- Rates of Reaction of the Sulfoxides and Sulfones of Sulfur Mustard and 2-Chloroethyl Ethyl Sulfide with Hydroxide Ion in Water
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The reactions of the sulfoxides and sulfones of sulfur mustard and an analogue, 2-chloroethyl ethyl sulfide, with hydroxide ion in aqueous solution at 25 deg have been studied.In contrast with the behaviour of the parent sulfides, for which exclusive substitution of chlorine is observed under comparable conditions, the oxidized compounds react through base-catalysed elimination of HCl to give corresponding alkenes.Second-order rate constants for these reactions are reported and implications for the metabolism of sulfur mustard are discussed.
- Tilley, R. Ian,Leslie, D. Ralph
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- Mo(VI) complex catalysed synthesis of sulfonees and their modification for anti-HIV activities
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An efficient method for the synthesis of sulfones has been developed using sugar derived cis-dioxo molybdenum(VI) complex as catalyst and urea hydrogen peroxide as oxygen source. Present method is highly specific for sulfide oxidation irrespective of presence of alkene and aldehyde groups in the same molecule. Synthesis of fifteen sulfones have been reported with 82–98% isolated yields and the catalyst has been reused five times without any loss in its activity. 2-(Phenylsulfonyl)aniline has been condensed with eight different aromatic aldehydes and the products are being explored for HIV-1 reverse transcriptase inhibition activities.
- Madduluri, Vimal Kumar,Baig, Noorullah,Chander, Subhash,Murugesan, Sankaranarayanan,Sah, Ajay K.
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- A safe and compact flow platform for the neutralization of a mustard gas simulant with air and light
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A low footprint, mobile, robust and frugal chemical neutralization technology is reported for the oxidative neutralization of a mustard gas simulant. It relies on the inherent properties of a highly engineered continuous flow setup and carefully optimized and simple, yet robust, experimental conditions. The neutralization protocol uses only non-toxic, widely available and cheap chemicals. The continuous flow setup integrates a singlet oxygen generator and exploits its oxidative power to neutralize 2-chloroethyl ethyl sulfide (CEES), the most common thioether mustard gas simulant. The flow reactor can be connected to either pressurized oxygen or air and handles CEES as a 1 M solution in EtOH containing a trace amount (0.06 molpercent) of a non-toxic and widely available photosensitizer (Methylene Blue). Upon irradiation with visible light (orange or white light), total and highly selective neutralization towards the corresponding non-toxic sulfoxide (1-chloro-2-(ethylsulfinyl)ethane, CEESO) is obtained with reactor effluents containing less than 1percent of the corresponding potentially toxic sulfone (1-chloro-2-(ethylsulfonyl)ethane, CEESO2). With a low footprint (L × W × H 94 × 42 × 40 cm), this neutralization technology can be equipped on a vehicle for on-site interventions, localized at a neutralization facility or both. This experimental work is also supported with the computational rationalization of the reactivity of CEES towards singlet oxygen.
- Bianchi, Pauline,Emmanuel, Noémie,Legros, Julien,Monbaliu, Jean-Christophe M.
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supporting information
p. 4105 - 4115
(2020/07/30)
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- Difluoro- and trifluoro diazoalkanes-complementary approaches in batch and flow and their application in cycloaddition reactions
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Herein we report on applications of fluorinated diazoalkanes in cycloaddition reactions, with the emphasis on studying subtle differences between diverse fluorinated diazo compounds. These differences led to two major synthetic protocols in batch and flow that allow the safe and scalable synthesis of fluoroalkyl-, sulfone-substituted pyrazolines.
- Hock, Katharina J.,Mertens, Lucas,Metze, Friederike K.,Schmittmann, Clemens,Koenigs, Rene M.
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supporting information
p. 905 - 909
(2017/08/14)
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- Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 15. Generation of alkoxycarbonyl(sulfenyl)carbenes and their intramolecular insertion to give alkenyl sulfides
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A range of 18 alkoxycarbonyl sulfinyl phosphorus ylides 9 have been prepared and their behaviour upon flash vacuum pyrolysis (FVP) at 600 deg C examined. For R1 = H, Me and Et they lose Ph3PO and in some cases Ph3P to give mixtures of products including the alkenyl sulfides 10, the sulfides 11, the disulfides 12 and the thioesters 14. The alkenyl sulfides 10 most likely arise from intramolecular insertion of the alkoxycarbonyl sulfenyl carbenes resulting from loss off Ph3PO to produce β-lactones which then lose CO2 and this is supported by the results from 13C labelled ylides. Possible mechanisms for the formation of 11 and 14 are also presented and the feasibility of various steps has been examined by preparation and pyrolysis of the proposed intermediates. In contrast, pyrolysis of the ylides 9 where R1 = Ph and the tert-butoxycarbonyl ylides 30 leads mainly to complete fragmentation with loss of Ph3PO and benzyl alcohol or 2-methylpropan-2-ol and does not give any useful sulfur-containing products. Four alkoxy-carbonyl sulfonyl diazo compounds 33 have been prepared and in three cases they give the alkenyl sulfones 34 upon FVP at 400 deg C, probably by an intramolecular insertion and decarboxylation process analogous to the formation of 10 from 9. On the other hand the alkoxycarbonyl carbenes produced by FVP of the amino acid-derived diazo compounds 35 undergo alternative proocesses with no sign of β-lactone formation. Fully assigned 13C NMR data are presented for 13 of the ylides.
- Aitken, R. Alan,Armstrong, Jill M.,Drysdale, Martin J.,Ross, Fiona C.,Ryan, Bruce M.
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p. 593 - 604
(2007/10/03)
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- Flash Vacuum Pyrolysis of Alkoxycarbonyl/Sulfinyl Stabilised Phosphorus Ylides: Generation and Intramolecular Insertion of Alkoxycarbonyl(sulfenyl)carbenes
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Flash vacuum pyrolysis of phosphorus ylides stabilised both by ester and sulfinyl groups results mainly in extrusion of Ph3PO to generate alkoxycarbonyl(sulfenyl)carbenes; these undergo intramolecular insertion into CH of the alkoxycarbonyl group giving β-lactones which under the conditions lose CO2 to afford alkenyl sulfides.
- Aitken, R. Alan,Drysdale, Martin J.,Ryan, Bruce M.
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p. 805 - 806
(2007/10/02)
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