2431-23-4

Upstream product

• 1075-47-4 4-methylphenylglyoxal 
• 71-43-2 benzene 
• 7446-70-0 aluminium trichloride 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 20080-09-5 3-(4-methylphenyl)-5-phenyl-4,5-dihydroisoxazole 
• 2431-02-9 2-hydroxy-1-phenyl-2-p-tolyl-ethanone 
• 52939-89-6 5-phenyl-4-p-tolyl-2,5-dihydro-oxazole 
• 2431-00-7 p-methylbenzil 
• 2001-28-7 2-phenyl-1-p-tolyl-ethanone 
• 106-38-7 para-bromotoluene 
• 532-28-5 (RS)-mandelonitrile 
• 4410-31-5 (RS)-mandelamide 
• 56637-44-6 2-(4-methylphenyl)-1,3-dithiane 
• 1569271-99-3 phenyl(2-p-tolyl-1,3-dithian-2-yl)methanol 

Downstream Products

• 41104-54-5 2-chloro-1-(4-methylphenyl)-2-phenyl-1-ethanone 
• 100-52-7 benzaldehyde 
• 99-94-5 p-Toluic acid 
• 62137-65-9 (+)-(1R,2S)-cis-1-(4-methylphenyl)-2-phenylethylene oxide 
• 73908-27-7 (1R,2S)-2-Chloro-2-phenyl-1-p-tolyl-ethanol 
• 2431-02-9 2-hydroxy-1-phenyl-2-p-tolyl-ethanone 
• 5359-57-9 ethyl α-phenyl-α-(4-methylphenyl)acetate 
• 127029-79-2 2-morpholinyl-2-phenyl-1-(4-methylphenyl)-1-ethanone 
• 62137-63-7 threo-p-Methyldiphenylethandiol 
• 2431-00-7 p-methylbenzil 

Relevant academic research and scientific papers

Synthesis of chiral α-diarylacetic esters by stereospecific 1,2-aryl migration promoted by in situ generated acetals from benzoins

A simple protocol for the synthesis of α-diarylacetic esters from benzoins is described. In situ generated acetal assists rapid 1,2-aryl migration in a stereospecific manner, paving the way to make enantioenriched α-diarylacetic esters from easily accessi

Mechanism of α-ketol-type rearrangement of benzoin derivatives under basic conditions

The mechanism of base-catalyzed rearrangement of ring-substituted benzoins in aqueous methanol was examined by kinetic and product analyses. Substituent effects on the rate and equilibrium constants revealed that the kinetic process has a different electron demand compared to the equilibrium process. Reactions in deuterated solvents showed that the rate of H/D exchange of the α-hydrogen is similar to the overall rate toward the equilibrium state. A proton-inventory experiment using partially deuterated solvents showed a linear dependence of the rate on the deuterium fraction of the solvent, indicating that only one deuterium isotope effect contributes to the overall rate process. All these results point to a mechanism in which the rearrangement is initiated by the rate-determining α-hydrogen abstraction rather than a mechanism with initial hydroxyl hydrogen abstraction as in the general α-ketol rearrangement.

An eco-friendly method for synthesis of symmetrical and unsymmetrical benzoin derivatives

A rapid, highly efficient and mild green synthesis of symmetrical and unsymmetrical benzoin derivatives was achieved from the reaction of benzaldehyde derivatives with potassium cyanide in dimethyl sulfoxide under argon gas and ultrasound. This simple method affords benzoin derivatives at room temperature in short reaction times with high yield and purity.

Samarium reagent-promoted formation of benzoins from diarylmethanones and DMF via a carbene rearrangement reaction

Prompted by samarium metal in DMF with TMSCl or iodine as an activator, or by SmI2/THF system, diarylmethanones react readily with DMF to afford benzoins in moderate to good yields via rearrangement of aryl groups. As for asymmetric diarylmethanones, products resulting from the migration of either aryl group were obtained, where the migration of aryl groups shows certain priority.

Direct Formation of Benzoins from Diarylmethanones via a Rearrangement Reaction Promoted by Samarium Metal in DMF

Diarylmethanones react readily with DMF when promoted by samarium metal in DMF with TMSCl or iodine as an activator, to afford benzoins in good to excellent yields via rearrangement of aryl groups. As for asymmetric diarylmethanones, products resulting from the migration of either aryl group were obtained, where the migration of aryl groups shows certain priority.

Antibody-Catalyzed Benzoin Oxidation as a Mechanistic Probe for Nucleophilic Catalysis by an Active Site Lysine

Aldolase antibody 24H6, which was obtained by reactive immunization against a 1,3-diketone hapten, is shown to catalyze additional reactions, including H/D exchange and oxidation reactions. Comparison of the H/D exchange reaction at the α-position of a wide range of aldehydes and ketones by 24H6 and by other aldolase antibodies, such as 38C2, pointed at the significantly larger size of the 24H6 active site. This property allowed for the catalysis of the oxidation of substituted benzoins to benzils by potassium ferricyanide. This reaction was used as a mechanistic probe to learn about the initial steps of the 24H6-catalyzed aldol condensation reaction. The Hammett correlation (ρ=4.7) of log(kcat) versus the substituent constant, σ, revealed that the reaction involves rapid formation of a Schiff base intermediate from the ketone and an active site lysine residue. The rate-limiting step in this oxidation reaction is the conversion of the Schiff base to an enamine intermediate. In addition, linear correlation (ρ= 3.13) was found between log(KM) and σ, indicating that electronic rather than steric factors are dominant in the antibody-substrate binding phenomenon and confirming that the reversible formation of a Schiff base intermediate comprises part of the substrate-binding mechanism.

Unusual redox behavior in the photoinduced electron-transfer reactions of amino ketones

Irradiation of a wet benzene solution of 1,2-diphenyl-2-piperidino-l-ethanone and 9,10-dicyanoanthracene leads to the formation of benzil and deoxybenzoin. We have interpreted these products as arising from deprotonation leading to net oxidation coupled with reductive elimination. The latter pathway is noteworthy in that we show reductive elimination of an electron donor can be a chief consequence of photochemical single electron transfer (SET) quenching.

Singlet oxygen mediated fragmentation of amino alcohols, 1,2-diamines, and amino ketones

Irradiation of aerated solutions of singlet oxygen sensitizers such as Rose Bengal, Rose Bengal derivative, or palladium tetraphenylporphyrin in the presence of substituted amines (amino alcohols, 1,2-diamines, and amino ketones) results in oxidative fragmentation of the amine in good chemical yield and with low-to-moderate quantum efficiency. For the amino alcohols and 1,2-diamines the reaction course is similar to that initiated by irradiation of electron-transfer "sensitizers" such as thioindigo or cyanoaromatics. In these cases the reaction has been shown to proceed via single electron transfer oxidation of the amine and subsequent cleavage of the amine cation radical. A similar mechanism is proposed for the reaction with singlet oxygen sensitizers in which singlet oxygen initiates reaction by SET oxidation of the amine donors and subsequent reaction from the resulting superoxide-amine cation ion radical pair. For reaction with amino ketones under the same conditions, irradiation results in formation of novel fragmentation products incorporating oxygen. Labeling studies with O-18 enriched oxygen indicate that air is the source of certain of the incorporated oxygen in the products and suggest a mechanism closely related to the other fragmentation processes.

The Chemistry of N-Substituted Benzotriazoles. Part 6. A New Synthetic Route to Aromatic Ketones

Lithiation of p-bis(benzotriazol-1-yl)methyltoluene (4) gives the carbanion (5) which affords substitution products with many electrophiles.Acidic hydrolysis of the lithiation products affords the corresponding aromatic ketones in good yield.The syntheses of simple ketones, of diketones, and of α-hydroxy ketones are described.

ASYMMETRIC REDUCTION OF BENZIL TO BENZOIN CATALYZED BY THE ENZYME SYSTEM OF A MICROORGANISM

Benzil was reduced by incubation with a bacterium in a nutrient medium to afford (R)-benzoin.Substituted benzils were also hydrogenated to the corresponding benzoins in a similar manner.