Primary Phosphine Oxides

New (α-Hydroxyalkyl)phosphorus Amphiphiles: Synthesis and Dissociation Constants

“…Such compounds have been synthesized from the nucleophilic addition of a phosphine to the carbonyl compounds in the presence of electrophilic trapping agents. ,− The reactions of phosphine PH 3 with aldehydes yield various products depending on their structure, the catalysts, and the solvent. Thus, with formaldehyde the corresponding phosphonium salt is obtained, whereas with other aldehydes various compounds are formed. 7a, The pecularity of these reactions is mostly due to transformations of unstable intermediate products of the condensation of one or two aldehyde molecules with the phosphine. ,, …”

“…Tetrakis( α -hydroxydodecyl)phosphonium chloride (4c): yield 70%; mp 109−111 °C (from hexane); 31 P NMR (81.01 MHz, CDCl 3 ) δ 23.5 (50%), 22.9 (16%), 22.0 (34%); 1 H NMR (250.13 MHz, CDCl 3 ) δ 5.30 (m, 4H), 4.78 (m, 4H), 1.26 (m, 80H), 0.88 (m, 12H); 13 C NMR (62.90 MHz, C 6 D 6 ) δ 62.84 (d, 1 J CP = 139.4 Hz), 43.92−22.09 (m), 14.10 (s); MS (positive FAB/glycerol) m / z 771 (M) + ; IR (KBr, cm -1 ) 3265.3 (OH). Anal.…”

Decomposition reactions of hydroxyalkylphosphorus compounds. II. Reaction of benzylbis(.alpha.-hydroxybenzyl)phosphine oxide with benzaldehyde imines

“…Oxide 1 was treated with Nbenzylidenebenzylamine (4) under several sets of conditions. Reaction occurred when the two were heated in refluxing benzene for 4 hr with or without catalysis by p-toluenesulfonic acid. The yield of 2 (R = benzyl) was higher without acid catalysis.…”

Phosphine in the synthesis of organophosphorus compounds

“…173 The 23 : 24 ratio depends on the structure of the initial ketone and increases in the sequence cyclohexanones< cyclopentanone < acetone < pentan-2-one < heptan-2-one < pentan-3-one < acetophenone < heptan-4-one from 1 : 9 (for cyclohexanone) to 9 : 1 (for heptan-4-one). 173,174 Trifluoro- 176,177 and hexafluoroacetone 172,177 react with phosphine without a catalyst at an elevated temperature (60 ± 100 8C) and pressure (10 ± 30 atm) to give primary phosphines 25 in 85% and 62% yields, respectively.…”