Joanna Adamiak

A study made on 2,4,6,8-tetraacetyl-10,12-dibenzyl-2,4,6,8,10,12-hexaazaisowurtzitane (TADBIW) nitrosation in acetic acid to 2,4,6,8-tetraacetyl-10,12-dinitroso-2,4,6,8,10,12-hexaazaisowurtzitane (TADNOIW) allows the reaction time to be considerably shortened. During the study, the reaction yield was found to be affected by variables such as temperature, time and UV radiation. The major factor controlling the reaction rate was found to be the concentration of NO2 molecules in the reaction mixture. Under optimal conditions the product is obtained in a 90–93% yield after 6 h of the reaction conducted at 70 °C. UV radiation increases the reaction rate, yet the product obtained is of inferior purity on account of the by-product formed.

A new catalyst, H3PO4/MoO3/SiO2, was prepared by modification of MoO3/SiO2 using phosphoric acid. The characterization of the catalyst was performed using scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and Raman and Infrared Spectroscopy. Molybdenum oxides in two polymorph forms (α and β) were identified along with phosphomolybdic acid, polymolybdates and polyphosphates in various combinations on the modified surface. The suitability of the catalysts was examined for toluene nitration in the presence of fuming nitric acid. The catalysts were very effective in toluene nitration and the selectivity and toluene conversion depend on the nature of species present on the surface. Since the catalysts have significantly reduced activity in subsequent reactions, a simple process of regeneration was found. The MoO3/SiO2 modification with H3PO4 causes new domains on the surface to be obtained and increases catalytic properties in comparison to unmodified MoO3/SiO2 system.

2,4,6,8,10,12-Hexaallyl-2,4,6,8,10,12-hexaazaisowurtzitane (HALLIW) was obtained in a condensation reaction of glyoxal with allylamine in the presence of a protonic acid as a catalyst. Optimization of the synthesis was accomplished by means of a mathematical experiment planning theory with the steepest descent method. The effect of the following parameters was examined: process temperature, amount of the catalyst, amount of the solvent, glyoxal addition time, reaction time, and the ratio of the substrates. As a result of the study an improved yield was achieved from 20 to 66.5%. The highest yield for the reaction was found for the conditions (mole ratios relative to glyoxal): catalyst (formic acid) 0.1 : 1; solvents: acetonitrile 9.35 : 1, water 0.18 : 1; allylamine 2.2 : 1; temperature 15 °C; glyoxal addition time 15 min, reaction time 60 min. The studies were conducted on a small laboratory scale where the yield and purity of the product obtained were examined. A method was developed for purification of HALLIW. NMR, IR spectroscopy, DSC, and TG analyses were employed in the study and their results are reported.