Article on the correlation and estimation of aqueous solubilities of polycyclic aromatic hydrocarbons.

Article discussing hydrolysis reactions in lamellar liquid crystalline media and octanol/water partition coefficients.

In order to explore the N-H stretching region of aliphatic amines, we performed a study of the Raman spectrum of n-propylamine at various concentrations in cyclohexane. Statistical analysis provided evidence of a second symmetric stretching vibration, which we were able to assign to nonhydrogen bonded NH2 groups. To obtain additional evidence on the existence of monomers in n-propylamine and to further study hydrogen bonding and Fermi resonance in aliphatic amines, we extended the investigation to the analysis of the Raman spectrum of this compound over an extended range of temperature in the neat liquid phase. This study corroborated our finding that the peak previously assigned to the symmetric stretching mode of hydrogen bonded amines is actually composed of two bands. Furthermore, trends in both the resolved band parameters and the Fermi resonance analysis were tabulated, allowing one to monitor the change in the N-H valence region with concentration and temperature.

The reaction of tert-butyllithium with chloromethylphenylvinylsilane at low temperatures in hexane gave a 48% yield of a mixture of the five isomers of 1,3-dimethyl-1,3-diphenyl-2,4-dineopentyl-1,3-disilacyclobutane, formed by the head-to-tail dimerization of both E- and Z-1-methyl-1-phenyl-2-neopentylsilenes, along with an acyclic dimer. These were separated and their stereochemistry was established by ('1)H- and ('13)C-NMR spectroscopy. The E- and Z-silenes were also trapped as their {4 + 2} cycloadducts with cyclopentadiene, 2,3-dimethyl-1,3-butadiene and anthracene, which also were separated and stereochemically characterized. A consistent mole ratio of 70:30 for the E- and Z-silene adducts is interpreted as evidence for stereochemical induction in the silene generation reaction. It is also suggested that the dimerization of the silenes to give the 1,3-disilacyclobutanes occurs by a nonstereospecific stepwise pathway. When E- or Z-1-methyl-1-phenyl-2-neopentylsilene was generated by the retro-Diels-Alder flow vacuum thermolysis of its corresponding cyclopentadiene or anthracene adduct at temperatures between 400 and 600(DEGREES)C and then trapped with 2,3-dimethyl-1,3-butadiene, the stereochemical distribution of the products is independent of the stereochemistry of the silene precursor, indicating that the silene is not configurationally stable towards cis-trans isomerization at these temperatures. Evidence that the intermolecular ene reaction and the {4 + 2} cycloaddition which occur with 2,3-dimethyl-1,3-butadiene are concerted is presented. …

The objective of this study was to develop new synthetical routes to natural and industrial products utilizing ketene cycioaddition reactions. The cycioaddition of diphenylketene with α,β-unsaturated imines yields (2+2) cycioaddition products, g-lactams. However, electron donating groups, such as dimethylamine, in the 4-position of the α,β-unsaturated imines result in (4+2) cycloaddition products, ∂-lactams. Dichloroketene reacted with α,β-unsaturated imines to yield (4+2) cycloaddition products, g-lactams. Large substituents in the 4-position of a, ^-unsaturated imines resulted in a (2+2) cycioaddition product, β-lactam. The ∂-lactams derived from dichloroketene are easily dehydrochlorinated to the corresponding 2-pyridornes.

Article on a kinetic study of the reactions of ground-state sodium atoms with the molecules CF₃Cl, CF₂Cl₂, CFCl₃, CF₃Br and SF₆ over the temperature range 644-918 K.

Article on the determination of the absolute second-order rate constant for the reaction Na + O₃ → NaO + O₂.

Article on the solubility of phenylacetic acid in binary solvent mixtures.

Article on temperature dependence of the absolute third-order rate constant for the reaction between Na + O₂ + N₂ over the range 571-1016 K studied by time-resolved atomic resonance absorption spectroscopy.

This article discusses excess molar volumes of binary mixtures of cyclohexane and y-butyrolactone with aromatic hydrocarbons.

Various modern spectroscopies have been utilized with considerable success in recent years to probe the dynamics of vibrational and reorientational relaxation of molecules in condensed phases. We have studied the temperature dependence of the polarized and depolarized Raman spectra of various modes in the following dihalomethanes: dibromomethane, dichloromethane, dichloromethane-d2, and bromochloromethane. Among other observed trends, we have found the following: Vibrational dephasing times calculated from the bend) and (C-Br stretch) lineshapes are of the same magnitude in CI^B^. The vibrational dephasing time of [C-D(H) stretch] is twice as long in CD2Cl2 as in CH-^C^, and the relaxation time of (C-Cl stretch) is greater in CI^C^ than in CD2CI2. Isotropic relaxation times for all three stretching vibrations are significantly shorter in C^BrCl than in CI^C^ or CI^B^. Application of the Kubo model revealed that derived modulation times are close to equal for equivalent vibrations in the various dihalomethanes. Thus, the more efficient relaxation of the A^ modes in CE^BrCl can be attributed almost entirely to the broader mean squared frequency perturbation of the vibrations in this molecule.

The reactions of tert-butyl-, sec-butyl-, and n-butyllithium with dimethylfluorovinylsilane include addition to the double bond to give both silene and silenoid intermediates, fluorine substitution, and a novel vinyl substitution. For the tert-butyllithium reaction, product stereochemistry and trapping experiments using both cyclopentadiene and methoxytrimethylsilane show that silenes are not formed in THF. In hexane about 67% of the 1,3-disilacyclobutanes obtained arise from silene dimerization while 33% are formed by silenoid coupling. In hexane the order of reactivity for addition, t-Bu > sec-Bu > n-Bu, is opposite that for fluorine substitution. The vinyl substitution is most significant with secondary alkyllithium reagents including the tert-butyllithium adduct to dimethylfluorovinylsilane and with sec-butyllithium itself. Evidence for the formation of vinyllithium or ethylene in the process could not be obtained.

Article on octanol-water partition coefficients of substituted alpha and N-diphenylnitrones and benzonitrile N-oxides.

Article on experimental artifacts and determination of accurate Py values.

Article on enthalpies of combustion of four N-phenylmethylene benzenamine N-oxide derivatives, of N-phenylmethylene benzenamine, and of trans-diphenyldiazene N-oxide and the dissociation enthalpy of the (N-O) bonds.

Article on an HTP kinetics study of the reaction between ground-state H atoms and NH₃ from 500 to 1140 K.

This article presents the non-linear least-squares routine KPS1 for the analysis of data from counting experiments which follow single exponential decays.

Article discussing the solubility in binary solvent systems and a comparison of predictive equations derived from the Nearly Ideal Binary Solvent (NIBS) model.

This article discusses solubility of pyrene in binary solvent mixtures containing cyclohexane.

Article on a high-temperature photochemistry kinetics study of the reaction of oxygen(³P) atoms with ethylene from 290 to 1510 K.

Article on high-temperature photochemistry and BAC-MP4 studies of the reaction between ground-state H atoms and N2O.

This article provides comments on "Thermochemical Investigations of Associated Solutions: Calculation of Solute-Solvent Equilibrium Constants from Solubility Measurements," published in the Journal of Pharmaceutical Sciences in 1983.

Article on the solubility of anthracene in binary solvent mixtures containing dibutyl ether.

Article on thermochemical investigations of associated solutions and calculation of carbazole-dibutyl ether association constants from measured solubility in binary solvent mixtures.