THE INVENTION OF RADICAL REACTIONS. PART XVIII. DECARBOXYLATIVE RADICAL ADDITION TO ARSENIC, ANTIMONY, AND BISMUTH PHENYLSULPHIDES - A NOVEL SYNTHESIS OF NOR-ALCOHOLS FROM CARBOXYLIC ACIDS
Carbon centered radicals obtained by decarboxylative transformation of suitable thiohydroxamate esters react with group Va trisphenylsulphides to give intermediates of general formula R-M(SPh)2 (M= As, Sb, Bi).These react spontaneously with air to give the corresponding alcohols.This procedure is especially useful in the case where M=Sb.It is thus sufficient to stir the thiohydroxamate ester with tris(phenylthio)antimony under air to obtain the nor alcohol directly and in high yield.The intermediate organometalloid could also be oxidised with nitrogen dioxide to give the expected nitroalkane albeit in only modest yield.The corresponding organobismuth intermediate derived from 3,3-diphenylpropionic acid could actually be isolated thereby providing strong evidence for the proposed mechanism.
Barton, Derek H. R.,Bridon, Dominique,Zard, Samir Z.
p. 2615 - 2626
(2007/10/02)
The Invention of New Radical Chain Reactions. Part 9. Further Radical Chemistry of Thiohydroxamic Esters; Formation of Carbon-Carbon Bonds
Carbon radicals derived from the esters of several types of thiohydroxamic acids have been trapped in a number of different ways.Particular attention has been paid to carbon-carbon bond formation by addition to suitably activated ethylenic linkages.Carboxylic acids can be conveniently converted into homo- and bishomo-acids by free radical chemistry based on thiohydroxamic esters.In a coda the tautomerism of the thiohydroxamic acids have been examined by physical methods.It is confirmed that the esters used are derivatives of the thione tautomer.
Barton, Derek H.R.,Crich, David,Kretzschmar, Gerhard
p. 39 - 54
(2007/10/02)
A Convenient High Yielding Synthesis of Nor-alcohols from Carboxylic Acids
Esters (mixed anhydrides) of carboxylic acids and thiohydroxamic acid (2) react with tris(phenylthio)antimony in the presence of oxygen and water to give high yields of nor-alcohols.
Barton, Derek H. R.,Bridon, Dominique,Zard, Samir Z.
p. 1066 - 1068
(2007/10/02)
FORMATION OF CARBON-CARBON BONDS WITH RADICALS DERIVED FROM THE ESTERS OF THIOHYDROXAMIC ACIDS
Radicals formed from the esters of thiohydroxamic acids readily add to electron deficient olefins to give adducts of potential synthetic value in variable yield.In certain cases the added sulphur function is easily eliminated with reformation of olefin.
Barton, Derek H. R.,Crich, David,Kretzschmar, Gerhard
p. 1055 - 1058
(2007/10/02)
RADICAL CHEMISTRY OF THIOHYDROXAMIC ACID ESTERS
Thiohydroxamic esters in general decompose smoothly by a radical chain reaction to give carbon radicals which can be quenched in a synthetically useful manner.
Barton, Derek H. R.,Kretzschmar, Gerhard
p. 5889 - 5892
(2007/10/02)
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