Robinson electronic theory

The torquoselectivity of the 4 r electrocyclic ring-opening reaction of 2-azetines has been reported to be controlled by the Brpnsted acidity of the catalyst and the polarity of the solvent." A review of the origin of the torquoselectivity in the thermal ring opening of cyclobutenes based on the Cplex-isoelectronic theory and expanded Robinson electronic theory has been reported." Cplex-isoelectronic theory is said to provide a rational for the torquoselectivities in the ring opening of cyclobutenes." ... 

Chemistry as it was realized substantially derives from the interae-tion of electrons. The electronic theory of chemistry, particularly of organic chemistry, emerged, explaining the great richness of chemical observations and transformation, as expressed by Ingold, Robinson, Hammett, and many others following in their footsteps. 

No mechanistic aspects of organic chemistry (or, for this reason, any reaction intermediates) were ever mentioned by Zemplen in his lectures or writings, nor did he consider or accept their existence. I never heard him mention the names of Meerwein, Ingold, Robinson, or any other pioneers of the mechanistic electronic theory of organic chemistry. The possible role of organic ions was similarly never mentioned. He was. 

Robinson, R. (1932). Two Lectures on an Outline of an Electrochemical Electronic) Theory of the Course of Organic Reactions. London Institute of Chemistry. 

A number of reaction pathways have been proposed for the Fischer indolization reaction. The mechanism proposed by Robinson and Robinson in 1918, which was extended by Allen and Wilson in 1943 and interpreted in light of modem electronic theory by Carlin and Fischer in 1948 is now generally accepted. The mechanism consists of three stages (I) hydrazone-ene-hydrazine equilibrium (II) formation of the new C-C bond via a [3,3]-sigmatropic rearrangement (III) generation of the indole nucleus by loss of... 

Robinson R (1932) Outline of an electrochemical (electronic) theory of the course of organic reactions. The Institute of Chemistry of Great Britain and Ireland, London... 

The Paris school included Robert Lespieau (18641947), Georges Dupont (18841958), Charles Prevost (18991983), and Albert Kirrmann (19001974). Principal figures in the London-Manchester school were Arthur Lapworth (18721941), Thomas Martin Lowry (18741936), Robert Robinson (18861975), Jocelyn Thorpe (18721940), and Christopher Ingold (18931970). A broadly defined German research school pursuing ionic and electronic theories of reaction mechanisms in organic chemistry does not enter into this history, because it did not exist. 

The 1947 Nobel Prize in chemistry was to be awarded to Robinson to honor his work in the synthesis of natural products, investigations that he pursued all through his career, and a field in which his wife both collaborated and worked independently.87 Yet, in his memoirs, Robert Robinson wrote that he considered the development of an electronic theory of reaction mechanisms "my most important contribution to knowledge."88 This suggests the seriousness with which he viewed scientific theories and his belief that scientific glory and reputation rest on theories, not discoveries. Let us turn now to these theories. 

W. O. Kermack and Robert Robinson, "An Explanation of the Property of Induced Polarity of Atoms and an Interpretation of the Theory of Partial Valencies on an Electronic Basis, JCS 121 (1922) 427ff quoted in Seddon, "Development of Electronic Theory," 25. W. O. Kermack was a member of the Royal College of Medicine at Edinburgh. 

Quoted in J. Shorter, "Electronic Theories of Organic Chemistry Robinson and Ingold," Natural Products Reports. Royal Society of Chemistry 4 (1987) 6166 on p. 63. 

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. 

Robinson s theory was one of electron displacements propagated by electrostatic induction along the length of a carbon chain. As a hydrogen atom at one end of a carbon chain becomes a weakly held proton, electron charge drifts... 

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. 

Research in fundamental chemistry, physical chemistry, and chemical physics was carried out only at Paris, Nancy, and Strasbourg. Advanced physical chemistry was taught only at four universities in France immediately after the Second World War. 132 As we saw in chapter 6, the interest of Prevost and Kirrmann in ionic and electronic theories of reaction mechanisms developed later than in England and took a different turn than the Robinson-Ingold theory. 133... 

This did not mean there was much sympathy with Brodie s algebraic alternative for molecular models or with Pearson s more sophisticated attempt to introduce the mathematics of ether squirts into chemistry. Nor were chemists ready to give up the periodic table and pictorial theories in the daily work of the laboratory. But, like Robinson, who said that he considered his electronic theory of reaction mechanisms his "most important contribution to knowledge," many chemists considered theory, not chemical fact or chemical production, to be the highest aim of science. 34 And many agreed with Coulson that you cannot have deep theory without mathematics. 

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

In the nineteen-twenties the examination of the directing effects of nitro, amino and related groups was prominent in the work of various research groups, particularly those involved in the controversies regarding electronic theories of organic chemistry which raged from 1924 for several years44-46. Thus in 1926-27 Robert Robinson and his... 

The Robinson-Frosch theory considers a resonance interaction between an initial electronic state and an electronic final state with weak coupling between the two states. The rate process then becomes ... 

Hammett s view of the scope of the subject is summarized in the rarely mentioned sub-title of his book Reaction Rates, Equilibria, and Mechanisms . His conception of the subject still defines its core, but requires amplifying certain other topics are now usually deemed part of physical organic chemistry. Thus the rationalization of the experimental results of studies of reaction rates, equilibria, and mechanisms involves the application of the electronic theory of the structures and reactions of organic molecules, either in its early forms as developed by Robinson, Ingold, and others on the basis of the electron-pair covalent bond, or in its later forms involving quantum mechanical treatments. 

Robinson and Ingold Electronic Theories and Reaction Mechanisms... 

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