From dipivaloylketene to tetraoxaadamantanes
Dipivaloylketene (2) is obtained by flash vacuum pyrolysis of furan-2,3-dione 6 and dimerizes to 1,3-dioxin-4-one 3, which is a stable but reactive ketene. The transannular addition and rearrangement of enols formed by the addition of nucleophiles to the ketene function in 3 generates axially chiral 2,6,9-trioxabicyclo[3.3.1]nonadienes (bisdioxines) 4. When arylamines are used as the nucleophiles under neutral conditions, decarboxylation occurs during the formation of bisdioxines 8. However, when water or alcohols are added to 3 under acidic conditions, bisdioxine-carboxylic acids and esters 10 and 11 are obtained. Acid hydrolysis of the bisdioxines proceeds through the addition of water to a C=C double bond and results in a second transannular oxa-Michael-type reaction and generation of tetraoxaadamantanes 5. This reaction is decarboxylative when free carboxylic acid functions are present in the bisdioxines, thus forming 21 and 22, but carboxylic acid derivatives are preserved to yield compounds 20, 23, 25, 28, and 29. A hydrogenolysis of the dibenzyl ester 23 yields the free dicarboxylic acid 24. The tetraoxaadamantanes are formed in high yields (65–95%) in most cases, but the addition of water to the concave inside of the bisdioxines becomes severely hindered in cyclic derivatives, so that the 38-membered ring compound 32 requires microwave heating at 170 °C to form tetraoxaadamantane 33, and the catenated compound 36 and calix[6]arene derivative 37 did not form tetraoxaadamantanes. The reaction mechanisms of bisdioxine and tetraoxaadamantane formation are discussed.
Synthesis of pyrimido[1,6-a]quinoxalines via intermolecular trapping of thermally generated acyl(quinoxalin-2-yl)ketenes by Schiff bases
Acyl(quinoxalin-2-yl)ketenes generated by thermal decarbonylation of 3-acylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones react regioselectively with Schiff bases under solvent-free conditions to form pyrimido[1,6-a]quinoxaline derivatives in good yields.
Soil organic matter and microbiological development of technosols in the South Wales Coalfield
Abstract Degraded land (formerly ‘reclaimed’) after surface-coal-mining is a serious problem in South Wales. This project uses forestation to foster soil development on opencast coal-mine spoil technosols. It compares records of humification and the soil microbiological system (microcoenosis) using paired data from the same plantings in 1998 and 2018. Statistical analysis finds no significant difference between samples collected under trees planted by the pit-planting versus trench planting method or trees planted using organic or mineral fertilizer. However, there are strong significant differences in both soil organic matter and microflora components and significant correlations with time since tree planting. Most components of the soil organic carbon (TOC) and the microflora increase, often significantly. However, compared to 2018, 1998 samples contain significantly greater maximum levels of Insoluble Carbon while the microflora had significantly more Ammonifying bacteria. Decreases in Insoluble Carbon explain the relatively small increase in TOC between 1998 and 2018. The % extracted with 0.1 N H2SO4 is significantly larger in 2018, suggesting active weathering. Similarly, both the maxima and minima of total Humic and Fulvic acids content, extracted with 0.1 M Na4P2O7 + 0.1 M NaOH, are significantly greater in 2018. Total microflora shows significant positive correlations with time-since-tree-planting as do the proportions of bacilli and actinomycetes but the correlation with ammonifying bacteria is negative. In 1998, the microflora was dominated by non-spore-forming bacteria while, in 2018, bacilli and actinomycetes prevail; both are involved in the transformation of complex organic compounds and humification. This indicates active transformation of more complex organic compounds and advancing humification. In sum, forestation of these degraded, formerly reclaimed, opencast coal-mine spoils has resulted in a massive increase in both the size and functioning of the soil organic system.