Acetyl Nitrate Mediated Conversion of Methyl Ketones to Diverse Carboxylic Acid Derivatives

The development of a novel acetyl nitrate mediated oxidative conversion of methyl ketones to carboxylic acid derivatives is described. By analogy to the haloform reaction and supported by experimental and...

Nitration of Hydrolysis Lignin in Water-Aprotic Solvent Mixtures

Industrial lignins are formed from native lignins during chemical or biochemical processing of plant raw materials. Lignins can be modified to produce valuable products, including monomers, polymeric materials, and composites. The article presents the results of a study of hydrolysis lignin nitration under various conditions. The aim of the study was to obtain a nitrated hydrolysis lignin with a maximum yield and maximum nitrogen content. Therefore, the nitration was carried out using nitric acid in a water-aprotic solvent binary mixtures (1,4-dioxane, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, acetonitrile). Acetyl nitrate, which is a mixed anhydride of nitric and acetic acids, was also used as a nitrating agent. In this regard, the consumption of acetic anhydride in the synthesis of acetyl nitrate was used taking into account the water present in concentrated nitric acid. Acetyl nitrate was obtained by the reaction of acetic anhydride and concentrated nitric acid at room temperature for 30 min. Acetyl nitrate is a mild nitrating agent opposed to nitric acid. Nitration was carried out under reflux in a boiling water bath for 2–5 min (with nitric acid) or 1–60 min (with acetyl nitrate). Upon completion of the nitration reaction, the products were filtered, washed with distilled water and dried to constant weight without heating. When nitration was performed with nitric acid, the maximum yield of nitrated hydrolysis lignin (83–101 %) was achieved using 1,4-dioxane, acetonitrile, and tetrahydrofuran; and the maximum nitrogen content (4.3–4.5 %) was achieved using 1,4-dioxane or acetonitrile. The use of dimethyl sulfoxide and dimethylformamide leads to a decrease in the product yield to 23–35 %, to a lower nitrogen content of 1.3–3.9 % and an increased oxygen content, which indicates the occurrence of not only nitration, but also depolymerization and oxidative transformations. When nitration with acetyl nitrate, the reaction takes place for 1–3 min, herewith the product contains up to 4.7 % of nitrogen. On the IR spectra of nitrated hydrolysis lignins, new absorption bands appear at 1555 and 1710 cm–1 due to the appearance of carboxyl and nitro groups.

Simulation of current and future tropospheric chemistry with the Earth System Model EMAC

<p>The increasing future methane (CH<sub>4</sub>) leads to changes in the lifetime of CH<sub>4</sub> and in the Hydroxyl radical (OH) and (O<sub>3</sub>) mixing ratios and distribution in the lower atmosphere. With increasing CH<sub>4</sub> the lifetime of CH<sub>4</sub> and the O<sub>3</sub> mixing ratios in the troposphere will increase, the tropospheric OH mixing ratios will decrease (Winterstein et al., 2019; Zhao et al., 2019). The CH<sub>4</sub> changes, together with the future Nitrous oxide (N<sub>2</sub>O) and temperature increase, will lead to a different tropospheric chemistry. For example, substances as acetone (CH<sub>3</sub>COCH<sub>3</sub>), ethane (C<sub>2</sub>H<sub>6</sub>), formic acid (HCOOH) or peroxy acetyl nitrate (PAN) will change their distribution and mixing ratios.</p><p>In different studies we could show that EMAC (ECHAM/MESSy Atmospheric Chemistry, Jöckel et al., 2010) has the ability to simulate some of the mentioned tropospheric substances in comparison to results of the GLORIA (Gimballed Limb Observer for Radiance Imaging of the Atmosphere) instrument, used on board of the research aircrafts Geophysica and HALO during the STRATOCLIM (July/August 2017) and WISE (August to October 2017) campaigns (Johansson et al., 2020; Wetzel et al., 2020).   </p><p>In this study, we will additional show the first results of the simulated future changes of tropospheric chemistry (especially with focus on CH<sub>3</sub>COCH<sub>3</sub>, C<sub>2</sub>H<sub>6</sub>, HCOOH and PAN and the upper troposphere) related to the future increase of CH<sub>4</sub>, N<sub>2</sub>O and temperature change as a result of climate change. For these we use different EMAC simulations from the project ESCiMo (Earth System Chemistry Integrated Modelling, Jöckel et al., 2016).</p><p>We will present some results of the comparison of EMAC to GLORIA and results with regard to the future development of the (upper) tropospheric chemistry in EMAC.    </p>

Peroxy acetyl nitrate (PAN) measurements at northern midlatitude mountain sites in April: a constraint on continental source–receptor relationships

Abundance-based model evaluations with observations provide critical tests for the simulated mean state in models of intercontinental pollution transport, and under certain conditions may also offer constraints on model responses to emission changes. We compile multiyear measurements of peroxy acetyl nitrate (PAN) available from five mountaintop sites and apply them in a proof-of-concept approach that exploits an ensemble of global chemical transport models (HTAP1) to identify an observational “emergent constraint”. In April, when the signal from anthropogenic emissions on PAN is strongest, simulated PAN at northern midlatitude mountaintops correlates strongly with PAN source–receptor relationships (the response to 20 % reductions in precursor emissions within northern midlatitude continents; hereafter, SRRs). This finding implies that PAN measurements can provide constraints on PAN SRRs by limiting the SRR range to that spanned by the subset of models simulating PAN within the observed range. In some cases, regional anthropogenic volatile organic compound (AVOC) emissions, tracers of transport from different source regions, and SRRs for ozone also correlate with PAN SRRs. Given the large observed interannual variability in the limited available datasets, establishing strong constraints will require matching meteorology in the models to the PAN measurements. Application of this evaluation approach to the chemistry–climate models used to project changes in atmospheric composition will require routine, long-term mountaintop PAN measurements to discern both the climatological SRR signal and its interannual variability.

Nitration of 5,11-dihydroindolo[3,2-b]carbazoles and synthetic applications of their nitro-substituted derivatives

A new general approach to double nitration of 6,12-di(hetero)aryl-substituted and 6,12-unsubstituted 5,11-dialkyl-5,11-dihydroindolo[3,2-b]carbazoles by acetyl nitrate has been developed to obtain their 2,8-dinitro and 6,12-dinitro derivatives, respectively. A formation of mono-nitro derivatives (at C-2 or C-6) from the same indolo[3,2-b]carbazoles has also been observed in several cases. Reduction of 2-nitro and 2,8-dinitro derivatives with zinc powder and hydrochloric acid has afforded 2-amino- and 2,8-diamino-substituted indolo[3,2-b]carbazoles, while reduction of 6,12-dinitro derivatives under similar reaction conditions has been accompanied by denitrohydrogenation of the latter compounds into 6,12-unsubstituted indolo[3,2-b]carbazoles. Formylation of 6,12-dinitro derivatives has proved to occur only at C-2, while bromination of these compounds has taken place at both C-2 and C-8 of indolo[3,2-b]carbazole scaffold. Moreover, 6,12-dinitro-substituted indolo[3,2-b]carbazoles have been modified by the reactions with S- and N-nucleophiles. Notably, the treatment of 6,12-dinitro compounds with potassium thiolates has resulted in the displacement of both nitro groups, unlike potassium salts of indole or carbazole, which have caused substitution of only one nitro group.

Regioselective Nitration of m-Xylene Catalyzed by Zeolite Catalyst

Nitration with nitric acid and acetic anhydride via acetyl nitrate as nitrating species is efficient with the substrate m-xylene as solvent. Zeolite Hβ with an SiO2/Al2O3 ratio of 500 was found to be the most active of the catalysts tried both in yield and regioselectivity in the nitration of m-xylene. The molecular volume of the reactants was calculated with the Gaussian 09 program at the B3LYP/6–311+G(2d, p) level and compared with the size of the zeolite Hβ channels. A range of other substrates were subjected to the nitrating system under the same conditions as those optimized for m-xylene and excellent selectivity was obtained.

Analysis of elevated spring-time levels of Peroxy Acetyl Nitrate (PAN) at the High Alpine research sites Jungfraujoch and Zugspitze

Largest atmospheric peroxy acetyl nitrate (PAN) mole fractions at remote surface sites in the Northern Hemisphere are commonly observed during the months April and May. Different formation mechanisms for this seasonal maximum have previously been suggested: hemispheric-scale production from precursors accumulated during the winter months, increased spring-time transport from up-wind continents, increased regional-scale production in the atmospheric boundary layer from recent emissions. The two high Alpine research sites Jungfraujoch (Switzerland) and Zugspitze (Germany) exhibit a distinct and consistent spring-time PAN maximum, too. Since these sites intermittently sample air masses of free tropospheric and boundary layer origin, they are ideally suited to identify the above mentioned PAN formation processes and attribute local observations to these. Here we present a detailed analysis of PAN observations and meteorological conditions during May 2008 when PAN levels were especially elevated at both sites. Highest PAN concentrations were connected with anti-cyclonic conditions, which persisted in May 2008 for about 10 days with north easterly advection towards the sites. A backward dispersion model analysis showed that elevated PAN concentrations were caused by the combination of favourable photochemical production conditions and large precursor concentrations in the European atmospheric boundary layer. The results suggest that the largest PAN values in spring 2008 at both sites were attributable to regional-scale photochemical production of PAN in the (relatively cold) planetary boundary layer from European precursors whereas the contribution of inter-continental transport or free tropospheric build-up was of smaller importance for these sites.

A semi-Lagrangian view of ozone production tendency in North American outflow in the summers of 2009 and 2010

The Pico Mountain Observatory, located at 2225 m a.s.l. in the Azores Islands, was established in 2001 to observe long-range transport from North America to the central North Atlantic. In previous research conducted at the observatory, ozone enhancement (> 55 ppbv) in North American outflows was observed, and efficient ozone production in these outflows was postulated. This study is focused on determining the causes for high d[O3] / d[CO] values (~1 ppbv ppbv−1) observed in the summers of 2009 and 2010. The folded retroplume technique, developed by Owen and Honrath (2009), was applied to combine upwind FLEXPART transport pathways with GEOS-Chem chemical fields. The folded result provides a semi-Lagrangian view of polluted North American outflow in terms of physical properties and chemical processes, including production/loss rate of ozone and NOx produced by lightning and thermal decomposition of peroxy acetyl nitrate (PAN). Two transport events from North America were identified for detailed analysis. High d[O3] / d[CO] was observed in both events, but due to differing transport mechanisms, ozone production tendency differed between the two. A layer of net ozone production was found at 2 km a.s.l. over the Azores in the first event plume, apparently driven by PAN decomposition during subsidence of air mass in the Azores–Bermuda High. In the second event, net ozone loss occurred during transport in the lower free troposphere, yet observed d[O3] / d[CO] was high. We estimate that in both events, CO loss through oxidation contributed significantly to d[O3] / d[CO] enhancement. Thus, it is not appropriate to use CO as a passive tracer of pollution in these events. In general, use of d[O3] / d[CO] as an indicator of net ozone production/loss may be invalid for any situation in which oxidants are elevated. Based on our analysis, use of d[O3] / d[CO] to diagnose ozone enhancement without verifying the assumption of negligible CO loss is not advisable.