Notizen: Preparation of Diethylphosphinic Nitrides

Bilbo, Andrew J.

doi:10.1515/znb-1960-0516

Cited by 17 publications

(6 citation statements)

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“…The non-geminal configurations were Reaction of liquid ammonia with diethyltrichlorophosphorane gave unidentified chlorine-containing, moisture-sensitive products; on heating, a 37% yield of hexaethylcyclotriphosphazene and a 20% yield of octaethylcyclotetraphosphazene were obtained. Both compounds were soluble in water, ligroin, benzene, chloroform, carbon disulfide, carbon tetrachloride, and ethyl alcohol; on pyrolysis, both compounds gave black resinous products and one mole of ethane per mole of cyclic phosphazene (43). A similar reaction of dimethyltrichlorophosphorane gave 3-5% yields of cyclic phosphazenes, but treatment with triethylamine and ammonium chloride increased the yields to 70-75% (318).…”

Section: Phosphazene Derivatives Containing Phosphorus-carbon Bondsmentioning

confidence: 99%

“…The relative basic strengths may depend on the structure of the aminophosphazene and on the nature of the solvent. It is possible that reported chlorine-containing intermediates, some of which have been regarded as open-chain end-stoppered phosphazene polymers (29,42,43,152,197,318), are hydrochlorides. NiPi(NMe2)i 104 (30,280,281) NsP.…”

Section: B Aminolysismentioning

confidence: 99%

“…Alkyl-and aryl-phosphazenes are not easily polymerized, and thermal decomposition occurs with evolution of hydrocarbons and formation of insoluble residues (43,152,197,318,324). The higher-melting octaphenylcyclotetraphosphazene and the lower-melting geminal tetraphenyltetrachlorocyclotetraphosphazene were converted to non-elastic products on heating for several hours at 300° ( 54,369).…”

Section: Thioestersmentioning

confidence: 99%

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The Phosphazenes (Phosphonitrilic Compounds).

Shaw¹,

Fitzsimmons²,

Smith³

1962

Chem. Rev.

178

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Section: Phosphazene Derivatives Containing Phosphorus-carbon Bondsmentioning

confidence: 99%

Section: B Aminolysismentioning

confidence: 99%

Section: Thioestersmentioning

confidence: 99%

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The Phosphazenes (Phosphonitrilic Compounds).

Shaw¹,

Fitzsimmons²,

Smith³

1962

Chem. Rev.

178

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“…Trimethylsilyl, -germyl, and -stannyl derivatives of 6 An excess of Me3SiCI (2.0 mL, 15.9 mmol) was added to 7 (2.52 mmol) in 50 mL ether. The reaction was vigorous and exothermic.…”

Section: N3p3me3(ch~br)3 (5b)mentioning

confidence: 99%

The formation and reactions of carbanionic derivatives of methyl phosphazenes

Gallicano¹,

Oakley²,

Paddock³

et al. 1981

Can. J. Chem.

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. Can. J. Chem. 59,2654Chem. 59, (1981. The cyclic phosphazenes N3P3Ph4Me2, N3P3Me6, and N4P4Me, are deprotonated by alkyllithiums. The resulting carbanions react with monofunctional electrophiles to form phosphazenes carrying the groups PCHzR (R = Me, Br, I, PhC(O), COOH AsMe,, Me3M (M = Si, Ge, Sn)). Two phosphazenyl groups can be joined either by the use of adifunctional halide or by oxidative coupling of organo-copper derivatives. The formation of the carbanions, the extent of deprotonation, substituent orientation, and the dependence of reactivity on ring size, are interpreted in terms of a balance between n-electron energies and electrostatic interactions. Chem. 59,2654Chem. 59, (1981. Les methylphosphazknes cycliques N3P3PbMe,, N3P,Me, et N4P4Me8 sont dkprotones par alkyllithiums. Les carbanions formes reagissent avec des electrophiles monofonctionnels en formant des phosphazenes substitues avec les groupements PCH,R (R = Me, Br, I, PhC(O), COOH, AsMe,, Me3M (M = Si, Ge, Sn)). Deux groupements phosphazenyliques peuvent 2tre unis, soit par un halogenure blfonct~onnel, soit par couplage oxidatif de derives organocupriens. La formation des carbanions, le degre de la deprotonation, I'orientation du substituent, et la dependence de la reactivitk en fonction de la largeur d'anneau, sont interpretes en fonction de I'equilibre entre les energies des electrons-x et des interactions electrostatiques. Introduction(10). Conjugative interactions, especially, are apThe trimeric and tetrameric methylphospha-Parent in the near-planarity of the Me,NP group in zenes (NPMe,),, were first prepared by the am-the dimeth~lamido~hos~hazenes, N4P4(NMe2)8 (11) monolysis of Me2PC13 (I), and a development of the being the earliest such examplemethod (2) allows the relative yields of the twoThe synthetic possibilities of the acceptor propcompounds to be controlled. The cyclic corn-erties of the ~hosphazene ring have been expounds (NPMe,),, have been synthesized by the ploited only to a limited extent, though they can be alkylation of the corresponding fluorides (3, 4), Seen at their most direct in the reactions of the and, by the use of Grignard reagents, the series has phosphazenyl formed a h~d r i d o~h o s been extended to (NPMe,),, ( 3 , and more recently ~h a z e n e (12). In a preliminary communication (13) to (NPMe,),,.2 There is little doubt that the series We described the deprotonation of neutral methylof ethylphosphazenes (NPEt,),, (6) could be ex-phosphazenes9 and extended the reaction to the tended in the same way. Until recently, the comes-preparation of azaphosphorins from the N-methyl ponding high polymers were not available; only quaternary iodides (NPM~,),.M~I, (n = 3, 4) (14). partial alkylation of (NPF,), could be carried out NOW thatalk~l~hosphazenes can be obtained more without extensive skeletal degradation (7). A poly-easily, a more detailed study of the de~rotonation merit form of (NPM~,), (n .V 650) has now been reaction and its synthetic possibilities is justified. prepared by the elimination of Me3SiX fr...

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“…For example, octaphenylcyclotetraphosphazene, [NP(CeH6)2]4, when heated to 320-500°, gave a mixture of trimer, pentamer, hexamer, and higher homologs of unspecified molecular weight,31,32 and the ethyl analogs, [NP(C2H6)2]3oT4, underwent side-group decomposition rather than polymerization when heated. 33 No polymers have been produced by ring-cleavage polymerization of phosphazene oligomers fully substituted by the most hindered side groups, in the third category, although a number of authors have reported attempted polymerizations. For example, the compound [NP(OCH2-CF3)2]3 was converted to the tetramer rather than the polymer after 50-hr refluxing at 340°.…”

Section: Introductionmentioning

confidence: 99%

Structural Effects in Heteroatom Systems. I. The Influence of Steric Effects on Oligomer-Polymer Interconversions in the Phosphazene (Phosphonitrile) Series. A Semiempirical Approach

Allcock¹

1966

Inorg. Chem.

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The influence of side-group steric repulsions on the relative thermodynamic stability of polymeric phosphazenes and on the relative polymerizability of cyclic phosphazenes is discussed. Increasing dimensions of the side groups should progressively lower the ceiling temperature until polymer can no longer exist as a stable entity. A simple, semiempirical, graphical method is employed for the estimation of the maximum overlap of van der Waals rotational boundaries for common side groups. The calculated polymerization and depolymerization tendencies were found to be reasonably consistent with the limited, qualitative experimental data at present available. The results also suggest that most polyorganophosphazenes should occupy a cfs-

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Notizen: Preparation of Diethylphosphinic Nitrides

Cited by 17 publications

References 0 publications

The Phosphazenes (Phosphonitrilic Compounds).

The Phosphazenes (Phosphonitrilic Compounds).

The formation and reactions of carbanionic derivatives of methyl phosphazenes

Structural Effects in Heteroatom Systems. I. The Influence of Steric Effects on Oligomer-Polymer Interconversions in the Phosphazene (Phosphonitrile) Series. A Semiempirical Approach

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