Theories of Organic Reactions

There is no doubt that the principles usually known as the Woodward-Hoffmann rules have provided a most valuable insight into our understandmg of organic reactivity, and in particular of pericydic reactions. Their applications in organic 

Levine and R. B. Bernstein, Molecular Reaction Dynamics , Clarendon Press, Oxford, 1974. 

There are many conceivable analogues of this reaction. We mention only the famous H2 + I2 reaction, long supposed to proceed via a rectangular transition state, but shown by Sullivan to involve iodine atoms. The rectangular transition state is, in the light of the Woodward-Hoifmann rules, obviously forbidden. 

These arguments, like their prototype, are based on the symmetry of the system, which is supposed to be maintained throughout the reaction. Pearsonhas indeed shown that the symmetry cannot change along a reaction co-ordinate, except at a 

Fleming, Frontier Orbitals and Organic Chemical Reactions, Wiley-Interscience, London, New York, 1976 (a) p. 99, (i) p. 103. 

Gilchrist and R. C. Storr, Organic Reactions and Orbital Symmetry , Cambridge University Press, London, 1972 R. E. Lehr and A. P. Mar-chand, Orbital Symmetry , Academic Press, London, New York, 1972 G. B. Gill and M. R. Willis, Pericyclic Reactions , Chapman and Hall, New York, 1974. 

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Naphthalene undergoes electrophihc substitutions at the a rather than p position. The Hueckel molecular orbital calculations show that all the carbons have the same jt electron density 1.0. This is not in agreement with the theory of organic reactions based on the Coulombic interaction that electrophilic attack occurs on the most negatively charged atom. Fukui [7] proposed the frontier orbital theory for the discrepancy between the theory and the experimental observation. The importance of... 

Palm, V. A., Osnovy Koiichestvennoi Teorii Organicheskikh Reaktsii (Principles of the Quantitative Theory of Organic Reactions), Izdatelstvo Khimiya, Leningrad, 1967, Ch. XII. 

The present volume continues the tradition. Once again the recent literature has been combed for new examples the better to exemplify principles of reactions. Of particular interest is an admirable chapter dealing with reactions controlled by orbital symmetry. Until I read it I was not convinced that this very important new development in the theory of organic reactions could be simply yet usefully communicated to students at an elementary level. To have succeeded in doing so only u nderlines further Dr. Sykes gifts as a teacher and writer and I am sure that this new edition of the Guidebook will more than equal the success of its predecessors. 

G Bekker The Introduction into Electronic Theory of Organic Reaction , The World", Moscow, 227, 1965, (russ.). 

Part Two concludes with an analysis in chapter 8 of Ingold s theory of organic reaction mechanisms, his construction of a new chemical language,... 

Christopher K. Ingold, "Principles of an Electronic Theory of Organic Reactions," Chemical Reviews 15 (1934) 225274. 

Lowry is best known to chemistry students through the tradition of eponymony, since the proton theory of acidity is known as the "Bronsted/Lowry theory" of proton donors. His most important experimental investigation likely was a long series of studies on optical rotatory dispersion.49 For our purposes, there is special interest in his discovery of mutarotation in camphor derivatives and his theory of dynamic tautomerism, which led him to an ionic theory of organic reaction mechanisms. 

Saltzman, "Sir Robert Robinson," 543548 Saltzman, "The Robinson-Ingold Controversy Precedence in the Electronic Theory of Organic Reactions," JChem.Ed. 57 (1980) 484488 and J. Shorter, "Electronic Theories of Organic Chemistry," 6166. 

As is well known, Robinson became convinced that Ingold had not given him proper credit for his, and Lapworth s, role in the development of an electronic theory of organic reaction mechanisms. In reply to a furious letter from Robinson, Thorpe tried to reassure Robinson about Ingold. 

However, within the next few years, Ingold s dominance in the field of organic reaction mechanisms theory became clearly established, following a 1933 paper on tautomerism in which he introduced the terms "nucleophilic" and "electrophilic" and a 1934 article in Chemical Reviews systematizing "Principles of an Electronic Theory of Organic Reactions." Burkhardt, one of Lapworth s collaborators, said, "ft was a complete takeover of terminology at the right time. "129... 

Burkhardt, "Arthur Lapworth and Others," 143. C. K. Ingold, "The Significance of Tautomerism and of the Reactions of Aromatic Compounds in the Electronic Theory of Organic Reactions," JCS (1933) 1120 and C. 

His magisterial review, "Principles of an Electronic Theory of Organic Reactions". . . was a kind of legal brief describing the way physical organic chemistry ought to be if only God had done his work properly. 

Busy with the move from Leeds to London in 1930, Ingold afterward was in residence at Stanford University in California in 1932, with some leisure to work out generalizations of the results already at hand. He soon published two widely read pieces "Significance of Tautomerism and of the Reactions of Aromatic Compounds in the Electronic Theory of Organic Reactions," in the Journal of the Chemical Society, and the essay review, "Principles of an Electronic Theory of Organic Reactions," in Chemical Reviews.58... 

The Robinson-Ingold Controversy Precedence in the Electronic Theory of Organic Reactions." JChem.Ed. 57 (1980) 484488. 

References 44-46 give references to the various accounts in which Robinson described the features of his electronic theory of organic reactions. The most comprehensive account was in R. Robinson, Outline of an Electrochemical (Electronic) Theory of the Course of Organic Reactions, Institute of Chemistry, London, 1932, 52pp. 

Epiotis, N. D. Theory of organic reactions. Berlin, Heidelberg, New York Springer 1978... 

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