STRUCTURE AND REACTIVITY OF ORGANIC COMPOUNDS (QUANTITATIVE LAWS)

Abstract

CONTENTS I. Introduction 471 II. The linear free energy (LFE) relationship 472 III. Effect of structural factors on reactivity. Fundamental principles 472 IV. Inductive constants of substituents 473 V. General applicability of inductive constants of substituents 474 VI. Steric constants of substituents from kinetic data on the acid hydrolysis of esters 475 VII. Quantitative calculation of the hyperconjugation effect 475 VIII. Quantitative calculation of conjugation between π bonds 476 IX. Polar effects of nuclear substituents on the reactivity of aromatic compounds. Hammett's equation 477 X. Polar and steric constants of ortho-substituents 481 XI. Problem of the quantitative separation of inductive and polar conjugative effects 481 XII. Generalisation of the concept of polar constants of substituents 484 XIII. Use of the LFE principle to obtain special correlation equations having a limited range of application 485 XIV. The problem of calculating the field effect 486 XV. Anchimeric assistance 488 XVI. Correlation schemes with a variable reactive centre 488 XVII. Correlation of polarographic half-wave potentials 489 XVIII. Use of the LFE principle for radical reactions 490 XIX. Correlation of dipole moments 490 XX. Some quantitative aspects of the dependence of reactivity on the nature of the solvent 491 XXI. Free energy as the sole universal measure of reactivity 493 XXII. Practical efficiency of linear correlation equations 494 XXIII. Conclusion 495