Products of the reaction of anabasine with phosgene
ConclusionsThe reaction of anabasine with phosgene has given the anabasinium salt of phosgene, anabasine-N-carbonyl chloride, and the urea derivative N,N′-carbonyldianabasine. In addition to the formation of these substances, the pyridine ring of anabasine is cleaved, giving the red substance 1-chloro-5-chloroformyl-amino-2-piperidin-2-yl)penta-1,3-diene.
Second-Generation Phosgene and Diphosgene Detection Tube
We have developed a second-generation detection tube for colorimetric and fluorescence detection of phosgene and diphosgene in air. The tube is packed with pellets made of a mixture of microcrystalline cellulose and magnesium aluminum metasilicate treated with a suitable monoterpene (camphor, menthol) to increase porosity and specific surface area. We impregnated the pellets with a specific o-phenylenediamine-pyronin (PY-OPD) based reagent. The detector with this novel indication charge enables phosgene or diphosgene to be selectively and sensitively detected at concentrations lower than as would those posing acute health risk. Owing to the analytical colorimetric and, at the same time, fluorescence signal, the detector is very robust while featuring good sensitivity and variability. The colorimetric limits of detection were 0.3 mg/m3 (tristimulus colorimeter), resp. 5 mg/m3 (with the naked eye), fluorescence detection limits of 0.3 mg/m3 (with the naked eye), all at an air sample volume of 1 dm3. The response was practically immediate, acid vapors and gases, or diethyl chlorophosphate as a simulant of nerve warfare chemical agents, were disruptive.
Diagnosis of the σ-, π- and (σ+π)-Aromaticity by the Shape of the NICSzz-Scan Curves and Symmetry-Based Selection Rules
The NICSzz-scan curves of aromatic organic, inorganic and “all-metal” molecules in conjunction with symmetry-based selection rules provide efficient diagnostic tools of the σ-, π- and/or double (σ + π)-aromaticity. The NICSzz-scan curves of σ-aromatic molecules are symmetric around the z-axis, having half-band widths approximately less than 3 A with the induced diatropic ring current arising from Tx,y-allowed transitions involving exclusively σ-type molecular orbitals. Broad NICSzz-scan curves (half-band width approximately higher than 3 A) characterize double (σ + π)-aromaticity, the chief contribution to the induced diatropic ring current arising from Tx,y-allowed transitions involving both σ- and π-type molecular orbitals. NICSzz-scan curves exhibiting two maxima at a certain distance above and below the molecular plane are typical for (σ + π)-aromatics where the π-diatropic ring current overwhelms the σ-type one. In the absence of any contribution from the σ-diatropic ring current, the NICSzz(0) value is close to zero and the molecule exhibits pure π-aromaticity.