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University M icrofilm s International 300 N. Zeeb Road Ann Arbor, Ml 48106 8518937 Fiscus, David Michael THE CHEMISTRY OF 3-DIAZO-3H-1.2.4-TRIAZOLE AND 3H-1,2,4-TRIAZOL-3- YLIDENE The Ohio State University Ph.D. 1985 University Microfilms International300 N. Zeeb Road, Ann Arbor, MI 48106 Copyright 1985 by Fiscus, David Michael All Rights Reserved The Chemistry of 3-Diazo-3H-1,2,4-triazole and 311-1,2,U-Triazol-3-ylidene Dissertation Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By David Michael Fiscus, B.S., M.A. ***«« The Ohio State University 1985 Reading Committee: Approved By Dr. D. Hart Dr. H. Shechter Dr. J. Swenton Adviser Department of Chemistry © 1985 DAVID MICHAEL FISCUS All Rights Reserved To Mr. and Mrs. Don Fiscus ii ACKNOWLEDGEMENTS Many people have contributed to my education, the preparation of this manuscript and personality development over the term of this graduate program. My thanks and recognition to their efforts follows: Dr. H. Shechter for allowing me to work in his laboratories and for providing the educational experiences resulting from this work; the taxpayers of Ohio and The National Institutes of Health for their financial support; the faculty and staff in the Chemistry Department at The Ohio State University from 1979 to present, particularly Dr. J. Hine, Dr. M. Platz, and Dr. V.A. Yagello for their instruction as well as Ms. B. Cassidy and Ms. P. Fonda for their secretarial assistance; Dr T. Engler, Dr. J. Glinka, Dr. D. Hart, Dr. S. Hoshino, and Dr. C.B. Rao for their advice and instructions in laboratory work; Mrs. J.E. Merritt (Chemical Abstracts Service) for her help in nomenclature, Ms. D. Tyler and Ms. B. Bennett for their role in preparing the final manuscript; Ms K. Willardson, Mr. B. Griffin, Mr. T. Schaefer, and Mr. J. Strode for their friendships; and the members of this reading committee for their participation in the final stages of this thesis. VITA March 23, 1954 Born - Columbus, Ohio May 1977 B.S., The University of Alaska, Fairbanks, Alaska May 1979 M.A., The University of Alaska, Fairbanks, Alaska TABLE OF CONTENTS Page Dedication.............................. ........................... ii Acknowledgements.................................................. iii Vita............................................................... iv List of Tables........ viii Statement of Problem.................................................1 I. Introduction..............................................2 II. Results and Discussion...................................34 Formation and Characterization of 3-Diazo-3H.-1,2,4-triazole.......................... 34 Cycloaddition Chemistry............................ 40 Reactions with Alcohols............................ 44 Preliminary Reactions with Aromatics............... 45 Synthesis of Authentic Samples..................... 65 Substituted-N-s_-triazol-4-ylbenzamidines....... 65 3-(Substituted)- 1H-1,2,4-triazoles............. 66 Reactions with Aromatics........................... 71 Electron-rich Aromatics........................ 74 Electron-poor Aromatics........................ 79 Competition Experiments............................ 97 ESR Study..........................................113 Kinetic Deuterium Isotope Study................... 113 Mechanism.................... 118 III. Experimental........................................... 146 General Comments...................................146 Materials..........................................147 Commercial Chemicals.......................... 147 General Synthesis of Reagent Chemicals........ 148 Detailed Syntheses of Reagent Chemicals........... 149 Amidine Synthesis..................................151 Acylthiosemicarbazide Synthesis................... 163 Triazole-thione Synthesis..........................164 Triazole Synthesis.................................168 Preparation of 3-Diazonium-1H.-1,2,4-triazole...... 183 Preparation of 3-Diazo-3H.-1,2,4-triazole.......... 184 Isolation of 3-Diazo-3]1-1,2,4-triazole............ 184 Explosive Behavior of 3-Diazo-3H.-1,2,4-triazole... .184 IR Spectrum of 3-Diazo-3J3-1,2,4-triazole.......... 185 ESR Spectrum.............. 186 Cycloaddition Chemistry............................187 Reactions of 3-Diazo-1P[-1,2,4-triazole with Alcohols......................................191 Thermolysis of 3-Diazo-3H.-1,2,4-triazole in Benzenoid Solvents.................................193 Photolysis of 3-Diazo-3H-1,2,4-triazole in Benzenoid Solvents.................................210 Competition Reactions of 3-Diazo-3JH-1,2,4- triazole in Benzenoid Solvents.................... 215 vi Kinetic Deuterium Isotope Study.................... 223 Reactions of 3-Diazo-3H.-1,2,^-triazole with Benzenoid/WaterEmulsions .......................... 22^ IV. Appendixes Appendix I........ ............................... 227 Appendix II....................................... 237 Appendix III...................................... 255 V. List of References..................................... 259 vii LIST OF TABLES Table Page 1. Reactions of 3-Diazo-5-phenyl-3H-1,2,4-triazole with Substituted Benzenes...........................................11 2. Thermal Reactivities of 3-Diazo-5-phenyl-3H-1,2,4-triazole with Substituted Benzenes Relative to Benzotrifluoride........ 11 3. Results of Reactions of Diazotetrachlorocyclopentadiene with Benzene..................................... 20 4. Products from Reactions of 3-Diazo-2,5-diphenylpyrrole with Monosubstituted Benzenes................................. 23 5. Products from Reactions of 3-.t.-Butyl-5-diazopyrazole with Monosubstituted Benzenes................................. 24 6 . Products from Reactions of 4-Diazoimidazole with Monosubstituted Benzenes...................................... 24 7. Products from Reactions of 2-Diazoimidazole with Monosubstituted Benzenes...................................... 26 8. Summary of Information Concerning Extraction of 3-Diazo-3H.-1 ,2,4-triazole from Aqueous Solutions.............. 39 9. Yields of Aldehydes or Ketones Produced in the Reactions of 3-Diazo-3H.-1,2,4-triazole with Various Alcohols............ 44 10. Summary of the Slopes and Intercepts of GLC Calibration Curves Used in the Competitive Experiments.................... 54 11. Slopes and Intercepts of the GLC Calibration Curves Used to Analyze the Products from the Reactions of _1_ with Chlorobenzene and Bromobenzene................................ 55 12. Summary of the Extinction Coefficients of 3-(Substituted Phenyl)-TH-1,2,4-triazoles in Ethyl Acetate at 254 nm......... 58 viii 13. Summary of the Actual and the Observed Mole Ratios and Percentages of the Isomers in Standard Samples of 3-(o^ and j)-Tolyl)-111-1,2,4-triazoles as Determined by HPLC Analysis.............................................. 62 14. Summary of the Solutions of 3-(o^ and j)-Chlorophenyl)- 1JH— 1,2,4-triazoles Used in Establishing the Accuracy of the HPLC Method of Analysis................................... 62 15. Summary of the Actual and the Observed Values of the Mole Ratios and the Percentages of the Isomers in a Standard Sample of 3-(o- and j3 -Chlorophenyl)-111-1,2,4-triazoles as Determined by HPLC Analysis................................... 63 16. Summary of the Data for Chromatography of the Product from Thermolysis of _1_ in Chlorobenzene........................ 63 17. Summary of the Results of the HPLC and GLC Analyses of the Product from Thermolysis in Chlorobenzene...................... 64 18. Summary of the Preparation and