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Styrene isomerization

Cyclohexene hydrogenation was catalyzed by Mo-Co clusters of different structural types. j jjg mixed-metal clusters 7-9 have been tested as homogeneous catalysts for the hydroformylation of 1-pentene and styrene. Isomerization of 1-pentene competes with hydroformylation to hexanal and 2-methylpentanal. Hydroformylation of styrene was achieved under mild conditions with moderate to high branched-to-normal selectivity when cluster 8 was employed. These clusters could be recovered in high yield (>90 X)) after catalysis. ... [Pg.629]

Acyl halides are intermediates of the carbonylations of alkenes and organic-halides. Decarbonylation of acyl halides as a reversible process of the carbo-nylation is possible with Pd catalyst. The decarbonylation of aliphatic acid chlorides proceeds with Pd(0) catalyst, such as Pd on carbon or PdC, at around 200 °C[109,753]. The product is a mixture of isomeric internal alkenes. For example, when decanoyl chloride is heated with PdCF at 200 C in a distillation flask, rapid evolution of CO and HCl stops after I h, during which time a mixture of nonene isomers was distilled off in a high yield. The decarbonylation of phenylpropionyl chloride (883) affords styrene (53%). In addition, l,5-diphenyl-l-penten-3-one (884) is obtained as a byproduct (10%). formed by the insertion of styrene into the acyl chloride. Formation of the latter supports the formation of acylpalladium species as an intermediate of the decarbonylation. Decarbonylation of the benzoyl chloride 885 can be carried out in good yields at 360 with Pd on carbon as a catalyst, yielding the aryl chloride 886[754]. [Pg.258]

The temperature of esterification has a significant influence on isomerization rate, which does not proceed above 50% at reaction temperatures below 150°C. In resins produced rapidly by using propylene oxide and mixed phthaUc and maleic anhydrides at 150°C, the polyester polymers, which can be formed almost exclusively in the maleate conformation, show low cross-linking reaction rates with styrene. [Pg.315]

Isomerization is faciUtated by esterification at temperatures above 200°C or by using catalysts, such as piperidine and morpholine (6), that are effective in raising isomerization of fumarate to 95% completion. Resins made by using fumaric acid are exclusively fumarate polymers, demonstrate higher reactivity rates with styrene, and lead to a complete cross-linking reaction. [Pg.315]

Reduction of indolenines with sodium and ethanol gives indolines. The pentachloropyr-role, obtained by chlorination of pyrrole with sulfuryl chloride at room temperature in anhydrous ether, was shown by spectroscopic methods to have an a-pyrrolenine (2H-pyrrole) structure (222). It is necessary, however, to postulate that it is in equilibrium with small but finite amounts of the isomeric /3-pyrrolenine form (3//-pyrrole 223), since pentachloropyrrole functions as a 2-aza- rather than as a 1-aza-butadiene in forming a cycloadduct (224) with styrene (80JOC435). Pentachloropyrrole acts as a dienophile in its reaction with cyclopentadiene via its ene moiety (81JOC3036). [Pg.84]

Prolonged reaction time causes the isomerization of (Z)-e-[2-(N,N-dimethylam1no)phenyl]styrene to the (E)-isomer. [Pg.43]

Fig. 2. To and We for isomers of polybutadiene and polyisoprene, and for typical average isomeric compositions in styrenic block copolymers. Fig. 2. To and We for isomers of polybutadiene and polyisoprene, and for typical average isomeric compositions in styrenic block copolymers.
In the biphasic batch reaction the best reaction conditions were found for the system [EMIM][(CF3S02)2N]/compressed CO2. It was found that increasing the partial pressure of ethylene and decreasing the temperature helped to suppress the concurrent side reactions (isomerization and oligomerization), 58 % conversion of styrene (styrene/Ni = 1000/1) being achieved after 1 h under 40 bar of ethylene at 0 °C with 3-phenyl-1-butene being detected as the only product and with a 71 % ee of the R isomer. [Pg.286]

Radical addition to conjugated systems is an important part of chain propagation reactions. The rate constants for addition of cyclohexyl radical to conjugated amides have been measured, and shown to be faster than addition to styrene. In additions to RCH=C(CN)2 systems, where the R group has a chiral center, the Felkin-Ahn rule (p. 148) is followed and the reaction proceeds with high selectivity. Addition of some radicals, such as (McsSijaSi-, is reversible and this can lead to poor selectivity or isomerization. ... [Pg.981]

FIGURE 26.56 Log Abrasion loss by a blade (solid lines) and log cut growth rate (dashed hnes) of noncrystallizing rubber compounds as function of log frictional and log tearing energy, respectively isomerized natural rubber (NR), 2 styrene-butadiene rubber (SBR), and 3 acrylate-butadiene rubber (ABR). (From Champ, D.H., Southern, E., and Thomas, A.G., Advances in Polymer Friction and Wear, Lieng Huang Lee (ed.), Plenum, New York/London, 1974, p. 134.)... [Pg.731]

The observed isomerization of j8- to a- substituted complexes probably occurs via this reaction sequence 163, 159). However, change of pH does not always change the nature of the product, e.g., styrene gives the -phenylethyl complex (CHjCHPhCo) at all pH s 163). In certain other cases one complex may react further or not at all, e.g., crotononitrile gives the a-substituted complex in neutral solution, but is reduced to butyro-nitrile in alkaline solution, while methylacrylonitrile gives the a-substituted... [Pg.356]

Thermal insertion occurs at room temperature when R is XCH2CHAr-, at 40° C when R is benzyl, allyl, or crotyl (in this case two isomeric peroxides are formed), but not even at 80° C when R is a simple primary alkyl group. The insertion of O2 clearly involves prior dissociation of the Co—C bond to give more reactive species. The a-arylethyl complexes are known to decompose spontaneously into CoH and styrene derivatives (see Section B,l,f). Oxygen will presumably react with the hydride or Co(I) to give the hydroperoxide complex, which then adds to the styrene. The benzyl and allyl complexes appear to undergo homolytic fission to give Co(II) and free radicals (see Section B,l,a) in this case O2 would react first with the radicals. [Pg.431]

Sulphated zirconia catalysts can be acidic or superacidic depending on the method of treatment. A variety of acid-catalysed reactions, referred to earlier in this section, can be carried out with sulphated zirconia. Yadav and Nair (1999) have given a state-of-the art review on this subject. Examples of benzylation of benzene with benzyl chloride / benzyl alcohol, alkylation of o-xylene with. styrene, alkylation of diphenyl oxide with 1-dodecene, isomerization of epoxides to aldehydes, acylation of benzene / chlorobenzene with p-chloro benzoylchloride, etc. are covered in the review. [Pg.137]

The related [1,2]-H shift in the isomeric triplet 1-phenylethylidene (53) was also investigated. The triplet carbene, generated from irradiation of the corresponding diazo compound, was characterized in low temperature inert matrices by EPR, IR, and UV/VIS spectroscopy. In this case, the carbene was stable in Ar up to the temperature limits of the matrix (36 K). Irradiation, however, readily converted the carbene to styrene. [Pg.441]

Photolysis of acyldisilanes at A > 360 nm (103,104) was shown, based on trapping experiments, to yield both silenes 22 and the isomeric siloxy-carbenes 23, but with polysilylacylsilanes only silenes 24 are formed, as shown by trapping experiments and NMR spectroscopy (104,122-124) (see Scheme 4). These silenes react conventionally with alcohols, 2,3-dimethylbutadiene (with one or two giving some evidence of minor amounts of ene-like products), and in a [2 + 2] manner with phenyl-propyne. Ketones, however, do not react cleanly. Perhaps the most unusual behavior of this family of silenes is their exclusive head-to-head dimerization as described in Section V. More recently it has been found that these silenes undergo thermal [2 + 2] reactions with butadiene itself (with minor amounts of the [2 + 4] adduct) and with styrene and vinyl-naphthalene. Also, it has been found that a dimethylsilylene precursor will... [Pg.33]

The monosulfonated PPh derivative, Ph2P(m-C6H4S03K) (DPM) and its rhodium complex, HRh(CO)(DPM)3 have been synthesized and characterized by IR and NMR spectroscopic techniques. The data showed that the structure was similar to [HRh(CO)(PPh3)3]. The catalytic activity and selectivity of [HRh(CO)(DPM)3] in styrene hydroformylation were studied in biphasic catalytic systems.420 421 Rh1 complexes [Rh(acac)(CO)(PR3)] with tpa (131), cyep (132), (126), ompp (133), pmpp (134), tmpp (135), PPh2(pyl), PPh(pyl)2, and P(pyl)3 were characterized with NMR and IR spectra. Complexes with (131), (132), and (126) were catalysts for hydrogenation of C—C and C—O bonds, isomerization of alkenes, and hydroformylation of alkenes.422 Asymmetric hydroformylation of styrene was performed using as catalyst precursor [Rh(//-0 Me)(COD)]2 associated with sodium salts of m-sulfonated diarylphosphines.423... [Pg.177]

A similar mechanism of chain oxidation of olefinic hydrocarbons was observed experimentally by Bolland and Gee [53] in 1946 after a detailed study of the kinetics of the oxidation of nonsaturated compounds. Miller and Mayo [54] studied the oxidation of styrene and found that this reaction is in essence the chain copolymerization of styrene and dioxygen with production of polymeric peroxide. Rust [55] observed dihydroperoxide formation in his study of the oxidation of branched aliphatic hydrocarbons and treated this fact as the result of intramolecular isomerization of peroxyl radicals. [Pg.37]


See other pages where Styrene isomerization is mentioned: [Pg.70]    [Pg.48]    [Pg.405]    [Pg.385]    [Pg.357]    [Pg.453]    [Pg.253]    [Pg.315]    [Pg.318]    [Pg.343]    [Pg.28]    [Pg.376]    [Pg.633]    [Pg.686]    [Pg.59]    [Pg.126]    [Pg.881]    [Pg.204]    [Pg.686]    [Pg.13]    [Pg.480]    [Pg.173]    [Pg.108]    [Pg.78]    [Pg.166]    [Pg.182]    [Pg.220]    [Pg.55]    [Pg.43]    [Pg.362]    [Pg.86]    [Pg.413]    [Pg.110]   
See also in sourсe #XX -- [ Pg.286 ]

See also in sourсe #XX -- [ Pg.286 ]

See also in sourсe #XX -- [ Pg.6 , Pg.286 ]




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Isomerization of styrene oxides

Styrene oxides, isomerization

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