A highly efficient green synthesis of 1, 8-dioxo-octahydroxanthenes

SmCl3 (20 mol%) has been used as an efficient catalyst for reaction between aromatic aldehydes and 5,5-dimethyl-1,3-cyclohexanedione at 120°C to give 1,8-dioxo-octahydroxanthene derivatives in high yield. The same reaction in water, at room temperature gave only the open chain analogue of 1,8-dioxo-octahydroxanthene. Use of eco-friendly green Lewis acid, readily available catalyst and easy isolation of the product makes this a convenient method for the synthesis of either of the products

Sulfur- and nitrogen-containing phenol-formaldehyde co-resites for probing the thermal behaviour of heteroatomic forms in solid fuels

In order to probe the formation of sulfur- and nitrogen-containing gases during the pyrolysis and combustion of coals and other solid fuels, non-softening model substrates are required. In this respect, phenol-formaldehyde (PF) resins are ideal since they readily facilitate the incorporation of individual heteroatomic functions into a highly crosslinked matrix. A series of sulfur- and nitrogen-containing co-resites have been prepared using phenol with, as the second component, thiophene, dibenzothiophene, diphenylsulfide, benzyl phenyl sulfide, thioanisole, 8-hydroxyquinoline and 2-hydroxycarbazole. A mole ratio of 3 : 1 (phenol: heteroatom-containing component) was adopted in order to ensure that a reasonably high degree of crosslinking was achieved. Resoles containing diphenyldisulfide were also prepared but, due to the comparable bond strengths of the S-S and C-O linkages, a curing temperature of only 130 degrees C was used to avoid cleavage of the disulfide bond. The virtually complete elimination of ether and methylol functions from the resoles by curing at 200 degrees C was monitored by solid-state C-13 nuclear magnetic resonance (n.m.r.) spectroscopy. The resultant resites were also characterized by sulfur K-edge X-ray absorption near-edge structure (XANES.) spectroscopy, X-ray photoelectron spectroscopy (X.p.s.) and differential scanning calorimetry (d.s.c.). Simple air oxidation was found to selectively convert the aliphatic-bound sulfur to a mixture of sulfones and sulfoxides. Applications of the resites in fuel science are described

Black Sea sapropels: relationship to kerogens and fossil fuel precursors

The organic structures in sapropels sampled from two cores obtained at known locations beneath the southern Black Sea have been characterised. Fluorescence petrography shows the sapropels to occur as layers of impure alginite, similar to 50 mu m thick, within Unit 2 of the sediments. Solid state C-13 NMR indicates the bulk chemical structures to be very similar to those in an immature Type 1 kerogen (lamosite) oil shale with an aromaticity of similar to 0.2. Consistent with the immaturity of the sapropels, which are between 3000 and 7000 years old, temperature programmed reduction showed aliphatic and aromatic sulphides to be the major organic sulphur forms. Alkanes formed from phytoplankton lipids, alkyl benzenes, alkyl naphthalenes and some phenols dominated the mix of volatile compounds identified by pyrolysis-gas chromatography/mass spectrometry. About half of the sapropels remained as an involatile, tarry residue after pyrolysis. The structure of the sapropels is consistent with their formation resulting from marine phytoplankton with only small terrigeneous inputs. Future catagenesis may be expected to decarboxylate the lipids, increase the aromaticity and to dry and compress the muds to form a source rock