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| 作者 |
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N.S.Isaacs
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| ISBN |
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7506234017
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| 页数 |
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877
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| 开本 |
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32开
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| 封面形式 |
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简裝本
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| 出版社 |
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世界图书出版公司
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| 出版日期 |
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1997-1-1
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| NT$ |
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1577
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配送说明： 国际快递 ， 海运邮递 。
付款说明： 1. VISA、MASTER線上刷卡 2. 信用卡传真刷卡付款 3.
邮政划拨 4. 银行汇款
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片断：
Anunderstandingofchemicalreactivitybeginswithanunderstandingof
chemicalbonding,theforceswhichrendercertainaggregatesofatoms
(i.e.thefamiliarmolecules)morestablethanothers.1-3Itisonthisbasis
thatchemicalreactions-changesinbonding-maybeapproachedand
arationalandconsistenttheoryoforganicchemistrydevised.Two
milestonesintheunderstandingofbondingmaybequoted.Thefirst,the
recognitionoftheelectron-paircovalentbondbyLewis4andbyLangmuir5
in1919,stillprovidesamodelforthedescriptionofmolecularstructure
adequateformostpurposesandwillbeextensivelyemployedinthe
followingtext.Accordingtothisconcept,valenceelectronsaresharedso
astocreatefilledshellconfigurationsandareregardedasessentially
localizedintheintemuclearspace.Forthefirstrowelementsofwhich
organiccompoundsarealmostentirelycomposed,thisistheoctet
(2s2,2p6);forhydrogen,lsl.Thesecondleapinunderstandingwasmade
bytheintroductionofquantummcchanicstochemistryfollowingthe
molecularorbitaldescriptionofbondinginthehydrogenmoteculeby
HeitlerandLondon,6in1929.Thisapproachsupersededtheconceptof
localizedelectronsandpavedthewaytoquantitativeunderstandingof
bonding,thesatisfactorycalculationsofbondingenergies,optimumbond
lengthsandgeometries.Itwillbenecessarytoturntothesemethods,
despitethenecessityofsomewhatlengthycomputation,whentheneed
arisestoconsiderspecificmolecularorbitalproperties(forexample,in
thetheoryofpericyclicreactions,Chapter14).Nonetheless,quantum
conceptspermeateanydescriptionsofchemicalbonding,thoughtwo
ratherdistinctmodelsmaybeusedwhichwillnowbebrieflydescribed.
I.I.IThevalencehond(VB)model'
Weknowthestructureofamoleculeinthatitcontainsdefinedatoms
locatedpreciselyinspace.Onebeginswiththisdeterminatepartof
molecularstructure(whichcanbeobtainedaccurately,byX-raycrystal
diffractionforinstance)bysettingallnucleiintheircorrectspatial
positions.Theindeterminatepart,thedispositionofthebondingelectrons,
12
SS*15
34
isthenaccomplishedbyaddingtheseinpairssuchthatnoatomexceeds
itsclosedshellnumber.Thereareinevitablymanywaysinwhichthiscan
beachieved,eachlocalizedstructure(knownasa'contributing'structure
or,intheolderliterature,a'canonical'structure)beingregardedas
contributing,insomemeasuredeterminedbyitsenergy,tothetrue
structure.Themoleculeisconceivedasa'resonancehybrid'ofmany
contributingstructureswhosecontributioncanbeexpressedasafraction
enteringintothewhole.Therelationshipbetweencontributingstructures,
whichdifferonlyinthedistributionofvalenceelectrons,isexpressedby
thedoublearrow,<->.Althoughforthepurposesofexactcalculationsof
molecularenergies,forinstance,manycontributingstructuresareneeded
evenforamoleculesuchasH2,itisfrequentlyfoundthatasingleVB
structuresufficestodescribethestructureadequatelyforqualitative
purposes.Forexample,methanemayberepresentedas1andcontributions
fromsuchstructuresas2ignoredfortheinterpretationofreaction
mechanisms.
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Forewordtofirstedition
Physicalorganicchemistry,thestudyoftheunderlyingprinciplesand
rationaleoforganicreactions,isovereightyyearsofage.Duringthis
periodofdevelopment,muchhasbeenlearnedwhichisnowenshrined
withinthepermanentfundofchemicalknowledge.Atthesametimethe
processofrefinementpfchemicaltheorycontinues,newtechniquesare
developedandviewpointsshifttheiremphasis.Acrucialissueofone
decadebecomesresolvedinanother.Thisthenunderliesthereasonfor
offeringanothertextonthesubjectofphysicalorganicchemistry,
continuingtheseriesofaccountswhichbeganwiththenotableandstill
usefulbookofthesametitleof1940writtenbyProfessorHammett.Itis
hopedthatthepresentworkwillhelptofilltheincreasinglylargegap
betweenpresentknowledgeandpracticeandthestatusofthesubjectas
treatedinearliertexts.Inparticular,thelastdecadehaswitnessedthe
increasinguseofsophisticatedinstrumentation,particularlynuclear
magneticresonancewhichcanprobethestructuresandeventheshapes
ofmoleculesinsolution.Othertrendshavebeentheadoptionthroughout
everybranchofthesubjectofcomputationaltechniquesincluding
molecularorbitaltheorybothofthesimpleHiickeltypeandalsoathigh
levelsandofmolecularmechanics.Theseaidstounderstandingare
increasinginimportanceasthereliabilityoftheresultsisimprovedand
asfastcomputersbecomemoreavailabletochemists.Thetrendislikely
tocontinueandcomputergraphics(coverdesign)asanaidtomaking
educatedguessesastomolecularpropertiesseemslikelytomakeamajor
contributionto(asWoodwardputit)'thearmamentariumofthechemist'.
Asaresultofthis,ourunderstandingofchemicalprocessesisshifting
moretowardstheframeworkofquantummechanics.Thepresenttexthas
beenwrittenwiththeobjectofpresentingtotheseniorundergraduate,
graduatestudentandresearchworkeranaccountofthemoreimportant
organicreactionsincludingboththetraditionalevidence-foritisa
subjectdependentonobservationandinference-andmodernapproaches.
Considerableamountsofdatahavebeenincludedsinceafirmgrasp
ofasubjectisbetteraidedbyperusalofcollectedinformationthanby
singlerepresentativevalues.Informationupto1986isincluded.Chapters
1to9dealwithunderlyingprinciplesofreactionpathways,ofthephysical
forceswhichshapebondingbetweenatomsandofthechangesofbonding
whicharechemicalreactions.Chapters10to16describepresentknowledge
andunderstandingofthevariousreactiontypeswhichmakeuporganic
chemistryanddiscusstheingenioustechniqueswhichhavebeendevised
formechanisticinvestigations.Spaceratherthanchoicehaspreventedthe
inclusionofcertaintopicsincludingtheorganicchemistryofsulphur,
phosphorus,siliconandmetals,nowofgreatimportancebutrequiringa
furtherbooktodothemjustice.
Oratitudeisextendedtothosecolleagueswhohavcadvisedmconthe
contentsandwhohavereadandcriticizedthistext,notablyProfessors
J.B.Lambert,L.K.MontgomeryandN.Turro,andtoDrA.Gilbert
forhishelponthephotochemicalchapter.
UniversityofReading,November,1986.
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Contents
Forewordtofirstedition
Forewordtosecondedition
Symbolsandabbreviations
Mechanisticdesignations
1Modelofchemicalbonding
1.1Covalencyandmolecularstructure
1.1.1Thevalencebond(VB)model
1.1.2Themolecularorbital(MO)model
1.2Approximatemolecularorbitaltheory
1.2.1TheHiickelmolecularorbital(HMO)method
1.2.2PropertiesofHiickelmolecularorbitals
1.2.3TherelationshipbetweenMOandVBmodels
1.2.4AdvancedMOmethods
1.3Propertiesofcovalentbonds
1.3.1Bondlengths
1.3.2Interbondangles
1.3.3Forceconstants
1.3.4Bondandmoleculardipolemoments
1.3.5Molecularandbondpolarizabilities
1.3.6Bonddissociationenthalpies(BDE)
1.3.7Groupadditivitiestobondenthalpies
1.4Intermolecularforces
1.4.1Electrostaticforces
1.4.2lon-pairs
1.4.3Short-rangeintermolecularforces
1.4.4Thehydrogenbond
1.4.5Charge-transfercomplexes
1.4.6Crowns,cryptates,calixarenesandcyclodextrins
Problems
2References
2.1Enthalpy
2.1.1Endothennicreactions
2.2Entropy
2.3TheGibbsfunction,G
2.4Factorsthatcontributetoentropy
2.5Chemicalequilibrium
2.6Someusefulthennodynamicrelationships
2.6.1Temperaturedependence
2.7Theapplicationofthennodynamicstorateprocesses
2.7.1Activation
2.7.2Thepotentialenergysurface
2.7.3Thetransitionstatemodel
2.8Propertiesofthetransitionstate
2.8.1Activationparameters
2.8.2Heatcapacityofactivation
2.8.3Variationofratewithpressure
2.9Theusesofactivationparameters
2.9.1Theempiricaltreatmentofratesofsimple
irreversiblereactions
2.9.2Therate-detenniningstep
2.9.3Relativerates
2.9.4Entropiesandvolumesofreaction
2.9.5Theisokineticrelationship
2.10Thelocationofthetransitionstate
2.10.1TheHammondPostulate
2.10.2Reactivityandselectivity
2.10.3Kineticandthennodynamiccontrolofproducts
2.10.4Theprincipleofleastmotion
2.10.5Theprincipleofmicroscopicreversibility
2.10.6Limitationsofthetransition-statetheory
Problems
References
3Reagntsandreactionmechanisms
3.1Polarandradicalpathways
3.1.1Polarreactions
3.1.2Nucleophiles
3.1.3Electrophiles
3.1.4Radicals
3.1.5Reactivity
3.2Aclassificationoffundamentalreactiontypes
3.2.1Bondfonnationandbondbreaking
3.2.2Transferrcactions
3.2.3Elimination(E)andaddition(Ad)
3.2.4Pericyclicreactions
3.2.5Oxidationsandreductions
3.3Reactionmechanism
3.3.1Theadvantagesofsynchronousreactions
3.4Electronsupplyanddemand
3.5Transition-statepropertiesandstructuralchange
Problems
References
4Corretationofstructurewithreactivity
4.1Electronicdemands
4.2TheHammettequation
4.3Substituentconstants
4.4Theoriesofsubstituenteffects
4.4.1Theresonanceeffect
4.4.2Theinductiveeffect
4.5Interpretationofo-values
4.5.1Unshared-pair(n)substituents
4.5.2Alkylgroups
4.5.3Electron-withdrawinggroups-Z
4.5.4Cationiccentres
4.6Reactionconstants,p
4.7DeviationsfromtheHammettequation
4.7.1Randomdeviations
4.7.2Mechanisticchange
4.7.3Enhancedresonance
4.7.4Variableresonanceinteractions
4.8Dual-parametercorrelations:thefloweringofLFER
4.8.1Inductivesubstituentconstants
4.8.2TheTaftmodel
4.8.3Otherchemicalmodelsystems:modernand
scales
4.9Molecularorbitalconsiderations
4.10Cross-interactiontenns
4.10.1Thesignof
Problems
References
5Solveneffectt
5.1Thestnuctureofliquids
5.2Solutions
5.3Solvation
5.3.1Polarity
5.3.2Polarizability
5.3.3Hydrogenbonding
5.3.4Donor-acceptorinteractions
5.4Themodynamicmeasuresofsolvation
5.4.1Freeenergiesofsolutionandtransferfunctions
5.4.2Activitiesofsolutes
5.4.3'Solvation'inthegasphase
5.5"Theeffectsofsolvationonreactionratesandequilibria
5.5.1Solventeffectsonrates
5.6Empiricalindexesofsolvation
5.6.1Scalesbasedonphysicalproperties
5.6.2Scalesbasedonsolvent-sensitivereactionrates
5.6.3Scalesbasedonspectroscopicproperties
5.6.4Scalesforspecificsolvation
5.7Relationshipsbetweenempiricalsolvationscales
5.8Theuseofsolvationscalesinmechanisticstudies
5.8.1Multiparametersolvationanalysis
Problems
References
6Acidsandbases,electrophiletandnutcleopbile
6.1Acid-basedissociation
6.2Thestrengthsofoxygenandnitrogenacids
6.2.1Theeffectofpressureonacid-basedissociation
6.2.2Theinterpretationof
6.3Linearfree-energyrelationships
6.4Ratesofprotontransfers
6.5Structuraleffectsonamineprotonation
6.5.1Linearfree-energyrelationships
6.6Aciditiesofcarbonacids
6.6.1Themeasurementofweakacidity
6.7Factorsthatinfluencecarbonacidity
6.7.1Electroniceffectsofadjacent-Rand-1groups
6.7.2Stabilizationbyd-orbitals
6.7.3s-Characterofcarbonhybridization
6.7.4Aromaticity
6.8Ratesofionizationofcarbonacids
6.9Gas-phaseacidityandbasicity
6.10Theoriesofprotontransfer
6.11Highlyacidicandhighlybasicsolutions
6.11.1Highlyacidicsolutions
6.11.2Highlybasicmedia
6.12Nucleophilicityandelectrophilicity
6.12.1Measurementofnucleophilicity:nucleophilicity
andbasicity
6.12.2Hardandsoftacidsandbases:frontierorbital
interactions
6.12.3Nucleophilicityscales
6.12.4Therelationshipbetweennucleophilicityand
nucleofugacity
6.12.5Thea-eflect'
6.12.6Ambidentnucleophiles
6.13Themeasurementofelectrophilicity
6.14Bronstedrelationshipsinnucleophilicreactions
6.15TheLefflerindex
Problems
References
7Kinetiisotopeeffects
7.1Isotopicsubstitution
7.2Theoryofisotopeeffects:theprimaryeffect
7.3Transition-stategeometry
7.4Secondarykineticisotopeeffects
7.4.1'Inductive'and'steric'isotopeeffects
7.5Heavyatomisotopeeffects
7.6Thetunneleffect
7.7Solventisotopeeffects
7.7.1Fractionationfactors
7.7.2Solventisotopeeffectsinmixedisotopicsolvents:
theprotoninventorytechnique
7.7.3Examplesofsolventisotopeeffects
Problems
References
8Stericandconformaitonalproperties
8.1Theoriginsofstericstrain
8.2Examplesofstericeffectsuponreactions
8.2.1Orthoeffects
8.2.2F-straineffects
8.2.3Bond-anglestrain
8.2.4Stericinhibitionofresonance
8.2.5Stericacceleration
8.2.6Stericenhancementofresonance
8.2.7Calculationofstericeffects:themolecular
mechanicsmethod
8.3Measurementofstericeffectsuponrates
8.3.1TheTaft-Ingoldhypothesis
8.3.2Otherstericparameters
8.3.3ExamplesofstericLFER
8.4Confonnationalbarrierstobondrotation
8.4.1Spectroscopicdetectionofindividualconformers
8.4.2Acycliccompounds
8.4.3Cycliccompounds
8.5Rotationsaboutpartialdoublebonds
8.5.1InversionatGroupVelements
8.6Chemicalconsequencesofconformationalisomerism:
theWinstein-Holness-Curtin-Hammettprinciple
Problems
9References
9.1Acidandbasecatalysis
9.1.1Specificandgeneralcatalysis
9.1.2Mechanismsofacidcatalysis
9.1.3MethodsofdistinguishingbetweenAlandA2
reactions
9.1.4Linearfree-energyrelationships;theBronsted
CatalysisLaw
9.1.5InterpretationoftheBronstedcoefficients
9.1.6Nucleophiliccatalysis
9.1.7Potential-energysurfacesforprotontransfers
9.1.8Solventisotopeeffects
9.1.9Electrophiliccatalysis
9.2Themechanismsofsomecatalysedreactions
9.2.1Substitutionsa-toacarbonylgroup
9.2.2Keto-enolequilibria
9.2.3Hydrolysesofacetals,ketalsorthoestersand
relatedcompounds
9.2.4Dehydrationofaldehydehydratesandrelated
compounds
9.2.5Thefonnationofoximessemicarbazonesand
hydrazones
9.2.6Decarboxylation
9.2.7Acid-catalysedalkene-alcoholinterchange
9.2.8Someacid-catalysedrearrangements
9.2.9Rate-limitingprotontransfers
9.3Catalysisbynon-covalentbinding
9.3.1Host-guestinteractions
Problems
References
10Substitutionsatsaturatedcarbon
10.1.1Nucleophilicsubstitution(SN2)
10.1.2Thebimolecularreaction,SN2
10.1.3Solvolyticreactions-theSNIspectrum
10.1.4Measurementofsolventparticipation
10.1.5Kineticisotopeeffects
10.1.6ThestructuresofintennediatesinSnlreactions
10.1.7Thephenomenonof'retum'
10.1.8Rearrangementcriteriaforretum
10.1.9The'special'salteffect:anioncxchangcinan
ion-pair
10.1.10Structuraleffectsuponionization
10.1.11Leaving-groupeffects
10.1.12Bridgeheadsystems
10.1.13Linearfree-energyrelationships
10.1.14Intramolecularassistanceinionization
10.1.15Activationparameters
10.1.16TheSNlreactions
10.1.17AliphaticSN2reactionsinthegasphase
Electrophilicsubstitutionsatsaturatedcarbon
10.2.1TheSE1mechanism
10.2.2TheSE2mechanism
10.2.3Electrophilicsubstitutionviaenolization
Nucleophilicdisplacementsatavinylcarbon
Electrophilicdisplacementsatanaromaticcarbon
10.4.lTimingofbond-breakingandmaking
10.4.2Thegeneralmechanismforelectrophilic
aromaticsubstitution
10.4.3Thenatureoftheelectrophilicreagents
10.4.4Kineticisotopeeffects
10.4.5KineticsofSE2-Arreactions
10.4.6Structuraleffectsonrates
10.4.7Theortho-paraselectivityratioSOP=(2F0/FP)
10.4.8Thenatureoftheintermediate
10.4.9Ipsoattack
10.4.10TheMOinterpretationofaromaticreactivity
Nucleophilicsubstitutionatanaromaticcentre
10.5.1Theaddition-eliminationpathway
(SNAr-Ad,E)
10.5.2Theunimolecularmechanism
10.5.3Thearynemechanism(E-Ad)
10.5.4Nucleophilicsubstitutionviaringopening:the
SN(ANRORC)route
Nucleophilicsubstitutionsatcarbonylcarbon
10.6.1Basichydrolysisofcarboxyliccsters
10.6.2Acidichydrolysisofesters
10.6.3Stereoelectronicfactorsinthedecompositionof
thetetrahedralintermediate
10.6.4Othermechanismsforesterhydrolysis
10.6.5Hydrolysisofamides,acylhalidesand
anhydrides
10.6.6Propertiesoftetrahedralintennediates
10.6.7Nucleophiliccatalysisincarbonylsubstitutions
Problems
References
11Eliminationreactions
11.1Base-promotedeliminationsinsolution
11.1.1Kineticcriteriaofmechanisms
11.1.2Structuraleffectsonratesofelimination
11.1.3Kineticisotopeeffects
11.1.4Variationofthebase-solventsystem
11.1.5Competitionbetweeneliminationand
substitution
11.1.6Orientationinproductformation
11.1.7StereochemistryofE2reactions
11.1.8Frontierorbitalconsiderations
11.1.9Elcbreactions
11.1.10EsterhydrolysisbytheElcbmechanism
11.2Intramolecularpyrolyticeliminations(theE,reactions)
11.2.1Esterpyrolysis
11.2.2TheChugaevreaction
11.2.3Amineoxide,sulphoxideandselenoxide
pyrolyses
11.2.4Pyrolysisofalkylhalides
11.3a-Eliminations
11.4Oxidativeeliminations
11.4.1Oxidationsofalcoholsbychromium(VI)
11.4.2TheMoffattoxidation
Problems
References
12Polaradditionreactions
12.1Electrophilicadditionstoalkenes
12.1.1Kinetics
12.1.2Effectofstructure
12.1.3Isotopeeffects
12.1.4Orientationandstereochemistry
12.1.5ThenatureoftheintermediatesinAdEreactions
12.2Miscellaneousadditions
12.2.1Hydroboration
12.2.2Additionwithringclosure;halolactonization
12.2.3Additionofcarbocations
12.2.4Additionstodienes,alkynesandallenes
12.3Nucleophilicadditionstomultiplebonds
12.3.1Michaeladdition
12.3.2Carbonyladditions
12.3.3Additionstoheterocumulenes
12.4Frontierorbitalconsiderations
12.5Vinylsubstitutionviaaddition/elimination
12.5.1Examples
12.5.2Stereochemistry
Problems
References
Intramolecularreacticnsl
13.1Neighbouring-groupparticipation
13.1.1Thescopeofneighbouring-groupeffects
13.1.2Methodsforrecognizingneighbouring-group
participation
13.1.3Thekineticcriterion
13.1.4Linearfree-energyrelationships
13.1.5Kineticisotopeeffects
13.1.6Solventeffects
13.1.7Participationincarbonylreactions
13.1.8Thestereochemicalcriterion
13.1.9Therearrangementcriterion
13.1.10Factorsinfluencingneighbouring-group
participation
13.1.11Observationandisolationofcyclic
intermediates
13.1.12a-andparticipation:thequestionofnon-
classicalions
13.2Enzymicreactions
13.2.1Thestructuresofenzymes
13.2.2Amodelforenzymeaction
13.2.3Mechanismsofsomeenzyme-catalysedreactions
13.2.4Enzymesthatusecofactors
13.2.5Enzymemodelsystems
Problems
References
15.4Factorsinfluencingthereactivitiesofradicals
15.4.1Radicalstability
15.4.2Polarinfluences
15.4.3Solventeffectsonradicalreactions
15.4.4Stericeffectsinradicalreactions
15.4.5Frontier-orbitalconsiderations
15.5Thestereochemistryofradicals
Problems
References
16Organicpbotochemistry
16.1Excitedelectronicstates
16.1.1Absorptionoflightbymolecules
16.1.2Verticalandhorizontalexcitation
16.1.3Spinmultiplicity:singletandtripletstates
16.1.4Sensitizationandquenching
16.1.5Techniquesofphotochemistry
16.2Photochemistryofthecarbon-carbondoublebond
16.2.1Geometricalisomerization
16.2.2Photochemicalpericyclicreactions
16.2.3Thedi-methanerearrangement
16.2.4Photoadditionstoatkenes
16.3Photoreactionsofcarbonylcompounds
16.3.1Carbon-carbonbondcleavage
16.3.2Cycloadditions
16.4Photochemistryofaromaticcompounds
16.4.1Photosubstitutionsatthearomaticring
16.4.2Thcphoto-Friesrearrangement
16.4.3Valenceisomerization
16.4.4Photocycloadditions
16.4.5Photo-oxidationswithoxygen
Problems
References
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