86508-70-5

Upstream product

• 3129-17-7 diphenylcarbene 
• 908093-98-1 diazodiphenylmethane 

Downstream Products

• 119-61-9 benzophenone 
• 983-79-9 benzophenone azine 
• 118017-04-2 diphenylcarbonyl oxide 
• 38494-89-2 5-methyl-3,3-diphenyl-[1,2,4]trioxolane 
• 691889-72-2 diphenylhydroperoxyacetate 
• 93-99-2 benzoic acid phenyl ester 

Relevant academic research and scientific papers

Activation of Molecular Hydrogen by Arylcarbenes

The hydrogenation reactions of diphenylcarbene 1, fluorenylidene 2, and dibenzocycloheptadienylidene 3 were investigated in solid H2 and D2 matrices and in H2- and D2-doped argon matrices at cryogenic temperatures. The reactivity of the carbenes towards H2 increases in the order 12, 2 and 3 react fast under the same conditions via quantum chemical tunneling. In D2 both 1 and 3 are stable, whereas 2 slowly reacts. The different reactivity of the three carbenes is rationalized in terms of differing carbene stabilization energies.

Reaction of diphenyldiazomethane with singlet oxygen studied by time-resolved IR spectroscopy

(Chemical Equation Presented) The mechanism of the reaction of diphenyldiazomethane 4a with singlet oxygen has been investigated by nanosecond time-resolved UV-vis (LFP) and IR (step-scan) spectroscopy. The experiments were performed with fullerene (C60) as photosensitizer for the generation of 1O2 in nonpolar solvents (toluene and CCl 4). The UV-vis experiments allowed us to monitor the formation of benzophenone O-oxide 1a, while in the IR experiments the bleaching of 4a and the formation of benzophenone 7a and N2O was observed. The kinetic data were evaluated using Monte Carlo simulation and DFT calculations. These methods allow us to present a consistent mechanistic scheme for the reaction of 4a with 1O2 and to explain why the elusive dioxadiazole 5a as key intermediate is not directly observed.

Direct observation for the cyclization of a diarylcarbonyl oxide

Trapping and laser flash spectroscopic experiments showed that the cyclization of diphenylcarbonyl oxide is turned into a very facile process by introducing p-methoxyl substituent, the lifetime of which is as short as 10 -8 s. The trapping with

Solvent effects on the kinetics of the reaction between diphenylcarbonyl oxide and olefins

The k11 rate constants for the reaction between diphenylcarbonyl oxide and seven olefins were determined by the method of pulsed photolysis. The k11 values depend on the natures of olefins and solvents and change from 11 ± 3 for styrene in acetonitrile to (6.0 ± 0.6) × 104 dm3 mol-1 s-1 for 1,4-dichlorobutene-2 in n-decane. The rate constants for symmetrical olefins such as 1,4-dichlorobutene-2, stylbene, and cis-1,2-dichloroethylene are 1-2 orders of magnitude larger than for styrene, hexene-1, n-butyl vinyl ether, and 2-bromopropene-1. Solvent effects on k11 are considered in terms of the Winstein-Gruenwald equation. An increase in solvent polarity stabilizes carbonyl oxide and decreases the rate constant for the reaction. The products formed in the reaction between Ph2COO and styrene were studied. A possible mechanism of the reaction is discussed.

Mechanistic Study on the Reaction of Phenyldiazomethanes with Singlet Oxygen: Formation and Cycloreversion of 1,2,3,4-Dioxadiazole Intermediates

The formation of carbonyl oxides in the singlet oxygen (1O2) oxidation of phenyldiazomethanes 1 has been investigated mechanistically. Product ratios of N2/N2O, which are indicative of the selectivity in the carbonyl oxide/ketone formation, were determined by gas chromatography/mass spectrometry (GC/MS). The yields of carbonyl oxides were not affected by changing solvents but were significantly increased with the increasing electron-donating ability of substituents on diazomethanes. Rate constants for the quenching of 1O2 by 1 as determined by monitoring the emission of 1O2 at 1270 nm were also insensitive to solvents. These results suggest the predominant formation of 1,2,3,4-dioxadiazole intermediates by the cycloaddition of 1O2 to 1 followed by its cycloreversion, the selectivity of which is controlled by the relative stability of resulting carbonyl oxides. The formation of carbonyl oxides, observable from its transient absorption at ～400 nm, was in good agreement with the decay of 1O2 within the experimental error, indicating that the 1,2,3,4-dioxadiazoles are a highly labile intermediate with the lifetime of less than 100 ns.

Generation and Transient Spectroscopy of Substituted Diaryl Carbonyl Oxides

Spectroscopic and kinetic parameters for a variety of substituted diaryl carbonyl oxides in solution at room temperature are reported.These species are generated by direct reaction of oxygen with the triplet carbene derived from the corresponding diazo compound or by reaction of the diazo compound with singlet oxygen.Typically, diaryl-substituted carbonyl oxides have absorption maxima in the 400-450-nm region and decay with second-order kinetics.For example, the parent benzophenone oxide (λmax 410 nm) can be formed by reaction of the carbene with oxygen (kO2 5.0E9 M-1s-1) or by reaction of singlet oxygen with the diazo precursor (kD = 1.0E9 M-1s-1).It decays by-self-reaction with k = 1.33E7 M-1s-1 in acetonitrile and can be readily scavenged by aldehydes, e.g. for acetaldehyde k3 = 3.1E6 M-1s-1.

Reaction of Diphenylmethylene and Phenylmethylene with Oxygen. A Matrix Isolation Study

The thermal and photochemical reactions of phenylcarbene and diphenylcarbene in oxygen-doped matrices have been investigated.The primary thermal adducts of free carbenes and O2 are carbonyl O-oxides, which are characterized by IR and UV spectroscopy.Most characteristic are intense O-O stretching modes in the IR (ν=900 cm1-) and ?-->?* transitions in the UV (λ=400 nm) spectra.The carbonyl O-oxides are very photolabile toward long-wavelength irradiation (500-630 nm) and either rearrange to dioxiranes or split off oxygen atoms.The distribution of photoproductsis determined by substituents: benzophenone O-oxide mainly gives diphenyldioxirane while benzaldehyde O-oxide gives the aldehyde and oxygen atoms.The strong chemiluminescence observed during the thermal reaction is explained by the reaction of free carbenes and oxygen atoms forming a C=O bond in situ.This reaction is highly exothermic and produces carbonyl compounds in their triplet states.

Optical Modulation Spectroscopy: A Study of the Self-Reaction of Benzophenone Oxide

The biomolecular self-reaction of benzophenone oxide was investigated by optical modulation spectroscopy and by product studies.The transient decayed to give benzophenone and oxygen and the rate constants for its disappearance, 2k, are described by the expression log (2k) = (9.1 +/- 0.2) - (1.8 +/- 0.3)/θ where θ = 2.30RT kcal/mol-1.The significance of these parameters is discussed in terms of the orientational requirements for self-reaction.Benzophenone oxide was found to react with octanal with a rate constant 2.0 * 104 M-1 s-1.