1. A Green Chemistry Module Nucleophilic Aromatic Substitution Presidential Green Chemistry Challenge Award Elimination of Chlorine in the Synthesis of 4-Aminodiphenylamine. A New Process Which Utilizes Nucleophilic Aromatic Substitution for Hydrogen

2. S N Ar Mechanism - addition / elimination

3. Benzyne Mechanism - elimination / addition Step-wise formation of Benzyne

4. Evidence for the Benzyne Mechanism Trapping in Diels/Alder Reaction Substrate Modification – absence of  hydrogens Isotopic Labeling

5. S N 1 Mechanism

6. S NR 1 Mechanism

7. Brown Chemistry Route to 4-ADPA

8. Atom Economy of the Traditional Chemistry Reagent formulaReagent FWUtilized AtomsWtUnutilized Atoms Wt 1 C 6 H 6 786C,4H532 H2 2 Cl 2 70------------02 Cl70 3 HNO 3 631 N141 H, 3 O49 4 C 7 H 7 NO1216 C, 6 H, 1 N921 C, 1 O, 1 H29 5 K 2 CO 3 98------------02 K, 1 C, 3 O98 6 H 2 22 H2--------------0 TOTAL 43212C,12H, 2N 161 2C,4H, 2C,2K, 7O248

9. Brown Chemistry Nucleophilic Aromatic Substitution for Chlorine  Large amount of chlorine storage handling  Waste stream components inorganic salts organics  Large amounts of water consumed  Heavy metal catalyst

10. Nucleophilic Aromatic Substitution for Hydrogen General Mechanism

11. Flexsys Route to 4-ADPA Base-Promoted Coupling Reaction

12. Flexsys - Anaerobic Oxidation to 4-NDPA

13. Flexsys - Intermolecular Oxidation Pathway

14. Atom Economy of the Flexsys Chemistry Reagent FormulaReagent FW Utilized Atoms WtUnutilized AtomsWt 1 C 6 H 6 786 C, 4 H762 H2 2 HNO 3 631 N141 H, 3 O49 3 C 6 H 7 N936 C, 6 H, N921 H1 4 H 2 22 H2-----------0 TOTAL 236 12C, 12 h, 2 n184 4H, 3O 52

15. Green Chemistry Advantages for Nucleophilic Aromatic Substitution for Hydrogen  Reduction in chemical waste generation elimination of 74% of organic waste 99% of inorganic waste  Eliminates use of chlorine  Reduction in waste water more than 97% savings  Eliminates use of xylene a SARA chemical  Improves process safety lower reaction temperatures