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FULLPAPER
DOI:10.1002/ejoc.201001636
TheMechanismoftheAcid-CatalyzedBenzidineRearrangementof
Hydrazobenzene:ATheoreticalStudy
GiovanniGhigo,*[a]SilvioOsella,[a]AndreaMaranzana,[a]andGlaucoTonachini[a]
Keywords:Densityfunctionalcalculations/Radicalions/Reactionmechanisms/Reactiveintermediates/Rearrangement
Theacid-catalyzedbenzidinerearrangementofhydrazo-scribestheelectronicstructureofallspeciesalongthereac-
benzeneyieldsp-benzidineanddiphenylineasthemaintionpathway.Therearrangementofthehydrazobenzenehas
productsandsomeothersecondaryproductssuchaso-benz-beenfoundtotakeplacethroughamulti-stepmechanismin
idine,o-semidineandp-semidine.Severalreactionmecha-whichcomplexeswithdicationdiradicalcharactersimilarto
nismshavebeenproposedforthisrearrangement,butnonethoseproposedbyDewarplayakeyrole.Forthefirsttime,
fullydescribesit.Inthisworkwepresenttheresultsofanthekineticisotopeeffectshavebeencalculatedandwere
unrestrictedDFT(M06-2X)studyinwhichthebenzidinere-foundtobeingoodagreementwiththeexperimentalfind-
arrangementofthehydrazobenzeneisfullydescribed.Someings.Therelativeyieldsofthemainproductswerealsocor-
relevantpointswerealsoanalyzedwiththeCASSCFandrectlyestimated.Finally,anexplanationofthegeneralacid
CASPT2methods.Ourtheoreticalapproachproperlyde-catalysisobservedinsomeexperimentsisoffered.
Introduction
alsinthemanufactureofazodyes.Beingclassifiedaspo-
Thename“BenzidineRearrangement”referstoaclasstentiallyhazardousandcarcino
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