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ROUTES to ACYLATED SYDNONE ESTERS a Thesis Submitted In ROUTES TO ACYLATED SYDNONE ESTERS A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science By AMANDA MARIE BALAGUER B.S., Wright State University, 2008 2011 Wright State University WRIGHT STATE UNIVERSITY GRADUATE SCHOOL July 28, 2011 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Amanda Marie Balaguer ENTITLED Routes to Acylated Sydnone Esters BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science. _________________________ Kenneth Turnbull, Ph.D. Thesis Director _________________________ Kenneth Turnbull, Ph.D. Chair Department of Chemistry College of Math and Science Committee on Final Examination _________________________ Kenneth Turnbull, Ph.D. _________________________ Eric Fossum, Ph.D. _________________________ Daniel M. Ketcha, Ph.D. _________________________ Andrew T. Hsu, Ph.D. Dean, Graduate School ii Abstract Balaguer, Amanda Marie., M.S., Department of Chemistry, Wright State University, 2011. Routes to Acylated Sydnone Esters Various 4-acyl-3-[2’-(carboalkoxy)phenyl]sydnones were synthesized by reaction of the parent sydnone with the corresponding anhydrides and Montmorillonite K-10. In the Q-tube, the acylation using acetic anhydride, which normally took 1.5 days for complete conversion thermally, was complete in 8.5 hours. Use of bismuth triflate as catalyst reduced the reaction time to 5 hours and, in the microwave, reactions were complete in 30 minutes and provided comparable yields. New sydnones were synthesized with acetic, propionic, butyric, and isobutyric anhydrides. Extension to various homogeneous metal triflates (lanthanum, yttrium, scandium, hafnium, gadolinium, and indium) was explored. Reactions were performed with 3-phenylsydnone as reactant, initially under thermal conditions overnight, individually with the six chosen catalysts. When optimal conditions were achieved, these predetermined parameters were employed for further optimization, performed under microwave irradiation. After multiple reactions, the best catalysts were determined to be the gadolinium and indium triflates. iii TABLE OF CONTENTS Page Introduction ……………………………………………………………………………….1 The Friedel-Crafts Reaction ………………………………………………………...1 I. The History of the Friedel-Crafts Reaction …………………………….1 II. Scope ………….………………………………………………………5 III. Friedel-Crafts Acylation ……………………………………………...8 A. Ketone Synthesis ……………………………………………..8 B. Introduction of Formyl Groups …..….……………..………16 C. Introduction of Carboxyl Groups ……………………………17 IV. Homogenous Catalyst …………………………………………..…...19 V. Heterogenous Catalyst ……………………………………………….24 Sydnones ……………………………………………………………………….…26 I. Reactions of Sydnones ………………………………………………...28 A. Electrophilic Aromatic Substitution Reactions………………29 1. Direct Acylation ………………………………………29 2. Halogenation ……………………………………….…30 B. Lithiation ……………………………………………………..32 C. Cycloaddition ………………………………………………...35 Aims of the Present Work …………………………………………………………….....39 Results and Discussion ………………………………………………………………….44 Experimental …………………………………………………………………………….86 References ………………………………………………………………………...……158 iv LIST OF TABLES Table Page 1. Molar Ratio of Sydnone to Acetic Anhydride ………………………………………..47 2. Thermal vs. Q-Tube Yields and Reaction Times for the Montmorillonite K-10 Catalyzed Syntheses of 3-(2’-Carbomethoxyphenyl)-4-acyl sydnones …………52 3. Q-Tube Yields and Reaction Times for the Montmorillonite K-10 and Bismuth Triflate Catalyzed Syntheses of 4-Acyl-3-[2’-(carboalkoxy)phenyl] sydnones ...………54 4. MWI Yields for the Bismuth Triflate Catalyzed Syntheses of 4-Acyl-3-[2’- (carboalkoxy)phenyl] sydnones 68 -71 and 75 -78 ……………………………….58 5. Cost of Metal Triflate catalysts.……………..……………………………...…………62 6. Acylation of 3-Phenylsydnone with Lanthanum Triflate …………………………….64 7. Acylation of 3-Phenylsydnone with Yttrium Triflate ………………………………...65 8. Acylation of 3-Phenylsydnone with Hafnium Triflate …………………………….....66 9. Acylation of 3-Phenylsydnone with Scandium Triflate ………………………………67 10. Acylation of 3-Phenylsydnone with Gadolinium Triflate ………………………..…68 11. Acylation of 3-Phenylsydnone with Indium Triflate ………………………………..69 12. Microwave Optimization of the Acylation of 3-Phenylsydnone ( 33 ) with Lanthanum Triflate and Acetic Anhydride ……………………………...…………...………72 13. Microwave Optimization of the Acylation of 3-Phenylsydnone ( 33 ) with Yttrium Triflate and Acetic Anhydride …………………………………………………..73 14. Microwave Optimization of the Acylation of 3-Phenylsydnone ( 33 ) with Scandium Triflate and Acetic Anhydride ……………………………...…………………...74 v 15. Microwave Optimization of the Acylation of 3-Phenylsydnone ( 33 ) with Hafnium Triflate and Acetic Anhydride ………………………………………………..…75 16. Microwave Optimization of the Acylation of 3-Phenylsydnone ( 33 ) with Gadolinium Triflate and Acetic Anhydride ……………………...…………………………...76 17. Microwave Optimization of the Acylation of 3-Phenylsydnone ( 33 ) with Indium Triflate and Acetic Anhydride ……………………………………………......…76 18. Comparison of Optimal Microwave Reactions for the Acylation of 3-Phenylsydnone (33 ) in ACN or Ac 2O …………………………………………………………....78 19. Reduction of 3-[2’-(Carbomethoxy)phenyl] sydnone ( 67 ) with DIBAL ………...…80 vi Acknowledgements First and foremost, I would like to thank Dr. Turnbull for enduring the struggle of me writing my thesis. You have helped mold me into the chemist I am today, helping me to achieve my educational goals. You have aided me both inside in the lab and in my personal life, and for that I am grateful. I would like to express thanks to Dr. Fossum for his guidance in chemistry and our Monday morning football talks. I tip my cup of coffee to you. Last, I would like to thank Dr. Ketcha for helping me realize that answers to questions in organic chemistry can be “Nobody knows”. Thank you to all of the current and past graduate and undergraduate chemistry students. You have helped me keep my sanity through reactions not working, no clean glassware, and rabblerousing students who do not understand labs. I have enjoyed our time together both working inside the lab and our escapades outside of the lab. I would also like to extend my gratitude to others in the Sydnone Institute, especially Ryan Selhorst for his work on optimization of metal triflate catalysts. Lastly, I would like to thank my parents for supporting me on my decision to go to grad school. You make sure I have a roof over my head and food on the table. There is nothing more I can ask for. I would also like to thank my sister, Emilie, for keeping me grounded and highly caffeinated. vii Introduction The Friedel-Crafts Reaction I. The History of the Friedel-Crafts Reaction The Friedel-Crafts reaction is one of the fundamental chemical reactions taught in basic organic chemistry courses. In this reaction, an aromatic compound can undergo either an alkylation or acylation with assistance from a metal catalyst. Though it is named after Charles Friedel and James Mason Craft, there were prior publications 1 that led them to their discovery. The first publication formally observed as an alkylation reaction that used a metal catalyst was from Zincke in 1869. 1 In this reaction, Zincke was attempting to synthesize an aromatic acid, β-phenyl propionic acid (3), from benzyl chloride (1) and chloroacetic acid (2) in benzene ( Scheme 1 ). 1 Scheme 1 O O Cl Zn OH Cl Cl 2 2 OH (1) (2) (3) He used zinc powder to react with the liberated chlorine to make zinc chloride. Instead of β-phenyl propionic acid, diphenylmethane (4) was produced from reaction with the benzene solvent ( Scheme 2 ). 1 1 Scheme 2 Cl Zn HCl (1) (4) Zincke furthered his investigation of this new transformation by reacting benzyl chloride (1) with just benzene, toluene, or xylene and using iron or silver as the metal catalysts. He stated that “the reaction is of such a peculiar nature that even now it is possible that a sufficient explanation has not been given.” 2 In other work preceding Friedel and Craft, Radzivanovskii found in 1874 the general reaction of halides with aromatic compounds in the presence of zinc. 3 In 1876, Doebner and Stackman used zinc oxide to alkylate phenol with chloroform to produce 2- hydroxy benzaldehyde ( Scheme 5 ). It was reported that zinc chloride was formed as an intermediate but the authors did not understand its purpose. 4 Later, Friedel and Craft would show that zinc chloride was the active condensing agent in all of the alkylation reactions. The first acylation to be reported was in 1873 by Grucarevic and Merz. Here, again, zinc dust was used to catalyze the reaction.5 In these reactions, the aromatic compounds were acylated by acid halides. Zincke had also performed an acylation reaction by reacting benzoyl chloride (5) in benzene with either copper, zinc, or silver in an attempt to make benzil (6) (Scheme 3 ). 6 2 Scheme 3 O O Cl 2 Cl Metal Catalyst 2 O (5) (6) The metal again was used to react with the liberated chlorine. The reaction did not take place as expected and benzophenone (7) resulted ( Scheme 4 ). 6 Scheme 4 O O Cl Metal Catalyst HCl (5) (7) During all of these reactions prior to Friedel and Craft’s studies, there was no mention of a metal halide remaining in the final reaction mixture. The first mention of the development of a metal halide in the reaction mixture was in a paper by Doebner and Stackman in 1876. 4 They added zinc oxide before the start of the reaction and, after filtration, it was observed that zinc chloride was present at the end ( Scheme 5 ). 4 Though it was noted in their paper
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