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Western Michigan University ScholarWorks at WMU Master's Theses Graduate College 4-1987 Reaction of 2,2,6-Trimethyl-1,3-Dioxin-4-One with Isocyanate Derivatives and the Synthesis of 2,3,4,6-Tetra-O-Acetyl- Dglucopyranosyl Phenyl Carbodiimide Tung Van Le Follow this and additional works at: https://scholarworks.wmich.edu/masters_theses Part of the Pharmacology Commons Recommended Citation Van Le, Tung, "Reaction of 2,2,6-Trimethyl-1,3-Dioxin-4-One with Isocyanate Derivatives and the Synthesis of 2,3,4,6-Tetra-O-Acetyl-Dglucopyranosyl Phenyl Carbodiimide" (1987). Master's Theses. 1258. https://scholarworks.wmich.edu/masters_theses/1258 This Masters Thesis-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Master's Theses by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. REACTION OF 2,2,6-TRIMETHYL-1,3-DIOXIN-4-ONE WITH ISOCYANATE DERIVATIVES AND THE SYNTHESIS OF 2,3,4,6-TETRA-O-ACETYL-D- GLUCOPYRANOSYL PHENYL CARBODIIMIDE by Tung Van Le A Thesis Submitted to the Faculty of The Graduate College in partial fulfillment of the requirements for the Degree of Master of Arts Department of Chemistry Western Michigan University Kalamazoo, Michigan April 1987 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. REACTION OF 2,2,6-TRIMETHYL-l,3-DIOXIN-4-ONE WITH ISOCYANATE DERIVATIVES AND THE SYNTHESIS OF 2,3,4,6,-TETRA-O-ACETYL- D-GLUCOPYRANOSYL PHENYL CARBODIIMIDE Tung Van Le, M.A. Western Michigan University, 1987 This research was undertaken to study the synthesis and reactions of isocyanates with diketenes, the synthesis of glycosyl carbodiimide. The 1,3-oxazine-2,4-dione compounds could be useful in the medicinal chemistry field and the agricultural field, the research using glycosyl carbodiimide as a synthon shows great promise for the medicinal chemistry field. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS To my project advisor, respected professor, Dr. Robert E. Harmon, I owe the greatest thanks. His development and keen insight into the unique problems associated with pro­ ject have guided it to its successful end. I would like to thank all the faculty members in the . Chemistry Department for their helpful advice. Tung Van Le Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. 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Zeeb Road Ann Arbor, Ml 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Order Number 1330390 Reaction of 2,2,6-trimethyl-l,3-dioxin-4-one with isocyanate derivatives and the synthesis of 2,3,4,6-tetra-O-acetyl-D-glucopyranosyl phenyl carbodiimide Le, Tung Van, M.A. Western Michigan University, 1987 U MI 300 N. Zeeb Rd. Ann Arbor, MI 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V . 1. Glossy photographs or pages_____ 2. Colored illustrations, paper or print _ 3. 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Further reproduction prohibited without permission. To My Parents, My Wife and Our First Child, My Sisters and Brothers Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS ACKNOWLEDGEMENTS.................. i i LIST OF TABLES..................... V LIST OF FIGURES . ............. .................. vi CHAPTER I. INTRODUCTION . .............. 1 II. EXPERIMENTAL............ 4 Instrumentation.................... 4 Preparations........... 4 2.3.4.6-Tetra-.Q-Acetyl-0(-D-Glucopyra- nosyl Bromide.......................... 4 Silver Cyanate............ 7 2,3,4,6 -Tetra-_Q-Acetyl -^-D-Glucopy ra- nosyl Isocyanate........... ............. 8 3,4-Dihydro—3-Cyclohexyl—6—Methyl-2—H- 1.3-Oxazine-2,4-Dion e ................... 9 2.2.6-Trimethyl-4H-l,3-Dioxin-4-One.... 10 3.4—Dihydro—3-Glycosyl—6-Methyl-2-H—l,3 — Oxazine-2 ,4-Dione ............. 10 III. RESULTS AND DISCUSSION........ 12 Mechanism. ............... .............. 15 IV. INTRODUCTION......... 17 V. EXPERIMENTAL........................... 21 Instrumentation....... 21 Preparations............ ............... 21 iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table of Contents— 'Continued CHAPTER 2.3.4.6-Tetra-O-Acetyl-tf-JD—Glucopy- ranosyl Chloride................... 21 2.3.4.6-Tetra-.0-Acetyl—f-JJ-Glycosyl Azide.................... 23 Triphenylphosphine-p-Chloropheny- limine .............. 24 2,3, 4,6-Tetra-O-Acetyl--D^Glucopy- ranosyl Phenyl Carbodiimide. ...... 25 General Comment.................. 25 Process A ....... 25 Process B .......... 26 VI. RESULTS AND DISCUSSION........ 27 Mechanism ............ 29 VII. CONCLUSIONS........ 32 VIII. REFERENCES........... 33 iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES 1. The Reactions of Diketene-Acetone Adducts with Phenyl Isocyanate........... 3 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF FIGURES 1. The General Reaction of Diketene-Acetone Adduct with Alkyl Isocyanates.......................... ..— 2 2. The Reaction of Diketene-Acetone Adducts with Phenyl Isocyanate ............................. ..' 2 3. The Reaction of D-Glucose with Bromine.............. 6 4. The Reaction of Silver Nitrate and Potassium Cyanate. ............... 7 5. The Reaction of 2,3,4, 6-Tetra-£-acetyl- ot -I)- glucopyranosyl Bromide and Silver Cyanate.......... 7 6. The Reaction of 3,4-Dihydro-3-cyclohexyl-6- methyl-2-H-l,3-oxazine-2,4-dione and Cyclohexyl Isocyanate........... 9 7. The Reaction of 1,3-Oxazine-2,4-dione and Gly­ cosyl Isocyanate...................... 10 8. The Forms of Ketenes.................... 12 9. The Formation and the Decomposition of Diketene.... 14 10. The Mechanism of the Reaction of Diketene-Acetone Adduct with Alkyl Isocyanate.................. 16 11. The Reaction of Ribosylazide and Triphenyl- phosphine.............................................. 17 12.

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