Disproportionation Kinetics of N‐Chloromethylamine and N‐Chloroethylamine

Antelo, Juan; Arce, F.; Parajó, M.; Rodrí­guez, Pilar Rodriguez

doi:10.1002/bscb.19921011207

Cited by 3 publications

(3 citation statements)

References 7 publications

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“…In this table, we can observe an increase in the catalytic constant k HAi with increasing the acid strength in the following sequence: Cl 2 CHCOOH/Cl 2 CHCOO − > ClCH 2 COOH/ClCH 2 COO − > CH 3 OCOOH/CH 3 OCOO − > CH 3 COOH/CH 3 COO − . These results are in concordance with those obtained in previous studies .…”

Section: Mechanism and Discussionsupporting

confidence: 94%

Oxidation of Bromide by Tert‐Butyl Hypochlorite

Pastoriza

Antelo

Crugeiras

2013

Int J of Chemical Kinetics

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The kinetics of the oxidation reaction of bromide by tert‐butyl hypochlorite (tBuOCl) was studied at 25°C, ionic strength 0.5 M, and under isolation conditions. A stopped‐flow spectrophotometer was employed for monitoring the reactions. Kinetic studies show that the reaction is first order with respect to [Br−] and [tBuOCl]. Linear dependences of the proton concentration, in perchloric acid medium, and the buffer solution concentration were found on the rate constant. The activation parameters were calculated using the Arrhenius and Eyring equations from the kinetic studies performed to analyze the influence of temperature on the rate constant. The results are consistent with a reaction mechanism of general acid catalysis. The catalytic constants were obtained for the oxidation of bromide by tert‐butyl hypochlorite. The slope obtained for the Brönsted relationship was 0.36.

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Section: Mechanism and Discussionsupporting

confidence: 94%

Oxidation of Bromide by Tert‐Butyl Hypochlorite

Pastoriza

Antelo

Crugeiras

2013

Int J of Chemical Kinetics

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“…In earlier studies of this reaction, the observation of weak buffer catalysis for chloramines with poor amine leaving groups led to the conclusion that simultaneous chlorine and proton transfer occur in the rate determining step. 10,15, 16 In contrast to these results, we were unable to detect general acid catalysis of the reaction of 4 with iodide ion. 13 We describe here a study of chlorine transfer to iodide ion from N-chlorodimethylamine (1), N-chloro-2,2,2-trifluoroethylamine (2) and N,N-dichlorotaurine (3) (Scheme 2) in H 2 O at 25 • C and I = 0.5 (NaClO 4 ).…”

Section: Methodscontrasting

confidence: 74%

“…This value agrees, to within 24%, with a value reported in earlier work. 16 log(k 2 ) o = logk L -pL (1) 1). Combination of the two rate constants gives a solvent deuterium isotope effect on the hydronium ion-catalysed reaction of k H /k D = (0.37 ± 0.01).…”

Section: Resultsmentioning

confidence: 99%

Acid-catalysed chlorine transfer from N-chloramines to iodide ion: experimental evidence for a predicted change in mechanism

2010

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Rate constants for acid catalysis of the reactions of N-chlorodimethylamine (1), N-chloro-2,2,2-trifluoroethylamine (2) and N,N-dichlorotaurine (3) with iodide ion were determined in H(2)O at 25 degrees C and I = 0.5 (NaClO(4)). The failure to detect significant catalysis by general acids of chlorine transfer from 1 to the nucleophile, together with the observed inverse solvent deuterium isotope effect on the hydronium ion-catalysed reaction (k(H)/k(D) = 0.37), indicates that this process occurs by protonation of 1 in a fast equilibrium step, followed by rate determining chlorine transfer to iodide ion. The appearance of general acid catalysis for the reactions of 2 and 3 shows that increasing the leaving group ability leads to a change to a concerted mechanism, which is suggested to be enforced by the absence of a significant lifetime of the protonated chloramine intermediate in the presence of iodide ion.

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Kinetic study of the decomposition ofN-chloramines

Antelo

Arce

Parajó

1996

J. Phys. Org. Chem.

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The decomposition of various N‐chloroalkylamines and N‐chloroalcoholamines was investigated kinetically at pH 4–12 and in strongly alkaline media. The rate of N‐chloramine decomposition increased with increasing pH above pH 10, remained virtually constant over the pH range 7–10 and again increased with decreasing pH in the acidic zone. The results are described by a rate equation involving general base catalysis terms. Experimental evidence suggests that the decomposition of N‐haloamines proceeds via an elimination mechanism that yields an imine. This β‐elimination process is a non‐synchronized concerted mechanism where cleavage of the N(SINGLE BOND)X bond has progressed to a greater extent than that of the Cα(SINGLE BOND)H by the time the transition state is reached, which is therefore ‘E1‐like’ (i.e. with a transition state having a certain nitrenium character).

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Disproportionation Kinetics of N‐Chloromethylamine and N‐Chloroethylamine

Cited by 3 publications

References 7 publications

Oxidation of Bromide by Tert‐Butyl Hypochlorite

Oxidation of Bromide by Tert‐Butyl Hypochlorite

Acid-catalysed chlorine transfer from N-chloramines to iodide ion: experimental evidence for a predicted change in mechanism

Kinetic study of the decomposition ofN-chloramines

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