Naphthalene diols : a new class of antioxidants intramolecular hydrogen bonding in catechols, naphthalene diols, and their aryloxyl radicals

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Journal titleJournal of Organic Chemistry
Pages51905196; # of pages: 7
SubjectAutoxidation; Antioxidants; Dissociation; Enthalpy; Free energy; Hydrogen bonds; Rate constants; Styrene; Vitamins; Naphthalene; 1,8 naphthalenediol derivative; 2,2 bis(4 tert octylphenyl) 1 picrylhydrazyl derivative; 2,3 naphthalenediol; 3,5 di tert butylcatechol; 4 methoxy 1,8 naphthalenediol; 6 hydroxy 2,2,5,7,8 pentamethylchroman; alpha tocopherol; antioxidant; catechol derivative; naphthalene derivative; naphthalenediol derivative; oxygen; phenol derivative; radical; unclassified drug; hydrogen; antioxidant activity; article; calculation; chemical reaction kinetics; chemical structure; dissociation; energy; enthalpy; hydrogen bond; proton transport; reaction analysis; chemistry; comparative study; kinetics; synthesis; thermodynamics; Antioxidants; Catechols; Comparative Study; Hydrogen; Hydrogen Bonding; Kinetics; Molecular Structure; Naphthalenes; Support, Non-U.S. Gov't; Thermodynamics; Vitamin E
Abstract1,8-Naphthalenediol, 5, and its 4-methoxy derivative, 6, were found to be potent H-atom transfer (HAT) compounds on the basis of their rate constants for H-atom transfer to the 2,2-di(4-toctylphenyl)-1-picrylhydrazyl radical (DOPPH ·), k ArOH/DOPPH ·, or as antioxidants during inhibited styrene autoxidation, k ArOH/ROO ·, initiated with AIBN. The rate constants showed that 5 and 6 are more active HAT compounds than the ortho-diols, catechol, 1, 2,3-naphthalenediol, 2, and 3,5-ditert-butylcatechol, 3. Compound 6 has almost twice the antioxidant activity, k ArOH/ROO · = 6.0 × 10 6 M -1 s -1, of that of the vitamin E model compound, 2,2,5,7,8-pentamethyl-6-chromanol, 4. Calculations of the O-H bond dissociation enthalpies compared to those of phenols, (ΔBDEs), of 1-6 predict a HAT order of reactivity of 2 < 1 < 3 ≈ 4 < 5 < 6 in general agreement with kinetic results. Calculations on the diols show that intramolecular H-bonding stabilizes the radicals formed on H-atom transfer more than it does the parent diols, and this effect contributes to the increased HAT activity of 5 and 6 compared to the activities of the catechols. For example, the increased stabilization due to the intramolecular H-bond of 5 radical over 5 parent of 8.6 kcal/mol was about double that of 2 radical over 2 parent of 4.6 kcal/mol. Linear free energy plots of log k ArOH/DOPPH · and log k ArOH/ROO · versus ΔBDEs for compounds 1-6 along with available literature values for nonsterically hindered monophenols placed the compounds on common scales. The derived Evans-Polanyi constants from the plots for the two reactions, α DOPPH · = 0.48 > α ROO= · = 0.32, gave the expected order, since the ROO · reaction is more exothermic than the DOPPH · reaction. Compound 6 is sufficiently reactive to react directly with oxygen, and it lies off the log k ArOH/ROO · versus ΔBDE plot.
Publication date
PublisherAmerican Chemical Society
AffiliationNational Research Council Canada
Peer reviewedYes
NPARC number21276643
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Record identifier489bf6ea-c7ae-4f4f-a366-b0ff338d365a
Record created2015-10-13
Record modified2017-03-16
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