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1、5534HENRYM.KISSMANANDB.R.BAKERVOl.79Itisacharacteristicofthisreactionthattheen-invariousrateprocessesz5andhasbeenwidelyergyofactivationvariesgreatlywiththesubstit-discussed,25’26noclear-cutexplanationhasbeenuentsandthatthischangeisaccompaniedbyagivenforit.Itusuallyhasbeenexplainedonthelargean
2、dparallelchangeinlogPZ.Thechangebasisofchangein~olvation,3,?~b~~~~butunfor-inentropyofactivationparallelsthatoflogPZ;tunatelytheeffectofstructuralchangesonthesol-thus,alargeentropyisassociatedwithalargeen-vationinthetransitionstatehasnotyetbeenin-ergyofactivationandasmallentropywithasmallvest
3、igatedindetail.Furtherinvestigations,nowenergy.inprogress,ontheeffectofstructuralchangeandTheenergiesofactivationplottedagainstlogsolvationmayprovideakeytothisproblem.PZ(valuesinTable11)givesastraightline;theAcknowledgment.-Theauthorswishtoex-relationshipisgivenbytheequationspresstheirsincere
4、appreciationtoProfessorhl.MurakamiandDr.I.MoritanifortheirnumerouslogPZ=0.60AE*-1.4andinvaluablesuggestionsinthiswork,andalsototheMinistryofEducationforthepartialfinan-AE*=1.7logPZf2.4cialsupportofthisresearch.=0.37AS*sb.zoOf23.9(25)(a)C.K,Hinshelwood,“KineticsofChemicalChange,”TheClarendonPr
5、ess,Oxford,1940,pp.257-261;(b)J.E.Leffler,J.Org.Chens.,20,1202(1955);(c)A.T.BlomquistandJ,A.Berstein,TheexistenceofthisrelationshipisevidencethatTHISJOURNAL,73,5546(1951);(d)W.K.WilmarthandS.Schwartz,thedecomposition.reactionsofthesubstitutedibid.,77,4543(1955).benzazidesproceedthroughthesame
6、mechanism,(2G)(a)M.G.Evansand11.Polanyi,Tvans.FaradaySOL.,32,inspiteoftheconsiderabledifferencesinenergy1333(1936);(b>A,Wassermann,J.Chens.Soc.,621,623(1912);(e)I<.W.Taft,Jr.,TI~ISJOURNAL,75,134(1953);(d)A.Sheppandandentropyofactivation.Althoughsuchafunc-S.H.Rauer,ibid.,76,2G5(1954);L.Slutsky
7、andS.H.Rauer,ibid.,tionalrelationshipbetweenenergiesandentropies76,270(1954).ofactivation,alinearrelation,hasbeenobservedOSAKA,JAPAN[COXTRIBUTIONFROMTHEORGANICCHEMICALRESEARCHSECTION,RESEARCHDIVISION,AMERICAh’CYASANIDCO3IPANY,LEDERLELABORATOR
