Topics In Organic Polarography

Even though the nwnber of requests for reprints and the number of quotations in the Science Citation Index has indicated an ever-increasing interest in topics of organic polarography, I have often felt that the reason that some work is less known may well be because the papers were published in less accessible journals. Therefore, I was pleased when I was asked to prepare a selection of my papers on organic polarography for reprinting. This collection of papers may indicate some of the possibilities offered by polarography in the study of properties of organic compounds. The fact that the papers are published in one volume, not only makes the information more easily accessible for the reader, but also enables a direct comparison of related topics. The mode of selection is discussed in the Introduction. The papers reprinted in this volume are mostly based on work carried out in the J. Heyrovsky Institute of Polarography of the Czechoslovak Academy of Sciences in Prague, in cooperation with my co-workers. I would like to take this opportunity of thanking all of them for the pleasure I got from this cooperation on the solution of varying problems of organic electrochemistry .

I. Introduction.- II. Techniques Used in Elucidation of Organic Electrode Processes.- 1. Preparative Methods Used in the Elucidation of Organic Electrode Processes.- III. Polarographic Reduction of Some Carbonyl Compounds.- 2. Polarographie Reduction of Aldehydes and Ketones. I. General Reduction Scheme.- 3. Polarographic Reduction of Aldehydes and Ketones. II. pH-Dependence of Polarographic Limiting Currents of Aryl Alkyl Ketones Governed by the Rate of Simultaneous Reactions with Several Acids Producing the Electroactive Species.- 4. Polarographic Reduction of Aldehydes and Ketones. III. Effects of Alkyl Groups in the Side Chain of the Half-Wave Potentials of Deoxybenzoins and Some Other Alkyl Aryl Ketones.- 5. Polarographic Reduction of Aldehydes and Ketones. IV. Linear Free Energy Treatment of Substituted Benzonphenones.- 6. Desorption of 3-Phenylpropionaldehyde Preceding Polarographic Reduction.- 7. Direct Polarographic Determination of Pyridoxal in the Presence of Pyridoxal-5-Phosphate.- 8. Polarography of Steroids. III. Polarographic Reduction of Steroids Containing an Aldehydic Group in Position 18. (in German).- 9. Polarographic Behaviour of p-Diacetylbenzene; an Example of a Compound with two Electroactive Centres.- 10. Further Examples of para- and ortho- Disubstituted Benzene Derivatives Reduced in a Reversible Two-Electron Step into Products of Limited Stability.- IV. Polarographic Reduction and Some Reactions of ?-Substituted Carbonyl Compounds.- 11. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. II. Polarographic Reduction of ?-Amino Ketones.- 12. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. V. Polarographic Study of Elimination of ?-Morpholino Propiophenone.- 13. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. IX. Polarographic Study of Addition of Primary Amines to Phenyl Vinyl Ketone.- 14. Polarographic Reduction of Aldehydes and Ketones. V. Reduction Course of some ?-Ketosulphides and Effects of Alkyl Groups on Sulphur.- 15. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. VIII. Elimination of ?-Piperidinoethyl Phenyl Vinyl Sulphone with Hydroxyl Ions.- 16. Slowly Established Acid-Base Equilibrium in Organic Polarography: Tautometric Changes between 3-Thianaphthenone and 3-Hydroxy-Thianaphthene.- V. Polarographic Reduction and some Reactions of ?, ?-Unsaturated Carbonyl Compounds.- 17. Role of Keto-Enol Tautomerism in the Polarographic Reduction of some Carbonyl Compounds.- 18. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. VII. Kinetics of Ketol Formation from ?, ?-Un saturated Ketones in Alkaline Media.- 19. Polarographic Reduction of Cinnamaldehyde; Comparison with 3-Phenylpropionaldehyde and Phenylpropargylaldehyde.- 20. The Polarography of Steroids. I. Directly Reducible Ketosteroids. (in German).- VI. Reduction of the Activated C—N, C—S and C—O Bonds.- 21. Fission of Activated Carbon—Nitrogen and Carbon—Sulphur Bonds. Introductory Remarks.- 22. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. I. Polarographic Reduction of the Single C—N Bond.- 23. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. VI. Polarographic Reduction of the C—N(+) Bond in ?-Aminonitriles.- 24. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. III. Reduction of the C-S(+) Bond in Methyl Butyl Phenacyl Sulphonium Perchlorate.- 25. A New Type of Maximum on the Limiting Current of the Reduction Wave of Phenacyl Sulphonium Ions.- 26. Polarography of Pyridoxine and some of its Derivatives.- 27. Polarographic Reduction of 2-(2-Methyl-3-Hydroxy-5-Hydroxymethyl-4-Pyridyl) Thiazolidine-4-Carboxylic Acid.- 28. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. X. Polarographic Reduction of Substituted Methyl Phenyl Sulphones.- 29. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. XI. Polarographic Reduction of Substituted Benzenesulphonamides.- VII. Reductions of Azome thine (C=N?) Bond and their Application.- 30. Polarographic Behaviour of Acetone.- 31. The Reaction of Carbonyl Compounds with Primary Amines, (in German).- 32. Quantitative Treatment of Substituent Effects in Polarography. V. Polarographie Reduction of some Semicarbazones.- 33. Qxime Derivatives. VIII. Polarographic Reduction of O- and N- Substituted Oximes.- 34. Polarographic Study of the Reaction of Pyridoxal with Hydroxylamine.- VIII. Polarographic Reduction of Substituted Benzonitriles.- 35. Quantitative Treatment of Substituent Effects in Polarography. VI. Polarographie Reduction of Benzonitriles m- and p-Substituted with Electronegative Groups.- 36. Fission of Activated Carbon-Nitrogen and Carbon-Sulphur Bonds. XII. Polarographic Reduction of Substituted Benzonitriles Bearing in para- Position a Carbonyl Group in Acidic Media.- 37. The Use of Simple Molecular Orbital Theory to Elucidate the Polarographie Behaviour of some para-substituted Benzonitriles.- IX. Polarography of Nonbenzenoid Aromatic Substances.- 38. Polarography of some Aromatic Compounds: Sydnones and Azulenes. (in German).- 39. Polarography of Nonbenzenoid Aromatic and Related Substances. II. The Course of the Reduction of Sydnones at the Dropping Mercury Electrode.- 40. Polarography of Nonbenzenoid Aromatic and Related Substances. III. The Course of the Reduction of N,N-Polymethylene-bis-Sydnones.- 41. Polarography of Nonbenzenoid Aromatic and Related Substances. IV. Polar Effects of Substituents in Phenylsydnones; The Application of Modified Hammett Equation.- 42. Polarography of Nonbenzenoid Aromatic and Related Substances. VII. A Polarographic Study of the Acid-Base Properties of the Tropylium Ion.- 43. Polarography of Nonbenzenoid Aromatic and Related Substances. VIII. Adsorption Processes during the Electroreduction of the Tropyliumlon.