The preparation and reactions of primary phosphine oxides

Bis(α‐hydroxycycloalkyl)phosphine Oxides Obtained from White Phosphorus via Phosphine Oxide H3PO: Synthesis, Molecular Structure, Coordination Properties and Biological Activity

“…Secondary phosphine oxides (SPOs) are widely used as ligands in transition metal complexes with applications in catalysis ranging from hydrolysis of nitriles, cross‐coupling reactions and cycloaddition reactions to asymmetric hydrogenation of imines and olefins . In general, SPOs can be synthesized from primary phosphines, RPH 2 , dichlorophenylphosphine, PhPCl 2 , dialkyl phosphites, HP(O)(OR) 2 and phosphine, PH 3 . However, these methods usually involve very harsh conditions and are accompanied by the formation of huge amounts of hydrogen chloride, organic phosphorus oxychloride derivatives and other by‐products.…”

“…It should be noted that these compounds cannot be prepared by reaction of the respective carbonyl compounds with PH 3 under the same conditions . Moreover, to the best of our knowledge, only phosphine oxides bearing one hydroxyl group at the α‐carbon atom have been reported; they were synthesized by reaction of ketones with PH 3 in a highly acidic medium at high temperature and high pressure . Unlike this chemical method, the used electrochemical way of phosphine oxide synthesis is simple, ecologically friendly and does not require complicated equipment.…”

Zur Chemie von Sulfiden und Seleniden primärer Phosphane — Die (1‐Hydroxyalkyl)‐organyl‐phosphansulfide und ‐selenide, neue Verbindungsklassen

“…C-NMR-naten der ( 1 -1 lydrnxyalkyl)-orga~iyl-pliosphansulti~c R(H)P(S)-CJ0H)K'R' H2-C'H?-CiH'-C1H2-CrH2c"/c" = 24,9(D)/45,2 Cz/C4 -22,7(1))/3,9 C' = 30,8(Tj/13,2 C'/C' -24,7(D)/45,3 C"/CJ = 22,h(D)/4,3 C' = 30,5(T)/12,5 126,8174 C,, = 132,3/10,1 C, = 128,6114 C,, = 132.81' 3-Me C, : 137,4 26,6/11,2; 6,5/10,3 C,, =126,7/4,4 C,, = 128,4 c,,, -128,l -,I) Die Zuordnung der Phenylkohletirtoffatome erfolgt rnit Hilfe selektivcr Phosphorenrkopplutig~experiincntc; ' ) Diastereomere; c, Liiiien konnten Irn Spektrum nicht eindeulig Iugeordnet werdcn -Zuordnung nicht gesichert, da die Verbindung im Geinisch init dcni zugehiirigen Phosphan und Phosphanselenid vorlag 1 -Hydroxyalkylreste nur ein Satz von I3C-Signalen. Da sicli die vicinalen P-C-Kopplungskonstanteri in der Form C besonders deutlich unterscheiden (1 1 ,O Hz bzw.…”

Copper(I) Chloride Cluster Complexes with Pentaphenyl‐Cyclopentaphosphane as Ligand

“…However, adding few drops of concentrated HCl(aq) to a thf solution of 2, leads to a complete conversion of 2 to phenylphosphane 3, phenylphosphane oxide 4, and phenylphosphinic acid 5. It has been previously observed that PhP(ϭ O)H 2 (4) irreversibly disproportionates to 3 and 5 according to: 2 4 Ǟ 3 ϩ 5 [18].…”

“…The primary phosphane oxide 4 is formally the hydrolysis product of 2 and is a valuable reagent (that is, 4 readily reacts with olefins, ketones, etc. [18]). We hoped that we may stabilize 4 through coordination of the basic oxygen atom to Zn 2ϩ and performed the reaction of c-(P 5 Ph 5 ) (2) with H 2 O in the presence of ZnCl 2 .…”