Alditols, sulfonic esters

In addition to these physical studies at the Bureau, Tipson was able to return to his synthetic interests, both alone and in collaboration with other staff members. He was especially pleased to prepare D-talose in crystalline form, an accomplishment that had eluded Emil Fischer. Pursuing his longstanding interest in the reaction of sulfonic esters with iodide and following an earlier observation that the tetratosyl ester of erythritol is converted into butadiene by the action of sodium iodide and zinc, he demonstrated (with A. Cohen) that nonterminal unsaturation may be conveniently introduced into alditol derivatives by reaction of contiguous secondary sulfonates with sodium iodide and zinc dust in boiling A.A-dimethylformamide. This Tipson-Cohen reaction subsequently proved of great utility in other hands for the conversion of more complex carbohydrate structures into vicinal dideoxy derivatives. 

Other examples of the solvolysis of sulfonates to give oxolanes have been reported. Thus, when 2,3-0-benzylidene-tri-0-(methylsulfonyl)-D-arabinitol, in a mixture of 9 M acetic acid and 10 M hydrochloric acid is heated for 30 minutes at 100°, it gives 2,5-anhydro-l,4-di-0-(methylsulfonyl)-D-arabinitol.88 Additional instances of the formation of internal anhydrides (not always well characterized) by acid hydrolysis of various sulfonic esters of alditols have been given by the same authors.88... 

The p-toluenesulfonic esters of alditols (Tipson, 1952) have bands at 1370-1350 and 1190-1175 cm" for the asymmetrical and symmetrical stretching modes of the —SO2— group (Onodera et al, 1965 Albano et al, 1966). Sulfonic esters of sugars... 

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