Advisor： Professor Guey-Sheng LiouReporter： Li-Wen Chen

2013.11.15

合成特論期末報告

Friedel-Crafts Reaction

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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

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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

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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

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Friedel–Crafts acylation reaction

J.J. Li, Name Reactions, 4th ed.

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Friedel–Crafts alkylation reaction

RCl

AlCl3

R

+ HCl

J.J. Li, Name Reactions, 4th ed.

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effect factor

Catalyst Temperature

Aromatic structureSolvent

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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

O SN

> > > > >

H

The aromatic ring with electron donating groups is facilitate the reaction.

9Solvent

most common polar solventPhNO2 (acyl)CH3NO2 (alkylation) CH3CH2NO2

CH3NO2, PhNO2 ,CS2 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 solventCS2

CCl4

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

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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.

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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

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Change catalyst

G. D. Yadav and A. A. Pujari, Green Chemistry, April 1999,69

Sulfatedzirconia

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

Change catalyst

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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.

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

Change solvent

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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

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O

+

CCl

O

ClC

O

O C

O

C

O

AlCl3 AlCl3

O C

O

C

O

n n

AlCl3

DCE

5oC 2hR.T. 16h

MeOH

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.

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+ 2 Cl2 ClCl

H2S + 2 NaOH Na2S + H2O

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

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Dye

pH  indicator9.3-10.5

Biological dye

James V. McCullagh* and Kelly A. Daggett, Journal of Chemical Education, 2007, 84,11

food coloring

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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

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ConclusionsSimple operationUsed in many  Organic SynthesesHigh efficiency and yield

Future work Green chemistryCatalystSolventEquipment corrosionEnvironmental pollution

Magnus Rueping and Boris J. Nachtsheim, Beilstein Journal of Organic Chemistry, 2010, 6, 1-24

Thank you for your attention