33451-32-0

Upstream product

• 134-81-6 benzil 
• 32368-69-7 benzoyl peroxynitrate 
• 2396-01-2 phenyl radical 
• 201230-82-2 carbon monoxide 
• 938-16-9 2,2-dimethylpropiophenone 
• 2652-65-5 benzoyl radical 

Downstream Products

• 93-59-4 Perbenzoic acid 
• 1854-28-0 benzoyloxy radical 
• 790674-36-1 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cation radical 
• 14546-48-6 manganese(III) ion 

Relevant academic research and scientific papers

Matrix isolation and IR characterization of the benzoyl and benzoylperoxy radicals

The benzoyl radical 1 was synthesized in argon matrices by the thermal reaction of the phenyl radical 2 with CO. The IR spectrum, with the C=O str. vibration at: 1824.4 cm-1 is in good agreement with DFT calculations. The formation of 1 is reve

Reactions of Mn(II) and Mn(III) with alkyl, peroxyalkyl, and peroxyacyl radicals in water and acetic acid

The kinetics of oxidation of Mn(II) with acylperoxyl and alkylperoxyl radicals were determined by laser flash photolysis utilizing a macrocyclic nickel complex as a kinetic probe. Radicals were generated photochemically from the appropriate ketones in the presence of molecular oxygen. In both acidic aqueous solutions and in 95% acetic acid, Mn(II) reacts with acylperoxyl radicals with k = (0.5-1.6) × 106 M-1 s-1 and somewhat more slowly with alkylperoxyl radicals, k = (0.5-5) x 10 5 M-1 s-1. Mn(III) rapidly oxidizes benzyl radicals, k = 2.3 × 108 M-1 s-1 (glacial acetic acid) and 3.7 × 108 M-1 s-1 (95% acetic acid). The value in 3.0 M aqueous perchloric acid is much smaller, 1× 107 M-1 s-1. The decarbonylation of benzoyl radicals in H2O has k = 1.2 × 106 s -1.

Photochemistry of 9-fluorenone oxime phenylglyoxylate: A combined TRIR, TREPR and ab initio study

The photochemistry of 9-fluorenone oxime phenylglyoxylate (1) in tetrachloromethane was investigated by a variety of time-resolved methods [STEP-SCAN TRIR and time-resolved EPR (TREPR)]. Photolysis of 1 yields the benzoyl radical, carbon dioxide and the f

Radiation-induced reactions of benzoyl chloride and acrylates in solution. A pulse radiolysis study

Using electron pulse radiolysis with optical detection, the radiation- induced reactions of benzoyl chloride and acrylates were studied in tetrahydrofuran and acetonitrile solution at room temperature. In both solvents electron transfer leads to the formation of transient radical anions of acrylates (k ? 2-3 x 1010 dm3 mol-1 s-1) and of benzoyl chloride (k ? 3 x 1010 dm3 mol-1 s-1). The latter dissociates into chloride ion and the benzoyl radical (k = 3 x 106 s-1), whereas the acrylate anion transforms by protonation into a ketyl-type radical. In mixed solutions a fast electron transfer from acrylate anions to benzoyl chloride is found (k ? 1 x 1010 dm3 mol-1 s-1). The benzoyl chloride anion reacts with the monomer (k = 2.8 x 109 dm3 mol-1 s-1) with simultaneous release of Cl- , forming species which may initiate polymerization. In the presence of oxygen the formation of benzoylperoxy radicals (k = 1.6 x 109 dm3 mol-1 s-1), showing a strong absorption band in the near-UV (λ(max) = 400 nm), is observed.

Unimolecular Decomposition of Peroxynitrates

Thermal decomposition rate constants of peroxynitric acid (HO2NO2) and chloromethyl peroxynitrate (CH2ClO2NO2) were measured as a function of temperature and total pressure in a photochemical reaction chamber of 420 l volume.Peroxynitrate concentrations were monitored by long-path IR absorption using a Fourier transform spectrometer.Analysis of these results in terms of unimolecular reaction rate theories yields kinetic parameters which allow to calculate decomposition rate constants of HO2NO2 and CH2ClO2NO2 for all pressures and temperatures which are of interest for atmospheric applications.These results, together with kinetic data on the thermal decomposition of other peroxynitrates previously obtained in our laboratory, allow to rationalize the change of the bond energies in peroxynitrates (RO2-NO2) with the nature of the group R.Combination of the decomposition data with experimental results on the reverse reactions from the literature are used to determine thermochemical data of peroxynitrates. - Keywords: Peroxynitric acid / Peroxynitrates / Thermal decomposition

Kinetic and Spectroscopic Studies on Acyl Radicals in Solution by Time-Resolved Infrared Spectroscopy

A number of acyl radicals, R=O, have been generated in hexane or di-t-butyl peroxide as solvent at room temperature by 308 nm laser flash photolysis, and their spectroscopic and kinetic properties have been examined by time-resolved infrared spectroscopy.The C=O stretching frequencies for the R=O radicals are found to be higher than those of the corresponding aldehydes, RCHO, by between 108 and 128 cm-1, an effect attributed to a higher C=O bond order in the radicals.For the R=O radicals some typical values of νC=O are: CH3=O, 1864 cm-1; (CH3)3C=O, 1848 cm-1; and C6H5=O, 1828 cm-1, while the corresponding acylperoxyl radicals, RC(O)OO, formed by reaction with oxygen have νC=O values of 1838, 1840 and 1820 cm-1, respectively.The acyl radicals exhibit a reactivity towards a variety of substrates that is roughly comparable to that of simple alkyl radicals.For reactions of the benzoyl radical some typical rate constants/M-1s-1 are: CCl4, 6.0*104; C6H5SH, 4.8*107; CCl3Br, 2.2*108; Tempo, 1.1+109; and oxygen, 1.8*109.Alkanoyl radicals have a rather similar reactivity to benzoyl.The propanoyl radical reacts with tributyltin deuteride with a rate constant of 3*105 M-1s-1.The hex-5-enoyl radical undergoes a 5-exo-trig cyclization to form the 2-oxocyclopentylmethyl radical with a rate constant of 2.2*105 s-1, a value which is almost identical to that for cyclization of the hex-5-enyl radical.It is hoped that our kinetic data will prove useful in the planning of organic synthetic strategies which involve acyl radical chemistry.

Reactivities of Acylperoxy Radicals in the Photoreaction of α-Diketones and Oxygen

The photoepoxidation of olefins with α-diketones and oxygen has been studied mechanistically focusing on the reactivities of intermediate radicals.One mole of α-diketone resulted in the formation of 2 mol of epoxide together with 2 equiv of C-C cleavage of olefins.The photoepoxidation proceeds via acylperoxy radicals RCO3* and the C-C cleavage of olefins is caused by acyloxy radical RCO2*.The addition of RCO3* to olefins was found to be ca.105-fold faster than that of acylperoxy radical ROO*.The relative reactivities of olefins suggest that acylperoxy radicals behave as a strongly electrophilic radical.That is, ρ values of -1 (vs.?+) obtained in the photoepoxidation of substituted styrenes are of the same magnitude as those in the epoxidation with molecular peracids.Although the relative reactivities of olefins toward the photoepoxidation roughly parallel those for the peracid epoxidations, the additivity of methyl substituent is not always operative.This is explained by a steric retardation by too many substituents on the carbon attacked by RCO3* in addition to the relative stabilities of resulting adduct radicals between olefins and RCO3*.Since acylperoxy radicals are not reactive towards sulfides, sulfoxides, or pyridine, a selective epoxidation of double bonds is possible.The relative reactivities of olefins toward benzoyloxy and methylperoxy redicals revealed a much less electrophilic nature of these oxy radicals, the ρ values for styrenes being -0.1 to -0.2.