Aromatic Halogenation. II. The Kinetics and Mechanism of Iodination of 4-Nitrophenol and 4-Nitrophenol-2,6-d2

Grovenstein, Erling; Aprahamian, Nazar S.

doi:10.1021/ja00861a018

Cited by 36 publications

(18 citation statements)

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“…We also added iodine to reaction mixtures, but no additional product was detected-iodine does react with p-nitrophenol in aqueous solutions at 50 ЊC. 8 Good pseudo-first order kinetics, for at least three half-lives, were obtained for S N 2 reactions of sodium p-nitrophenoxide with an excess of CH 3 I in degassed dry acetone (Table 1, Fig. 1), and good pseudo-first order kinetics were reported for similar reactions of tetramethylammonium p-nitrophenoxide in dry acetonitrile.…”

Section: Discussionmentioning

confidence: 99%

Reinterpretation of the kinetic data and the non-steady state hypothesis (two-step mechanism) for the SN2 reaction between p-nitrophenoxide and methyl iodide in aprotic solvents containing water

Humeres

Bentley

2003

Org. Biomol. Chem.

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Kinetic data obtained by conventional spectrophotometry for reaction of sodium p-nitrophenoxide with methyl iodide in degassed acetone are reported. The rate constants obtained from the first 10% of reaction do not differ significantly from those obtained over longer reaction times (e.g 50% reaction)--the main criteria of Parker et al. (Org. Biomol. Chem., 2003, 1, 36-38) for a non-steady state two-step mechanism. Reactions are accelerated by crown ether, suggesting a mechanism via a free ion pair. Product studies by high performance liquid chromatography of reactions in aqueous acetonitrile (used by Parker et al.) show that the yield of methylated product is strongly affected by at least two base-neutralising side reactions.

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Section: Discussionmentioning

confidence: 99%

Reinterpretation of the kinetic data and the non-steady state hypothesis (two-step mechanism) for the SN2 reaction between p-nitrophenoxide and methyl iodide in aprotic solvents containing water

Humeres

Bentley

2003

Org. Biomol. Chem.

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“…For example, iodine will only react with aromatic amines because the iodide precipitates as a salt; otherwise an oxidizing agent must be added to oxidize the iodide ion to iodine (4)(5)(6). Iodine chloride has also been used and tends to be a better iodinating agent (4).…”

Section: Reactions Ivith Phenols and Anilinesmentioning

confidence: 99%

Electrophilic additions of iodonium nitrate to unsaturated substrates

Lown¹,

Joshua²

1977

Can. J. Chem.

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Iodonium nitrate (generated by reaction of iodine chloride with silver nitrate in chloroformpyridine) reacts with a variety of unsaturated substrates to form the following: 1,4-conjugate addition products of the type alkenyl pyridinium nitrates; alkyliodopyridinium nitrates; products of aromatic iodination of both phenols and anilines; substituted benzodihydrofurans; tetrahydrofurans and tetrahydropyrans; polycyclic bridged ethers; lactones; thiazolines.

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“…A search through the literature reveals the paucity of such quantitative investigations contrary to reports in nonaqueous solutions. Berliner has studied the iodinations of chlorophenol and anisole in acidic solutions , whereas Grovenstein and Aprahamain have reported those of dibromo phenols . Schutte and Havinga have studied the base catalysis for the iodination of imidazole and p ‐cresol .…”

Section: Introductionmentioning

confidence: 99%

A Quantitative Structure–Reactivity Assessment of Phenols by Investigation of Rapid Iodination Kinetics Using Hydrodynamic Voltammetry: Applicability of the Hammett Equation in Aqueous Medium

Borkar¹,

Bonde²,

Dangat³

2013

Int J of Chemical Kinetics

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Halogenations of aromatic substrates in aqueous medium are essentially electrophilic substitutions proceeding at rates concomitant with the nature of the substrates and substituent motifs. Kinetics as an investigatory tool for the quantitative assessment of the structure–reactivity correlation in these reactions for a diverse range of substrates has rarely been reported, presumably due to the rapidity of these reactions in aqueous medium. We have used hydrodynamic voltammetry to investigate the rapid kinetics of uncatalyzed iodination of phenol and eight substituted phenols by iodine monochloride at constant pH in aqueous medium. The Arrhenius plots for these reactions yield comprehensive kinetic and thermodynamic data. The quantitative structure–reactivity correlation stemming from the regio‐ and stereospecificity of the substituent motifs on the substrates has been examined through the Hammett plot, which shows a negative slope of 1.87. The magnitudes of the rate constants, energies of activation, frequency factors, and entropy change obtained for the nine fast reactions reported, reflect the relative ease of the reaction dynamics in quantitative terms thereby ascertaining the relative reactivities of the phenols studied herein.

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Aromatic Halogenation. II. The Kinetics and Mechanism of Iodination of 4-Nitrophenol and 4-Nitrophenol-2,6-d₂

Cited by 36 publications

References 0 publications

Reinterpretation of the kinetic data and the non-steady state hypothesis (two-step mechanism) for the SN2 reaction between p-nitrophenoxide and methyl iodide in aprotic solvents containing water

Reinterpretation of the kinetic data and the non-steady state hypothesis (two-step mechanism) for the SN2 reaction between p-nitrophenoxide and methyl iodide in aprotic solvents containing water

Electrophilic additions of iodonium nitrate to unsaturated substrates

A Quantitative Structure–Reactivity Assessment of Phenols by Investigation of Rapid Iodination Kinetics Using Hydrodynamic Voltammetry: Applicability of the Hammett Equation in Aqueous Medium

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