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• 2037-26-5 ⁽²⁾H₈-toluene 
• 25837-05-2 ethylbenzene-d10 
• 84272-90-2 ethyl-α,α-d2-benzene-d5 
• 143800-05-9 perfluoroacetyldiisopropylmethyl radical 
• 3229-40-1 phthalimide N-oxyl 
• 18860-15-6 phenylmethanide 

Relevant academic research and scientific papers

Multiphoton Ionization Detection of Gas-Phase Benzyl Radicals

Benzyl and benzyl-d7 radicals generated in a flow reactor were detected by mass-resolved, resonance-enhanced multiphoton ionization spectroscopy.The strongest features of the spectra were observed between 500 and 510 nm.In both isotopic species an electro

Deuterium isotope effects on photodecomposition of alkylbenzenes

Photodissociation of 11 alkylbenzenes (toluene, ethylbenzene, butylbenzene, and their deuterated compounds) have been studied by the ArF (193 nm) laser photolysis.Formation rate constants of benzyl radical were measured under collision free conditions.The

Formation of D Atoms in the Pyrolysis of Toluene-d8 behind Shock Waves. Kinetics of the Reaction C7D8 + H -> C7D7H + D

Dilute mixtures (5-20 ppm) of toluene-d8 in argon were pyrolyzed behind reflected shock waves at temperatures of 1410-1730 K and total pressures of 3 atm.In a second group of experiments, mixtures of 20 ppm toluene-d8 and 5 ppm neopentane (which acted as a source of H atoms) were similarly pyrolyzed at 1200-1460 K.Progress of the reaction was followed by analysis for H and D atoms by using resonance absorption spectroscopy.For the reaction C6D5CD3 -> C6D5CD2 + D under the experimental conditions, k1D = 1.1 x 1E14 exp(-82000 cal/RT) s-1.After allowance for isotope effects and unimolecular falloff, the high-pressure rate constant for the reaction C6H5CH3 -> C6H5CH2 + H is calculated to be k1, infinite = 2.7 x 1E14 exp(-83000 cal/RT) s-1 over the range 1000-1800 K.Estimated uncertainties are a factor of 1.5 in k1D and 2 in k1, infinite.For the reaction D + C6D5CD3 -> C6D5CD2 + D2, k2D2 = 2.1 x 1E15 exp(-15000 cal/RT) mol-1 cm3 s-1 over the range 1300-1800 K, with an uncertainty of a factor of 1.5, while after correction for isotope effects the rate constant for H + C6H5CH3 -> C6H5CH2 + H2 over the range 600-1800 K can be expressed by the non-Arrhenius equation k2 = 7.6 x 1E-5T5.5 exp(-340 cal/RT) mol-1 cm3 s-1, with an uncertainty of a factor of 2.Data were also obtained on the exchange reaction by which H atoms add to the ring of C6D5CD3, and D atoms are eliminated.For this reaction k4D = 3.5 x 1E13 exp(-3700 cal/RT) mol-1 cm3 s-1 in the range 1200-1500 K, with an estimated uncertainty of a factor of 1.5.

Kinetic Study of the Phthalimide N-Oxyl Radical in Acetic Acid. Hydrogen Abstraction from Substituted Toluenes, Benzaldehydes, and Benzyl Alcohols

The phthalimide N-oxyl (PINO) radical was generated by the oxidation of N-hydroxyphthalimide (NHPI) with Pb(OAc)4 in acetic acid. The molar absorptivity of PINO. is 1.36 × 103 L mol -1 cm-1 at λmax 382 nm. The PINO radical decomposes slowly with a second-order rate constant of 0.6 ± 0.1 L mol-1 s-1 at 25°C. The reactions of PINO . with substituted toluenes, benzaldehydes, and benzyl alcohols were investigated under an argon atmosphere. The second-order rate constants were correlated by means of a Hammett analysis. The reactions with toluenes and benzyl alcohols have better correlations with σ+ (ρ = -1.3 and -0.41), and the reaction with benzaldehydes correlates better with σ (ρ = -0.91). The kinetic isotope effect was also studied and significantly large values of kH/kD were obtained: 25.0 (p-xylene), 27. 1 (toluene), 27.5 (benzaldehyde), and 16.9 (benzyl alcohol) at 25°C. From the Arrhenius plot for the reactions with p-xylene and p-xylene-d10, the difference of the activation energies, EaD - E aH, was 12.6 ± 0.8 kJ mol-1 and the ratio of preexponential factors, AH/AD, was 0.17 ± 0.05. These findings indicate that quantum mechanical tunneling plays an important role in these reactions.

Structure and reactivity of perfluorinated branched α-ketoradicals

Fluoroaliphatic hydroxyketoradicals prepared by photochemical reduction of the corresponding α-diketones and (i-C3F7)2CC(O)CF3 react with hydrogen abstraction (according to ESR data). The hydroxyketor

One-Electron Oxidation of Alkylbenzenes in Acetonitrile by Photochemically Produced NO3.: Evidence for an Inner-Sphere Mechanism

The reaction between NO3. and polyalkylbenzenes was studied using 308-nm laser flash photolysis of cerium(IV) ammonium nitrate in the presence of the alkylbenzenes in acetonitrile solution.For all benzenes, with the exception of monoalkylbenzenes and o- and m-xylene, the reaction with NO3. was found to yield the corresponding radical cations and to proceed in an apparently straightforward bimolecular manner.For monoalkylbenzenes and o- and m-xylene, radicals were seen which are derived from the parents by formal loss of H. from the side chain of the aromatic.This reaction proceeds via a complex between the aromatic and NO3. with the decomposition of the complex being rate determining at higher concentrations of aromatic (rate constants for decomposition between 6 * 105 and 4 * 107 s-1).In the complex, electron transfer from the aromatic to NO3. is suggested to be concerted with deprotonation of the incipient radical cation.Formation of a complex between NO3. and aromatics is likely even in those cases where radical cations are observed, with the assumption that in these cases the complex decomposition rate is greater than 6 * 107 s-1.

Gas-Phase Proton Transfer from Toluenes to Benzyl Anions

Gas-phase proton-transfer kinetics of PhCH2(1-) + ArCH3 -> ArCH2(1-) + PhCH3 were studied for reactions having ΔH0rxn = 0 to -20 kcal/mol.These reactions are very slow in the absence of thermodynamic driving force; their reaction efficiencies range from 0.004 to 0.7.RRKM theory was applied to obtain energy differences between the proton-transfer transition state and the loose orbiting transition state from reaction efficiencies.Marcus theory provides a general model for a rate-equilibrium relationship with a constant intrinsic energy barrier of 7 kcal/mol forthe degenerate proton transfer from toluene to benzyl anion.The barrier is inferred from an RRKM fit to the energy difference of -5 kcal/mol between the proton-transfer transition state and the energy of the reactants and an estimated -12 kcal/mol for the energy of the collision complex relative to the reactants.In the reaction involving 3-nitrotoluene, electron transfer, which is some 11-12 kcal/mol less favorable than proton transfer, dominates almost exclusively.