Reductive alkylation of illinois No. 6 coal. 1H and 13C n.m.r. spectra of the 13C-enriched alkylation products

The reductive alkylation of Illinois No. 6 coal has been carried out using potassium and naphthalene in tetrahydrofuran and methyl-¹³C and butyl-1 -¹³C iodides to alkylate the resultant polyanion. The soluble products of the reductive alkylation reaction were isolated by extraction and chromatography. Proton and carbon n.m.r. spectra were recorded. The intense resonance signal at δ3.95 which appears in the proton n.m.r. spectra of Illinois No. 6 coal butylated with unenriched butyl iodide is split into a doublet by the ¹³C nuclei. Similar results were obtained for the methylation products. The chemical shift and coupling interaction establish that aryl ethers are a very important constituent of the alkylated coal. The carbon n.m.r. spectra of the coal alkylated with ¹³C-enriched alkyl iodides are intense. The resonances of the C-alkylation products appear in a single broad band with a maximum intensity in spectral regions compatible with the formation of the reductive alkylation products of certain polynuclear aromatic hydrocarbons or the base-catalysed alkylation of certain benzylic carbon atoms. The resonances of the N -alkylation products appear in two distinct bands. These resonances are tentatively assigned to amines produced as a result of reductive alkylation of heterocyclic compounds. The resonances of the 0-alkylation products appear in three distinct bands which can be assigned to alkyl aryl ethers, alkyl aryl ethers with substituents at the adjacent positions, and to alkyl carboxylates. The ratio of ethers to carboxylates in the soluble alkylation products was determined to be 7.8 for butylation and 8.0 for methylation. The Chromatographic fractions contain different amounts of C-, N-, and 0-alkylation products. This finding suggests that the coal structure is not highly uniform.