2,6-Diazidohexaphenylcyclophosphonitrile Tetramer

Sharts, Clay M.; Bilbo, Andrew J.; Gentry, David Raymond

doi:10.1021/ic50046a014

Cited by 16 publications

(14 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…An example also exists of the cis-trans rearrangement of an azido phosphazene (111) in boiling acetonitrile in the presence of lithium azide. 348 Since azido groups often function as pseudohalogeno units, the possibility exists that the rearrangement could proceed via reversible ionization of these units from phosphorus.…”

Section: Rearrangement Reactionsmentioning

confidence: 99%

See 1 more Smart Citation

Recent advances in phosphazene (phosphonitrilic) chemistry

Allcock¹

1972

Chem. Rev.

332

165

View full text Add to dashboard Cite

Section: Rearrangement Reactionsmentioning

confidence: 99%

“…Only one amine group undergoes reaction. A bis(phosphazenyl)cyclophosphazene (126) is formed when 1,5-bis(azido> reacts with triphenylphosphine.348 Cage-type compounds can be formed with diphosphines 348.…”

mentioning

confidence: 99%

Recent advances in phosphazene (phosphonitrilic) chemistry

Allcock¹

1972

Chem. Rev.

332

165

View full text Add to dashboard Cite

“…Despite these potential advantages, only a few phosphazene azide compounds have been prepared. These include the shock-sensitive hexaazido cyclic trimer [NP(N 3 ) 2 ] 3 , a triazido−trichloro trimer (N 3 P 3 Cl 3 (N 3 ) 3 ), a pentafluoro− azido trimer (N 3 P 3 F 5 (N 3 )), a pentaphenyl−azido trimer (N 3 P 3 (C 6 H 5 ) 5 (N 3 ), a hexaphenyl−diazido tetramer (N 4 P 4 (C 6 H 5 ) 6 (N 3 ) 2 ), a tetraziridino−diazido trimer (N 3 P 3 (C 2 H 2 N) 4 (N 3 ) 2 , and several ethylenediamino−tetrazido trimers . Little investigation of the nitrene chemistry of phosphazene azides has been conducted, and no evidence of insertion chemistry has been described.…”

Section: Introductionmentioning

confidence: 99%

Azidophosphazenes as Functionalized Intermediates

1999

View full text Add to dashboard Cite

The synthesis of phosphazene cyclic trimers with azido side groups and aryloxy, alkoxy, or dialkylamino cosubstituent groups was accomplished. The compounds have the basic structure N(3)P(3)(R)(x)()(N(3))(6)(-)(x)(), where R represents phenoxy, trifluoroethoxy, dimethylamino, or diethylamino groups and x = 3-5. Experiments were also conducted to determine the ability of these materials to undergo a reaction unique to azido compounds known as nitrene insertion. The aryloxy derivative, N(3)P(3)(OC(6)H(5))(5)(N(3)), yielded a nitrene insertion product when heated with 1-phenylnonane at 280 degrees C. The alkoxy derivative, N(3)P(3)(OCH(2)CF(3))(5)(N(3)), produced a nitrene insertion product when ultraviolet irradiated in an aliphatic solvent. The dialkylamino derivative, N(3)P(3)(N(CH(3))(2))(4)(N(3))(2), did not undergo nitrene insertion. The aryloxy and alkoxy azido trimers reacted with various phosphorus(III) compounds to form phosphinimines via the Staudinger reaction. Finally, sodium phenoxide displaced azides from both the alkoxy- and aryloxyphosphazene trimers while n-butylamine displaced only the azide on the alkoxy trimer.

show abstract

“…In some cases, such as N 3 P 3 (OPh) 4 (N 3 ) 2 and N 3 P 3 (OPh) 3 (N 3 ) 3 , mixtures of the cis and trans isomers were obtained even when the pure cis -non-gem-dichlorophosphazene isomer was utilized. This type of racemization has been detected in other azido phosphazenes . So far, attempts to separate the individual isomers have been unsuccessful.…”

mentioning

confidence: 77%

“…Despite these potential advantages, only a few phosphazene azide compounds have been prepared. These include the shock-sensitive hexa-azido cyclic trimer [NP(N 3 ) 2 ] 3 , a triazido-trichloro trimer (N 3 P 3 Cl 3 (N 3 ) 3 ), a pentafluoroazido trimer (N 3 P 3 F 5 (N 3 )), a pentaphenylazido trimer (N 3 P 3 (C 6 H 5 ) 5 (N 3 )), a hexaphenyldiazido tetramer (N 4 P 4 (C 6 H 5 ) 6 (N 3 ) 2 ), and several ethylenediaminotetrazido trimers. − Little investigation of the nitrene chemistry of phosphazene azides has been conducted, and no evidence of insertion chemistry has been reported.…”

mentioning

confidence: 99%