Phosphine 2- vinyl diphenyl

Reaction with phosphorus compounds. Hydrozirconation of vinyl(diphenyl)-phosphine at C-l is feasible, while ring cleavage of l-phenylphospha-3-cyclopentene to give homoallylic phosphines is observed. (l-Benzyl-3-pyrroline and dihydro-furan also undergo similar cleavage.)... 

Photoinitiators 2-hydroxy-2-methyl propiophenone and diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide both gave at least 100 MEKDR with no damage to the film surface when cured at a dosage as low as 0.5 J/cm2. This preference in photoinitiators has been observed in other studies of the maleate/vinyl ether system.1011... 

Nickel, dichloro [ethylenebis(dimethyl-phosphine)], 58, 133 Nickel, dichloro[ethj lenebis(diphenyl-phosphine)], 58,133 [Ni (-)-diop Cl2 ], (-)-diop=2,3-0-iso-propylidene-2,3-dihydroxy-l,4-bis(di-phenylphosphino)butane, 58, 133 Nickel, dichloro [ trimethylenebis(diphenyl-phosphine)], 58,133 NITRILES, alkylation of, 55, 91 NITRILES FROM KETONES, 58, 101 NITRILES, a vinyl, 55, 99, 101 p-Nitrobenzenesulfonyl cyanide, 57, 89 p-Nitrobenzyl alcohol, 57, 72 p-NITROBENZYL FLUORIDE, 57, 72 Nitro compounds, 56, 36 Nitronates, 56, 36... 

Simultaneously with Tilley, we studied the hydroboration of diphenyl (vinyl)phosphine with dialkylboranes (Scheme 29). 54,55 The reactions can be conducted in toluene as well as THF, and required a slightly elevated temperature for 9-H-BBN (60 °C) compared to Cy2BH (room temperature). PBs 40e and 40f were obtained in near quantitative yields as extremely hygroscopic white solids. The P-B adducts [(vinyl)Ph2P-BHR2] are likely intermediates in these hydroboration reactions. The 31P and rlB NMR data substantiate monomeric open structures for both 40e and 40f in solution. 

The variety of C2-bridged PBs was further extended by Muhoro via hydroboration of diphenyl(vinyl)phosphine with catechol- and pinacol-boranes (Scheme 29).56 To compensate for the low Lewis acidity of these boronates, the hydroboration reactions were carried out in the presence of 5 mol% of titanocene bis(catecholborane) as catalyst. The desired products 40g and 40h were obtained with complete anti-Markovnikov selectivity. The spectroscopic data and the crystallographic study performed on 40h showed the expected monomeric open structure. 

The rhenium complex 76 related to 74b was also prepared recently by Labinger and Bercaw using another synthetic strategy. 2 In this case, the pendant borane moieties were introduced by hydroboration of unsaturated phosphines in the coordination sphere of the metal. The cationic rhenium complex 75 featuring two diphenyl(vinyl)phosphines was readily converted into the corresponding bis(phosphine-borane) complex 76 (Scheme 45). The coordination mode of 76 was substantiated spectroscopically (5 nB = 87.7 ppm) and crystallographically. 

Unsubstituted secondary phosphine 2 was obtained by the reaction of the dichloride 101 with phosphine PH3 in a toluene/dimethyl sulfoxide (DMSO)/water mixture (75% yield). The reactivity of the PH function of 2 and its BH3 adduct 3 was examined in deprotonation and alkylation reactions. Compounds 2 and 3 were shown to readily react with diphenyl(vinyl)phosphine and 2-vinylpyridine to give 4 and 5, respectively. Compound 5 was converted into free trisubstituted phosphine 6 upon treatment with diethylamine <1998IC6408>. 

Phosphines add to alkenes to give alkyl phosphines and to alkynes to give vinyl phosphines. In the presence of an ytterbium (Yb) catalyst, diphenylphosphine added to diphenyl acetylene to give the corresponding vinyl phosphine. A palladium catalyst was used for the addition o-diphenylphosphine to terminal alkynes, giving the anti-Markovnikov vinyl phosphine but a nickel catalyst led to the Markovnikov vinyl phosphine.Alkenes also react with diarylphosphines... 

Other reactions of allyl- and vinyl-phosphine oxides include a detailed study of their intermolecular cyclization by a Friedel-Crafts-type procedure. In certain cases, the unsaturated oxides are generated in situ from /S-hydroxyalkyl(diphenyl)-phosphine oxides. Examples are given in Scheme 12 for the oxides (54)—(56). Control of double-bond position in the products of acid treatment of the oxides (57) has been achieved by using an organosilicon substituent. Thus simple alkyl... 

E = As, Sb or Bi) react similarly with Grignard reagents, providing routes to cyclic arsines, stibines and bismuthines. Leung s group has reported further applications of asymmetric Diels-Alder cyclisation reactions in phosphine synthesis. A platinum complex chiral auxiliary has been used to promote the asymmetric [4-1-2] Diels-Alder addition of diphenyl(vinyl)-phosphine to 3-diphenylphosphinofuran, giving the eradocycloadduct (70) as the predominant stereoisomer. Related cycloadditions between 3,4-dimethyl-1 -phenylphosphole and ester-functionalised allylic phosphines have provided chemoselective routes to optically-pure P-chiral 1,2- and... 

Polymerised phosphine oxides are generally much more stable than polymerised phosphines. A high-molecular-weight polymer can be obtained from diphenyl(vinyl)phosphine oxide using either free radical or anionic initiation (12.176). 

C=C double bond of aP-unsaturated steroidal esters. Several reports of addition reactions catalysed by transition metal compounds have also appeared. Diphenyl-phosphine adds to alkyl vinyl ethers with a high regioselectivity, in the presence of nickel(ii) and palladium(ii) complexes, giving the Markownikolf adducts (99). ... 

Garbamylphosphine oxides. Vinyl isocyanate added to a soln. of diphenyl-phosphine /Oxide in acetone, then a few drops of triethylamine hdded as catalyst, and the product isolated after several hrs. N-vinylcarbamyldiphenyl-phosphine oxide. Y 80%. F. e. s. R. C. Schulz and H. Hartmann, M. 93, 905 (1962). 

Bisphenol A based poly(arylene ether triphenylphosphine oxide/diphenyl sulfone) copolymers were solution blended with Bisphenol A dimethacrylate vinyl ester/styrene and cured with peroxide [921]. Increasing the triphenyl phosphine oxide content in the copolymer yielded improved solubihty in the vinyl ester/styrene mixture as well as the apparent miscibility of the crosslinked blend. With 100% triphenyl phosphine oxide in the copolymer, transparent blends with the cured vinyl ester were observed. Intermediate levels of the triphenyl phosphine oxide, however, gave the best fracture toughness (controlled phase separation appeared to be desired). 

The iron species [Fe(X)2 CN(PP)CH(Me) = CH(Me)N(Pr ) ] (X = Cl, Br), containing highly donating imidazolyidene ligands, have been found to be extremely active and efficient catalysts for the atom transfer radical polymerisation of styrene and methylmethacrylate. A variety of indenyl ruthenium complexes containing either phenylacetylide (C = CPh) or vinyl (CH = CHPh) ligands have been found to catalyse the dimerisation of phenylacetylene to ( )-and (Z)-l,4-diphenyl-l-en-3-yne with the activity of the catalyst dependent upon the nature of the phosphine co-ligand bound to ruthenium. The vinylidene-ruthenium(II) complexes [Ru(Cl)(L)2(C = CHR)] (R = Bu, ferrocenyl L =... 

The catalyst-free and catalyzed addition of >P(0)H species to allenyl-and alkynylphosphine oxide was investigated. The reaction of diphenyl-allenylphosphine oxide with Ph2P(X)H was performed without solvent and catalyst. In this case, the major product was the a-methylene-ethylene(bis-phosphine) derivative, while the methyl-vinyl(bisphosphine derivative) was... 

Scheme 52). Cherkasov et ah also studied the bis(Kabachnik-Fields) reaction and recent results of the Kabachnik-Fields reaction including the preparation of a-aminophosphine oxides have been reviewed. p-Aminophosphine oxides were obtained by the addition of primary and secondary amines to diphenyl(vinyl)phosphine oxide in water as the reaction medium (Scheme 53). ... 

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