4299-49-4

Upstream product

• 2725-67-9 Trichlordimethylphosphoran 
• 593-51-1 methylamine hydrochloride 
• 73296-38-5 BrMe₂P=NSiMe₃ 
• 44027-52-3 Dimethyl-dichlor-phosphonium 
• 95036-78-5 dichloro-dimethyl-phosphonium; chloride 

Downstream Products

• 79807-04-8 2-[2,4,4,6,6,8-Hexamethyl-8-(2-oxo-2-phenyl-ethyl)-2λ⁵,4λ⁵,6λ⁵,8λ⁵-[1,3,5,7,2,4,6,8]tetrazatetraphosphocin-2-yl]-1-phenyl-ethanone 

Relevant academic research and scientific papers

Reaction of octafluorocyclotetraphosphonitrile with methyllithium

Octafluorocyclotetraphosphonitrile reacts with methyllithium to give methyl, dimethyl, trimethyl, and tetramethyl derivatives and finally octamethylcyclotetraphosphonitrile. All five dimethyl derivatives were found, and two of them (geminal and trans-antipodal) were characterized completely by 31P, 1H, and 19F nmr spectroscopy. Trimethylation was exclusively geminal; of the five trimethyl derivatives, the geminal-vicinal and geminal-antipodal compounds have been characterized in detail with the help of their decoupled 1H and 19F nmr spectra. The single tetramethyl derivative isolated exemplifies a novel orientation pattern in phosphonitrilic chemistry, viz., geminal substitution followed by reaction at an antipodal site. The orientation pattern and the bond length inequalities observed in the structure of gem-dimethylhexafluorocyclotetraphosphonitrile are interpreted in terms of perturbation theory applied to a delocalized π-electron system.

Synthesis and reactivity of phosphine-stabilized phosphoranimine cations, [R3P·PR′2=NSiMe3]+

A series of phosphine-stabilized phosphoranimine cations [R 3 P·PR′ 2 =NSiMe 3 ] + , which canbe regarded as derivatives of the proposed transient reactive intermedi ate [PR′ 2 =NSiMe 3 ] + in the thermalcondensation polymerization of phosphoranimines (R″O) PR′2 =NSiMe 3 to form poly(alkyl/arylphosphazenes) [PR′ 2 =N] n at 180-200°C, have been prepared. The bromide salts [R 3 P·PR′ 2 =NSiMe 3 ]Br [R′ = Me ([6] + ), OCH 2 CF 3 ([8] + ); R 3 P = Me 3 P (a), Et 3 P (b), n Bu 3 P (c), dmpm (d, dmpm = dimethylphosphinomethane), dmpe (e, dmpe = dimethylphosphinoethane)] were prepared from the direct reactions between BrMe 2 P=NSiMe 3 (5) and Br(CF 3 CH 2 O) 2 P=NSiMe 3 (7)and the corresponding tertiary phosphines R 3 P or the diphosp hines Me 2 P(CH 2 ) n PMe 2 (n = 1, 2). Cations of the type [6] + and [8] + , with electron-donating and -withdrawing groups at the phosphoranimine phosphorus center, respectively, undergo facile phosphine ligand substitution with the strong N-donor 4-dimethylaminopyridine (DMAP) to yield the corresponding DMAP-stabilized salts [DMAP·PR 2 =NSiMe 3 ]Br [R = Me ([9] + ), OCH 2 CF 3 ([10] + )]. Cations [6] + with Br - anions are particularly labile: for example, [6a]Br slowly releases PMe 3 , BrSiMe 3 , and forms cyclic phosphazenes such as [Me 2 P=N] 4 . Anion exchange reactions between the salts [6b]Br or [8c]Br and AgOTf (OTf = CF 3 SO 3 ) quantitatively afforded the corresponding and more stable triflate salts [6b]OTf and [8c]OTf.Phosphine ligand abstraction reactions with B(C 6 F 5) 3 were observed for the bromide salts [6b]Br and [8c]Br, which regenerated the phosphoranimines 5 and 7, respectively, and formed the adduct R 3 P·B(C 6 F 5 ) 3 . In contrast, the triflate salts [6b]OTf and [8c]OTf were unreactive under the same conditions. X-ray structural analysis of the P-donor stabilized cations revealed longer P-P and P-N bond lengths and smaller P-N-Si bond angles for cations [6] + compared to analogs [8] + . These structural differences were rationalized using the negative hyperconjugation bonding model. In addition, the ...

RING SYSTEMS DERIVED FROM N-SILYLPHOSPHORANIMINES

The N-silylphosphoranimines, Me3SiN=PR2X, undergo a variety of useful reactions such as condensation polymerization, Si-N bond cleavage, nucleophilic substitution at phosphorus, and deprotection of pendent P-methyl group.Several ring systems, including cyclic phosphazenes and novel B-N/P-N hybrid derivatives, are accessible from these Si-N-P reagents.