Potential facile separation strategy for mixtures of 3- and 4-methylpyridine by employing N,N′-bis(9-phenyl-9-xanthenyl)ethylenediamine as an alternative host compound

In the present work, a plausible host candidate is provided for the separation of 3-methylpyridine (3MP) from 4-methylpyridine (4MP), isomers that are extremely difficult to separate by conventional means. Host compound N,N′-bis(9-phenyl-9-xanthenyl)ethylenediamine (H2), when recrystallized from an equimolar mixture of 3MP and 4MP, contained 91.6% 3MP, a significantly improved outcome compared with the alternate host compound N,N′-bis(9-phenyl-9-thioxanthenyl)ethylenediamine (H1) which only enclathrated 70% of this isomer in the same experimental conditions. Single crystal diffraction and thermoanalytical experiments were conducted in order to investigate this preference for 3MP by considering both host?guest interactions and relative complex stabilities. Many of the guest components in 3(H2)·5(3MP)·0.268(O) experienced at least one other short contact measuring less than the sum of the van der Waals radii of the involved atoms, an observation that may explain the selectivity of H2 for this guest since this was not the case in complexes containing PYR and 4MP. Results from the thermal analyses were less informative.

     

Compounds N,N′-bis(9-cyclohexyl-9-xanthenyl)ethylenediamine and its thio derivative,N,N′-bis(9-cyclohexyl-9-thioxanthenyl)ethylenediamine,as potential hosts in the presence of xylenes and ethylbenzene: Conformational analyses and molecular modelling considerations

Two novel crystalline compounds, N,N′-bis(9-cyclohexyl-9-xanthenyl)ethylenediamine (OED) and its thio derivative, N,N′-bis(9-cyclohexyl-9-thioxanthenyl)ethylenediamine (SED), were designed and synthesized in our laboratories, and assessed for their potential as host compounds for the four C8 aromatic compounds, namely o-, m- and p-xylene (o-Xy, m-Xy, p-Xy), and ethylbenzene (EB). Despite the only difference between the two compounds being the heteroatoms in their B rings, immense behaviour differences were noted: only OED displayed host behaviour in these conditions, clathrating all but m-Xy, while SED failed to form complexes with any of the four organic solvents. These observations prompted an investigation into the conformations of OED and SED through single crystal diffraction (SCXRD) analyses as well as computational studies with surprising results. SCXRD was also employed to analyse the three complexes that successfully formed with OED, and thermal analyses (TA) assisted in understanding the selectivity behaviour of OED when presented with mixed guests.     

trans-α,α,α′,α′-Tetraphenyl-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol and its tetra(p-chlorophenyl) derivative: roof-shaped host compounds for the purification of aromatic C8H10 isomeric guest mixtures

Journal of Inclusion Phenomena and Macrocyclic Chemistry - Roof-shaped host compounds trans-α,α,α′,α′-tetraphenyl-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol...     

Tannin fingerprinting in vegetable tanned leather by solid state NMR spectroscopy and comparison with leathers tanned by other processes

Solid state 13C-NMR spectra of pure tannin powders from four different sources--mimosa, quebracho, chestnut and tara--are readily distinguishable from each other, both in pure commercial powder form, and in leather which they have been used to tan. Groups of signals indicative of the source, and type (condensed vs. hydrolyzable) of tannin used in the manufacture are well resolved in the spectra of the finished leathers. These fingerprints are compared with those arising from leathers tanned with other common tanning agents. Paramagnetic chromium (III) tanning causes widespread but selective disappearance of signals from the spectrum of leather collagen, including resonances from acidic aspartyl and glutamyl residues, likely bound to Cr (III) structures. Aluminium (III) and glutaraldehyde tanning both cause considerable leather collagen signal sharpening suggesting some increase in molecular structural ordering. The 2?Al-NMR signal from the former material is consistent with an octahedral coordination by oxygen ligands. Solid state NMR thus provides easily recognisable reagent specific spectral fingerprints of the products of vegetable and some other common tanning processes. Because spectra are related to molecular properties, NMR is potentially a powerful tool in leather process enhancement and quality or provenance assurance.