174644-99-6Relevant academic research and scientific papers
Reactions of tris(2,6-dimethoxyphenyl) arsine, tris(2,6-dimethoxyphenyl) stibine and tris(2,6-dimethoxyphenyl) bismuthine and their derivatives
Wada, Masanori,Miyake, Shin-Ichi,Hayashi, Shinji,Ohba, Hiroshi,Nobuki, Shin-Ichi,Hayase, Shuichi,Erabi, Tatsuo
, p. 53 - 63 (2007/10/03)
Tris(2,6-dimethoxyphenyl)arsine and tris(2,6-dimethoxyphenyl)stibine (Φ3M(Φ = 2,6-(MeO)2C6H3; M = As an Sb)) reacted with common alkyl halides (RX) to give [Φ3M-R]X, while Φ3Bi was unreactive in benzene, or it decomposed in hot alcohols. The reactions of Φ3M (As,Sb) with butyl bromide in acetonitrile were much faster than that of triphenylphosphine. Treatments of Φ3M (P,As,Sb) with N-bromosuccinimide (NBS) gave [Φ3M-OH]Br, while Φ3Bi decomposed to give 1-bromo-2,6-dimethoxybenzene. [Φ3M-OH]Br are soluble in water, and the acidity decreased in the order M = P > As > Sb. Treatments of Φ3M (As,Sb) with aqueous hydrogen peroxide gave the oxides as hydrates, Φ3MO. xH2O (x = 1 for M = As and x = 3 for M = Sb), while Φ3Bi was unreactive or decomposed. Φ3PO was brominated by NBS to give Φ′3PO.H2O (Φ′ = 3-Br-2,6-(MeO)2C6H2), which did not react with perchloric acid. In contrast, Φ3MO.xH2O (P,As,Sb) reacted with the acid to form the stable hydroxyonium salts [Φ3M-OH]ClO4. [Φ3P-OH]ClO4 formed crystals of stable 1 : 1 adducts with a variety of amines. [Φ3As-OH]ClO4 formed 1 : 1 adducts when treated with excess amounts of several amines (triethylamine,diethylamine,isobutylamine and piperidine), but they were unstable to leave amines by recrystallization. [Φ3Sb-OH]ClO4 formed unstable adducts with these amines, or it did not form. [Φ3P-SH]ClO4 formed 1 : 1 adducts with several amines, or it was deprotonated to give Φ3PS. Φ3MO.xH2O (P,As) reacted with common RX (X = Br or I) to give [Φ3M-OR]X, but Φ3SbO.3H2O reacted to give [Φ3Sb-OH]X. [Φ3P-OR]X decomposed reversibly to give Φ3PO in solutions, although [Φ3M-OR]ClO4 (P,As) could be recrystallized.
