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Phosphonitrilic Chlorides from Phosphorus Pentachloride
Author(s) -
BeckeGoehring Margot,
Fluck Ekkehard
Publication year - 1962
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.196202811
Subject(s) - phosphorus pentachloride , chemistry , chloride , medicinal chemistry , yield (engineering) , ring (chemistry) , salt (chemistry) , sulfur , ion , inorganic chemistry , polymer chemistry , organic chemistry , materials science , metallurgy
Under suitable conditions, PCL 5 reacts and quantitatively with NH 4 Cl to form [Cl 3 P = N–PCl 3 ] [PCl 6 ], which, with additional PCl 5 and NH 4 Cl, is transformed to [Cl 3 P = N–PCl 2 = N–PCl 3 ] [PCl 6 ].The cation of the latter compound and the NH   4 +ion react with ring closure to form [NPCl 2 ] 3 , together with longer chains which can yield with NH   4 +either [NPCl 2 ] 4 or, for example, Cl 3 P = N‐(PCl 2 = N) n ‐PCl 2 = NH. The salt‐like intermediates of the phosphonitrilic chloride synthesis react with S0 2 to form the oxygen‐containing products, Cl 3 P = N–P(O)Cl 2 and Cl 3 P = N–PCl 2 = N–P(O)Cl 2 . Sulfur analogs are also easily obtained. The constitution of the compounds was determined by nuclear magnetic reasonance spectroscopy.

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