The ammonolysis of a chlorophosphorane is characterised by the side by side substitution and condensation competing with one another. The different results fit into one reaction model from which the determining factors may be derived. Within the normal temperature range condensation proceeds only as long as both Cl and NH2 functions at the phosphorus are present.Presubstitution by dialkylamines reduces condensation. Thus the partially alkylsubstituted tetraamino phosphonium and hexaamino diphosphorus nitride salts P (NR2)2(NH2)2⊕, N [P (NR2) (NH2)2] 2⊕ and N [P (NR2) 2 (NH2)] 2⊕ are synthesised.
Bei der Cycloaddition der Methylenamino-phosphane wird der Ausgleich zwischen nucleophilem und elektrophilem Dipolende durch die Ausbildung einer Phosphazen-(pd)n-Bindung ermoglicht. Er bleibt sicher schwlcher als -: -: =&-I
yidiphosphazene removes 2 molar equivalents of phenol from triphenyl phosphite (2a). The diphenyl alkylphosphonites (26) 131 and (2c) react similarly. The products correspond in composition t o the expected cyclotriphosphazadienes (3) but d o not have the sensitivity t o oxidation expected for such compounds; they are un-Temp. of prepn. ("C) M.p. ("C) vPH (cm-1)flask arranged for distillation. The phenol released distills into the receiver. The residue is recrystallized from benzene or acetonitrile, affording the cyclotriphosphazene (4) as colorless needles in 70-80 % yield.
Das Cyclotri‐(phosphazen) (I) addiert Carbonyl‐ Verbindungen (II), p‐Benzochinon (IV), Isothiocyanate (VI) und elektronenarme Olefine (VIII) zu den im Formelschema angegebenen Derivaten.
4-Amino-diphosphazene (1) haben sich bereits mehrfach zum Aufbau von Phosphazen-Hetero-cycle bewährt 2-4. Sie bringen dazu eine bifunktionelle fünfgliedrige PN-Kette und die Nucleophilie eines Phosphinimins mit. Ihre jetzt untersuchte Umsetzung mit Thiophosphonsäureanhydriden (2), deren Vierring durch Basen bekanntermaßen leicht aufgespalten wird, führt zu einer neuen Synthese von Cyclotriphosphazenen bestimmter Substitution.
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