Ester chlorides side-reaction accompanying

In this context our interest was focused on sulfonic acid esters of starch, derived fh)m the reaction of organic sulfonyl chloride (e.g. benzene, methane, or toluene sulfonyl chloride). These derivatives can be employed as partially protected and reactive intermediates. Up to now, especially the reaction of starch with p-toluenesulfonyl chloride in pyridine was studied, i.e. under heterogeneous reaction conditions, which may be accompanied by several side reactions. Alternatively, a homogeneous procedure was published using dimethyl sulfoxide as solvent for starch. However, the sulphur contents of the products were very low and an extensive degradation of the polymer occured . The extent of / toluenesulfonyIation of primary and secondary groups was determined by the iodination method. It was revealed that the reaction proceeds faster at 0-6 than at 0-2 and 0-2... 

The acetyl and benzoyl derivatives are obtained by the reaction of the corresponding acyl chloride with the thiol . These thioesters are in effect active esters prone to attack by nucleophiles in general and very susceptible to dilute base. The protecting groups are removed completely by very dilute alkali within 20 min, but with dilute ammonia solution only 50% cleavage occurs during the same time. The hydrolytic cleavage is accompanied by a 3-elimination as a side-reaction, especially in cysteine derivatives (reaction 14). This side-reaction can be avoided in low... 

Ring closure of (3-hydroxy-a-amino acids with sulfuryl chloride/triethylamine 68 is accompanied by formation of (3-chloroalanine,16 1 whereas cyclization of urethane-protected serine and threonine by the Mitsunobu reaction 54 69 70 leads to oxazoline and dehydroalanine formation as side products. 47,71 Formation of dehydroalanine can be prevented by bulky carboxy protecting groups such as tert-butyl esters. 69 ... 

---