Styrene deuterated

Molecular weights of polymers from styrenes deuterated in the side chain are the same as those of polystyrene prepared under the same conditions [78], and this is true also of polymers from ethylene and deuteroethylene [79]. If hydride ion transfer were rate determining an isotope effect would be expected with higher molecular weights in the deuterated polymers. The rate determining step would therefore appear to be coordination of monomer followed either by rapid transfer or insertion into the polymer chain. 

Styrene, deuterated Bates and Wignall (1968), Yang et al. (1986b)... 

Styrene is difficult to purify and keep pure. Usually contains added inhibitors (such as a trace of hydroquinone). Washed with aqueous NaOH to remove inhibitors (e.g. rert-butanol), then with water, dried for several hours with MgS04 and distd at 25° under reduced pressure in the presence of an inhibitor (such as 0.005% p-tert-butylcatechol). It can be stored at -78°. It can also be stored and kept anhydrous with Linde type 5A molecular sieves, CaH2, CaS04, BaO or sodium, being fractionally distd, and distd in a vacuum line just before use. Alternatively styrene (and its deuterated derivative) were passed through a neutral alumina column before use [Woon et al. J Am Chem Soc 108 7990 1986 Collman J Am Chem Soc 108 2588 1986]. 

Deuterated monomers (styrene, butadiene, oxirane, hexamethylcyclotrisiloxane)... 

FIGURE 6.42 Oxidation of 3-oxa-chromanol 58 in the presence of 1 equivalent of water mechanistic study hy means of selectively deuterated starting material. The initially formed ortho-quinone dimethide 63 rearranges into styrene derivative 64, which then reacts with water to provide acetophenone 61. 

Bruder and Brenn (1992) studied the spinodal decomposition in thin films of a blend of deuterated polystyrene (dPS) and poly(styrene-co-4-bromostyrene) (PBrxS) by TOF-ERDA. They examined the effect of different substrates on the decomposition process. In one series of experiments, a solution of the polymers in toluene was spread on a silicon wafer to form a film of thickness 550 nm which was then heated in vacuum at 180°C for various times. 

Baldwin et al. have used the same catalyst/diazo ester combination for the synthesis of optically active deuterated phenylcyclopropanes (Scheme 28) 197). From cis-1,2-dideuteriostyrene, d/-menthyl a-deuteriodiazoacetate and (+)-195d, the cis- and mnw-cyclopropanes 196 were obtained, both with 90% optical purity. The dominant enantiomer of trans-196 had (+)-(15, IS, 35) configuration. Analogously, the cyclopropanes c -198 and trans-198, obtained from styrene, d/-menthyl a-deuteriodiazoacetate and (+)-195d with subsequent transesterification of cisjtrans-197, had optical purities of 86 and 89%, respectively. The major optical isomer of cis-198 had (IS, 2R) configuration, that of trans-198 (IS, 2S) configuration. 

The ion 28 loses H2 by CID with argon to form [(PHOX)Ir(styrene)]+ (29). Compound 29 then undergoes H-D exchange with D2 gas to form the mixture of iso-topomers 29, 29-dh and 29-d2 (Scheme 13.3). When combined, these observations show that the oxidative addition of H2 to 29 is followed by alkene hydride insertion, and that both these steps occur rapidly and reversibly in the gas phase. These results thereby provide gas-phase analogues for catalytic elementary steps that are proposed to occur in solution. Support for this proposed sequence of steps was obtained from a solution-phase catalytic deuteration of styrene. Analysis showed no deuterium incorporation in the unreacted styrene at various conversions, and clean formation of dideuterio ethylbenzene as sole product. 

The data in Table 6.7 illustrate that when the non-racemic (ebthi)Zr system is used to catalyze the hydrogenation of prochiral alkenes, moderate levels of enantiofacial differentiation are observed (23—65% ee). Enantioselective deuteration of pentene occurs in low yield but shows noticeable enantioselection (23% ee). The same reaction with styrene proceeds in 61% yield and with moderate enantioselectivity (65% ee). Hydrogenation of 2-phenyl-l-pentene proceeds in excellent yield but with poor control of stereochemistry (95% yield, 36% ee). 

The enantioselectivity is determined in an irreversible step after the chiral atom has been formed. Deuteration experiments have shown that styrene... 

Zhao and Brittain [280-282] reported the LCSIP of styrene on planar silicon wafers using surface modifications of 2-(4-(ll-triethoxysilylundecyl)phenyl-2-methoxy-propane or 2-(4-trichlorosilylphenyl)-2-methoxy-d3-propane respectively. Growth of PS brushes from these SAMs has been successfully achieved factors that influence PS thickness included solvent polarity, additives and TiC concentration. Sequential polymerization by monomer addition to the same silicate substrate bearing the Hving polymer chains resulted in thicker PS films. FTIR-ATR studies using a deuterated initiator indicated that the initiator efficiency is low, and the... 

Reaction of atomic carbon with alkenes generally involves both DBA and vinyl C—H insertion. An interesting example is the reaction of C atoms with styrene in which the major products are phenylallene (21) and indene (22). The synthesis of a number of specifically deuterated styrenes and the measurement of the deuterium isotope effects on the 21/22 ratio led to the conclusion that 21 was formed by DBA followed by ring expansion and by C—H(D) insertion into and followed by rearrangement of the resultant frawi-vinylcarbene (23). The indene was formed by C—H(D) insertion into Xb followed by cyclization of the resultant cw-vinylcarbene (24) (Eq. 18). An examination of the product ratios and their label distributions when atoms are used leads to the conclusion that the ratio of C=C addition to C—H insertion is 0.72 1 in this case. 

Cpsymmetric organolanthanide complexes exhibit moderate to good enantioselectivities in the hydrogenation and deuteration of styrene and 2-phenyl-1-butene.433 Cationic iridium-phosphanodihydrooxazole complexes are more efficient catalysts for the asymmetric hydrogenation of unfunctionalized aryl-substituted alkenes. The best catalyst (42) gives high yield (>99%) and excellent enantioselectivity (97% ee) in the hydrogenation of ( )-l,2-diphenyl-l-propene 434... 

The glyoxime-Co(II)-catalyzed asymmetric cyclopropanation shown in Scheme 94 is noteworthy (226). The results of the detailed kinetic study are consistent with the mechanism of Scheme 92, however, the intermediary Co carbenoid species has substantial radicaloid properties, and only styrene and other conjugated olefins can be used as substrates. Simple alkenes are not cyclopropanated by diazo compounds. The reaction of deuterated styrene proceeds in non-stereospecific manner without retention of geometrical integrity. 

The majority of studies of asymmetric hydroformylation with rhodium and platinum complexes have made use of DIOP (49) as a ligand. With either the complex [RhCl(CO)(DIOP)] or [RhCl(C2H4)2]2 plus DIOP, styrene was hydroformylated to 2-phenylpropanal with optical yields of only 16%.366 When a-monodeuterostyrene was used as substrate, with DIOP and complex (34) as catalyst, essentially the same optical yield was obtained.367 The same catalyst with non-deuterated styrene under different conditions gave an optical yield of 25%.368... 

Figure 1.8 [45] shows a demonstration of the screening effect by King et al. [55] who investigated polystyrene in deuterated toluene by SANS the abscissa b denotes the polymer concentration in terms of the mole fraction of styrene residues. 

Such hydrophilic macromonomers (DPn=7-9) were radically homopolymer-ized and copolymerized with styrene [78] using AIBN as an initiator at 60 °C in deuterated DMSO in order to follow the kinetics directly by NMR analysis. The macromonomer was found to be less reactive than styrene (rM=0.9 for the macromonomer and rs=1.3 for styrene). Polymerization led to amphiphilic graft copolymers with a polystyrene backbone and poly(vinyl alcohol) branches. The hydrophilic macromonomer was also used in emulsion polymerization and copolymerized onto seed polystyrene particles in order to incorporate it at the interface. 

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