139030-18-5

Upstream product

• 100-52-7 benzaldehyde 
• 611-73-4 Benzoylformic acid 

Downstream Products

• 38719-29-8 2-Hydroxy-1,2-diphenyl-ethanol anion 

Relevant academic research and scientific papers

Gas-Phase Ion-Molecule Reactions of the Nitric Oxide Anion

The chemical reactivity of nitric oxide anion (NO(1-)) with a variety of organic neutrals at ambient energies and in argon bath gas has been probed using the flowing afterglow technique.The reactions fall into four main classes: electron transfer, dissociative electron transfer and/or displacement, collisional detachment, and clustering.Electron transfer can occur when the neutral reactant possesses a positive electron affinity greater than the electron affinity of NO., but does not always do so.Bimolecular substitution at sulfur is shown to occur with dimethyldisulfide, but for other substrates, distinguishing between displacement and dissociative electron transfer is not possible.Collisional detachment is the exclusive reaction channel observed for a few of the molecules examined and occurs to some extent with many of the neutrals tested.Cluster ion formation between NO(1-) and a number of the reactant neutrals which possess permanent dipole moments is observed.Additional pathways were observed for several of the neutrals examined.The collected observations are discussed in light of the general theory of ion-molecule reactions.

Phenylhydroxycarbene

Phenylhydroxycarbene (Ph-C-OH, 1), the parent of all arylhydroxycarbenes, was generated by high-vacuum flash pyrolysis of phenylglyoxylic acid at 600 °C and spectroscopically characterized (IR, UV-vis) via immediate matrix isolation in solid Ar at 11 K. The identity of 1 was unequivocally confirmed by the precise agreement between the observed IR bands and (unscaled) anharmonic vibrational frequencies computed from a CCSD(T)/cc-pVDZ quartic force field. The UV-vis spectrum of 1 displays a broad band with maximum absorption at 500 25 nm (2.5 ± 0.1 eV) that extends to ～640 nm (1.9 eV), in full accord with combined CCSD(T)/cc-pVQZ and EOM-CCSD/cc-pVTZ computations that yield a gas-phase vertical (adiabatic) excitation energy of 2.7 (1.9) eV. Unlike singlet phenylchlorocarbene, 1 does not undergo photochemical ring expansion. Instead, 1 exhibits quantum-mechanical hydroGenetunneling to benzaldehyde underneath a formidable barrier of 28.8 kcal mol-1, even at cryogenic temperatures. The remarkable hydroGenetunneling mechanism is supported by the temperature insensitivity of the observed half-life (2.5 h) and substantiated by a comparable theoretical half-life (3.3 h) determined from high-level barrier penetration integrals computed along the intrinsic reaction path. As expected, deuteration turns off the tunneling mechanism, so d-1 is stable under otherwise identical conditions.

Diffusion of electrically neutral radicals and anion radicals created by photochemical reactions

Diffusion processes of the intermediate radicals created by the photochemical reactions of ketones in alcoholic solvents are investigated by using the transient grating (TG) method. The electrically neutral radicals and the anion radicals of acetophenone, benzaldehyde, xanthone, benzophenone and benzil were created selectively by controlling the concentration of sodium hydroxide (NaOH) in alcoholic solvents. The translational diffusion constants (D) of the anion radicals, the neutral radicals, and the parent stable molecules can be successfully measured under the same conditions by this method. It is found that both the neutral and anion radicals diffuse slower than the parent molecules. Values of D of the anion radicals, the neutral radicals and the parent molecules are compared in detail in wide ranges of solvent viscosities, solute sizes and temperatures. Under any conditions, D values of the charged radicals are similar to those of the neutral radicals. A possible origin of such a similarity is discussed in term of the intermolecular charge polarizabilities of the radicals.

Radical Anions of Chlorinated Benzaldehydes in Aqueuos Solution

The hydrated electron and H-atom reduction of aqueous benzaldehyde as well as 2-, 3-, and 4-chlorobenzaldehyde has been studied by pulse radiolysis.The electron attachment occurs on the aldehyde group.In alkaline solutions the radical anions C6H5CHO.- and ClC6H4CHO.- are formed by reaction with eaq- as well as with (CH3)2.COH and CO2.- radicals.In acid solution the protonated forms of these anion radicals, C6H5CHOH. and ClC6H4CHOH., are obtained, pK = 8.2-8.5.The rate constants for the reaction with eaq- have been determined to be k(eaq- + C6H5CHO) = (2.4 +/- 0.2)x1010 dm3 mol-1 S-1 and k(eaq- + ClC6H4CHO = (2.2 +/- 0.2)x1010 dm3 mol-1s-1 for all three isomers.The electron transfer process from (CH3)2.COH and CO2.- to the benzaldehydes is much slower, k = (0.7-2.2)x108 dm3mol-1s-1 and k = (5.4-16)E8 dm3mol-1s-1, respectively, depending on the position of the halide.The anion radicals of the chlorobenzaldehydes undergo neither intramolecular electron transfer nor dehalogenation.This is confirmed by γ-radiolysis experiments, where neither chloride nor HCHO could be detected as final products.The carbonyl radicals decay by bimolecular processes, 2k = (1.8-2.6)E8 dm3 mol-1 s-1 at pH 10 and 2k = (0.7-1.5)109 dm3mol-1s-1 at pH 3.5.The reactions of H atoms with benzaldehyde and 2,- 3,- and 4-chlorobenzaldehyde, k(H+substrates) = (0.8-1.4)x109 dm3mol-1s-1, yield cyclohexadienyl radicals, which decay in dimolecular reactions, 2k = (2.5-3.0)x109 dm3mol-1s-1.The absorption spectra of the carbonyl radicals and carbonyl radical anions as well as that of the H-adducts of each individual substrate were measured in the range 290-500 nm and their spectroscopic characteristics determined.