7364-22-9

Upstream product

• 67-56-1 methanol 
• 1517-63-1 4-methylphenyl(phenyl)methanol 
• 24247-44-7 (+/-)-4-methylbenzhydryl hemiphthalate 
• 779-14-6 p-methyl-a-phenylbenzylchloride 
• 124-41-4 sodium methylate 
• 82361-68-0 triphenyl-p-tolyl-methane 
• 1125-88-8 benzaldehyde dimethyl acetal 
• 2417-95-0 p-tolyllithium 
• 538-86-3 benzyl methyl ether 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 134-84-9 4-Methylbenzophenone 
• 125847-10-1 1-(4-methylphenyl)-1,2,2-triphenylethane 
• 14845-80-8 (4-methylphenyl)phenylmethylene 
• 624-31-7 4-tolyl iodide 

Downstream Products

• 5632-44-0 1-[3-(4-methylphenyl)-3-phenylpropyl]-N,N-dimethylamine 

Relevant academic research and scientific papers

Dialkyl Ether Formation by Nickel-Catalyzed Cross-Coupling of Acetals and Aryl Iodides

A new substrate class for nickel-catalyzed C(sp3) cross-coupling reactions is reported. α-Oxy radicals generated from benzylic acetals, TMSCl, and a mild reductant can participate in chemoselective cross-coupling with aryl iodides using a 2,6-bis(N-pyrazolyl)pyridine (bpp)/Ni catalyst. The mild, base-free conditions are tolerant of a variety of functional groups on both partners, thus representing an attractive C-C bond-forming approach to dialkyl ether synthesis. Characterization of a [(bpp)NiCl] complex relevant to the proposed catalytic cycle is also described.

Electronic effects on the substitution reactions of benzhydrols and fluorenyl alcohols. Determination of mechanism and effects of antiaromaticity

A range of substituted benzhydrols and fluorenols were prepared and subjected to acid catalysed methanolysis. Analysis of the rates of each of these processes showed correlation with Hammett σ+ parameters as is consistent with the significant build-up of positive charge adjacent to the ring. In combination with the similarity of the electronic susceptibility of the processes, these data suggest that both reactions proceed through a unimolecular rate-determining step. This shows that the effect of fusion of the phenyl systems (and hence potentially introducing an antiaromatic carbocation intermediate) is only to slow the rate of reaction rather than change the mechanism of the process.

Simple and direct sp3 C-H bond arylation of tetrahydroisoquinolines and isochromans via 2,3-dichloro-5,6-dicyano-1,4- benzoquinone oxidation under mild conditions

The 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-mediated sp3 C-H bond arylation of tetrahydroisoquinolines and isochromans is described. The corresponding products were facilely synthesized via a simple nucleophilic addition reaction betwee

Asymmetric nucleophilic substitution of acetals

Benzaldehyde dimethylacetal (1) and 2-aryl-1,3-dioxolanes 5 react with organolithium reagents 2 in the presence of chiral ligands such as sparteine (3), 1-alkoxy-2-aminoethanes, or 1,2-dialkoxyethanes and BF3 to afford monosubstitution products in high yields and in up to 81% enantiomeric excess. The enantioselectivity is strongly influenced by steric effects in the acetal and in the reagent. The highest ee was achieved with 2-(2-isopropyl)-1,3-dioxolane (5c) on treatment with 2-ethylphenyllithium (2i) in the presence of sparteine. The approach was applied to the synthesis of enantioenriched (S)-(-)-neobenodine (17) with 49% ee.

Kinetics and Mechanism of Reactions of Benzhydryl Chlorides with Anilines

Nucleophilic substitution reactions of substituted benzhydryl chlorides with anilines in acetonitrile and methanol are investigated.The reactions are found to proceed by the attack of nucleophile on the preformed carbocation, I, within the ion pair.The cr

RADICAL-ANIONS OF AROMATIC COMPOUNDS. XXII. THE EFFECT OF SUBSTITUENTS IN THE RADICAL-ANIONS OF BENZOPHENONE DERIVATIVES ON THE RATIO OF THE COMPETING PATHS AND ON THE COMPOSITION OF THE PRODUCTS FROM THE REACTION OF THEIR POTASSIUM SALTS WITH N,N,N-TRIMETHYLPHENYLAMMONIUM PERCHLORATE

The reaction of the potassium salts of the radical-anions of ketones C6H5COC6H4X (where X = 4-CH3, 3-CH3, 3-CH3O, and 3-F) with N,N,N-trimethylphenylammonium perchlorate in tetrahydrofuran was studied.The ratio of the rates of the processes, including nucleophilic attack at the methyl group of the ammonium cation by the radical-anion (SN) and electron transfer from the radical-anion to the electrophile (ET), and also the ratio of the products corresponding to phenylation of the ketone (the precursor of the radical-anion) formed in the latter case hardly depend at all on the nature of the substituent X.In contrast, the yield of the products corresponding to C-methylation of the radical-anion in the SN process increases with increase both in the electron-donating and in the electron-withdrawing characteristics of the substituents X.

Radical ions in photochemistry. Carbon-carbon bond cleavage of radical cations in solution: Theory and application

The cleavage of radical cations of two series of alkanes, 1,1,2-triaryl- and 1,1,2,2-tetraarylalkanes, generated by photoinduced single electron transfer in acetonitrile-methanol, occurs with formation of radical and carbocation fragments. The radical cations of some unsymmetrically substituted alkanes cleave to give all four of the possible products, two hydrocarbons emanating from the radicals and two methyl ethers from the carbocations, in proportion to the oxidation potentials of the two possible radical fragments. There is an excellent linear correlation between the logarithm of the observed ratio of products and that calculated from the reported electrochemically determined oxidation potentials (r = 0.998, 5 points). The proportionality constant (1.27) for this relationship is close to unity which indicates that the product ratio is determined by the relative rates of cleavage in the two possible modes or by equilibration of the radicals and carbocations before separation of the geminate radical carbocation pair and not by equilibration upon reencounter of freely solvated radical and carbocation fragments. The effect of temperature on the relative oxidation potentials of the radicals studied is small and can be neglected when radicals of the same order (i.e., both secondary or both tertiary) and of similar size are compared. The ratio of products obtained upon cleavage of the radical cation at 25 °C can be used to determined standard oxidation potentials of radicals. The oxidation potential of the diphenylmethyl radical (0.350 V vs SCE) has been accepted as the primary standard and the (4-methyl-phenyl)phenylmethyl (0.265 V) and bis(4-methylphenyl)methyl (0.188 V) radicals are established as secondary standards against which the oxidation potentials of other radicals can be measured. Oxidation potentials of several 4-substituted cumyl radicals have been determined by this photochemical method. There is a good (r = 0.987, 5 points) linear correlation between the measured oxidation potentials and the σ+ substituent constants. The reaction constant is appropriately negative and large (p = -6).

Photolysis of Tetraarylmethanes and 3-(Triarylmethyl)pyridines

Upon UV irradiation in benzene-methanol (1:2) tetraarylmethanes or 3-(triarylmethyl)pyridines underwent an α,α-elimination of two aryl groups to give biaryls or 3-arylpyridine, and two corresponding carbene intermediates.The latters afforded methyl ethers by O-H insertion to methanol.

The Absolute Kinetics of Several Reactions of Substituted Diphenylcarbenes

4,4'-dibromo-, 4-bromo-, 4,4'-dichloro-, 4-chloro-, 4-methyl-, 4,4'-dimethyl-, 4-phenyl-, 4-carbomethoxyl-, 4-cyano-, 4-cyano-4'-methyl-, and 4,4'-dimethyldiphenyldiazomethane were studied by laser flash photolysis.Excitation of the diazo compounds at 308 nm produced the corresponding diarylcarbenes.The kinetics of the reaction of the substituted carbenes with alkanes and methanol were examined.Hydrogen abstraction rates are largely insensitive to ring substitution, while the methanol reaction is accelerated considerably by p-methyl substitution and retarded by a para electron-withdrawing substituent.