36909-52-1

Upstream product

• 119-61-9 benzophenone 
• 33966-50-6 SEC-BUTYLAMINE 
• 124-38-9 carbon dioxide 
• 62268-73-9 diphenylcarbene 
• 4971-41-9 hydroxy-diphenyl-methyl 
• 98509-09-2 {3-[1-(3-Dimethylamino-phenyl)-ethyl]-phenyl}-phenyl-methanone 
• 98509-10-5 {4-[1-(4-Dimethylamino-phenyl)-ethyl]-phenyl}-phenyl-methanone 
• 2036-66-0 lithium diphenylcarbinolate 
• 119-61-9 benzophenone radical anion 

Downstream Products

• 119-61-9 benzophenone 
• 61770-88-5 W(2,6-diisopropylphenylisocyanide)₆ 
• 137528-43-9 {OC(C₆H₅)2C(C₆H₅)2O}UCl₂ 
• 4971-41-9 hydroxy-diphenyl-methyl 
• 25052-92-0 dimethylaniline radical 

Relevant academic research and scientific papers

Photochemistry of Benzophenone in Aliphatic Amines Studied by Laser Photolysis in the Temperature Range 300-77 K

Laser photolysis studies of benzophenone in both sec-butylamine and triethylamine were carried out in the temperature range 300-77 K.For the sec-butylamine solution of benzophenone, the transients observed after laser pulsing are found to be the ketyl and anion radicals of benzophenone.The ratio of the yield for the formation of ketyl radical to that of the anion radical is markedly dependent on temperature: the ketyl radical is the major product at high temperatures while the anion radical becomes predominant at low temperatures.On the other hand, the triethylamine solution of benzophenone gives solely the ketyl radical as a photoproduct in the temperature range studied.The photochemical reaction of benzophenone in both sec-butylamine and triethylamine is markedly suppressed on going from high to low temperatures.These results are discussed in detail on the basis of the photochemical reaction mechanism involving the formation of the triplet charge-transfer complex (i.e., triplet exciplex) between triplet benzophenone and an amine molecule.The solvent effects on the photoreaction are also discussed.

Origin of Benzophenone Ketyl in Reactions of Benzophenone with Lithium Dialkylamides. Implications for Other Possible Electron-Transfer Reactions

A reaction scheme is presented for the formation of benzophenone ketyl in reactions of lithium dialkylamides containing β-hydrogen atoms with benzophenone.The key steps are fast concerted β-hydride reduction of benzophenone to give lithium benzhydrolate, rate-limiting deprotonation of the lithium benzhydrolate to give dilithium benzophenone dianion, and fast electron transfer from the dianion to benzophenone to give two molecules of ketyl.Benzophenone is supplied throughout the course of the reaction by a retro-aldol reaction of the lithium salt of aldol-like adduct 4 formed early in the reaction.The r eaction scheme was confirmed by kinetic studies of the individual steps.The velocity of the retro-aldol reaction was orders of magnitude faster than that of ketyl formation.The deprotonation of lithium benzhydrolate by lithium diisopropylamide (LDA) in tetrahydrofuran at 22 deg C occurred with an apparent second-order rate constant which was approximately equal to one-half of the apparent second-order rate constant for ketyl formation when benzophenone was treated with LDA under similar conditions.The possibility that related sequences of reactions could occur when weak organic oxidants are treated with reagents that can act as hydride donors and bases is discussed.

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.

An Investigation by Diffusion Layer Imaging of Coupled Homogeneous Chemical Reactions of the Benzophenone Radical Anion in N,N-Dimethylformamide

The electrochemical reduction of benzophenone (BP) to its primary radical anion BP.- with coupled homogeneous chemical reactions was investigated in N,N-dimethylformamide.Protonation of BP.- with benzoic acid and with o-cresol, respectively, used as proton donors, and disproportionation of BP.- in the presence of excess Li+ ions were studied by DLI technique.Rate constants for protonation and disproportionation as well as equilibrium constants for ion association were evaluated.Possible reaction pathways, and the effect of ion association on the kinetic behaviour are discussed. - Keywords: Chemical Kinetics / Diffusion / Electrochemistry / Spectroelectrochemistry

Medium Effects in the Electroreduction of Benzophenone in Aprotic Solvents

The kinetics of electroreduction of benzophenone have been studied at a mercury ultramicroelectrode in seven aprotic solvents.In addition, the temperature dependence of the standard rate constant was determined in three solvents, and the effect of tetraalkylammonium cations on the kinetic parameters was assessed in acetonitrile.On the basis of an analysis of the solvent effects, it is shown that this fast electron-transfer reaction is adiabatic.A model for solvation of the activated complex based on three contiguous spheres corresponding to the two phenyl rings and the carbonyl group is described and used to assess the outer-sphere contribution to the Gibbs activation energy for electron transfer.

Quenching of Triplet Benzophenone by 1,4-Diazabicyclooctane in Acetonitrile Revisited

In conditions of laser flash photolysis, the kinetics of decay of the absorption of the benzophenone radical anion show that free, solvated ions are formed after electron transfer between the title compounds in neat, dry acetonitrile.Furthermore, it is shown that the opposite conclusion claimed by Devadoss and fessenden (J.Phys.Chem., 1990, 94, 4540), i.e., no ion pair dissociation, results from a misinterpretation of the transient decay rate.

Photochemistry of diphenylkeyl radicals in polar solvents

The photolysis of diphenylketyl radicals in acetonitrile leads to their photobleaching with a quantum yield of 0.10. The decay of the excited radicals occurs by four different pathways; (a) doublet-doublet fluorescence; (b) radiationless decay; (c) electron photoejection, which accounts for 20% of the observed bleaching; (d) O-H bond cleavage leading to benzophenone, which is presumed to account for the remaining 80% of the bleaching. The electrons produced in acetonitrile are trapped by ground-state benzophenone to yield its radical (λmax 710 nm); addition of electron scavengers (N2O or acetone) the formation of Ph2CO*-.

Reactions of alkali metal anions. XV. Reaction of ketones with alkali metal anions

The potassium anions were found to react with ketones to39 yield both alcoholates and enolates. On the basis of the ESR and K NMR measurements the mechanism of this reaction is proposed. According to the proposed mechanism in the first step a ketyl radical is formed which after disproportionation yields an enolate and an alcoholate but only in the case of ketones having hydrogen atom in α-position in respect to carbonyl group.

COMPARISON OF PHOTOINDUCED ELECTRON TRANSFER REACTIONS OF AROMATIC CARBONYL VS. CYANO COMPOUNDS WITH ELECTRON DONORS IN CONDENSED PHASE: THE IMPORTANCE OF THE SPIN STATE OF THE GEMINATE ION PAIR FOR OBTAINING HIGH ION YIELDS.

Photoinduced electron transfer reactions in acetonitrile with benzophenone, anthraquinone, 9-cyanoanthracene and 9,10-dicyanoanthracene as electron acceptors, and with 1,4-diazabicyclooctane and N,N-dimethylaniline as electron donors have been studied with ns-laser flash photolysis and fluorescence quenching measurements.For these systems the resulting free ion yield depends on the spin state of the geminate ion pair: its separation is very efficient if formed in a triplet state (carbonyl compounds/donors), while it is very inefficient if formed in a singlet state (cyanoantracenes/donors).In the triplet systems, geminate back electron transfer is limited by the rate of spin flip.

Altered Condensed-Phase Electron Affinities of Carbonyl- 13C-, 14C-, and 17O-Substituted Ketones

Electron spin resonance experiments have shown that the solution electron affinities of both benzoquinone (BQ) and benzophenone (BZO) in liquid ammonia are diminished when a 13C replaces the 12C in the carbonyl position.For the reaction *R+R.-=*R.-+R, where *R represents the 13C-substituted material (either BZO-13C or BQ-13C), the equilibrium constants (Keq) are 0.80 and 0.50 at -75 deg C for the BQ and BZO systems, respectively.The reduction of radioactive samples of benzophenone (mixtures of BZO and BZO-14C, 14C substitution at the carbonyl carbon) with deficient amounts of sodium metal in liquid ammonia followed by removal of the ammonia leaves a solid mixture of benzophenone and benzophenone ketyl.Sublimation of the neutral benzophenone from the anion radical salt produces benzophenone that is enhanced in radioactivity relative to the starting BZO/BZO-14C mixture.This enhancement in radioactivity is consistent with the equilibrium constant again being less than unity when *R represents the 14C-substituted benzophenone.In contrast to these results, substitution of the oxygen atom with 17O results in an increase in the relative solution electron affinity.This is explained in terms of the increase in "bonding" involving the oxygen upon reduction, due to ion association.