Relative Basicities of ortho-, meta-, and para-Substituted Aryllithiums

Relative Basicities of ortho-, meta-, and para-Substituted Aryllithiums

The relative basicities of aryllithiums bearing methoxy, chlorine, fluorine, trifluoromethyl and trifluoromethoxy substituents at the ortho, meta, and para positions have been assessed. To this end, two aryllithiums of comparable basicity were equilibrated together with the corresponding bromo- or i...

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Veröffentlicht in:Journal of organic chemistry 2009-01, Vol.74 (1), p.222-229
Hauptverfasser: Gorecka-Kobylinska, Joanna, Schlosser, Manfred
Format: Artikel
Sprache:eng
Schlagworte:
Chemical reactivity
Chemistry
Exact sciences and technology
Lithium - chemistry
Molecular Structure
Noncondensed benzenic compounds
Organic chemistry
Organometallic Compounds - chemistry
Preparations and properties
Reactivity and mechanisms
Stereoisomerism
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container_title Journal of organic chemistry
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creator Gorecka-Kobylinska, Joanna
Schlosser, Manfred
description The relative basicities of aryllithiums bearing methoxy, chlorine, fluorine, trifluoromethyl and trifluoromethoxy substituents at the ortho, meta, and para positions have been assessed. To this end, two aryllithiums of comparable basicity were equilibrated together with the corresponding bromo- or iodoarenes in a 1: 2 mixture of pentanes with tetrahydrofuran at −50, −75, or −100 °C. The “basicity” (protodelithiation) increments ΔΔG derived from the equilibrium constants are linearly correlated with the relative protonation enthalpies of the corresponding aryl anions in the gas phase. However, the correlation factor proves to be position-dependent. Compared with “naked” aryl anions, the basicity of aryllithiums mirrors the effects of ortho, meta, and para substituents to the extent of 36%, 30%, and 25%, respectively.
doi_str_mv 10.1021/jo8020083
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subjects Chemical reactivity
Chemistry
Exact sciences and technology
Lithium - chemistry
Molecular Structure
Noncondensed benzenic compounds
Organic chemistry
Organometallic Compounds - chemistry
Preparations and properties
Reactivity and mechanisms
Stereoisomerism
title Relative Basicities of ortho-, meta-, and para-Substituted Aryllithiums
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