1. Advisor ： Professor Guey-Sheng Liou Reporter ： Li-Wen Chen 2013.11.15 合成特論期末報告 Friedel-Crafts Reaction

2. Outline ● Introduction ▫History ▫Synthesis ▫Effect factor ● Improve the Friedel-Crafts Reaction ▫Change catalyst ▫Change solvent ● Applications of Friedel-Crafts Reaction ▫Poly(ether ketone) ▫ Dye ● Conclusions 2

3. Outline ● Introduction ▫History ▫Synthesis ▫Effect factor ● Improve the Friedel-Crafts Reaction ▫Change catalyst ▫Change solvent ● Applications of Friedel-Crafts Reaction ▫Poly(ether ketone) ▫ Dye ● Conclusions 3

4. History Charles Friedel James Mason Crafts (March 8, 1839 – June 20, 1917) (12 March 1832 – 20 April 1899) French chemist and mineralogist American chemist Charles Friedel and James Mason Crafts in 1877 to attach substituents to an aromatic ring Friedel-Crafts Reaction 4

5. Friedel–Crafts acylation reaction J.J. Li, Name Reactions, 4th ed. 5

6. Friedel–Crafts alkylation reaction J.J. Li, Name Reactions, 4th ed. 6

7. effect factor Catalyst Temperature Aromatic structureSolvent 7

8.  Friedel - Crafts reaction temperature is generally less than 90 ~ 100 ℃.  Temperature control can effectively reduce the side reaction.  High activity catalyst reactants still require the high temperature. Temperature Aromatic structure  The aromatic ring with electron donating groups is facilitate the reaction. 8

9. Solvent most common polar solvent PhNO 2 (acyl) CH 3 NO 2 (alkylation) CH 3 CH 2 NO 2  CH 3 NO 2, PhNO 2,CS 2 are the best reaction solvent, but because the high toxicity should be avoided.  1,2 - dichloroethane and methylene chloride is also a good solvent. most common non-polar solvent CS 2 CCl 4 Lewis acid Catalyst The amount of catalyst:  activity of the structure  aromatics, acylating reagents  reaction temperature Brønsted acids  Large amount of catalyst can not be recycled  Must be used under anhydrous conditions  Equipment corrosion  Environmental pollution 9

10. Friedel-Crafts Reaction Advantage  Simple operation  High efficiency and yield Disadvantage  Large amount of catalyst can not be recycled  Equipment corrosion  Environmental pollution To maintain selectivity, a long reaction time (hours) at a low temperature is necessary. The use of traditional liquid acid or Lewis acid catalysts and organic solvents cause many problems in cost, apparatus and environment. After the reaction, the catalyst and the solvent have to be separated from the reaction mixture and either purified for recycling or disposed of. 10

11. Outline ● Introduction ▫History ▫Synthesis ▫Effect factor ● Improve the Friedel-Crafts Reaction ▫Change catalyst ▫Change solvent ● Applications of Friedel-Crafts Reaction ▫Poly(ether ketone) ▫ Dye ● Conclusions 11

12. Change catalyst G. D. Yadav and A. A. Pujari, Green Chemistry, April 1999,69 Sulfated zirconia 12

13. Rueping, M.; Nachtsheim, B. J.; Ieawsuwan, W. Adv. Synth. Catal., 2006, 348, 1033–1037 Change catalyst 13

14. Change catalyst Wang, B.-Q.; Xiang, S.-K.; Sun, Z.-P.; Guan, B.-T.; Hu, P.;Zhao, K.-Q.; Shi, Z.-J. Tetrahedron Lett. 2008, 49, 4310–4312. 14

15. Cozzi, P. G.; Zoli, L. Angew. Chem. 2008, 120, 4230–4234 Change solvent 15

16. Outline ● Introduction ▫History ▫Synthesis ▫Effect factor ● Improve the Friedel-Crafts Reaction ▫Change catalyst ▫Change solvent ● Applications of Friedel-Crafts Reaction ▫Poly(ether ketone) ▫ Dye ● Conclusions 16

17. poly(ether ketone) Yoshimitsu Sakaguchi*, Masaya Tokai and Yasuo Kato, POLYMER, 1993, 34, 7 Advantage  Excellent wear resistance at high temperatures.  Excellent hydrolysis resistance at high temperatures.  High temperature performance for all mechanical properties.  Excellent electrical performance at high temperatures.  Excellent chemical resistance at high temperatures. © Gharda Chemicals Limited. 17

18. poly(phenylene sulfide) Advantages  Excellent chemical resistance  High temperature performance  High modulus when reinforced Ryton® / Techtron® / PPS (Polyphenylene Sulfide) Special Topics on Polymers Synthesis lecture 3 18

19. Dye pH indicator 9.3-10.5 Biological dye James V. McCullagh* and Kelly A. Daggett, Journal of Chemical Education, 2007, 84,11 food coloring 19

20. Outline ● Introduction ▫History ▫Synthesis ▫Effect factor ● Improve the Friedel-Crafts Reaction ▫Change catalyst ▫Change solvent ● Applications of Friedel-Crafts Reaction ▫Poly(ether ketone) ▫ Dye ● Conclusions 20

21. Conclusions  Simple operation  Used in many Organic Syntheses  High efficiency and yield Future work  Green chemistry Catalyst Solvent  Equipment corrosion  Environmental pollution Magnus Rueping and Boris J. Nachtsheim, Beilstein Journal of Organic Chemistry, 2010, 6, 1-24 21

22. Thank you for your attention