Synthesis of Phospha- and Diphospha-1,3,5-triazines by Cyclizing Transamination with Aminophosphazenes

✍ Scribed by Dr. A. Schmidpeter; Dipl.-Chem. J. Ebeling

• Publisher: John Wiley and Sons
• Year: 1967
• Tongue: English
• Weight: 231 KB
• Volume: 6
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.196705651

✦ Synopsis

The products are colorless, crystalline compounds that do not decompose over a considerable period of time at -20 OC but are unstable at room temperature. When heated they decompose more or less violently; the phenyl compounds deflagrate with formation of much soot.

The 3IP-NMR signals are shifted downfield compared with the corresponding chlorophosphoranes. When plotted against the number of phenyl groups the values lie to a good approximation on a parabola with its minimum at n M 1.2.

They agree with those of the hexachloroantimonates [(C6H5),PC14_,]SbC16 (2) which were prepared for comparison. The position of the 31P signal of a solution of PC14C104 in nitromethane is comparable 131 with the signals of [PC14]AlC14 (-86.5 ppm) [4J, of [PC14]+ in crystalline PCls (-96, -92 ppm)[5,6], and of PC12F3 (-95 ppm)[61.

Compounds (1) are thus to be considered as chlorophosphonium perchlorates.

Chlorophosphonium perchlorates :

An equivalent amount of an approximately 1 M solution of anhydrous HC1O4 in CHzCI2 is stirred into a solution or suspension of a chlorophosphorane (C6H5)nPC15-n, n = 0 to 3, in CH2C12 at 20 'C. The perchlorates crystallize spontaneously or after cautious concentration. The solubility increases greatly with increase in n.