1016-09-7

Usage

Synthesis Reference(s)

The Journal of Organic Chemistry, 23, p. 233, 1958 DOI: 10.1021/jo01096a022Synthesis, p. 633, 1974 DOI: 10.1055/s-1974-23387

Upstream product

• 67-56-1 methanol 
• 91-01-0 1,1-Diphenylmethanol 
• 117-34-0 2,2-diphenylacetic acid 
• 71964-91-5 benzhydryl-trimethyl-ammonium; bromide 
• 2235-01-0 dimethoxydiphenylmethane 
• 77-78-1 dimethyl sulfate 
• 776-74-9 Bromodiphenylmethane 
• 908093-98-1 diazodiphenylmethane 
• 119-61-9 benzophenone 
• 74-87-3 methylene chloride 
• 57977-95-4 dimethyl (1-methoxyethyl)phosphonate 
• 124-41-4 sodium methylate 
• 5655-25-4 2,2,4-triphenylchromane 
• 74-88-4 methyl iodide 

Downstream Products

• 464-72-2 tetraphenylethane-1,2-diol 
• 985-93-3 1,2-dimethoxy-1,1,2,2-tetraphenyl-ethane 
• 386-90-3 1-(2-fluoro-phenyl)-2,2-diphenyl-ethanone 
• 1733-63-7 1,2,2-triphenylethan-1-one 
• 7475-61-8 methoxy-diphenyl-acetic acid 
• 5152-68-1 benzhydryl sodium 
• 102319-30-2 methyl-(1,1,2-triphenyl-ethyl)-ether 
• 599-67-7 1,1-diphenylethanol 
• 1103-83-9 α-Methoxy-α,α'-diphenyl-bibenzyl 
• 20017-67-8 3,3-diphenylpropan-1-ol 
• 60344-55-0 5,5-Diphenyl-1-pentanol 
• 3540-95-2 fenpiprane 
• 119-61-9 benzophenone 
• 101-81-5 Diphenylmethane 

Relevant academic research and scientific papers

Iron-catalyzed solvent-free conversion of alcohols and phenols into diphenylmethyl (DPM) ethers

A catalytic amount of iron salts enables the solvent-free preparation of diphenylmethyl (DPM) ethers of alcohols and phenols at moderate temperatures.

THE EFFECT OF OXYGEN ON THE MATRIX CHEMISTRY OF DIPHENYLCARBENE

The effect of oxygen on the matrix chemistry of diphenylcarbene is described.

Heat of reaction and reaction volume for the formation of ethers from diazo compounds in methanol

The heat of reaction and reaction volume for formation of ethers from several diazo compounds with two phenyl groups in methanol were determined by the transient grating and photoacoustic methods. It was found that the reaction volume significantly contri

Redox reaction of benzyl radicals with aromatic radical ions photogenerated. The Marcus inverted region and the selective formation of carbocations or carbanions

Efficient redox reactions of benzyl-type radicals were achieved by irradiating an aromatic donor/acceptor pair with substituted dibenzyl ketones as a radical precursor in MeOH-MeCN. In this system, the aromatic radical ion pair was generated by photoinduced electron transfer followed by one-electron oxidation and reduction of photogenerated benzyl radicals (R·) by the radical ions to afford benzyl cations (R+) and anions (R-). The cations and anions were trapped by MeOH to yield ROMe and RH, respectively. The relative product ratios were determined for a variety of donor-acceptor pairs, reflecting the relative efficiencies of the redox reaction of benzyl radicals with a steady-state concentration of radical ions. The selective formation of carbocations or carbanions was achieved in some sets of donor/acceptor pairs. Assuming that the radical ions exist in a 1:1 ratio in the steady state, the product ratios are equal to the relative electron transfer rates, which are analyzed in terms of the free energy changes of the processes. The present results indicated that the rates became maximal at the energy gap of ca. -0.5 eV, representing a novel example of the Marcus inverted region. This interpretation is discussed in comparison with other related cases and in relation to recent theories on electron transfer rates.

GENERAL METHOD FOR THE PHOTOGENERATION OF BENZOLATED CATIONIC AND ANIONIC SYSTEMS IN AQUEOUS SOLUTION. TEST OF RELATIVE STABILITY OF THESE SYSTEMS IN THE EXCITED STATE.

A general method for the photogeneration of dibenzolated carbocations and carbanions is described with the aim of testing the relative stability of these species as a function of number of pi-electrons in the excited state.

Structural Control of the Triplet-Singlet Equilibrium in Cyclophane Diarylcarbenes

The absolute reactivities of paracyclophane analogues of diphenylcarbene have been investigated by using the technique of laser flash photolysis.The results are consistent with theoretical predictions that the relative stabilities of the triplet and singlet states of these species can be controlled by changing the hybridization at the carbenic center and the torsional angle of the aryl rings.

REACTION OF DIPHENYLCARBENE WITH METHANOL.

The reaction of triplet diphenylcarbene with methanol is believed to proceed via thermal excitation to the singlet state followed by reaction of that state with the alcohol. Analysis of the related reaction kinetics led to a reported enthalpy difference of 3-5 kcal mol** minus **1 between the singlet and its triplet ground state. The authors report measurements of the activation energy, E//o//b//s//d, for reaction of triplet diphenylcarbene with methanol in various solvents and find, for example, E//o//b//s//d equals 1. 66 plus or minus 0. 20 kcal mol** minus **1 in acetonitrile. These and other results are inconsistent with published interpretations of the data and dictate a reevaluation of earlier experiments and the mechanistic conclusions drawn from them.

Electron transfer between neutral radicals generated from photolysis of diphenylmethyl 1-naphthalenecarboxylate in polar solvents

From the fact that photolysis of diphenylmethyl 1-naphthalenecarboxylate in methanol, ethanol, and 2-propanol afforded the corresponding alkoxydiphenylmethanes in addition to 1,1,2,2-tetraphenylethane and other products, it is proposed that the radical pairs of Ph2CH· and ArCO2· resulting from the photolysis undergo electron transfer to give Ph2CH+ and ArCO2- with a rate constant comparable to radical recombination in the solvent cage.

Two-photon chemistry in the laser jet: Photoionization of the diphenylmethyl radical generated by norrish type I photocleavage of benzhydryl phenyl ketone

It is shown that in the laser jet (LJ) mode (argon ion laser) the benzhydryl phenyl ketone (1) undergoes a two-photon reaction in CC14 to yield benzhydryl chloride. The one-photon products are 1,1,2,2-tetraphenylethane (3), benzophenone, and 1,1,1-trichloro-2,2-diphenylethane (4). In methanol, on the other hand, our results suggest even a three-photon reaction in which benzhydryl methyl ether (5) is produced besides the one-photon products 3 and benzophenone. The ratios of the three-photon to one-photon products, i.e. 5 to 3, depended on the wavelength (333 or 351 nm). The three-photon mechanism was established by a competition experiment, in which ketone 1 was irradiated in mixtures of CCI4 and methanol. The ratio of the two high-intensity products ether 5 and benzhydryl chloride showed a strong intensity dependence. We propose that the electronically excited diphenylmethyl radical 2*is photochemically ionized to the diphenylmethyl cation 2+ under the high-intensity LJ photolysis conditions and the latter trapped with methanol and deuteriomethanol to give the identical benzhydryl methyl ether (5). The fact that no deuterium-incorporated ether 5 was observed eliminates the carbene mechanism proposed in the literature, at least under our LJ photolysis conditions.

Reinvestigation of the Chemistry of Arylcarbenes in Polycrystalline Alcohols at 77 K. Secondary Photochemistry of Matrix-Isolated Carbenes

Photolysis of diphenyldiazomethane (DPDM) in frozen alcoholic matrices gives ground-state triplet diphenylcarbene (DPC).At 77 K 3DPC reacts primarily with alcohols by OH insertion to give ethers.Photolysis of 3DPC produces an excited carbene 3DPC* which reacts with the matrix by H-atom abstraction to ultimately give alcohol-type products.Secondary photolysis of triplet fluorenylidene at 77 K is not as prevalent as that of 3DPC.