This short review presents the current main chemical warfare agents and their most relevant simulants, and the recent catalytic and selective methods for their soft neutralization, potentially usable in the future as an alternative to “heavy” methods for decontamination.

The aim of this review is to present the latest developments in the stereoselective synthesis of conjugated dienes, covering the period 2005-2010. Since the use of this class of compounds is linked to the nature of their appendages (aryls, alkyls, electron-withdrawing, and heterosubstituted groups), the review has been categorized accordingly and illustrates the most representative strategies and mechanisms to access these targets.

The reproducible crystallisation of elusive polymorphs and solvates of molecular compounds at high pressure has been demonstrated through studies on maleic acid, malonamide, and paracetamol. These high-pressure methods can be scaled-up to produce bulk quantities of metastable forms that can be recovered to ambient pressure for subsequent seeding experiments. This has been demonstrated for paracetamol form II and paracetamol monohydrate. The studies also show that the particular solid form can be tuned by both pressure and concentration

Unexpectedly high reactivity of nitrogenated aromatics protected as amides or carbamates, when compared to sulfonamides, can be explained by a decrease of the aromaticity due to a greater ability of the carbon-centered groups to achieve delocalisation of the nitrogen lone pair, resulting in stronger global withdrawing effects.

Non-stabilized azomethine ylide 4a reacts smoothly at room temperature with a variety of uncomplexed aromatic heterocycles and carbocycles on the condition that the ring contains at least one or two electron-withdrawing substituents, respectively. Aromatic substrates, including pyridine and benzene derivatives, participate as 2π components in [3+2] cycloaddition reactions and interact with one, two, or three equivalent(s) of the ylide, depending on their structure and substitution pattern. Thus, this process affords highly functionalized polycyclic structures that contain between one and three pyrrolidinyl ring(s) in useful yields. These results indicate that the site selectivity of the cycloaddition reactions strongly depends on both the nature and the positions of the substituents. In most cases, the second 1,3-dipolar reaction occurs on the opposite face to the one that contains the first pyrrolidinyl ring. DFT calculations on model compounds indicate that a concerted mechanism features a low activation barrier.

No abstract

The fast and effective neutralization of the mustard-gas simulant 2-chloroethyl ethyl sulfide (CEES) using a simple and portable continuous flow device is reported. Neutralization takes place through a fully selective sulfoxidation by a stable source of hydrogen peroxide (alcoholic solution of urea-H O adduct/MeSO H freshly prepared). The reaction progress can be monitored with an in-line benchtop NMR spectrometer, allowing a real-time adjustment of reaction conditions. Inherent features of millireactors, that is, perfect control of mixing, heat and reaction time, allowed the neutralization of 25 g of pure CEES within 46 minutes in a 21.5 mL millireactor (t =3.9 minutes). This device, which relies on affordable and nontoxic reagents, fits into a suitcase, and can be deployed by police/military forces directly on the attack site.

No abstract