Phosgene

Bast, Cheryl B; Glass-Mattie, Dana F.

doi:10.1016/b978-0-12-800159-2.00025-7

Cited by 22 publications

(16 citation statements)

References 50 publications

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“…Phosgene is a serious threat to human and public safety due to its easy availability and various ways of poisoning. Thus, it is essential to develop facile, fast, and reliable molecular probes . In recent years, the design and synthesis of phosgene fluorescent probes have attracted extensive attention .…”

Section: Resultsmentioning

confidence: 99%

Rapid and Effective Reaction of 2-Methylpyridin-N-oxides with Triphosgene via a [3,3]-Sigmatropic Rearrangement: Mechanism and Applications

Xia

Nie

et al. 2021

J. Org. Chem.

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A facile and effective synthesis of 2-chloromethylpyridines was developed by a one-pot reaction of 2-alkylpyridin-N-oxides and triphosgene at room temperature. As starting materials, N-oxides of 2-alkylpyridine derivatives, including 2-alkylpyridines, 2-methyl quinolines, and phenanthroline, can react rapidly with triphosgene in the presence of triethylamine, affording 2-chloromethylpyridines in good to excellent yields (52–95%). Using the 2-methylquinoline substrate for the mechanistic study, it has been well demonstrated that the chlorination reaction undergoes a [3,3]-sigmatropic rearrangement, which can be observed as a reversible process by monitoring the intermediates. Moreover, the chlorination reaction can be used to construct a rapid and sensitive fluorescent probe for the detection of phosgene.

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Section: Resultsmentioning

confidence: 99%

Rapid and Effective Reaction of 2-Methylpyridin-N-oxides with Triphosgene via a [3,3]-Sigmatropic Rearrangement: Mechanism and Applications

Xia

Nie

et al. 2021

J. Org. Chem.

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“…Phosgene (COCl 2 ) is a harmful colorless gas that causes severe lung damage and leads to pulmonary complications such as noncardiogenic pulmonary edema, pulmonary emphysema, and even death. − It is anticipated that ∼80% of the total deaths caused by poisonous gases resulted from the lethal chemical warfare agent (CWA) phosgene in World War I. − The exposure to the colorless phosgene gas is not recognized because its very light odor is similar to the odor of freshly scythed hay. , Minimal exposure also causes a delayed effect that may not be noticeable for up to 48 h . Severe lung injuries have been found upon exposure to 20 ppm of phosgene for 2 min, and it becomes fatal for humans and all animals at 90 ppm after exposure for 30 min. , While the production and usage of lethal nerve agents such as sarin, soman, and tabun are strictly prohibited by international law, phosgene is widely used for the synthesis of chemical intermediates in pesticides, pharmaceuticals, resins, aniline dyes, and isocyanate-based polymers in industry. , Because of these detrimental effects, the risk of accidental release and the risk of a phosgene terrorist attack have become a potentially serious threats to public health .…”

Section: Introductionmentioning

confidence: 99%

Ruthenium(II) Polypyridine Complex-Based Aggregation-Induced Emission Luminogen for Rapid and Selective Detection of Phosgene in Solution and in the Gas Phase

2021

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A bis-heteroleptic ruthenium(II) complex, Ru-1, of 4,7-bis(2-aminoethylamino)-1,10-phenanthroline for selective “turn-on” detection of highly toxic chemical warfare agent phosgene is presented. Probe Ru-1 exhibits aggregation-induced emission (AIE), and the restricted intramolecular motion is responsible for the AIE activity. In a CHCl3/CH3CN [95:5 (v/v)] solvent mixture, a unique self-assembled vesicular structure was formed after aggregation, which was supported by transmission electron microscopy, field emission scanning electron microscopy, and atmoic force microscopy studies. Probe Ru-1 showed a rapid and highly selective luminescence turn-on response for phosgene over other competitive chemical warfare agents with a low detection limit (13.9 nM) in CH3CN. The 2-aminoethylamino groups in Ru-1 act as a reacting site for nucleophilic addition to the carbonyl center of phosgene and undergo intramolecular cyclization. The final product of the phosgene-mediated reaction, Ru-1-Phos, contains 2-imidazolidinone groups, which has been confirmed by electrospray ionization mass spectometry and 1H nuclear magnetic resonance (NMR) spectroscopy. 1H NMR titration of Ru-1 with phosgene supported the reaction mechanism and also pointed to the simultaneous reaction of phosgene at two 2-aminoethylamino sites. For the first time, the crystal structure of the phosgene reaction product, Ru-1-Phos, containing the cyclized 2-imidazolidinone group was confirmed by single-crystal X-ray diffraction, which indubitably validates the reaction mechanism. Triplet state time-dependent density functional theory calculations showed that the weak luminescence of Ru-1 was mostly due to the population of the non-emissive 3MC state. The cyclization reaction with phosgene and the corresponding 2-imidazolidinone product formation populated the emissive 3MLCT state in Ru-1-Phos and is the key reason for the enhanced luminescence. Furthermore, a low-cost portable test paper strip has been fabricated with Ru-1 for the real-time selective monitoring of phosgene gas at the nanomolar level.

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“…Phosgene (COCl 2 ) is a widely used colorless and highly toxic gas, so it was used as a chemical weapon agent (CWA) during World War I . Exposure to phosgene will cause noncardiogenic pulmonary edema and pulmonary emphysema and can even lead to individual death .…”

mentioning

confidence: 99%

BODIPY-Based Fluorescent Sensor for the Recognization of Phosgene in Solutions and in Gas Phase

2017

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As a highly toxic and widely used chemical, phosgene has become a serious threat to humankind and public security because of its potential use by terrorists and unexpected release during industrial accidents. For this reason, it is an urgent need to develop facile, fast, and selective detection methods of phosgene. In this Article, we have constructed a highly selective fluorescent sensor o-Pab for phosgene with a BODIPY unit as a fluorophore and o-phenylenediamine as a reactive site. The sensor o-Pab exhibits rapid response (∼15 s) in both colorimetric and turn-on fluorescence modes, high selectivity for phosgene over nerve agent mimics and various acyl chlorides and a low detection limit (2.7 nM) in solutions. In contrast to most undistinguishable sensors reported, o-Pab can react with phosgene but not with its substitutes, triphosgene and biphosgene. The excellent discrimination of o-Pab has been demonstrated to be due to the difference in highly reactive and bifunctional phosgene relative to its substitutes. Furthermore, a facile testing paper has been fabricated with poly(ethylene oxide) immobilizing o-Pab on a filter paper for real-time selective monitoring of phosgene in gaseous phase.

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Phosgene

Cited by 22 publications

References 50 publications

Rapid and Effective Reaction of 2-Methylpyridin-N-oxides with Triphosgene via a [3,3]-Sigmatropic Rearrangement: Mechanism and Applications

Rapid and Effective Reaction of 2-Methylpyridin-N-oxides with Triphosgene via a [3,3]-Sigmatropic Rearrangement: Mechanism and Applications

Ruthenium(II) Polypyridine Complex-Based Aggregation-Induced Emission Luminogen for Rapid and Selective Detection of Phosgene in Solution and in the Gas Phase

BODIPY-Based Fluorescent Sensor for the Recognization of Phosgene in Solutions and in Gas Phase

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