1. Steven Stewart Dr. Katherine Stumpo Dr. Phillip Shelton MICROWAVE-ASSISTED COMPETITIVE NITRATION OF AROMATIC COMPOUNDS

2. HISTORY OF MICROWAVE ASSISTED CHEMISTRY Microwave irradiation introduced as a form of energy, implemented for domestic use Late 1940’s Microwave Assisted Organic Synthesis 1986 Gedye, Giguere and Majetich Utilized domestic microwave ovens Advancements in instrumentation through 1980’s-1990’s CEM Website; Microwave Chemistry: How it all Works; http://cem.com/page130.html, accessed 4/25/2013

3. HISTORY OF MICROWAVE ASSISTED CHEMISTRY Modern instrumentation allows programmable control of Temperature Pressure Power Other advancements Stirring for uniform heating Specially designed reaction vessels Monitoring and recording Applications in organic, inorganic, and analytical chemistry

4. MICROWAVE-ASSISTED ORGANIC SYNTHESIS (MAOS) Some common synthesis reactions utilizing MAOS Diels-Alder reaction Hydrolysis Oxidation Esterification Williamson ether synthesis Biodiesel synthesis Zovinka, Edward; Stock, Anne; Microwave Instruments: Green Machines for Green Chemistry, J Chem Ed, 2010, 87, 4, pp. 350-352

5. MICROWAVE-ASSISTED ORGANIC SYNTHESIS (MAOS) Competitive Electrophilic Aromatic Substitution http://chemistry2.csudh.edu/rpendarvis/tolBenzNitr.GIF

6. COMPETITIVE AROMATIC NITRATION

7. Laboratory objectives Illustrate simple organic synthesis Demonstrate relative reactivity Activating vs. deactivating Demonstrate isomeric distribution of products Ortho/para vs. meta directors Devenyi, Jozsef; Organic Chemistry Loboratory Experiments, 4 th Ed., UT Martin Dept. of Chemistry, 2011

8. COMPETITIVE AROMATIC NITRATION Research Objectives Develop a MAOS method for use in the undergraduate laboratory setting Determine effects of microwave irradiation vs. conventional method

9. RESULTS Reactivity and Product distribution via conventional method Reactivity and Product distribution via MAOS % Ortho NT % Meta NT % Para NT Reactivity T/B Mean 56.632.6740.7037.81 Std. Dev. 0.370.090.281.98 RSD (%) 0.653.300.695.24 % Ortho NT % Meta NT % Para NT Reactivity T/B Mean 54.743.6241.6423.72 Std. Dev. 0.080.030.061.24 RSD (%) 0.140.940.145.24

10. RESULTS Successful MAOS method developed for use in undergraduate laboratory Isomeric product distribution relatively unchanged Significant change in relative reactivity of benzene Effects of differing microwave parameters

11. ACKNOWLEDGEMENTS Dr. Jozsef Devenyi Dr. Genessa Smith Dr. Smith’s Organic Lab Students UT Martin Department of Chemistry and Physics CENS Grant from UT Martin

12. QUESTIONS?