| Squaric acid N-hydroxylamides: synthesis, structure, and properties of vinylogous hydroxamic acid analogues. | |
| | |
MedLine Citation:
|
PMID: 14629141 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
|
The synthesis of squaric acid N-hydroxylamide esters 5 and amides 6 from dimethyl squarate 2a is described. These derivatives are analogues of the naturally occurring iron(III) chelator hydroxamic acid. On the basis of a comparative reactivity study, a concerted retro-Cope mechanism for the formation of the N-hydroxylamide esters 5 by reaction of dimethyl squarate with hydroxylamines is proposed. A preliminary iron(III) binding study of these hydroxamic acid analogues is presented, demonstrating binding of iron(III) to amides 6 in aqueous solutions, while the esters 5 did not show any sign of metal ion binding. 13C NMR spectroscopic data (chemical shift and spin-lattice relaxation time determination) of these and related derivatives delineate the resonance structures predominant in these molecules. The resonance structures of the derivatives rationalize their spectroscopic data, chemical reactivity, and iron(III) binding properties. Single-crystal X-ray structure analyses of squaric acid N-hydroxylamide ester 5b and squaric acid N-hydroxylamide amide 6c confirm their connectivity and provide structural evidence supporting the spectroscopically derived conclusions. The squaric acid N-hydroxylamides are potentially useful in the construction of chemosensors for iron(III). |
| | |
Authors:
|
Nathaniel C Lim; Martha D Morton; Hilary A Jenkins; Christian Brückner |
Publication Detail:
|
Type: Comparative Study; Journal Article; Research Support, Non-U.S. Gov't |
Journal Detail:
|
Title: The Journal of organic chemistry Volume: 68 ISSN: 0022-3263 ISO Abbreviation: J. Org. Chem. Publication Date: 2003 Nov |
Date Detail:
|
Created Date: 2003-11-21 Completed Date: 2004-03-24 Revised Date: 2006-11-15 |
Medline Journal Info:
|
Nlm Unique ID: 2985193R Medline TA: J Org Chem Country: United States |
Other Details:
|
Languages: eng Pagination: 9233-41 Citation Subset: IM |
Affiliation:
|
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, USA. |
Export Citation:
|
APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
|
Binding, Competitive Crystallography, X-Ray Cyclobutanes / chemical synthesis*, chemistry Ferric Compounds / analysis, chemistry Hydroxamic Acids / chemical synthesis*, chemistry Hydroxylamines / chemistry* Magnetic Resonance Spectroscopy Models, Chemical Models, Molecular Molecular Structure Structure-Activity Relationship Vinyl Compounds / chemical synthesis*, chemistry |
| Chemical | |
Reg. No./Substance:
|
0/Cyclobutanes; 0/Ferric Compounds; 0/Hydroxamic Acids; 0/Hydroxylamines; 0/Vinyl Compounds; 2892-51-5/squaric acid |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
Previous Document: The alpha-effect in the stereochemistry of kinetic ketonization of enols.
Next Document: Regio- and stereoselective C-2 and C-3 cleavage of 2-(1-aminoalkyl)aziridines with alcohols, carboxy...