1962",
month = "12",
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language = "English",
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journal = "Journal of the Chemical Society",
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178. the use of aprotic solvents for nucleophilic substitution reactions at C(3) and C(17) in steroids. / Henbest, H. B.; Jackson, W. R.

In: Journal of the Chemical Society (Resumed), 01.12.1962, p. 954-959.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - 178. the use of aprotic solvents for nucleophilic substitution reactions at C(3) and C(17) in steroids

AU - Henbest, H. B.

AU - Jackson, W. R.

PY - 1962/12/1

Y1 - 1962/12/1

N2 - Cholestanes containing 3α-substituents (cyano, azido, bromo, fluoro, acetoxy) have been obtained in good yields (>70%) from reactions of cholestan-3β-yl toluene-9-sulphonate with nucleophiles in aprotic solvents. In comparison, reactions of cholestan-3α-yl toluene-p-sulphonate with cyanide and acetate ions gave more elimination, but the 3β-cyanide and 3β-acetate were obtained in 40% and 57% yields, respectively. Use of aprotic solvents inhibits structural rearrangement in nucleophilic replacement reactions at C(17), and good yields of 17α-azido-, -bromo-, -chloro-, and -fluoro-compounds were obtained from testosterone toluene-p-sulphonate. Reaction of this ester with acetate anion in N-methylpyrrolidone gave the 17α-acetate (34%) and 3-oxoandrosta-4,16- diene (57%).

AB - Cholestanes containing 3α-substituents (cyano, azido, bromo, fluoro, acetoxy) have been obtained in good yields (>70%) from reactions of cholestan-3β-yl toluene-9-sulphonate with nucleophiles in aprotic solvents. In comparison, reactions of cholestan-3α-yl toluene-p-sulphonate with cyanide and acetate ions gave more elimination, but the 3β-cyanide and 3β-acetate were obtained in 40% and 57% yields, respectively. Use of aprotic solvents inhibits structural rearrangement in nucleophilic replacement reactions at C(17), and good yields of 17α-azido-, -bromo-, -chloro-, and -fluoro-compounds were obtained from testosterone toluene-p-sulphonate. Reaction of this ester with acetate anion in N-methylpyrrolidone gave the 17α-acetate (34%) and 3-oxoandrosta-4,16- diene (57%).

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M3 - Article

SP - 954

EP - 959

JO - Journal of the Chemical Society

JF - Journal of the Chemical Society

SN - 0368-1769

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