1634-11-3

Upstream product

• 187737-37-7 propene 
• 101-81-5 Diphenylmethane 
• 78-84-2 isobutyraldehyde 
• 71-43-2 benzene 
• 6317-10-8 2,2-diphenyl-1,3-dithiolane 
• 920-39-8 isopropylmagnesium bromide 
• 5048-63-5 2,2-dimethyl-1-(phenylsulfonyl)aziridine 
• 10474-14-3 1,2-dibromo-3-chloro-2-methylpropane 
• 781-33-9 2-methyl-1,1-diphenylpropene 
• 60763-39-5 isopropyl diphenyl phosphate 
• 40685-26-5 2-methyl-1,3,3-triphenyl-propan-1-one 
• 606-86-0 1,3,3-triphenylpropan-1-one 
• 119-61-9 benzophenone 
• 5292-53-5 diethyl benzalmalonate 

Relevant academic research and scientific papers

SN2 Reaction of Diarylmethyl Anions at Secondary Alkyl and Cycloalkyl Carbons

The substitution reaction of the diethyl allylic and propargylic phosphates with Ar2CH anions was applied to sec-alkyl phosphates to compare reactivity and stereoselectivity. However, the substitution took place on the ethyl carbon of the diethyl phosphate group. We then found that the diphenyl phosphate leaving group ((PhO)2PO2) was suited for the substitution at the sec-alkyl carbon. Enantioenriched diphenyl sec-alkyl phosphates with different substituents (Me, Et, iPr) on the vicinal position underwent the substitution reaction with almost complete inversion (>99% enantiospecificity). The substitution reactions of cyclohexyl phosphates possessing cis or trans substituents (Me and/or tBu) at the C4, C3, and C2 positions of the cyclohexane ring were also studied to observe the difference in reactivity among the cis and trans isomers. A transition-state model with the phosphate leaving group ((PhO)2PO2) in the axial position was proposed to explain the difference. This model was supported by computational calculation of the virtual substitution reaction of the structurally simpler “dimethyl” cyclohexyl phosphates (leaving group = (MeO)2PO2) with MeLi. Furthermore, the calculation unexpectedly indicated higher propensity of (PhO)2PO2 as a leaving reactivity than alkyl phosphate groups such as (MeO)2PO2 and (iPrO)2PO2.

Formation of cyclopropanes by the reductive coupling of 1,3-dihalides promoted by titanocene(II) species

The treatment of various 1,3-dihalides including the ones bearing an ester group with the titanocene(II) species produced cyclopropanes in good yields. The reaction of dihalides possessing two secondary halogens proceeded stereoselectively to afford trans

Formation of cyclopropanes by homolytic substitution reactions of 3- iodopropyl radicals: Preparative and rate studies

Reduction of 2-substituted 1,3-diiodopropane derivatives with tin hydride provides substituted cyclopropanes. The reaction occurs through a homolytic substitution of the 3-iodopropyl radical, which has a rate constant of about 5 x 105 s-1 at 80°C.

Activation conditions play a key role in the activity of zeolite CaY: NMR and product studies of Bronsted acidity

CaY, activated under different conditions, was characterized with 1H, 31P, and 1H/27A] double resonance MAS NMR. The 1H MAS NMR spectra of CaY, calcined in an oven at 500 °C, shows resonances from H2O (bound to Ca2+ and the zeolite framework), CaOH+, aluminum hydroxides, silanols, and Bronsted acid sites. No evidence for Lewis acidity is observed on adsorption of trimethylphosphine, and an estimate of ≈16 Bronsted acid sites per unit cell is obtained for this sample. CaY activated in an oven at higher temperatures contains less water, but all the other species are still present. In contrast, CaY activated by slow ramping of the temperature under vacuum to 500 or 600 °C shows a much lower concentration of Bronsted acid sites (1/unit cell). Again, no evidence for Lewis acidity was observed. These NMR results have been utilized to understand the very different product distributions that are observed for reactions of 1,1- and 1,2-diarylethylenes in zeolite CaY activated in an oven (in air) and under vacuum. Samples with high concentrations of Bronsted acid sites react stoichiometrically with these sites, yielding diarylalkanes. At low concentrations, the Bronsted acid sites can act catalytically resulting in isomerization reactions.

Decarbonylative diarylation reaction of N-tosylated α-amino acids

The reaction of various N-tosylated α-amino acids with arenes in the presence of sulfuric acid afforded the corresponding diarylated derivatives in moderate yields, which were generated via decarbonylative arylation followed by Friedel-Crafts reaction of the generated tosylamide derivatives.

Modern Friedel-Crafts Chemistry. Part 24. Alkylation of Benzene with 1,2-Dibromo-3-chloro-2-methylpropane in the Presence of Lewis and Bronsted Acid Catalysts

The major alkylation products of benzene with 1,2-dibromo-3-chloro-2-methylpropane are 1-X-2-methyl-3,3-diphenylpropane (X = Cl, Br) with AlCl3 and 1,4-bis-(1-bromo-3-chloro-2-methylpropyl)benzene with AlCl3-CH3NO2 or K10 montmorillonite (K10 Clay); minor products include di- and tri-phenylated butanes and/or 2-methyl-1-phenylindane.

Catalytic activity of K10-montmorillonite in reaction of arenes with some mono- and di-functional alkylating agents, mostly derived from isobutane and isobutene

K10-montmorillonite has been tested as Friedel-Crafts catalyst in the alkylation of benzene, toluene and anisole with one or more of the alkylating agents 1-10. The reaction products consisted essentially of 1,1- and 1,2-diaryl-2-methylpropane derivatives (e.g. 11 and 12 respectively) together with side products resulting from transalkylation, monoalkylation, hvdride transfer and elimination. K 10-montmorillonite has also been used to catalyse the alkylation of naphthalene with benzyl alcohol whereby a mixture of α-and β-benzylnaphthalene is obtained. The results, explained in terms of carbocation transformations, show K 10-montmorillonite to be a mild catalyst with no subsequent side-chain isomerising ability just like FeCl3, AlCl3-CH3NO2, TiCl4 and ZrCl4.

Modern Friedel-Crafts chemistry. XVIII. Alkylation of benzene with 1,2-dibromo-2-methylpropane, 1-chloro-2-methyl-2-phenylpropane, 3-chloro-2-methyl-1-propene and 1-bromo-2-methyl-1-propene

Alkylation of benzene with the title compounds gave similar product mixture containing isomeric 1,2-diphenyl-2-methylpropane (9), 1,1-diphenyl-2-methylpropane (10) and dl and meso-2,3-diphenylbutane (11) in alkylations catalysed by appreciable amounts of AlCl3 or Al-HCl(g) and of 9 and 10 only in alkylations catalysed by the milder catalysts AlCl3-CH3NO2, ZrCl4 and TiCl4.In almost all cases, 9 and 10 were always produced in an apparent equilibrium ratio of approximately 2 : 1.These new results disproved numerous earlier reports claiming the products from these reactions to contain only 9 and meso-11 depending on catalyst and conditions.Mechanistic interpretations are given to account for the results.

Reductive electrophilic substitution of diarylmethyl methyl ethers: Synthetic applications

The reductive cleavage of diarylmethyl methyl ethers with Li metal in THF led to quantitative formation of the corresponding diarylmethyl anions. Quenching with electrophiles afforded substituted diarylmethanes in good to excellent yields.