| The reaction of (ethoxycarbonyl)carbene (1), formed by the mild thermal reaction of ethyl diazoacetate (2), with an Illinois No. 6 HVCB coal has been studied. Soxhlet extraction (with a toluene-methanol mixture) showed up to 40% more extractables than unreacted coal. Thermogravimetric analysis (TGA) and derivative plots (DTG) showed significantly more weight loss, and more importantly, lower temperatures at which the weight loss occurred for the treated coal. Diffuse reflectance FT-IR (DRIFT) spectra showed that 1 is, indeed, incorporated into the coal. Capillary GC and GPC analyses indicated that the major reaction is with the coal since small amounts of by-products of 1 and 2 were found. A new pyrazoline tetramer, synthesized independently, also was formed in small amounts in the coal. These results, as well as the results of preliminary GC and GC-MSA analyses, indicate that the reaction of 1 with coal should prove to be a useful tool in studying the molecular structure of coal.;The thermal decomposition of 2 with 22 minerals, many of which are known to be in coal, was studied kinetically by monitoring the evolution of nitrogen versus temperature. The thermal decomposition of 2 with a subbituminous, bituminous and anthracite coal was studied and the kinetic profiles are consistent with minerals containing Fe(III) and/or Cu(II) being the active catalyst in the coal.;Finally, the relative rates of the reaction of thermally generated 1 towards 22 fused aromatics, heteroaromatics and benzo-fused aromatics versus naphthalene were measured. Contrary to the commonly accepted belief that 1 is rather indiscriminate in its reaction with aromatic compounds, it has been found that ring systems such as furan and pyrrole show a selectivity of up to a factor of 100 relative to toluene. The pyridine, quinoline and acridine series, unlike all of the other systems studied, appears to react with 1 by an ylide mechanism, and in these cases the selectivities are even larger, up to almost 150 relative to toluene. |
