51314-23-9

Upstream product

• 74-83-9 methyl bromide 
• 62268-73-9 diphenylcarbene 
• 74-87-3 methylene chloride 
• 431-47-0 trifluoroacetic acid-methyl ester 
• 612-00-0 1,1'-ethylidenebis-benzene 
• 599-67-7 1,1-diphenylethanol 
• 4985-62-0 phenylthiyl 
• 530-48-3 1,1-Diphenylethylene 
• 2025-56-1 ethyl radical 
• 4630-45-9 isobutyl radical 
• 2348-55-2 sec-Butyl-Radikal 
• 2348-46-1 ethanol radical 
• 2669-89-8 vinyl radical 
• 2597-43-5 hydroxymethyl radical 

Relevant academic research and scientific papers

Monomer- and polymer radicals of vinyl compounds: EPR and DFT studies of geometric and electronic structures in the adsorbed state

Electron paramagnetic resonance (EPR) spectroscopy was applied to study the paramagnetic species formed from styrene, 1,1-diphenylethylene, α-methylstyrene, β-methylstyrene and methylmethacrylate adsorbed on amorphous silica gel after γ-irradiation at 77

Twisted molecular geometry and localized electronic structure of the triplet excited gem-diphenyltrimethylenemethane biradical: Substituent effects on thermoluminescence and related theoretical calculations

Substituent effects on the energies of electronic transitions (ETs) between the triplet excited and ground states of gem-diphenyltrimethylenemethane biradicals (32a) were explored by using thermoluminescence (TL) spectroscopy and density functi

Kinetics of hydrogen atom transfer from (η5-C 5H5)Cr(CO)3H to various olefins: Influence of olefin structure

Treating (η5-C5H5)Cr(CO)3H (1) or (η5-C5H5)Cr(CO)3D (1-d1) with an excess of olefin containing the opposite isotope generally leads to H/D exchange, althoug

An evolved explanation for the molecular geometry and electronic structure of diphenyl-substituted cyclic trimethylenemethane in the ground state: A nearly planar conformation with a considerably localized electronic state

We reinvestigated the molecular geometry and electronic structure of the diphenyl-substituted, five-membered cyclic trimethylenemethane (TMM) diradical (Berson's TMM, 3..) using UV/VIS absorption and emission spectroscopy combined with density

The reactivity of ketyl and alkyl radicals in reactions with carbonyl compounds

A parabolic model of bimolecular radical reactions was used for analysis of the hydrogen transfer reactions of ketyl radicals: >C+OH + R1COR2 → >C=O + R1R2C+OH. The parameters describing the reactivity of the reagents were calculated from the experimental data. The parameters that characterize the reactions of ketyl and alkyl radicals as hydrogen donors with olefins and with carbonyl compounds were obtained: >C+OH + R1CH=CH2 → >C=O + R1C+ HCH3; >R1CH=CH2 + R2C+HCH2R3 → R2C+HCH3 + R2CH=CHR3. These parameters were used to calculate the activation energies of these transformations. The kinetic parameters of reactions of hydrogen abstraction by free radicals and molecules (aldehydes, ketones, and quinones) from the C-H and O-H bonds were compared.

1,1-Diphenylethylene adsorbed onto acid zeolites: Nature of the blue (605-nm) species

Diffuse reflectance spectra of HY (Si/Al 15) and Hβ (Si/Al 13) zeolites after adsorption of 1,1-diphenylethylene (DPE) show an intense 605-nm absorption band characteristic of an elusive blue species observed a long time ago for DPE-silica-alumina solids. This blue species was wrongly attributed to the corresponding DPE+. radical cation or a complex of DPE with Lewis sites of these solids. In our case, EPR spectra of DPE samples adsorbed on HY and Hβ zeolites indicate that the spin population of these samples is too low (15 spin · g-1) to contain significant amounts of any paramagnetic species. In addition, IR spectra of the organic material incorporated within HY and Hβ is very similar to those of some DPE dimers. Product studies after solid-liquid extraction of zeolites and silica-alumina in which DPE has been adsorbed also show the formation of the corresponding dimers derived from the acid-catalyzed mechanism. Variable amounts of oxidation products are also formed when the adsorption is carried out in the open air. In addition, 13C-NMR spectra in solution of blue samples generated by treatment of DPE with sulfuric acid in dimethyl sulfate also indicate the presence of the same dimer distribution and the absence of detectable low-field signals that could be attributed to any carbenium ion. With these data, it is clear that in spite of the intense color developed in these samples, the bulk of the organic material adsorbed on the zeolites does not correspond to any intermediate, but to dimers. Semiempirical ROHF calculations using the ZINDO program provide some support to the possibility that the blue color could be due to 1,1,3,3-tetraphenyl-1-butylium cation, the reaction intermediate involved in the DPE dimerization mechanism.

Evaluation of dissociation energies of S-H bonds in thiophenols and thioalcohols on the basis of kinetic measurements

Kinetic data on the reactions of alkyl and benzyl radicals with thiophenol C6H5SH were analyzed within the framework of the parabolic model of transition state. The values of the parameter that establishes a correlation between the activation energy of a reaction and its enthalpy were calculated for reactions of alkyl and benzyl radicals with the C6H5SH. The equations of the parabolic model were used to calculate the bond dissociation energies for 11 thiophenols and 4 thioalcohols. The activation energies for reactions of 12 thiophenoxy radicals with cumene and of C6H5S? radical with several alkyl-aromatic hydrocarbons were obtained.

Generation, Thermodynamics, and Chemistry of the Diphenylcarbene Anion Radical (Ph2C.-)

Dissociative electron attachment with Ph2C=N produced Ph2C.- (m/z 166).The reactions of Ph2C.- with potential proton donors of known gas-phase acidity were used to bracket PA(Ph2C.-) = 380 +/- 2 kcal mol-1 from which ΔHf0(Ph2C.-) = 81.8 +/- 2 kcal mol-1 was calculated.The reactions of Ph2C.- with CH3OH and C2H5OH proceeded with major and minor amounts, respectively, of a H2.+-transfer channel, forming Ph2CH2, RCHO, and an electron.The kinetic nucleophilicity of Ph2C.- in SN2 displacement reactions with CH3X and C2H5X molecules was shown to be medium, which requires a significant intrinsic barrier in these reaction.The reactions of Ph2C.- with various aldehydes, ketones, and esters were fast and established two principal product-forming channels: (1) H+ transfer if the neutral reactant contains activated C-H bonds and (2) carbonyl addition followed by radical β-fragmentation of one of the groups originally attached to the carbonyl carbon.The order for the ease of radical β-fragmentation in the tetrahedral intermediates was RO > alkyl >> H, and CO2CH3 > CH3.Since the reactions of Ph2C.- with the simple esters HCO2CH3 and CH3CO2CH3 were fast, it should now be possible to examine the reactions of carbonyl-containing organic molecules, which are expected to react slower than these esters and obtain their relative reactivities.

PHOTOPHYSICS OF ARYLMETHYL RADICALS AT 77 K. STRUCTURE-PHOTOREACTIVITY CORRELATION

Five arylmethyl radicals, Ph2CH(.), DBHP(.), Ph2C(.)CH3, Ph3C(.), and Ph2C(.)-c-Pr were generated in glassy matrices at 77 K and their absorption, excitation, and emission spectra were studied in detail.Under similar conditions, fluorescence quantum yield

Photophysics and Photochemistry of Arylmethyl Radicals in Liquids

A series of arylmethyl radicals (including Ph2CH, 10,11-dihydro-5H-dibenzocyclohepten-5-yl (=DBHP.), Ph2CCH3, Ph2C-c-Pr, and Ph3C.) have been produced pulse radiolitically in a variety of solvents and then excited with λ=347 nm ruby laser pulses.Ph2C