4794-07-4

Upstream product

• 98-82-8 Isopropylbenzene 
• 108-20-3 di-isopropyl ether 
• 98-82-8 cumene radical cation 
• 142-96-1 dibutyl ether 
• 4985-62-0 phenylthiyl 
• 253185-03-4 tert-butylbenzene 
• 157462-14-1 2,2,6,6-tetramethyl-1-((2-phenylpropan-2-yl)oxy)piperidine 
• 1233319-93-1 CumOP_.(Oi-Pr)3 
• 1233319-91-9 CumOP_.(OEt)3 
• 1233319-89-5 CumOP_.(OMe)3 
• 77956-18-4 [(13)CO]-α,α'-dimethyldeoxybenzoin 
• 934-53-2 cumenyl chloride 
• 98-83-9 isopropenylbenzene 
• 775305-80-1 Methyl 2-(methoxycarbonyl)-2,3-dimethyl-3-phenylbutanoate 

Downstream Products

• 157462-14-1 2,2,6,6-tetramethyl-1-((2-phenylpropan-2-yl)oxy)piperidine 
• 344299-98-5 2-(9-azabicyclo[3.3.1]nonane-N-oxy)-2-phenylpropane 
• 98-82-8 Isopropylbenzene 
• 98-83-9 isopropenylbenzene 
• 41115-74-6 2-Methoxyphenoxyl radical 
• 1889-67-4 dicumene 

Relevant academic research and scientific papers

Reaction of Cumene with Ozone To Form Cumyl Hydrotrioxide and the Kinetics of Decomposition of Cumyl Hydrotrioxide

Cumene forms a charge-transfer complex with ozone in a number of solvents (e.g. with absorption at 360 nm in acetone).When this CT complex is photolyzed at -75 deg C or warmed above -40 deg C, reaction occurs to form both cumyl hydrotrioxide and ring-ozonated products (in ratio of about 70/30).The decomposition of the hydrotrioxide, PhCMe2OOOH, can be monitored by proton NMR in acetone-d6 using either the CH3 or the OOH hydrogens; the decomposition is first order and gives activation parameters of E = 16.0 +/- 0.1 kcal/mol and log A = 10.4 +/- 0.1.These values agree with literature data on the decomposition of aroyl hydrotrioxide (from the reaction of ozone with aromatic aldehydes) and on the decomposition of trioxides of cyclic and acyclic acetals, but they are far from the values of E = 23 kcal/mol and log A = 16 calculated using thermokinetic methods.The low activation parameters undoubtedly result from a chain decomposition of the trioxide.Therefore, we also studied the decomposition in the presence of an inhibitor, 2,6-di-tert-butyl-4-methylphenol (BHT), to eliminate the chain decomposition.In the presence of BHT, the activation parameters become E = 23.9 +/- 0.1 kcal/mol and log A = 16.4 +/- 0.1, in agreement with theory.In addition, we can follow the disappearance of the phenolic hydrogen of BHT, and it disappears with the same rate constant as does cumyl hydrotrioxide, indicating that every decomposition of the hydrotrioxide leads to two scavengeable free radicals.In the presence of BHT, the hydrotrioxide decomposes to give cumyl alcohol as the only organic product; in the absence of BHT a small yield of acetophenone also is formed, perhaps as a result of the production of the cumyltrioxyl radical in a chain process and its exothermic loss of dioxygen and subsequent β-scission of the cumyloxyl radical.This is the first time that the hydrotrioxide of a hydrocarbon has been charaterized by NMR and that Arrhenius parameters for decomposition of a hydrotrioxide have been obtained that agree with thermokinetic predictions.

Monomer- and polymer radicals of vinyl compounds: EPR and DFT studies of geometric and electronic structures in the adsorbed state

Electron paramagnetic resonance (EPR) spectroscopy was applied to study the paramagnetic species formed from styrene, 1,1-diphenylethylene, α-methylstyrene, β-methylstyrene and methylmethacrylate adsorbed on amorphous silica gel after γ-irradiation at 77

Alkyl group dissociation during corona excitation of alkylbenzenes

Well-resolved vibronic emission spectra were recorded in the visible region from the corona discharge of precursor alkylbenzenes in a technique of corona excited supersonic expansion using a pinhole-type glass nozzle. From the observed spectra, we found t

The role of structural effects on the reactions of alkoxyl radicals with trialkyl and triaryl phosphites. A time-resolved kinetic study

(Figure presented) A time-resolved kinetic study on the reactions of alkoxyl radicals with trialkyl and triaryl phosphites ((RO)3P: R = Me, Et, i-Pr, t-Bu; (ArO)3P: Ar = C6H5, 2,4-(t-Bu)2C6H3) has been carried out. In the (RO)3P series, the alkoxyl radicals (cumyloxyl (CumO ·) and benzyloxyl (BnO·)) undergo addition to the phosphorus center with formation of intermediate tetraalkoxyphosphoranyl radicals (R′OP·(OR)3: R = Me, Et, i-Pr, t-Bu; R′ = Bn, Cum). The addition rate constants are influenced by steric effects, decreasing on going from R = Me to R = t-Bu and from BnO · to CumO·. Rate constants for β-scission of the phosphoranyl radicals R′OP·(OR) 3 have also been determined, increasing, for a given alkyl group R, in the order R′ = tert-butyl · reacts with triaryl phosphites (ArO) 3P to give phenoxyl radicals, with rate constants that are influenced to a limited extent by substitution of the aromatic rings. The radical scavenging ability of these substrates is briefly discussed.

Effect of nitroxide radicals on chemically induced dynamic electron polarization of spin-correlated radical pairs in aqueous micellar solutions of sodium dodecyl sulfate

The multispin systems consisting of spin-correlated radical pairs (SCRPs) and stable nitroxide radicals, localized in micelles of sodium dodecyl sulfate (SDS), were studied by ESR and pulse laser photolysis techniques. In all the systems studied, the stab

Spectroscopic evidence of α-methylbenzyl radical in the gas phase

We report the observation of the spectroscopic evidence of the α-methylbenzyl radical in a corona excited supersonic expansion using a pinhole-type glass nozzle for the first time. The precursors, toluene, ethylbenzene, and isopropylbenzene, seeded in a l

Kinetics of hydrogen atom transfer from (η5-C 5H5)Cr(CO)3H to various olefins: Influence of olefin structure

Treating (η5-C5H5)Cr(CO)3H (1) or (η5-C5H5)Cr(CO)3D (1-d1) with an excess of olefin containing the opposite isotope generally leads to H/D exchange, althoug

Evidence for significant through-space and through-bond electronic coupling in the 1,4-diphenylcyclohexane-1,4-diyl radical cation gained by absorption spectroscopy and DFT calculations

Photoinduced single-electron-transfer promoted oxidation of 2,5-diphenyl-l,5-hexadiene by using N-methylquinolinium tetrafluoroborate/ biphenyl co-sensitization takes place with the formation of an intense electronic absorption band at 476 nm, which is attributed to the 1,4-diphenylcyclohexane-1,4-diyl radical cation. The absorption maximum (λob) of this transient occurs at a longer wavelength than is expected for either the cumyl radical or the cumyl cation components. Substitution at the para positions of the phenyl groups in this radical cation by CH3O, CH3, F, Cl, and Br leads to an increasingly larger redshift of λob. A comparison of the ρ value, which was obtained from a Hammett plot of the electronic transition energies of the radical cations versus σ+, with that for the cumyl cation shows that the substituent effects on the transition energies for the 1,4-diarylcyclohexane-1,4-diyl radical cations are approximately one half of the substituent effects on the transition energies of the cumyl cation. The observed substitu_ent-induced redshifts of λob and the reduced sensitivity of λob to substituent changes are in accordance with the proposal that significant through-space and -bond electronic interactions exist between the cumyl radical and the cumyl cation moieties of the 1,4-diphenylcyclohexane-1,4-diyl radical cation. This proposal gains strong support from the results of density functional theory (DFT) calculations. Moreover, the results of time-dependent DFT calculations indicate that the absorption band at 476 nm for the 1,4-diphenylcyclohexane-1,4-diyl radical cation corresponds to a SOMO-3-SOMO transition.

Entropy control of the cross-reaction between carbon-centered and nitroxide radicals

Absolute rate constants for the cross-coupling reaction of several carbon-centered radicals with various nitroxides and their temperature dependence have been determined in liquids by kinetic absorption spectroscopy. The rate constants range from 5 M-1 s-1 to 2.3 × 109 M-1 s-1 and depend strongly on the structure of the nitroxide and the carbon-centered radical. Grossly, they decrease with increasing rate constant of the cleavage of the corresponding alkoxyamine. In many cases, the temperature dependence shows a non-Arrhenius behavior. A model assuming a short-lived intermediate that is hindered to form the coupling product by an unfavorable activation entropy leads to a satisfactory analytic description. However, the behavior is more likely due to a barrierless single-step reaction with a low exothermicity where the free energy of activation is dominated by a large negative entropy term.

Co-solvent effects on the indirect reduction of alkyl and benzyl halides: Experimental evidence of a link between electron transfer and SN1-like processes

The influence of using water as co-solvent in N,N-dimethylformamide on the electron transfer process between electrochemically generated electron donors and alkyl and benzyl halides has been investigated. While the solvent effect in general is modest for