0000000000313963
AUTHOR
Jacek Hetper
Synthesis of peptides with α,β‐dehydroamino acids, V. coupling experiments with C‐terminal dehydrophenylalanine and dehydroalanine residues
N-Protected model dipeptides of C-terminal (Z)-ΔPhe and ΔAla couple with glycine esters after activation with either diphenyl phosphorazidate (DPPA), N-cyclohexyl-N′-[2-(N-methylmorpholinio)ethyl]carbodiimide p-toluenesulfonate (WSC), N,N′-dicyclohexylcarbodiimide + 1-hydroxybenzotriazole (DCC + HOBt), or the mixed anhydride (MA) with isobutyl chlorocarbonate to give in good or mostly moderate yields the (Z)-ΔPhe-containing tripeptides 1 – 9 and ΔAla-containing tripeptides 11 – 19, respectively. In the MA and DPPA methods, further acylation products 20a – d are formed to a great extent, expecially during the ΔAla peptide syntheses. (E)-TFA-Gly-ΔPhe and Gly-OtBu, irrespective of the activati…
Thermal degradation of novolac resins by pyrolysis-gas chromatography with a movable reaction zone
Abstract A previously described, a pyrolysis device with a movable reaction zone was used in the present work for thermal degradation of novolac resins. The products of thermal reactions were analysed by pyrolysis–GC. Owing to the heating of reaction zone to the maximal temperature of the chromatographic column, the high boiling pyrolysis products could be analysed. Bisphenols and trisphenols with aromatic rings coupled by methylene bridges and its methyl derivatives have been found among the compounds. The structure of the heavy pyrolysis products has been confirmed using GC–MS.
High-resolution pyrolysis–gas chromatography with a movable reaction zone
Abstract A new device was constructed for pyrolysis–gas chromatography and it was laboratory tested. The device enables the thermal degradation of polymers inside a capillary pre-column and transfer of the reaction zone into a column oven. The pyrolysis procedure described protects the thermally sensitive compounds prior to pyrolysis, prevents the process of irreversible condensation of high-boiling pyrolysis products during the chromatographic process and eliminates extracolumn effects on the peak broadening.
Pyrolysis-gas chromatography-mass spectrometry of cured phenolic resins.
A previously described pyrolysis device with a movable reaction zone was used in the present work for thermal degradation of cured novolac and resol resins. After the pyrolysis the usual major components were identified, as well as relatively low-volatile aromatic compounds which were revealed after their separation in a capillary chromatographic column. Among the latter components, for both types of cured resins, xanthene and its methyl derivatives were found. The isomers of bis(hydroxyphenyl)methane were found in considerable quantities only in the case of partially cured novolac resins which contained any linear sequences in their structure.
Pyrolysis/gas chromatography/mass spectrometry analysis of 5,10,15,20-tetraphenyl-21H,23H-porphyrin and some of its derivatives
A coupled on-line pyrolysis/gas chromatography/mass spectrometry technique (Py/GC/MS) was applied to identify products of pyrolysis of 5,10,15,20-tetraphenyl-21H,23H-porphyrin (1a) and its methyl and hydroxyl substituted derivatives (1b and 1c). The mass spectra of some important pyrolitic products are presented and mass fragmentation of this type compounds is discussed. From the investigation it can be concluded that the direction of the main thermal (pyrolytic) reactions is similar for all compounds studied: namely breaking of the porphyrin macrocycle followed by splitting of molecule fragments containing one, two or three pyrrole and/or benzene rings. The products of pyrolysis can be sim…
Thermodynamic Interaction Parameters of Tetra-n-undecylcalix[4]resorcinarenes with Selected Solvents Studied by Inverse Gas Chromatography
The basic thermodynamic parameters, characterising intermolecular interactions of tetra-n-undecylcalix[4]resorcinarene and its octaacetate derivative with simple organic solutes, were calculated by using the inverse gas chromatography method. Free energy, enthalpy and entropy of sorption were determined.