
%0 Journal Article
%A Ahmed, S 
%A Alauddin, M 
%A Caddy, B 
%A Martin-Smith, M 
%A Sidwell, WTL 
%A Watson, TR 
%T Bisquaternary ammonium salts derived from 3&#945;,12&#945;-Diamino-5&#946;-cholane and 3&#945;,12&#945;-Diamino-24-nor-5&#946;-cholane
%J Australian Journal of Chemistry
%D 1971/03/01
%V 24
%N 3
%P 521-547
%K 
%R https://doi.org/10.1071/CH9710521
%U https://www.publish.csiro.au/paper/CH9710521 
%X The preparation of 3&#945;,12&#945;-bisdimethylamino-5&#946;-cholane dimethiodide, 3&#945;,12&#945;-bisdimethylamino-5&#946;-cholane dimethiodide, 3&#945;,12&#945;- bisdimethylamino-24-nor-5&#946;-cholanedimethiodide, and 3&#945;,12&#945;- bisdimethylamino-24-nor-5&#946;-cholanediethiodide, from deoxycholic acid are described. During this work it was found that attempted copper- quinoline decarboxylation of dehydrocholic acid gives rise to lactol formation, and that what had previously been considered to be 3&#945;,12&#945;- dihydroxy-5&#946;-cholane is a mixture of this compound and 12&#945;,24- dihydroxy-5&#946;-cholane. Comparable selectivity of attack by methanesulphonyl chloride and toluene-p-sulphonyl chloride occurs with various polyhydric alcohols derived from bile acids, as evidenced from the products of reduction of the sulphonates with lithium aluminium hydride. With both 5&#945;- and 5&#946;-cholane derivatives, a C 3 equatorial hydroxyl group exhibits comparable reactivity to the terminal primary hydroxyl group, generated from the bile acid carboxylic group, towards both sulphonyl chlorides. With axial hydroxyl groups at C 7 and C 12, toluene-p-sulphonate formation is much more difficult than methane- sulphonate formation. Reduction by means of lithium aluminium hydride of equatorial sulphonate esters at C 7 and C 12 gives rise to a methylene group, but the axial sulphonates under the same conditions give the axial alcohol. The same clear distinction between equatorial and axial sulphonate esters is not observed at C 3 and C 6, but 17&#945;- methanesulphonyloxy-5&#945;-androstane gives 5&#945;-androstane and the 17&#946;- ester gives 17&#946;-hydroxy-5&#945;-androstane. Reduction of 12-oximino groups in both 5&#945;- and 5&#946;-cholanes with sodium and ethanol, hydrogen in the presence of a catalyst, or lithium aluminium hydride gives solely the 12&#945;-amino compound. 
