William W. Paudler

Nitrogen bases in solvent-refined coal

Abstract The basic components contained in a coal liquefaction product obtained from the Wilsonville, Alabama coal liquefaction pilot plant were examined by means of capillary-column Chromatographic-mass spectroscopy. A total of 62 of the 150 components observed were identified. The most interesting of the newly identified compounds are phenoxazine, butyl quinolines and isoquinolines, diarylamines and aminobiphenyl derivatives. The possibility of removing amino aromatics from coal liquefaction products by condensing them with the phenols in the mixture is discussed.

Mechanism of the reaction of 2-haloketones with 2-aminopyridine

Abstract Time-dependent 1H NMR spectra of DMSO-d6 solutions of p-substituted phenacyl bromides and 2-aminopyridine indicate that the formation of imidazo[1,2-a]pyridines occurs via two relatively long-lived intermediates, C and D, which are in equilibrium with each other. The assigned structures are in accord with chemical shifts, pKa estimates, and substituent effects (-OMeCH3, -H, and -NO2) on both the equilibrium constant (C⇌D) and rates of reaction. The slowest step in the reaction with phenacyl bromide is conversion of the intermediate D to product E. With phenacyl chloride no intermediates are observed and initial formation of C determines the overall rate. Even through the intermediate D is already protonated, its conversion to E is subject to acid catalysis. Compared to the p-OMe substituent, the p-NO2 group enhances the rate of formation of C and D by a factor of only 2.6. The same rate enhancement is observed in the reaction of pyridine with phenacyl bromides. Rates of reaction of a given phenacyl halide with pyridine and 2-aminopyridine are similar. It is concluded that the initial reaction is alkylation of the pyridine nitrogen atom to give C and that the other possible initial condensation product, the carbinolamine F, cannot be a kinetically significant intermediate. Reasons for preferred N-alkylation are presented. Recommendations for improved syntheses of imidazo[1,2-a]pyridines are included.

Conversion of cellulose to hydrocarbons

Abstract The transformation of cellulose into hydrocarbon products is affected by the action of elemental iodine and hydrogen at a reaction pressure of approximately 20.7 MPa and temperature of 325 °C. The more volatile components were characterized by g.c.-m.s., elemental analysis and i.r. Of the 86 major components observed, 53 were identified. These compounds were found to be very similar to the ring systems observed in solvent-refined coal, with the exception that nitrogen was not present.