In:
Zeitschrift für Naturforschung B, Walter de Gruyter GmbH, Vol. 22, No. 6 ( 1967-06-1), p. 587-596
Abstract:
Ethylpolyphosphates have been prepared by reacting P 4 O 10 with either triethylorthophosphate or with ethylether. Phenylpolyphosphates were prepared from P 4 O 10 and triphenylorthophosphate at 300 °C. By the same procedure, o-kresylpolyphosphates could also be obtained, but not p-nitro-phenylpolyphosphates. The various polyphosphate esters were subjected to nuclear magnetic resonance analysis to characterize the distribution of phosphate moieties present, branching groups, middle groups, end groups, and orthophosphates. A true equilibrium between the units was found for ethylpolyphosphates and the systems could be accurately described by the theory of van Wazer. This theory does not seem to hold for the present results with polyphenylphosphates. However, the experimental data can be described quantitatively with a modified form of the theory. Ethylpolyphosphates can either phosphorylate or alkylate nucleophilic groups and alkylation is favored by the presence of protons. Only phosphorylation is observed with phenylpolyphosphates. Solvolysis of the polyphosphate esters with water or n-butanol leads to a very rapid disappearance of branching groups and a slow disappearance of the middle groups. The amount of reactive phosphorus can be calculated from the nuclear magnetic resonance data. The application of phenylpolyphosphates for a number of synthetic procedures is discussed.
Type of Medium:
Online Resource
ISSN:
1865-7117
,
0932-0776
DOI:
10.1515/znb-1967-0604
Language:
Unknown
Publisher:
Walter de Gruyter GmbH
Publication Date:
1967
detail.hit.zdb_id:
2078109-X
detail.hit.zdb_id:
124635-5
