Kinetic study of the decomposition ofN-chloramines

Antelo, Juan; Arce, F.; Parajó, M.

doi:10.1002/(sici)1099-1395(199607)9:7<447::aid-poc778>3.0.co;2-x

Cited by 34 publications

(4 citation statements)

References 20 publications

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“…The N-chloramines obtained from aliphatic amines in a neutral medium are quite stable, increasing their decomposition rate in a strong acid medium or basic medium. [36][37][38][39] To select the suitable conditions for kinetic monitoring, a preliminary spectrophotometric study of all the reactants and of the reaction mixture was performed between 200 and 400 nm. The superposition of all of them allows us to justify that, upon mixing of the reactants, the formation of the N-chloro compound takes place.…”

Section: Preliminary Studies: Wavelength Selectionmentioning

confidence: 99%

Kinetic study of the formation of N‐chloro compounds using N‐chlorosuccinimide

Pastoriza

Antelo

Crugeiras

et al. 2014

J of Physical Organic Chem

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b Second-order rate constants were determined for the chlorination reaction of 2,2,2-trifluoethylamine and benzylamine with N-chlorosuccinimide at 25°C and an ionic strength of 0.5 M. These reactions were found to be of first order in both reagents. According to the experimental results, a mechanism reaction was proposed in which a chlorine atom is transferred between both nitrogenous compounds. Kinetics studies demonstrate that the hydrolysis process of the chlorinating agent does not interfere in the chlorination process, under the experimental conditions used in the present work. Free-energy relationships were established using the results obtained in the present work and others available in the literature for chlorination reactions with N-chlorosuccinimide, being the pK a range included between 5.7 and 11.22.

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Section: Preliminary Studies: Wavelength Selectionmentioning

confidence: 99%

Kinetic study of the formation of N‐chloro compounds using N‐chlorosuccinimide

Pastoriza

Antelo

Crugeiras

et al. 2014

J of Physical Organic Chem

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“…The chloramines occupy a key position in the disinfection process because they are temporary reservoirs of disinfection capacity, both moderating and sometimes prolonging disinfection capability (3). They are also intermediates in reactions leading to undesirable byproducts such as cyanogen chloride, various nitriles, and aldehydes (4)(5)(6)(7)(8)(9)(10)(11)(12). They are suspected of facilitating slow halocarbon formation through hydrolysis and halogen transfer reactions (13).…”

Section: Introductionmentioning

confidence: 99%

Role of Amide Nitrogen in Water Chlorination: Proton NMR Evidence

Jensen

Lam

Helz

1999

Environ. Sci. Technol.

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A large fraction of the dissolved amino-N in natural waters and wastewaters is contained in amide groups, for example, in proteins. Whether this N pool reacts with and modifies the chemical behavior of chlorine during water disinfection is unclear. To investigate this issue, water-suppressed, proton NMR spectra have been obtained for aqueous, acetylated glycine, alanine, and alanylalanylalanine before and after treatment with NaOCl at near-neutral pH. N-Chlorination of N-acetylglycine (aceturic acid) induced cis−trans rotation about the amide bond at ambient temperature. N-Bound Cl+ induced a measurable downfield chemical shift in the acetyl methyl resonance in N-acetylglycine, ∂δ = 0.15 ppm (cis) and ∂δ = 0.3 ppm (trans), and in N-acetylalanine methyl resonances, acetyl methyl ∂δ = 0.3 ppm (trans) and side chain methyl ∂δ = 0.2 ppm. Chlorination of N-acetylalanylalanylalanine produced ∂δ values similar to N-acetylalanine. The spectral effects were reversible, the original spectra being regenerated upon dechlorination with sulfite. Negligible substrate decomposition was observed. Rate constants for chlorination of N-acetylalanine near neutral pH are k f = 1.58 × 10-3 M-1 s-1 and k b = 7.57 × 10-7 s-1 where K eq = 2.1 × 103. Because of both sluggish formation kinetics and an unfavorable equilibrium constant, N-chloramides are predicted to be unimportant under typical disinfection conditions.

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“…N -Chloramines are versatile reagents, however, their availability is restricted by their stability, so useful would be in situ methods to produce and use them [ 1 – 2 ]. The continuous-flow methodology is useful in this context, enabling control over reaction exotherms and improved measures for containment.…”

Section: Introductionmentioning

confidence: 99%

A general and atom-efficient continuous-flow approach to prepare amines, amides and imines via reactive N-chloramines

Jolley¹,

Chapman²,

Blacker³

2018

Beilstein J. Org. Chem.

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Chloramines are an important class of reagents, providing a convenient source of chlorine or electrophilic nitrogen. However, the instability of these compounds is a problem which makes their isolation and handling difficult. To overcome these hazards, a continuous-flow approach is reported which generates and immediately reacts N-chloramines directly, avoiding purification and isolation steps. 2-Chloramines were produced from the reaction of styrenes with N-alkyl-N-sulfonyl-N-chloramines, whilst N-alkyl or N,N’-dialkyl-N-chloramines reacted with anisaldehyde in the presence of t-BuO2H oxidant to afford amides. Primary and secondary imines were produced under continuous conditions from the reaction of N-chloramines with base, with one example subsequently reduced under asymmetric conditions to produce a chiral amine in 94% ee.

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Kinetic study of the decomposition ofN-chloramines

Cited by 34 publications

References 20 publications

Kinetic study of the formation of N‐chloro compounds using N‐chlorosuccinimide

Kinetic study of the formation of N‐chloro compounds using N‐chlorosuccinimide

Role of Amide Nitrogen in Water Chlorination: Proton NMR Evidence

A general and atom-efficient continuous-flow approach to prepare amines, amides and imines via reactive N-chloramines

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