in order to find the susceptibility of the claisen rearrangement and next proton shift reaction of ally) aryl etherto the substiment effects in pan position, the kinetic and the:rmodynamie parameters are calculated at the33 ltp level using 6-3110. b asis set. the calculated activation energies for the rearrangements and protonshift reactions are around 3133 kcaumol and 52.16 kcal/mol, nap.. liv...

This study concerns the structural change of lignin during auto-catalyzed ethanol-water pulping of aspen by 1H-NMR. The results showed that the linkages of alkyl-aryl ether of lignin, such as the α-ether linkages (α-O-4) and the β-ether linkages (β-O-4), were broken and the alkyl part formed carbenium at the Cα and Cβ of the aliphatic branch. Meanwhile, the aryl part of ether accepted one H and...

Study of the kinetics of intramolecular aryl ether C-O bond cleavage by Ni was facilitated by access to a family of metal complexes supported by diphosphines with pendant aryl-methyl ethers. The nature of the aryl substituents was found to have little effect on the rate of cleavage. In contrast, soluble Lewis acidic additives accelerate the aryl ether cleavage dramatically. The effect of AlMe3 ...

Study of the kinetics of intramolecular aryl ether C-O bond cleavage by Ni was facilitated by access to a family of metal complexes supported by diphosphines with pendant aryl-methyl ethers. The nature of the aryl substituents was found to have little effect on the rate of cleavage. In contrast, soluble Lewis acidic additives accelerate the aryl ether cleavage dramatically. The effect of AlMe3 ...

Inhibitors of sulfatase-2 are putative anticancer agents, but the discovery of potent small molecules targeting this enzyme has proved challenging. Based on molecular modelling, two series of sulfatase-2 inhibitors have been developed with biphenyl and biphenyl ether scaffolds judiciously substituted with sulfamate, carboxylate and other polar groups (e.g. amino). Inhibition of aryl sulfatase A...

Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) in the presence of tetramethylammonium hydroxide (TMAH) was applied to kenaf (Hibiscus cannabinus) fibers in order to clarify the chemical composition of in situ lignin. The core and bast samples obtained from the middle position of variety Chinpi-3 were pyrolyzed at 500 °C for 4 s with TMAH. The core pyrogram revealed peaks retaining th...

An analytical method for lignins has been developed that involves derivatization followed by reductive cleavage (DFRC), depolymerization, and quantitative (31)P NMR spectroscopy. This technique detects and quantifies the various ether linkages present in softwood residual kraft lignins (RKL) and milled wood lignins (MWL). In addition, the technique supplies new quantitative information about be...

Preparation of (di)benzocrown-substituted aryl-zinc or -boron reagents and their palladium-catalysed cross-coupling with functionalised aryl halides is described for convenient synthesis of novel crown ether systems.

Aryl ethers are important linking units in the structure of lignins and low rank coals that are thermally labile at 375°C. Mass transport limitations experienced in these cross-linked macromolecular solids can lead to alterations in thermochemical processing kinetics and product yields. The molecular level details of these alterations on reaction pathways are revealed through studies of model c...

Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from com...