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Dediazoniations of Arene Diazonium Ions in Homogeneous Solution. Part VI: Solvolyses in 2,2,2-trifluoroethanol/water mixtures and exclusion of a potential aryne mechanism

✍ Scribed by Peter Burri; George H. Wahl Jr.; Heinrich Zollinger

Publisher
John Wiley and Sons
Year
1974
Tongue
German
Weight
402 KB
Volume
57
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

The rates and products of dediazoniation of benzenediazonium tetrafluoroborate in 2,2,2‐trifluoroethanol (TFE)/water mixtures has been determined. The results are not consistent with a mechanism in which TFE and water enter the rate‐determining part of the reaction as nucleophiles. The influence of the solvent composition on product ratios and rates is explained as a solvent effect, the formation of a (solvated) aryl cation being the rate‐determining part of the reaction. The magnitude of the preexponential factor of the Arrhenius equation is consistent with this interpretation. Since the solvolysis of p ‐chlorobenzenediazonium tetrafluoroborate in TFE yields no detectable m‐products, an aryne‐like mechanism is excluded.

📜 SIMILAR VOLUMES

Dediazoniations of Arene Diazonium Ions
Dediazoniations of Arene Diazonium Ions in Homogenous Solution. Part IV: Change-over from a heterolytic to a homolytic mechanism in 2,2,2-trifluoroethanol pyridine mixtures
✍ Peter Burri; Hana Loewenschuss; Heinrich Zollinger; Gene K. Zwolinski 📂 Article 📅 1974 🏛 John Wiley and Sons 🌐 German ⚖ 484 KB

## Abstract There are only two dediazoniation products of benzenediazonium tetrafluoroborate in 2,2,2‐trifluoroethanol (TFE), namely phenyl 2,2,2‐trifluoroethyl ether (**1**) and fluorobenzene (**2**). The reaction kinetics are strictly first‐order with respect to the diazonium salt. The addition o

Dediazoniations of Arene Diazonium Ions
Dediazoniations of Arene Diazonium Ions in Homogeneous Solution. Part III: Heterolytic arylations in 2,2,2-trifluoroethanol - an SN1-or an SN2-reaction?
✍ Peter Burri; Heinrich Zollinger 📂 Article 📅 1973 🏛 John Wiley and Sons 🌐 German ⚖ 791 KB

## Abstract Benzenediazonium tetrafluoroborate in 2,2,2‐trifluoroethanol decomposes to give fluorobenzene and phenyl 2,2,2‐trifluoroethyl ether. In the presence of benzene, toluene, trifluoromethyl‐benzene or anisole, the respective biphenyl derivatives are formed in addition to fluorobenzene and t