PHOSPHORUS-NITROGEN COMPOUNDS. PART 61¹. THE REACTIONS OF OCTACHLOROCYCLOTETRA-PHOSPHAZATETRAENE WITH ETHANEDIOL, 1,3-PROPANEDIOL AND 1,4-BUTANEDIOL. SYNTHETIC AND NUCLEAR MAGNETIC RESONANCE SPECTROSCOPIC INVESTIGATIONS

Synthesis and Structural Characterization of Singly, Doubly, and Triply Bridged Derivatives of Hexachlorocyclotriphosphazene with Bis(2-hydroxyethyl) Ether and 2,2-dimethylpropane-1,3-diol

“…Preliminary reports of these investigations have appeared. 1,2 Here, we report the following new compounds: two open-chain (dangling) derivatives (4, 9.2%) and (5, 6.9%), one singly bridged derivative (6, 35.4%), two doubly bridged derivatives (8,16.6%) and (9,15.5%) as well as two triply bridged derivatives (10,8.9%) and (11,7.7%) (see Schemes 1 and 2).…”

PHOSPHORUS-NITROGEN COMPOUNDS. PART 67.1THE REACTIONS OF OCTACHLOROCYCLO-TETRAPHOSPHAZATETRAENE WITH DIETHYL BIS(HYDROXYMETHYL)MALONATE. COMPARISON OF PRODUCT TYPE AND OF THE31P,1H AND13C NUCLEAR MAGNETIC RESONANCE SPECTRA WITH THOSE OF THE DERIVATIVES OF PROPANE-1,3-DIOL AND 2,2-DIMETHYLPROPANE-1,3-DIOL

“…Whilst six-and seven-membered spiro derivatives based on the octachloride, (4), and derived from aliphatic and aromatic diols are readily i~o l a t e d ,~,~ those diols which gave rise to five-membered spiro derivatives with the trimer,3,9 gave only breakdown products with the tetramer. 5 The subject has been recently reviewed. 'O …”

The Reactions of Octachlorocyclotetraphosphazene with Difunctional Bis(2-Hydroxyethyl) Ether. Nuclear Magnetic Studies of the Products

“…The same pertains, with even greater force to the less investigated difunctional reagents and hitherto little was known in the literature. 2,45,48,49,52,53 Only two derivatives of (1), N 4 P 4 Cl 6 [NMe(CH 2 ) 2 NMe], 1a-c and N 4 P 4 Cl 6 [NH(CH 2 ) 3 NH], 1 had been isolated as such, two further ones, N 4 P 4 Cl 6 [NH(CH 2 ) 2 NH], 1 and N 4 P 4 Cl 6 [NH(CH 2 ) 2 NH], 1 merely on derivatization. Only resinous material was obtained from the reactions with ethylene glycol and diaminoethane.…”

“…The nucleophilic substitution reactions of the eight-membered ring system, N 4 P 4 Cl 8 (1) with monofunctional 18 and difunctional 1a,1c,2,49 reagents have received much less attention than those of its lower homologue, N 3 P 3 Cl 6 (2). The reactions of difunctional reagents with both of the cyclophosphazenes (1 and 2) have been of significant interest because they lead to the formation of regioisomers in substitution reactions: spiro-, ansa-, bridged-derivatives and their mixtures.…”

“…[39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54] The octachlorocyclophosphazene (1), is more reactive than the hexachlorocyclophosphazene (2); the former can also, in principle, give rise to a much larger number of products, and hence structure determination is more difficult. 2,19,51 The reactions of secondary amines, NHR 2 , gave mainly nongeminal products, although stoichiometry, reaction temperature, and solvent influence the nature of the products and their relative proportions. 3,4,19,51 From the reactions of primary amines, NH 2 R, quite a lot of resinous materials were observed, probably polymeric in nature, due to cross-linking reactions, which in essence, make the primary amines difunctional.…”