Biphenyl, theoretical studies

Pedersen LG, Darden TA, Oatley SJ, et al. 1986. A theoretical study of the binding of polychlorinated biphenyls (PCBs), dibenzodioxins, and dibenzofuran to human plasma prealbumin. Journal of Medicinal Chemistry 29 2451-2457. 

Eskandaii K, Van Alsenoy C (2014) Hydrogen-hydrogen interaction in planar biphenyl a theoretical study based on the Interacting Quantum Atoms and Hirshfeld atomic energy partitioning methods. J Comput Chem 35 1883-1889... 

Dewar and his co-workers, as mentioned above, investigated the reactivities of a number of polycyclic aromatic compounds because such compounds could provide data especially suitable for comparison with theoretical predictions ( 7.2.3). This work was extended to include some compounds related to biphenyl. The results were obtained by successively compounding pairs of results from competitive nitrations to obtain a scale of reactivities relative to that of benzene. Because the compounds studied were very reactive, the concentrations of nitric acid used were relatively small, being o-i8 mol 1 in the comparison of benzene with naphthalene, 5 x io mol 1 when naphthalene and anthanthrene were compared, and 3 x io mol 1 in the experiments with diphenylamine and carbazole. The observed partial rate factors are collected in table 5.3. Use of the competitive method in these experiments makes them of little value as sources of information about the mechanisms of the substitutions which occurred this shortcoming is important because in the experiments fuming nitric acid was used, rather than nitric acid free of nitrous acid, and with the most reactive compounds this leads to a... 

A series of compounds that has been studied extensively, both theoretically and experimentally, is the poly phenyls (38-40). In considering these compounds it is very helpful if one has at least a little understanding of the significance of the X-ray crystallographic results. Biphenyl, the first of the series, is known to be nonplanar in the gas phase, with a torsional angle about the central bond of 42°. This is interpreted in terms of relief of steric interference between the... 

The torsional motion about the central C—C bond of biphenyl and related compounds has been extensively studied by gas electron diffraction and by several other experimental and theoretical methods. The fact that biphenyl itself undergoes conformational changes by phase transition 69a 208, indicates that the barrier to... 

To summarize, there is agreement between the spectrum computed and the large amount of spectral information. The theoretical data confirm the sensitivity of the excitation energies to the structure of the ground state, which varies from nearly planar in crystals to 44°C twisted in the gas phase. The appearance of the first Rydberg transition has been predicted. It has been shown that no excited state of symmetry appears below 5.85 eV. As far as we are aware, this represents the first ab initio study of BP. Comparison with earlier semiempirical studies shows that they are not able to account for all features of the electronic spectrum of biphenyl (see the discussion in Ref. 94). 

The solvent-induced stereochemical behaviour of a bile acid-based biphenyl phosphite has been studied experimentally using circular dichroism (CD) spectroscopy, and theoretically using DFT quantum mechanical methods. " The FTIR, Raman and surface-enhanced Raman scattering (SERS) spectra of phenyl phosphate disodium salt have been recorded and its vibrational wavenumbers, calculated using the Hartree-Fock/6-31G basis set, compared with experimental values. From SERS spectra study, the molecule is adsorbed on the silver surface with the benzene ring in a tilted orientation. The presence of the phenyl ring and the phosphate group vibrations in the SERS spectrum reveal the interactions between the phenyl... 

Model Studies. General Procedure. The theoretical amount of sodium or potassium hydroxide (corrected for the amount of water present), an equivalent amount of 4-methylphenol, 0.05 equivalent of the phase transfer catalyst, biphenyl (internal standard, 0.25 equivalents) and methylene chloride or a 3 to 1 mixture of chloro-benzene/methylene chloride were heated at reflux. The amount of solvent used was chosen to give a solution which would be 20% in final product (g of formal/ml of solvent X 100 = 20%). Aliquots were removed at timed intervals and were worked up with methylene chloride and 1.2N HCl. These samples were analyzed by vpc and the yields of the product were calculated, based on an internal standard... 

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