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Synthesis of Barbituric Acid and 1,3-Dimethylbarbituric

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Synthesis of Barbituric Acid and 1,3-Dimethylbarbituric SYNTHESIS OF BARBITURIC ACID AND 1,3-DIMETHYLBARBITURIC ACID DERIVATIVES A THESIS Presented to The Faculty of the Division of Graduate Studies and Research By Chao-tze Ho In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry Georgia Institute of Technology March, 1976 SYNTHESIS OF BARBITURIC ACID AND 1,3-DIMETHYLBARBITURIC ACID DERIVATIVES Approved: es A. Stanfield, Chairman Drury^. faille III Date approved by Chairman ii ACKNOWLEDGMENTS The author is most grateful to Dr. James A. Stanfield for his invaluable direction and supervision during this work. Appreciation is also expressed to Dr. Drury S. Caine III and Dr. Leon H. Zalkow for serving as members of the reading committee. In addition, the author is grateful to Dr. William M. Spicer and Dr. James A. Bertrand for the offer of a Graduate Teaching Assistantship during her study at the Georgia Institute of Technology. The author wishes to express special appreciation to her husband for his understanding and encouragement during her graduate studies. iii TABLE OF CONTENTS Page ACKNOWLEDGMENTS 11 LIST OF TABLES vii LIST OF FIGURES viii SUMMARY xi Chapter I. INTRODUCTION 1 II. EXPERIMENTAL 9 Instrumentation, Equipment, and General Procedures Preparation of 5-Phenylbarbituric Acid Preparation of 5-Bromo-5-phenylbarbituric Acid Attempted Reaction of 5-Bromo-5-phenylbarbituric Acid with Phenothiazine Reaction of 5-Bromo-5-ethylbarbituric Acid with Phenothiazine Preparation of Ethyl Bromophenylmalonate Attempted Reaction of Ethyl Bromophenylmalonate with Phenothiazine Attempted Reaction of Ethyl Bromophenylmalonate with Carbazole Synthesis of 10-(3-Chloropropyl)phenothiazine Synthesis of 10-(3-Methylaminopropyl)phenothia- zine Attempted Preparation of 5-Phenyl-5-[N-(3-pheno- thiazinylmethylamino)]-barbituric Acid iv TABLE OF CONTENTS (Continued) Page Chapter II. EXPERIMENTAL (Continued) Synthesis of 9-(y-Chloropropyl)carbazole Synthesis of 9-(y-Methylaminopropyl)carbazole Synthesis of 5-Phenyl-5-[N-(3-carbazolylpropylmethyl- amino)]-barbituric Acid Synthesis of 2-Trifluoromethylcarbazole Synthesis of 9-(y-Chloropropyl)-2-trifluoromethyl­ carbazole Synthesis of 9-(y-Methylaminopropyl)-2-trifluoro­ methylcarbazole Synthesis of 5-Phenyl-5-[N-(2'-trifluoromethyl-3- carbazolylpropylmethylamino)]-barbituric Acid Reaction of 5-Bromo-5-phenylbarbituric Acid with Indole Attempted Reaction of 5-Bromo-5-phenylbarbituric Acid with 2-Phenylindole Reaction of 5-Bromo-5-phenylbarbituric Acid with 3-Methylindole Reaction of 5-Bromo-5-phenylbarbituric Acid with Indoline Synthesis of l-(y-Chloropropyl)indole Synthesis of l-(y-Methylaminopropyl)indole Reaction of 5-Bromo-5-phenylbarbituric Acid with 1-(y-Methylaminopropyl)indole Synthesis of l-Methylindole-3-acetonitrile Synthesis of 1-Methyltryptamine V TABLE OF CONTENTS (Continued) Page Chapter II. EXPERIMENTAL (Continued) Reaction of 5-Bromo-5-phenylbarbituric Acid with 1-Methyltryptamine Reaction of 5-Bromo-5-ethylbarbituric Acid with 1-Me thy11 ryp t amine Reaction of 5-Bromo-5-phenylbarbituric Acid with trans-2-Phenylcyclopropylamine Reaction of 5-Bromo-5-ethylbarbituric Acid with trans-2-Phenylcyclopropylamine Synthesis of 5-Phenyl-5-[N-(cyclopropylamino)]- barbituric Acid Reaction of 5-Phenylbarbituric Acid with trans- 2-Phenylcyclopropylamine Synthesis of l,3-Dimethyl-5-phenylbarbituric Acid Synthesis of l,3-Dimethyl-5-bromo-5-phenylbarbi- turic Acid Synthesis of l,3-Dimethyl-5-phenyl-5-[N- (n-propylamino)]-barbituric Acid Synthesis of l,3-Dimethyl-5-phenyl-5-[N- (cyclopropylamino)]-barbituric Acid Synthesis of l,3-Dimethyl-5-phenyl-5-[N- (2-methoxyethylamino)]-barbituric Acid Synthesis of l,3-Dimethyl-5-phenyl-5-[N- (benzylamino)]-barbituric Acid Synthesis of l,3-Dimethyl-5-phenyl-5-[N- (p_-phenetidino) ]-barbituric Acid Synthesis of l,3-Dimethyl-5-phenyl-5-[N- (pyrrolidino)]-barbituric Acid vi TABLE OF CONTENTS (Concluded) Page Chapter II. EXPERIMENTAL (Concluded) Synthesis of 1,3-Dimethyl-5-phenyl-5-[N- (piperidino)]-barbituric Acid Synthesis of l,3-Dimethyl-5-phenyl-5-[N- (morpholino)]-barbituric Acid Synthesis of 1,3-Dimethyl-5-phenyl-5-[N- (4-methylpiperazino)]-barbituric Acid Synthesis of 1,3-Dimethyl-5-phenyl-5-[N- (Nf-$-hydroxylethylpiperazino)]-barbituric Acid Synthesis of 1,3-Dimethyl-5-phenyl-5-[N- (ethylisonipecotato)]-barbituric Acid Synthesis of 1,3-Dimethyl-5-phenyl-5-[N- (1,2,3,4-tetrahydroisoquinolino)]-barbituric Acid Attempted Preparation of 1,3-Dimethyl-5-phenyl- 5-[N-(2,2,6,6-tetramethylpiperidino)]-barbituric Acid III. DISCUSSION OF RESULTS 55 IV. CONCLUSIONS 75 V. RECOMMENDATION 77 APPENDIX A 78 APPENDIX B 91 APPENDIX C 96 LITERATURE CITED 102 VITA 106 vii LIST OF TABLES Table Page 1. New Derivatives of Phenothiazine and Carbazole . 64 2. New Derivatives of l,3-Dimethyl-5-phenylbarbituric Acid 72 3. NMR Shift Values in Units of 6 for Derivatives of Phenothiazine and Cabazole 92 4. NMR Shift Values in Units of 6 for Amino-1,3-dimethyl- 5-phenyl Barbituric Acids 93 5. Mass Spectral Data of Derivatives of Phenothiazine and Carbazole 97 6. Mass Spectral Data of Amino-1,3-Dimethyl-5-phenyl Barbituric Acids 99 viii LIST OF FIGURES Figure Page 1. Barbiturates 2 2. Phenothiazine Derivatives 4 3. Typical N-Substituted Reactions of Phenothiazine 5 4. Proposed Reaction Sequences 6 5. Nucleophilic Substitution of Bromobarbituric Acid .... 55 6. Oxidation Degrees of Phenothiazine 57 7. "Tetragonal Folded" Configurations of Phenothiazine ... 59 8. Proposed New Approach of Synthesizing Phenothiazine - Barbituric Acid Adduct 61 9. Possible Reaction Pathway of Indole and 5-Bromo- 5-phenylbarbituric Acid 65 10. Typical Bromination Reactions of N-Acetylindole 66 11. Possible Mechanism of Salt Formation 67 12. Reactions of Cyclopropylamines with 5-Bromo-5-phenyl- barbituric Acid 69 13. Tautomeric Structures of the Two Barbituric Acids .... 71 14. Infrared Spectrum of 10-(3-Chloropropyl)phenothiazine . 79 15. Infrared Spectrum of 10-(3-Methylaminopropyl)- phenothiazine Hydrochloride 79 16. Infrared Spectrum of yChloropropylcarbazole 80 17. Infrared Spectrum of 5-Phenyl-5-[N-(3-carbazolyl- propylmethylamino)]-barbituric Acid 80 18. Infrared Spectrum of m-Trifluoromethylphenylhydrazine . 81 ix LIST OF FIGURES (Continued) Figure Page 19. Infrared Spectrum of 5-Phenyl-5-[N-(2f-trifluoromethyl- 3-carbazolylpropylmethylamino)]-barbituric Acid 81 20. Infrared Spectrum of l-(Y-Chloropropyl)indole 82 21. Infrared Spectrum of 1-Methyltryptamine 82 22. Infrared Spectrum of 5-Phenyl-5-[N-(cyclopropylamino)]- barbituric Acid 83 23. Infrared Spectrum of l,3-Dimethyl-5-phenylbarbituric Acid 83 24. Infrared Spectrum of l,3-Dimethyl-5-bromo-5-phenyl- barbituric Acid 84 25. Infrared Spectrum of 1,3-Dmethyl-5-pheny1-5-[N-(pyrro­ lidine) ] -barbituric Acid 84 26. Infrared Spectrum of 1,3-Dimethyl-5-phenyl-5- [N-(cyclopropylamino)]-barbituric Acid 85 27. Infrared Spectrum of the Salt of 5-Phenylbarbituric Acid and trans-2-Phenylcyclopropylamine 85 28. Infrared Spectrum of l,3-Dimethyl-5-phenyl-5- [N-(morpholino)]-barbituric Acid 86 29. Infrared Spectrum of l,3-Dimethyl-5-phenyl-5-[N-(l,2,3,4- tetrahydroisoquinolino) ]-barbituric Acid 86 30. Infrared Spectrum of 1,3-Dimethyl-5-phenyl-5- [N-(benzylamino)]-barbituric Acid 87 31. Infrared Spectrum of l,3-Dimethyl-5-phenyl-5-[N-(Nf-3- hydroxylethylpiperazino)]-barbituric Acid 87 32. Infrared Spectrum of 1,3-Dimethyl-5-phenyl-5- [N-(4-methylpiperazino)]-barbituric Acid 88 33. Infrared Spectrum of 1,3-Dimethyl-5-phenyl-5- [N-(n-propylamino)]-barbituric Acid 88 34. Infrared Spectrum of l,3-Dimethyl-5-phenyl-5- [N-(p_-phenetidino) ]-barbituric Acid 89 X LIST OF FIGURES (Continued) Figure Page 35. Infrared Spectrum of l,3-Dimethyl-5-phenyl-5-[N-(ethyl- isonipecotato)]-barbituric Acid 89 36. Infrared Spectrum of l,3-Dimethyl-5-phenyl-5-[N-(2- methoxyethylamino)]-barbituric Acid 90 37. Infrared Spectrum of l,3-Dimethyl-5-phenyl-5- methoxybarbituric Acid 90 xi SUMMARY The purpose of this research was to study the reactions of 5-bromo-5-phenylbarbitur.ic acid and l,3-dimethyl-5-bromo-5-phenyl- barbituric acid with various amines in order to prepare compounds in which synergistic effects might be unusual. The starting bromo- barbituric acids were obtained via bromination of their respective 5-phenylbarbituric acid in 0.6 N aqueous sodium hydroxide with bromine water. Phenothiazine, with its known pharmacological properties such as anthelmintic and antihistaminic activities, was selected as the first model amine compound. From the failure of the formation of substitution derivative, namely 5-phenyl-5-[N-(phenothiazinyl)]- barbituric acid, it was suggested that two possible factors, the facile oxidation process of phenothiazine or the steric hindrance around the nitrogen atom, might be responsible. In order to study these possibilities, the phenothiazine derivative, 10-(3-methylaminopropyl)phenothiazine which would be free of steric hindrance at the reactive nitrogen position, was synthesized in two steps: the preparation of 10-(3-chloropropyl)phenothiazine and the reaction of this with methyl amine. The possibility of a steric hindrance around the nitrogen atom was eliminated or at least minimized but even so, the reaction with 5-bromo-5-phenylbarbituric acid yielded no substitution product. Another approach was studied by reacting the compound carbazole (which has essentially the same carbon skeleton xii as phenothiazine except it lacks a sulfur atom in the ring) with 5-bromo-5-phenylbarbituric acid. Although no reaction was observed in this case, its derivative,
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