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DakinReaction

TheDakinReactionallowsthepreparationofphenolsfromarylaldehydesorarylketonesviaoxidationwith hydrogenperoxideinthepresenceofbase.Thearylformateoralkanoateformedasanintermediateis subsequentlysaponifiedtoyieldthesubstitutedphenolproduct. Orthoorpara+Msubstituents(NH2,OH)favorthisreaction.

MechanismoftheDakinReaction SeeBaeyerVilligerOxidationfortheoxidationstep.

BaeyerVilligerOxidation

TheBaeyerVilligerOxidationistheoxidativecleavageofacarboncarbonbondadjacenttoacarbonyl, whichconvertsketonestoestersandcyclicketonestolactones.TheBaeyerVilligercanbecarriedoutwith peracids,suchasMCBPA,orwithhydrogenperoxideandaLewisacid. Theregiospecificityofthereactiondependsontherelativemigratoryabilityofthesubstituentsattachedto thecarbonyl.Substituentswhichareabletostabilizeapositivechargemigratemorereadily,sothatthe orderofpreferenceis:tert.alkyl>cyclohexyl>sec.alkyl>phenyl>prim.alkyl>CH3.Insomecases, stereoelectronicorringstrainfactorsalsoaffecttheregiochemicaloutcome.

MechanismoftheBaeyerVilligerOxidation

tardreaction
Thetardreactionisachemicalreactionthatinvolvesthedirectoxidationofanaromaticorheterocyclic boundmethylgrouptoanaldehydeusingchromylchloride.[1][2][3]ItisnamedfortheFrenchchemist AlexandreLontard(5January1852,Alenon1May1910).Forexample,toluenecanbeoxidizedto benzaldehyde:

ReactionMechanism
Thereactionmechanismproceedsviaanenereactionwithchromylchloride,formingtheprecipitatedtard complex.Thetardcomplexisthendecomposedbya[2,3]sigmatropicrearrangementunderreducing conditionstopreventfurtheroxidationtoacarboxylicacid.Reducingconditionsforthedecompositionofthe tardcomplexareprovidedbysaturatedaqueoussodiumsulphite.Typicalsolventsforthereactioninclude carbondisulfide,chloroform,andcarbontetrachloride,withcarbontetrachloridebeingthemostcommon.To obtainahighlypurifiedaldehydeproduct,thetardcomplexprecipitateisoftenpurifiedbefore decompositioninordertopreventreactionwithanyunreactedreagent.Thereactionisnormallycarriedout forafewdaystoseveralweeksandtheyieldsarehigh.[4][5]

Limitations
Thetardreactionismostcommonlyusedasarelativelyeasymethodofconvertingtolueneinto benzaldehyde.Obtainingspecificaldehydeproductsfromreagentsotherthantoluenetendstobedifficult duetorearrangements.Forexample,npropylbenzeneisoxidizedtopropiophenone,benzylmethylketone, andseveralchlorinatedproducts,withbenzylmethylketonebeingthemajorproduct.[6][7]Anotherexample arisesfromthetardreactionoftransdecalinwhichresultsinamixtureoftrans9decalol,spiro [4.5]decan6one,trans1decalone,cis1decalone,9,10octal1one,and1tetralone.[8] Otheroxidationreagentslikepotassiumpermanganateorpotassiumdichromateoxidizetothemorestable carboxylicacids. [edit]Uses Oxidationoftoluenetobenzaldehydeisquiteausefulconversion.Benzaldehydeisroutinelyusedforits almondflavor.Thealdehydeiscomparativelyreactiveandreadilyparticipatesinaldolcondensations. Benzaldehydecanserveasaprecursorforvariouscompounds,includingdyes,perfumes,and pharmaceuticals.Forexample,thefirststepinthesynthesisofephedrineiscondensationofbezaldehyde withnitroethane.Additionally,benzaldehydeisinstrumentalinthesynthesisofphentermine.[9]Unlikeother oxidisingagents(likeKMnO4orCr2O3etc.),chromylchloridedoesNOToxidisealdehydetocarboxylic acid.