Poly(N-vinylpyrrolidone)-hydrotribromide: A new gel-type resin for alcohol oxidation and alkene dibromination

Koshy, Ebey P.; Zacharias, Jose; Pillai, V. N. Rajasekharan

doi:10.1016/j.reactfunctpolym.2005.11.012

Cited by 7 publications

(12 citation statements)

References 23 publications

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“…There are a number of families of polymeric systems capable of acting as oxidants . Among them, polymer-bound halogenating and oxidizing agents such as halamines (halogenated imide, amide, or amine groups), pyridine- and pyrrolidone-based molecular halogen complexes, and ion-exchange resins in anionic form, seem to be quite amenable for utilization in protective materials and industrial collective and individual protective equipment due to their compatibility with a variety of other polymeric matrices and a great multitude of available processing options. − There is a significant body of literature related to the utilization of N -haloamines as biocidal, antiseptic, halogenating and oxidizing agents in polymeric coatings, resins, fibers, paints, etc. − Pyrrolidone-based molecular halogen complexes such as poly( N -vinylpyrrolidone) (PVP)-bromine complexes have been utilized in alcohol and acetal oxidation, alkene dibromination, oxidative cleavage of silyl ethers, and conversion of dithioacetals to oxothioesters. − Functionality of PVP stems from its hydrophilicity, benign nature, film-forming properties, ease of cross-linking, and ability to form adduct-type complexes with halogens. , PVP-based networks are water-dispersible and can be synthesized in situ by UV-initiated polymerization. Monomer and cross-linker solutions of such systems can be applied to porous surfaces such as in textiles by either batch coating or dip coating, followed by cross-linking and halogenation .…”

Section: Introductionmentioning

confidence: 99%

Degradation of Chemical Threats by Brominated Polymer Networks

Bromberg

Pomerantz

Schreuder-Gibson

et al. 2014

Ind. Eng. Chem. Res.

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Poly(N-bromomaleimide) (PMAi-Br), poly(N-vinylpyrrolidone)-bromine adducts (PVP–Br), and poly(ethylene-alt-N-bromomaleimide) (PEMAi-Br) and their cross-linked networks are introduced as reactive, self-decontaminating components of protective barriers. Synthetic routes toward polymaleimides include free-radical copolymerization of maleimide with divinyl cross-linkers as well as amidation of poly(ethylene-alt-maleic anhydride) with urea. The polymers are brominated by bromine in carbon tetrachloride or by copper(II) bromide in dimethylformamide, with the active bromine contents up to and above 4 mequiv/g, or >30 wt %. The brominated polymer networks exhibit considerable swelling in water and possess reversible redox peak potentials in cyclic voltammetry experiments due to the redox reactions of the bromine present in the polymer structures. In acidic aqueous media, PVP–Br, PMAi-co-DVB-Br, and PEMAi-Br materials are able to degrade 100% of hydrazine, monomethylhydrazine, and 1,1-dimethylhydrazine down to concentrations below detectable levels of 0.15–0.25 mM. The hydrazine is converted to nitrogen gas. The insecticide malathion, tested as a simulant of a combat warfare agent VX, is efficiently and selectively oxidized to malaoxon in the presence of the brominated networks, whereas 2-(chloroethyl)ethyl sulfide (CEES), a simulant of the sulfur mustard agent, is rapidly oxidized, in both vapor and liquid states, into its less-toxic sulfone derivative, 1-chloro-2-(ethylsulfinyl)ethane (CEESO), with the only side product being 1,2-bis(ethylthio)ethane. The oxidation of CEES is proven to be selective, in that no toxic overoxidized CEES analogue, 1-chloro-2-(ethylsulfonyl)ethane, is formed. The developed brominated polymer networks are versatile materials with potential applications in coatings, filters, fabrics, and sorbents.

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Section: Introductionmentioning

confidence: 99%

Degradation of Chemical Threats by Brominated Polymer Networks

Bromberg

Pomerantz

Schreuder-Gibson

et al. 2014

Ind. Eng. Chem. Res.

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“…[20] Bromination can also be performed in ionic liquids (entry 4, Table 1). [21] Employing carrying agents as a transport medium for bromine reduces the hazardous potential of molecular bromine, examples include; sol-gel-entrapped pyridinium hydrobromide perbromide (PHPB@s.g., entry 5, Table 1), [22] poly (vinylpyrrolidone) (PVP, entry 6 [23] ), [23,24] pyridine hydrobromide (entries 7 and 8), [25,26] pentylpyridinium bromide (entry 9), [27] 1,2-dipyridiniumdibromide-ethane (entry 10), [28] N-octylquinolinium bromide (entry 11), [29] and tetrameric DABCO (TM)-bromine (DABCO = 1,4-diazabicyclo-…”

Section: Resultsmentioning

confidence: 99%

“…However, during the bromination step, a range of technological equipment is required to handle certain substances such as solvents that have toxicological (n-hexane, chloroform and carbon tetrachloride in entries 1, 3, 5, 12, 14, 20, 22, Table S1 in the Supporting Information) and chronic effects on health (nhexane, dichloromethane, chloroform, carbon tetrachloride, entries 1, 3, 5, 6, 12, 14-18, 20, 22, Table S1). A number of the solvents used in Methods I-III are flammable (3-5, 7, 10-13, 16, 17, 19, 23, 24) and may form explosive peroxides (entries 4,11,18,19,24). Owing to these hazardous substances, the safety standard of the available technological equipment is possibly already safe enough for the application of molecular bromine.…”

Section: Discussionmentioning

confidence: 99%

Electrophilic Bromination of Alkenes: Environmental, Health and Safety Aspects of New Alternative Methods

Eissen

Lenoir

2008

Chemistry A European J

106

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More than twenty new alternative methods for bromination of alkenes have been evaluated taking into consideration their resource demands, waste production as well as environmental, health and safety aspects. The cost of bromine and the substances designated to circumvent the application of molecular bromine have also been taken into account. As bromine is only one of several problematic substances being used, its avoidance-by applying bromine supported on solid material or by performing the in situ generation of bromine-does not significantly reduce the technological requirements. On the contrary, the resource demands and amount of waste produced by most new methods are significantly higher compared to the standard methods, especially if the recycling of a carrying agent is not efficient. The method using hydrobromic acid and hydrogen peroxide can be regarded as a competitive alternative to the standard method. The application of certain carrying agents could be interesting, because solvents such as carbon tetrachloride or chloroform used during synthesis could be replaced with less problematic ones during work-up. However, problems associated with these alternatives are not resolved as yet.

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“…From the titre value, the bromine capacity was calculated and found to be 2.60 mmol/g of the polymeric reagent. 46…”

Section: Methodsmentioning

confidence: 99%

Microwave-assisted oxidative coupling of thiols using polystyrene supported bromoderivatives of 2-oxazolidone

Mathew

Koshy³

2021

Polymers and Polymer Composites

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Polymer-supported reagents have become popular in synthetic organic chemistry over the past decades. But the kinetics of polymer-supported reactions is slow compared to solution phase synthesis because of the poor diffusion of the reactants through the macromolecular polymer matrix. This difficulty can be reduced to a great extent by performing polymer-supported reactions under microwave (MW) conditions. The present work is focussed on the design and development of an innovative, powerful, MW stable and recyclable polymeric reagent prepared by attaching bromoderivative of 2-oxazolidone into the macromolecular matrix of polystyrene. 3% cross-linked polystyrene was prepared by free radical aqueous suspension polymerization technique using tetra ethylene glycol diacrylate as the cross-linking agent and the resulting beads were functionalized by chloromethylation followed by reaction with 2-oxazolidone. Bromine functionality is introduced into the polymer by treating with bromine in carbon tetrachloride. The synthetic utility of the prepared polymeric reagent was demonstrated by the oxidative coupling of thiols to disulfides under MW irradiation. No over oxidation was observed in this protocol and the utilization of polystyrene support simplifies work up and product isolation. The synthesised polymeric reagent displayed good cyclic stability up to five cycles without any substantial decrease in bromine content and satisfactory storage stability under normal laboratory condition. Moreover this may be the first report that uses MW energy for the oxidation of thiols to disulfides using polymer-supported reagents. [Formula: see text]

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Poly(N-vinylpyrrolidone)-hydrotribromide: A new gel-type resin for alcohol oxidation and alkene dibromination

Cited by 7 publications

References 23 publications

Degradation of Chemical Threats by Brominated Polymer Networks

Degradation of Chemical Threats by Brominated Polymer Networks

Electrophilic Bromination of Alkenes: Environmental, Health and Safety Aspects of New Alternative Methods

Microwave-assisted oxidative coupling of thiols using polystyrene supported bromoderivatives of 2-oxazolidone

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