4.5- diphenyl-2-vinyl

Bazan and co-workers [93] coupled four branches of stilbene chromophores to a central C atom, leading to tetrastilbenylmethane [C(STB)4, 46a] tetrakis (4-ferf-butylstyryIstiIbenyljmethane [C(f-BuSSB)4, 46b], and the higher homolo-gue tetrakis 4-[4 -(4"-terf-butyl-styryl)styryl]stilbenyl methane [C(4R—f-Bu)4, 46c]. For 46b, Tg is 190°C, and for 46c it is as high as 230°C. Tetrakis(4,4 -2,2-diphenyl-vinyl)-l,l -biphenyl]methane [C(DPVBi)4, 47a] and the cyano derivative 47b exhibit the glass transition at 142 and 174°C, respectively. Similar compounds to 46a and 46b have also been synthesized with silicon and adaman-tane as the tetrahedral center. 

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. 

In the work of Wilkie et al.,55,56 oligomers of styrene, vinylbenzyl chloride, and diphenyl vinyl-benzylphosphate and diphenyl vinylphenylphosphate (DPVPP) have been prepared and reacted with an amine and then ion-exchanged onto clay. The resulting modified DPVPP clays have been melted blended with polystyrene and the flammability was evaluated. XRD and TEM observations proved the existence of intercalated nanocomposite structures. Cone calorimeter tests have shown a substantial reduction in the PHRR of about 70% in comparison with pure PS. According to the authors, this reduction was higher than the maximum reduction usually obtained with PS nanocomposites. Other vinylphosphate modified clay nanocomposites were also elaborated. The reduction in PHRR was greater with higher phosphorus content than for DPVPP. Consequently, the reduction in PHRR seemed attributed to both the presence of the clay and to the presence of phosphorus. 

Diphenyl-vinyl-phosphanoxid wird durch Natriumhydroxid in Wasser/Methanol in 7,2-Bis-[diphenylphosphinyl]-ethan umgewandelt. Man muB annehmen, daB sich primar Ethen und Natriumdiphenylphosphinit bilden, wobei letzteres in einer Art Michael-Addition an das noch vorhandene aktivierte Aiken addiert411. 

Diphenyl-vinyl-phosphanoxid addiert auch prim, oder sek. Amine, so z.B. Piperazin zu l,4-Bis-[2 diphenylphosphinyl-ethyl]-piperazin (67% Schmp. 279-280°) oder 1,2-Diamino-ethan zu 1,2-Bis-[2-diphenylphosphinyl-ethylamino]-ethan (56% Schmp. 143-145°)412. 

Diphenyl-(2-methyl-propyl)- XII/1, 171 Diphenyl-pentafluorphenyl- E2, 90 Diphenyl-phenylcthinyl- E2, 91 Diphenyl-(2-phenyl-l-propenyl)- E2, 91 Diphenyl-(2-phenyl-vinyl)- E2, 82, 91 Diphenyl-(frarcs-1-propenyl)- E2, 91 Diphenyl-1-propinyl- E2, 91 Diphenyl-2-pyridyl- XII/1, 170 Diphenyl-(l-triphenylsfannyl-cthyl)- E2, 90 Diphenyl-vinyl E2, 90 Di-l-propinyl-phenyl- E2, 83 Dipropyloxy- XII/2 84ff., E2, 730, 786 Ethoxy-ethyl- E2, 449... 

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>. 

The polymerization of bis( 1,1-diphenyl vinyl) monomers 59a-d gave polymers with indane units 61 and 62 and unsaturated unit 60 in the main chain (Fig. 10) [20]. Indane unit 61 or unsaturated unit 60 could be selectively obtained under the appropriate reaction conditions [20]. 

Figure 10 Indane structural units obtained by the polymerization of 1,1-diphenyl vinyl monomers 59a-d. (From Ref. 20.)...

Sinicropi et al. (1996) measured hole mobilities of N,N -bis(2,2-diphenyl-vinyl)-N,N -diphenylbenzidine (ENA-B) doped PS. ENA-B is a weakly polar molecule with a dipole moment of 0.86 Debye. In agreement with earlier work of Sugimura et al. and Han et al., the mobilities were unexpectedly high, exceeding 10-3 cm2/Vs at high concentrations and high fields. Figure 61 shows the field dependencies of the room temperature mobilities for different... 

The achiral reaction with diphenyl vinyl sulfonium triflate 73 (Table 8) has been extended to an asymmetric process in the synthesis of five- and six-membered tings, using the chiral vinyl sulfonium salt 74, with very good levels of asymmetric induction being achieved (Table 8) <2006AGE7066>. 

Poly(dimethyl diphenyl-vinyl siloxane) Chloromethylated polydiphenylsiloxane Poly(trimethylstannylstyrene-co-chlorostyrene) Poly(trimethylsilylstyrene-co-chloromethylstyrene)... 

Dimethyl-phenyl-silyloxy)-2-(2,2-diphenyl-vinyl)-1,1,2-triphenyl-866... 

Ein klassischcs Beispiel1 ist die Photoumlagerung von 3,3-Dimethyl-l,l, 5,5-tetra-phenyl-pentadien-(1,4) (I) bei direkter Bestrahlung in 3,3-Dimethyl-2-(2,2-diphenyl-vinyl)-l,1-diphenyl-cyclopropan (II) ... 

A new synthetic route for the preparation of polyisobutylene (PIB) based block copolymers was developed by combining living carbocationic and anionic polymerizations. Living PIB chains were quantitatively end-capped with 1,1-diphenylethylene (DPE) leading to 1,1-diphenyl-l-methoxy (DPOMe) and/or 2,2-diphenyl vinyl (DPV) termini. This end-capping process is very sensitive to temperature, and retroaddition of DPE occurs in an equilibrium reaction above about -70 °C. Both the DPOMe and DPV terminated PIBs, and the mixtures of the two endgroups were quantitatively metalated with K/Na alloy, Cs metal and Li dispersion in THF at room temperature. 

It has been recently found that one-pot end-quenching of LCCP with DPE, a non-homopolymerizable olefin in cationic polymerization, may yield either 1-meth-oxy-l,l-diphenylethyl (DPOMe) or 2,2-diphenyl vinyl (DPV) chain ends depending on the conditions during quenching and workup. 

Both the 2,2-diphenyl vinyl and the l-methoxy-l,l-diphenylethyl chain ends are potential endgroups for the anionic polymerization of a variety of monomers by metalation. Our earlier results indicate that quantitative metalation of the 2,2-diphenylvinyl endgroups with alkyllithium cannot be achieved, most likely because of steric hindrance. However, as described recently, the ether cleavage of 1-methoxy-l,l-diphenyl-3,3,5,5-tetramethylhexane or electron transfer to 3,3,5,5-tetra-methyl-l,l-diphenylhex-l-ene by K/Na alloy, Cs or Li led to quantitative metalation resulting in nearly quantitative initiation of the polymerization of methacrylic monomers. Both precursors led to identical (macro)initiators verified by H NMR. These compounds can be considered as models of PIB chain ends formed by LCCP of IB and subsequent end-capping with DPE. The present study deals with the application of this method to the synthesis of different AB and ABA block copolymers by the combination of LCCP and living anionic polymerization. 

Azobenzene (138) and diphenylacetylene (139) (2 mol) gave 8-(l,2-diphenyl-vinyl)-2,3,4-triphenyl-2,3-dihydrocinnoline (140) [reactants mixed together at 85°C Co(N2) (PPh3)3j, portionwise (gasj) then 85°C, 2 h Such... 

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). 

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