| Kinetics of the solvolyses of benzhydryl derivatives: basis for the construction of a comprehensive nucleofugality scale. | |
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MedLine Citation:
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PMID: 16320366 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
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A series of 21 benzhydrylium ions (diarylmethylium ions) are proposed as reference electrofuges for the development of a general nucleofugality scale, where nucleofugality refers to a combination of leaving group and solvent. A total of 167 solvolysis rate constants of benzhydrylium tosylates, bromides, chlorides, trifluoroacetates, 3,5-dinitrobenzoates, and 4-nitrobenzoates, two-thirds of which have been determined during this work, were subjected to a least-squares fit according to the correlation equation log k(25 degrees C) = sf(Nf + Ef), where sf and Nf are nucleofuge-specific parameters and Ef is an electrofuge-specific parameter. Although nucleofuges and electrofuges characterized in this way cover more than 12 orders of magnitude, a single set of the parameters, namely sf, Nf, and Ef, is sufficient to calculate the solvolysis rate constants at 25 degrees C with an accuracy of +/-16 %. Because sf approximately 1 for all nucleofuges, that is, leaving group/solvent combinations, studied so far, qualitative discussions of nucleofugality can be based on Nf. |
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Authors:
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Bernard Denegri; André Streiter; Sandra Jurić; Armin R Ofial; Olga Kronja; Herbert Mayr |
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Publication Detail:
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Type: Journal Article; Research Support, Non-U.S. Gov't |
Journal Detail:
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Title: Chemistry (Weinheim an der Bergstrasse, Germany) Volume: 12 ISSN: 0947-6539 ISO Abbreviation: Chemistry Publication Date: 2006 Feb |
Date Detail:
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Created Date: 2006-02-07 Completed Date: 2007-06-05 Revised Date: 2009-08-04 |
Medline Journal Info:
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Nlm Unique ID: 9513783 Medline TA: Chemistry Country: Germany |
Other Details:
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Languages: eng Pagination: 1648-56 Citation Subset: IM |
Affiliation:
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Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovacića 1, 10000 Zagreb, Croatia. |
Export Citation:
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APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
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Benzhydryl Compounds
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chemical synthesis* Electrochemistry Hydrogen Bonding Indicators and Reagents Kinetics Solutions Thermodynamics |
| Chemical | |
Reg. No./Substance:
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0/Benzhydryl Compounds; 0/Indicators and Reagents; 0/Solutions |
| Comments/Corrections | |
Erratum In:
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Chemistry. 2006 Jul 17;12(21):5415 |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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