ORGANIC CHEMISTRY: PHYSICAL CHEMISTRY FOR MEDICAL, PHARMACEUTICAL, AND BIOLOGICAL STUDENTS (WITH PRACTICAL EXERCISES)
CONTENTS CHAPTER FREE ENERGY RELATIONSHIPS MECHANISM AND STRUCTURE 1 1 1 INTERCONVERSION OF STATES – REACTION AND ENCOUNTER COMPLEXES UNIVERSAL MEASURE OF POLARITY CLASSES OF FREE ENERGY RELATIONSHIP ORIGIN OF FREE ENERGY RELATIONSHIPS SIMILARITY AND THE LE?ER ?-PARAMETER BONDING IN TRANSITION STRUCTURES FURTHER READING REFERENCES CHAPTER THE EQUATIONS THE HAMMETT EQUATION (CLASS II) THE TAFT EQUATION (CLASS I) 2 2 1 STERIC DEMAND AT REACTION CENTRES INDUCTIVE POLAR CONSTANTS ?I 2 3 1 CHOICE OF ? VALUE THE BRØNSTED EQUATION (CLASS I) THE EXTENDED BRØNSTED EQUATION (CLASS II) EQUATIONS FOR NUCLEOPHILIC SUBSTITUTION 2 6 1 THE SWAIN–SCOTT EQUATION (CLASS II) 2 6 2 THE RITCHIE EQUATION (CLASS II) SOLVENT EQUATIONS 2 7 1 THE GRUNWALD–WINSTEIN EQUATION (CLASS II) 2 7 2 THE KOSOWER Z AND REICHARDT ET SCALES (CLASS II) 2 7 3 THE HANSCH EQUATION (CLASS II) OTHER STANDARD PROCESSES 2 8 1 SPECTROSCOPIC TRANSITIONS 2 8 2 ACIDITY AND BASICITY FUNCTIONS 2 8 3 MOLAR REFRACTIVITY 2 10 PROBLEMS 2 11 REFERENCES E?ECTIVE CHARGE EQUILIBRIA 3 1 1 MEASURING E?ECTIVE CHARGE IN EQUILIBRIA 3 1 2 A GROUP TRANSFER OF BIOLOGICAL INTEREST 3 1 3 ADDITIVITY OF E?ECTIVE CHARGE IN REACTANTS AND PRODUCTS RATES 3 2 1 ADDITIVITY OF E?ECTIVE CHARGE IN TRAN- SITION STRUCTURES 3 2 2 E?ECTIVE CHARGE MAPS FOR MORE THAN TWO BOND CHANGES PROBLEMS MULTIPLE PATHWAYS TO THE REACTION CENTRE STRENGTH OF THE INTERACTION ADDITIVITY OF INDUCTIVE SUBSTITUENT E?ECTS MULTIPLE INTERACTIONS 4 3 1 THE JA?É RELATIONSHIP 4 3 2 RESONANCE E?ECTS 4 3 3 THE YUKAWA–TSUNO EQUATION 4 3 4 OTHER TWO-PARAMETER EQUATIONS THE DEWAR–GRISDALE EQUATION THE SWAIN–LUPTON EQUATION THE EDWARDS EQUATION FOR NUCLEOPHILIC ALIPHATIC SUBSTITUTION THE MAYR EQUATION MULTI-PARAMETER SOLVENT EQUATIONS 4 4 1 EXTENSION OF THE GRUNWALD–WINSTEIN EQUATION 4 4 2 THE SWAIN EQUATION 4 4 3 EXTENDED HANSCH EQUATIONS 4 4 4 SOLVENT EQUATIONS BASED ON MACRO- SCOPIC QUANTITIES COUPLING BETWEEN BONDS IN TRANSITION STRUCTURES OF DISPLACEMENT REACTIONS CROSS AND SELF INTERACTION BETWEEN TWO OR MORE SUBSTITUENT E?ECTS 5 1 1 HAMMOND AND CORDES–THORNTON COE?CIENTS SHAPES OF ENERGY SURFACES FROM COUPLING COE?CIENTS 5 2 1 GENERAL ACID-CATALYSED ADDITION OF THIOL ANIONS TO ACETALDEHYDE 5 2 2 REACTION OF AMINES WITH PHOSPHATE MONOESTERS 5 2 3 ELIMINATION REACTIONS OF 2-ARYLETHYLQUINUCLIDINIUM IONS MAGNITUDE AND SIGN OF CORDES–THORNTON COE?CIENTS IDENTITY REACTIONS ANOMALIES, SPECIAL CASES AND NON-LINEARITY FREE ENERGY RELATIONSHIPS ARE NOT ALWAYS LINEAR 6 1 1 MARCUS CURVATURE THE REACTIVITY–SELECTIVITY POSTULATE BORDWELL’S ANOMALY MICROSCOPIC MEDIUM E?ECTS AND DEVIANT POINTS STATISTICAL TREATMENT OF BRØNSTED PLOTS ARE FREE ENERGY RELATIONSHIPS STATISTICAL ARTIFACTS? THE ORTHO E?ECT TEMPERATURE E?ECTS 6 10 PROBLEMS 6 11 REFERENCES APPLICATIONS DIAGNOSIS OF MECHANISM 7 1 1 MECHANISM BY COMPARISON 7 1 2 E?ECTIVE CHARGE DISTRIBUTION OF THE TRANSITION STRUCTURE E?ECTIVE CHARGE MAPS AND CONSERVATION OF E?ECTIVE CHARGE CHARGE AND BOND ORDER BALANCE DEMONSTRATION OF INTERMEDIATES 7 2 1 CURVATURE IN PH-PRO?LES DEMONSTRATION OF PARALLEL REACTIONS 7 3 1 CONCAVE CURVATURE IN PH-PRO?LES DEMONSTRATION OF CONCERTED MECHANISMS 7 4 1 TECHNIQUE OF QUASI-SYMMETRICAL REACTIONS 7 4 2 CRITERIA FOR OBSERVING THE BREAK E?ECTIVE CHARGE MAP FOR A PUTATIVE STEPWISE PROCESS CALCULATION OF PHYSICO-CHEMICAL CONSTANTS 7 5 1 DISSOCIATION AND EQUILIBRIUM CONSTANTS 7 5 2 RATE CONSTANTS 7 5 3 PARTITION COE?CIENTS AND OTHER CONSTITUTIVE MOLECULAR PROPERTIES RESOLUTION OF KINETICALLY EQUIVALENT MECHANISMS 7 6 1 GENERAL BASE VERSUS NUCLEOPHILIC REACTION 7 6 2 GENERAL ACID CATALYSIS VERSUS SPECI?C ACID–GENERAL BASE CATALYSIS SOME BIOLOGICAL APPLICATIONS 7 10 REFERENCES