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Reactions of Elemental Phosphorus with Electrophiles in Super Basic Systems: XVII. Phosphorylation of Arylalkenes with Active Modifications of Elemental Phosphorus

“…Thus, 2* P n reacts with 2-vinylnaphthalene in the KOH3DMSO system at 90396oC (7 h, argon) The main product of the reactions of 2-vinylnaphthalene both with white and with ordinary red phosphorus is tertiary phosphine oxide V [24], yields 58 and 44%, respectively ( Hence, with the example of styrene and 2-vinylnaphthalene we obtained evidence to show that the available activated red phosphorus can be used to success in organophosphorus synthesis. It compares in reactivity with white phosphorus, but offers the advantage of safety, since, like ordinary commercial red phosphorus, it only ignites in air at temperatures above 250oC, and is much less toxic than white phosphorus [11,17,18].…”

“…All experiments were carried out under argon. Compounds I, II, and IV3VI were identified by means of NMR and IR spectroscopy using authentic samples [23,24]. Activated red phosphorus (( 1* P n and 2* P n ) was prepared at room temperature by 60 Co irradiation of saturated solutions of white phosphorus in benzene with capacity of absorbed dose 1.17 Gy/s (for 1* P n ) and 0.78 Gy/s (for 2* P n ).…”

Nucleophilic and free-radical additions of phosphines and phosphine chalcogenides to alkenes and alkynes

“…53 Under similar conditions, secondary phosphines 1a,f,h, 9, diphenyl-, bis(3-fluorophenyl)-, bis(4-fluorophenyl), bis(3-trifluoromethylphenyl)phosphines (10a-d), as well as phosphine oxide 5a, diphenyl-and bis[2-(2-methyl-5-pyridyl)ethyl]phosphine oxides (11a,b) add to styrene, 60,61,[92][93][94] and vinylpyridines 94 to form 2-aryl-and 2-pyridylethyldiorganylphosphines 12a-h or phosphine oxides 13a-c (the yields are 47-95%) (Scheme 6), prospective building blocks for design of complex-forming luminophores, 32,38 P,N-chelating ligands 37 and flame retardants. 13,33 13a-c …”

“…4 Later, 53,54 it has been shown that superbasic systems allows hydrophosphination of weakly electrophilic double bonds of aryl-and hetarylethenes with phosphine to synthesize previously unknown or difficult-to-prepare secondary or tertiary phosphines. [53][54][55][56][57][58][59][60][61] In these processes, instead of pure phosphine, a phosphine-hydrogen mixture generated from red phosphorus suspensions in organic solvents (dioxane, toluene) under the action of aqueous KOH 53 (or NaOH) was used.…”

“…[53][54][55][56][57][58][59][60][61] Thus, bis(2-arylethyl)-and bis(2-hetarylethyl)phosphines (1a-i) were selectively synthesized (Scheme 1) in 60-80% yield upon slow addition of alkene to a heated (45)(46)(47)(48)(49)(50)(51)(52)(53)(54)(55)(56)(57)(58)(59)(60) o C)…”