Controlled tosylation of 1,4:3,6-dianhydro-D-mannitol and -D-sobitol is studied. The nature of amines that act both as reaction activators and hydrogen chloride acceptors exerts a considerable effect on the ratio and structure of the resulting products.
We have previously shown that by means of the reaction of 1,4:6,3-dianhydro-D-sorbite I with N,N-diethylamide of phenylphosphonous acid chloride or tetraethyldiamide of phosphorous acid chloride II it is possible to prepare new oligomeric systems containing terminal phosphorus functions [1].It this report we show that by increasing of molar ratio of diol I and acid chloride II from 1 : 2 [1] to 3 : 2 it is possible to prepare phosphorus-containing oligomers of another type which contain terminal free hydroxy groups. Reaction was carried out in pyridine ÄÄÄÄÄÄÄÄÄÄÄÄ at 20oC. Reaction progress was controlled by means of 31 P NMR spectroscopy (the signals of reaction product III were observed at d P 147 and 148 ppm). It is important that the addition of extra two moles of reagent II does not cause the expected phosphorylation of free hydroxy groups. In 31 P NMR spectrum only the signal of the starting phosphorylating agent at 153 ppm and the above-mentioned signals of oligomer III are observed. Heating of reaction mixture for 4 h at 60oC does not cause further phosphorylation of free hydroxy groups.
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