Solvolyses of <b>4</b>‐methylbenzenediazonium ions in trifluoroethanol/water mixtures: Effects of [TFE], acidity and temperature on the kinetics and mechanism of the reaction

Fernández-Alonso, Alejandra; Bravo‐Díaz, Carlos

doi:10.1002/poc.1730

Cited by 5 publications

(2 citation statements)

References 38 publications

(64 reference statements)

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“…7 For solvent mixtures, as in the solvolysis of 4-methylbenzenediazonium ions in 2,2,2-trifluoroethanol−water, the kinetic and thermodynamic results suggest that the rate-determining step for dediazoniation is the formation of a highly reactive aryl cation that traps any nucleophile available in its solvation shell. 8 The major products of the dediazoniation of 2-, 3-, and 4-methylbenzenediazonium ions in ethanol/water mixtures are ethyl methylphenyl ethers and cresols. 9 All three compounds produce equal amounts of products in a water molar fraction (x water = n water /(n water + n solvent )) equal to 0.36.…”

Section: ■ Introductionmentioning

confidence: 99%

Molecular Dynamics Simulations of the Initial-State Predict Product Distributions of Dediazoniation of Aryldiazonium in Binary Solvents

Cruz¹,

Lima²,

Dias³

et al. 2015

J. Org. Chem.

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The dediazoniation of aryldiazonium salts in mixed solvents proceeds by a borderline SN1 and SN2 pathway, and product distribution should be proportional to the composition of the solvation shell of the carbon attached to the -N2 group (ipso carbon). The rates of dediazoniation of 2,4,6-trimethylbenzenediazonium in water, methanol, ethanol, propanol, and acetonitrile were similar, but measured product distributions were noticeably dependent on the nature of the water/cosolvent mixture. Here we demonstrated that solvent distribution in the first solvation shell of the ipso carbon, calculated from classical molecular dynamics simulations, is equal to the measured product distribution. Furthermore, we showed that regardless of the charge distribution of the initial state, i.e., whether the positive charge is smeared over the molecule or localized on phenyl moiety, the solvent distribution around the reaction center is nearly the same.

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Section: ■ Introductionmentioning

confidence: 99%

Molecular Dynamics Simulations of the Initial-State Predict Product Distributions of Dediazoniation of Aryldiazonium in Binary Solvents

Cruz¹,

Lima²,

Dias³

et al. 2015

J. Org. Chem.

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“…In nonaqueous solvents, products associated with free radicals, for example, biphenyl derivatives and replacement of N 2 + by H are often observed, especially when electron-withdrawing groups are present on the arenediazonium ion [4,[17][18][19][20][21]. In this context heterolytic dediazoniation has been reported to occur with ortho-, meta-and para-methylbenzenediazonium (2MBD, 3MBD, 4MBD) and para-nitrobenzenediazonium (4NBD) ions in an aqueous medium [10,22], while other authors interpreted their results as showing evidence of heterolytic and homolytic processes during the thermal and photochemical dediazoniation of several arenediazonium ions in trifluoroethanol and ethanol [19][20][21].…”

Section: Introductionmentioning

confidence: 99%