Phosphonium nitrites, reactions

A kinetic study of the previously reported substitution of aromatic nitro groups by tervalent phosphorus has established an aromatic 5n2 mechanism. Similarities in values of activation energies, and in relative reactivities of phosphite and phosphonite esters, between this displacement and the Arbusov reaction suggest a related mechanism (31), while the lack of reactivity of p-dinitrobenzene is attributed to the need for intramolecular solvation (32). The exclusive formation of ethyl nitrite, rather than other isomers, is confirmed from the decomposition of triethoxy-(ethyl)phosphonium fluoroborate (33) in the presence of silver nitrite. A mechanism involving quinquevalent phosphorus (34) still seems applicable, particularly in view of the recent mechanistic work on the Arbusov reaction. ... 

Kenawy 64) immobilized ammonium and phosphonium peripheral functionalized dendritic branches on a montmorillonite supported chloromethylstyrene/methyl methacrylate copolymer (74-75). These polymer/montmorillonite-supported dendrimers were used as phase transfer catalysts (PTC) for the nucleophilic substitution reaction between -butyl bromide and thiocyanate, cyanide, and nitrite anions in a toluene or a benzene/water system. These PT catalysts could be recycled by filtration of the functionalized montmorillonite from the reaction mixture. Generally,... 

The vinylogous nitroso-substituted TTF 807 was obtained in the Wittig reaction of the phosphonium salt 800 with the aldehyde 806. The second nitroso group in 807 was introduced by nitrosation using isoamyl nitrite to give 808 (Scheme 122) <1997JOC2616>. 

If Ar = HiCO, a good yield of benzoyl cyanide is obtained. Allylic triphenyl-phosphonium halides react similarly with pentyl (isoamyl) nitrite and the products are decomposed by ethanolic potassium hydroxide to nitriles, for example, -methylcinnamonitrile is obtained in 57% yield and famesyl cyanide in 87% yield [127J. N-Nitroso compounds give nitriles on reaction with triphenylphos-phine alkylenes [128], for example... 

---