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Oxidation of Aryl Ketoximes and Hydrazones with Cerium (IV) Salts Samuel Paul Thackaberry Iowa State University

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Oxidation of Aryl Ketoximes and Hydrazones with Cerium (IV) Salts Samuel Paul Thackaberry Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1968 Oxidation of aryl ketoximes and hydrazones with cerium (IV) salts Samuel Paul Thackaberry Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Thackaberry, Samuel Paul, "Oxidation of aryl ketoximes and hydrazones with cerium (IV) salts " (1968). Retrospective Theses and Dissertations. 3700. https://lib.dr.iastate.edu/rtd/3700 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. This dissertation has been microfilmed exactly as received g 8-14,825 THACKABERRY, Samuel Paul, 1940- OXroATION OF ARYL KETOXIMES AND HYDRAZONES WITH CERnjM(IV) SALTS. Iowa State University, Ph,D., 1968 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan OXIDATION OF ARYl KET0XIME8 AND HYDRAZONES WITH CERIUM(IV) SALTS by Samuel Paul Thackaberry A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject : Organic Chemistry Approved : Signature was redacted for privacy. Signature was redacted for privacy. Head Major Department Signature was redacted for privacy. De^ of Graduate' Iowa State University Of Science and Technology Ames, Iowa 1968 il TABLE OF CONTENTS Page INTRODUCTION 1 HISTORICAL 7 Oxidation of Organic Compounds with Cerium(IV) 7 Oxidation of alcohols 9 Oxidation of aldehydes and ketones 21 Oxidation of hydrocarbons 24 Miscellaneous oxidations 27 Oxidation of oximes 51 Oxidation of hydrazones 68 RESULTS AND DISCUSSION 90 Oxidation of Aryl Ketoximes by Cerium(iv) Salts 96 General considerations 96 The reactions 101 The products 122 Isotopic labeling experiments 222 Electron spin resonance studies 253 Oxidation of aryl ketoximes by nitric acid 245 Mechanistic speculations 255 Mass spectra of geminal-dinitro compounds 288 Mass spectra of azine monoxides 511 Oxidation of Hydrazones by Ceric Ammonium Nitrate 521 Reactions and products 522 Mechanistic speculations 555 Mass spectra of azines 544 EXPERIMENTAL 558 Instruments and Methods 558 Materials 559 Experimental for the Oxidation of Oximes by Cerium(iV) Salts 559 Chromatographic procedure 560 ill Experimental for the Oxidation of 9-Fluorenone Oxime (CLVI) by Ceric Ammonium Nitrate )6o Oxidation of 9-fluorenone oxime (CLVI) in methanol ^60 Oxidation of 9-fluorenone oxime (CLVI) in methanol at 0°C )66 Oxidation of 9-fluorenone oxime (CLVI) in deoxygenated methanol ^67 Oxidation of 9-fluorenone oxime (CLVI) in aqueous methanol 370 Oxidation of 9-fluorenone oxime (CLVI) in methanol containing nitric acid Reaction of 9,9-dinitrofluorene (LXIl) with nitric acid in methanol 375 Oxidation of 9-fluorenone oxime (CLVl) in methanol containing ammonium hydroxide 376 Reaction of 9-fluorenone oxime (CLVI) with ammonium hydroxide in methanol 377 Reaction of 9,9-dinitrofluorene (LXIl) with ceric ammonium nitrate in methanol 377 Oxidation of 9-fluorenone oxime (CLVI) in acetone 378 Oxidation of 9-fluorenone oxime (CLVl) in deoxygenated acetone 379 Reaction of 9-fluorenone azine monoxide (CLXIl) with ceric ammonium nitrate in acetone 381 Oxidation of 9-fluorenone oxime (CLVI) in aqueous acetone 383 Oxidation of 9-fluorenone oxime (CLVI) in aqueous acetone containing ammonium nitrate 384 Titration of CLVI in methanol 384 Preparation of 9-fluorenone azine monoxide (CIXII) 385 Preparation of 9-fluorenone azine (CXVIIl) 386 Experimental for the Oxidation of 9-Fluorenone Oxime (CLVI) by Ceric Potassium Nitrate 387 Purification of ceric potassium nitrate 387 Oxidation of 9-fluorenone oxime (CLVI) in methanol 387 Experimental for the Oxidation of 9~Fluorenone Oxime (CLVl) by Ceric Ammonium Sulfate 389 Oxidation of 9-fluorenone oxime (CLVl) in aqueous methanol 389 iv Reaction of Q-fluorenone oxirae (CLVl) with 9-fluorenone azine monoxide (CLXII)in ^ benzene ' 392 Experimental for the Oxidation of 9-Fluorenone Oxime (CLVI) by Ceric Sulfate 393 Oxidation of 9-fluorenone oxime (CLVl) in aqueous methanol 393 Oxidation of 9-fluorenone oxime (CLVl) in methanol containing sulfuric acid 39^ Experimental for the Oxidation of Benzophenone Oxime (LXXVIl) by Ceric Ammonium Nitrate 395 Oxidation of benzophenone oxime (LXXVIl) in methanol 395 Oxidation of benzophenone oxime (LXXVIl) in deoxygenated methanol 398 Oxidation of benzophenone oxime (LXXVIl) in aqueous methanol 400 Oxidation of benzophenone oxime (LXXVIl) in methanol containing nitric acid 402 Oxidation of benzophenone oxime (LXXVIl) in acetone 403 Oxidation of benzophenone oxime (LXXVIl) in deoxygenated acetone 405 Preparation of benzophenone azine monoxide (LXXVIII) 407 Reaction of dinitrodiphenylmethane (LXIX) with nitric acid in methanol 408 Experimental for the Oxidation of 1-Indanone Oxime (CLXIIl) by Ceric Ammonium Nitrate 409 Oxidation of 1-indanone oxime (CLXIIl) in methanol 409 Oxidation of 1-indanone oxime (CLXIIl) in acetone 411 Oxidation of 1-indanone oxime (CLXIIl) in deoxygenated acetone 412 Titration of 1-indanone oxime (CLXIII) 4l4 Reaction of 1,1-dinitroindane (CLXXl) with ceric ammonium nitrate 417 Experimental for the Oxidation of p-Nitroaceto- phenone Oxime (CLXIV) by Ceric Ammonium Nitrate 4l8 Oxidation of p-nitroacetophenone oxime (CLXIV) in methanol 4l8 V Oxidation of £-nitroacetophenone oxime (CLXIV) in aqueous methanol 422 Oxidation of ^-nitroacetophenone oxime (CLXIV) in acetone 426 Experimental for the Oxidation of a-Phenylaceto- phenone Oxime (CLXV) by Ceric Ammonium Nitrate 428 Oxidation of a-phenylacetophenone oxime (CLXV) in methanol 428 Oxidation of a-phenylacetophenone oxime (CLXV) in acetone 432 Experimental for the Oxidation of Acetophenone Oxime (CLXVl) by Ceric Ammonium Nitrate 435 Oxidation of acetophenone oxime (CLXVl) in methanol 435. Oxidation of acetophenone oxime (CLXVl) in acetone 438 Experimental for the Oxidation of p_-Methylaceto- phenone Oxime (CLXVll) by Ceric Ammonium Nitrate / 439 Oxidation of £-methylacetophenone oxime (CLXVIl) in methanol 439 Oxidation of £-methylacetophenone oxime (CLXVIl) in acetone 442 Experimental for the Oxidation of 2,4-Dimethyl- acetophenone Oxime (CLXVIIl) by Ceric Ammonium Nitrate 443 Oxidation of 2,4-dimethylacetophenone oxime (CLXVIIl) in methanol 443 Oxidation of 2,4-dimethylacetophenone oxime (CLXVIIl) in acetone 446 Experimental for the Oxidation of Anthraquinone Monoxime (CLIII) by Ceric Ammonium Nitrate 448 Oxidation of anthraquinone monoxime (CLIII) in methanol-benzene 448 Oxidation of anthraquinone monoxime (CLIII) in acetone 449 VI Experimental for the Oxidation of 9-Xanthenone Oxime (CLXIX) by Ceric Ammonium Nitrate 451 Oxidation of 9-xanthenone oxime (CLXIX) in methanol 451 Oxidation of 9-xanthenone oxime (CLXIX) in aqueous methanol 455 Oxidation of 9-xanthenone oxime (CLXIX) in acetone 456 Experimental for the Oxidation of Oximes by NitrateLabeled Ceric Ammonium Nitrate 457 Preparation of nitrate-^^N labeled ceric ammonium nitrate 457 Oxidation of 9-fluorenone oxime (CLVl) in methanol 457 Oxidation of 1-indanone oxime (CLXIIl) in methanol 462 Reaction of 9-fluorenone oxime (CLVl) with ammonium nitrate in methanol 464 Reaction of 1-indanone oxime (CLXIIl) with ammonium nitrate in methanol 466 Experimental for Electron Spin Resonance Studies 466 Apparatus 466 Results 471 Experimental for the Oxidation of Oximes by Nitric Acid 476 Procedure 476 Oxidation of 9-fluorenone oxime (CLVI) 476 Oxidation of benzophenone oxime (LXXVIl) 477 Oxidation of 1-indanone oxime (CLXIIl) 478 Oxidation of acetophenone oxime fCLXVl) 479 Oxidation of 9-xanthenone oxime (CLXIX) 480 Experimental for the Oxidation of Hydrazones by Ceric Ammonium Nitrate 480 Chromatographic procedure 48l Experimental for the Oxidation of 9-Fluorenone Hydrazone (CXVIl) by Ceric Ammonium Nitrate 48l Oxidation of 9-fluorenone hydrazone (CXVII) in ethanol 481 Preparation of 9-(iiazofluorene (LXXXVIl) 485 vil Oxidation of 9-diazofluorene (LXXXVIl) by eerie ammonium nitrate in ethanol 486 Experimental for the Oxidation of Benzophenone Hydrazone (CXIX) by Ceric Ammonium Nitrate 488 Oxidation of benzophenone hydrazone (CXIX) in ethanol 488 SUMMARY 492 LITERATURE CITED 495 ACKNOWLEDGMENT 504 \ viii I LIST OF FIGURES Page Figure 1. Reaction of diazomethanes with nitric oxide 47 Figure 2. Mechanisms for the oxidation of aliphatic ketoximes by lead tetraacetate 6o Figure 3. Mechanisms for the lead tetraacetate oxidation of hindered ketoximes and aldoximes 67 Figure 4. Mechanism for the peracetic acid oxidation of hydrazones 76 Figure 5. Mechanism for the lead tetraacetate oxi­ dation of N,N-disubstituted ketohydrazones 78 Figure 6. Mechanism for the lead tetraacetate oxi­ dation of N-alkyl and N-arylhydrazones 80 Figure 7. Mechanism for the peracetic acid oxidation of aliphatic ketone- and aldehyde-N-aryl- and N-alkylhydrazones 85 Figure 8. Mechanism for the peracetic acid oxidation of aromatic aldehyde phenylhydrazones 84 Figure 9. Dependence of product formation on temper­ ature in the manganese dioxide oxidation of henzophenone and benzaldehyde phenyl­ hydrazones 85 Figure 10. Mechanism for the manganese dioxide oxi­ dation of ketone phenylhydrazones 86 Figure 11. Mechanism for the manganese dioxide oxi­ dation
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