Document Detail


Kinetics of the solvolyses of benzhydryl derivatives: basis for the construction of a comprehensive nucleofugality scale.
MedLine Citation:
PMID:  16320366     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
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.
Authors:
Bernard Denegri; André Streiter; Sandra Jurić; Armin R Ofial; Olga Kronja; Herbert Mayr
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  12     ISSN:  0947-6539     ISO Abbreviation:  Chemistry     Publication Date:  2006 Feb 
Date Detail:
Created Date:  2006-02-07     Completed Date:  2007-06-05     Revised Date:  2009-08-04    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  Germany    
Other Details:
Languages:  eng     Pagination:  1648-56     Citation Subset:  IM    
Affiliation:
Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovacića 1, 10000 Zagreb, Croatia.
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MeSH Terms
Descriptor/Qualifier:
Benzhydryl Compounds / chemical synthesis*
Electrochemistry
Hydrogen Bonding
Indicators and Reagents
Kinetics
Solutions
Thermodynamics
Chemical
Reg. No./Substance:
0/Benzhydryl Compounds; 0/Indicators and Reagents; 0/Solutions
Comments/Corrections
Erratum In:
Chemistry. 2006 Jul 17;12(21):5415

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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