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JournalofChemistry Vol4,No1(2013)

ISSN: 20101589

JournalofChemistry
journalhomepage:http://icoci.org/joc

AnImprovedMethodforSynthesisofoHydroxyKetoneUnderUltrasoundCondition
SampatB.Suryawanshi,PramodS.Kulkarni*
Dept.Chemistry DepartmentofChemistry,HutatmaRajguruMahavidyalayaRajgurunagarPune (Maharastra)India410505
CorrespondingAuthorEmail:pramodskulkarni3@gmail.com RECEIVEDDATE(2011313)

Abstract : Methane sulphonic acid has high acid strength and biodegradable acid. We use its high acid strength in ortho acylationofphenolundersonochemicalcondition. Themeritsofthisreactionarehighyield,shortreactiontime,useofnon conventionalenergy,avoiduseoftoxic reagentandcatalystisinexpensiveandecofriendly. Introduction Hydroxyarylalkylketonesarekeyintermediateinthe synthesis of natural productandmany biologically active molecules. oHydroxy acetophenone is involved as a synthetic precursors for synthesis of flavonoinds, lamellarin alkaloids and 2hydroxychalcone which is keyintermediateinflavonoidssynthesis[1,2,3]and synthesis ofheterocyclicmolecules [4]. Synthesis ofhydroxylaryl alkylketones areachievedbyFriesrearrangement[5,6]andundermicrowavecondition[7].Inrecentyearsvariousmethodsaredevelopedforortho acylationofphenolusing,Lewisacid[8]orBronstedacidlikesuperacid[9],heteropolyacidsandtheirsalts[10].Recently,itisfound that MSA/alumina, MSA/ graphite and MSA is efficiently converted phenolic substrate into ortho acylated phenols. However, these methodssufferfromdrawbackslikelowyields,longerreactiontime,harshreactioncondition,useofhazardoussolventinreactionand product isolation from the extraction process [11]. Our continued interest in developing novel synthetic methodologies for carbon heteroatombondformation[12].Herein,wereportoacylationofphenolusingMSAundersolventfreeandultrasoundcondition. Inrecentyearsultrasoundreactionattractedattentionofmostoftheresearchersduetoreactionsarefast,carriedoutsolventfreeand useof nonconventional heating. Using ultrasound condition organic transformation catalyzed are synthesis of ethyl cyanocinnamates [13], green synthesis of Hexahydro triazines [14], synthesis of anhydrides from acyl chlorides [15], synthesis of the BaylisHillman adducts[16]. Experimental: Allpurchasedchemicalswereofanalyticalgradeandusedwithoutfurtherpurification.The 1HNMRspectrawereobtainedonaBruker DRX300 Avance instrument using CDCl3 as solvent and TMS as internal standard at 300MHz. All products are known compounds theirphysicalandspectroscopicdatawerecomparedwiththosereportedintheliteratureandfoundtobeidentical. Synthesisoforthohydroxyacetophenone: A mixture of 5mmole of substituted phenol, 1ml of acetic acid and 0.5mmole of Methane sulphonic acid was irradiated under sonochemical condition at 33KHz for 12 minute. The progress of the reaction was monitored by TLC. After completion of reaction, reaction mixture was poured in 10 ml cold water and extracted with chloroform. After evaporating solvent afforded ortho hydroxyacetophenoneandpurifiedbycolumnchromatography. ResultsandDiscussion Methanesulphonicacidisastrongacidandundergoesionizationin0.1maqueoussolution.Thishighstrengthisresponsibletocatalyze manyorganic transformations[17]. The othermerits ofthis acid overother acid areitisbiodegradableacidforming sulfate and CO2 [18]. WefirststudythereactionbetweenpcresolandaceticacidusingMSAunderultrasoundirradiationat33Hzandweobserved that thereaction is proceeding in forwarddirectionin12 minutes. The scopeof reactionwas studied with various substituted phenol and we get excellent results in most cases. When an electron withdrawing substituent present on phenol, the yield of o

JournalofChemistry Vol4,No1(2013)

ISSN: 20101589

hydroxyacetophenoneislowduetothelonepaironoxygenatomisdonatedtoaromaticringandisnotavailabletodonateelectrophilic thatisacyl.

OH Aceticacid/MSA R )))) R

OH O

Figure1 SynthesisofoHydroxyacetophenoneUsingMSAunderUltrasoundcondition
Table1:SynthesisofsubstitutedoHydroxyacetophenone Entry 1 SubstitutedPhenol oHydroxyacetophenone Time(Minute) 3 %Yield 87

OH

OH O

OH

OH O

83

Cl OH

Cl OH O

92

OH OH

OH OH O

15

34

NO 2
5

NO 2 OH O OH
2 89

OH

OH O

93

HO

OH

HO

OH

82

O
8

O N 2

OH

NoReaction

10

3
9

JournalofChemistry Vol4,No1(2013)

ISSN: 20101589
4 84

OH Br Br

OH

O
10

OH

OH

89

O
Tablefootnote

Conclusion: Inconclusion,herewereportshortandefficientsynthesisoforthohydroxyacetophenoneusingMSAunderultrasoundcondition.This methodhasmeritsovermethodsarehighyield,shortreactiontime,andpollutionfree.

ACKNOWLEDGMENT: One of the author PSK thanks to WRO UGC Pune for financial assistance and Principal H.R.M. RajgurunagarforprovidingLaboratorySpacetocarryoutthiswork.
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