Green Oxidations with Tungsten Catalysts. by Mike Kuszpit Michigan State University

Transcription

1 Green xidations with Tungsten Catalysts by Mike Kuszpit Michigan State University

2 xidations in rganic Chemistry [] [] R 1 R 1 R 1 [] R 1 R 2 R 1 R 2 [] R 1 R 2 R 1 R 2 R 1 R 2 [] R 1 R 2 Essential as building blocks in synthesis

3 Classical xidations Cl CCl 3 Cl 1 2 Cr 2 S 4 / Acetone 2 Cr N Cr Cl DCM Cr N Cl 2 Zweifel, G. S.; Nantz, M.. Modern rganic Synthesis An Introduction; Freeman W.. and Company: New York, NY, 2007

4 Classical xidations Cl Cl DMS C C 2 2eqs TEA S 2 TEACl 3 1eq 2 2 1eq DCM C 2 2 C 2 Zweifel, G. S.; Nantz, M.. Modern rganic Synthesis An Introduction; Freeman W.. and Company: New York, NY, 2007

5 Large Scale Reactions Small Scale vs. Large Scale Reactions Goal Quality of Reaction Purification Reagents / Solvents Atom Economy 100% is ideal E (Environmental) Factor is ideal

6 Principles of Green Engineering 1. Minimize the use of hazardous inputs 2. Minimize waste high atom economy 3. Design for good separation 4. Maximize efficiency Sheldon, R. A. Green Chem. 2007, 9,

7 Principles of Green Engineering Cont. 5. Minimize energy/labor manage inventory 6. Minimize process complexity 7. Design products to only last their useful commercial life 8. Meet the need of the chemical process and don t t over engineer for excess Sheldon, R. A. Green Chem. 2007, 9,

8 Principles of Green Engineering Cont. 9. Limit reagent and product diversity 10. Use local energy and resources 11. Design for commercial after life 12. Use renewable resources as opposed to depleting resources Sheldon, R. A. Green Chem. 2007, 9,

9 Atom Economy Atom Economy = MW Desired Product / Sum of MWs of all products produced Assume 100% yield Does not include any reagents used in purification N Cr Cl DCM 106 Cr 2 N Cl Atom Economy = 106/ ( ) = (106/323.4)*100 = 33% Sheldon, R. A. Green Chem. 2007, 9,

10 Cl Cl Atom Economy 2eqs TEA DMS 2 TEACl C C 2 S Atom Economy 24% 1 2 Cr 2 S 4 / Acetone 2 Cr 37% Cl CCl 3 Cl 45% 3 1eq 2 2 1eq DCM C 2 2 C 2 89% Zweifel, G. S.; Nantz, M.. Modern rganic Synthesis An Introduction; Freeman W.. and Company: New York, NY, 2007

11 E (Environmental) Factor E factor = Kg Waste / Kg Product Waste Every reagent used that is not incorporated into the product including solvent losses (solvents are recycled) Water used in purification is not considered waste (only any organic/inorganic products in the water) Water produced is waste Excess reagents used are waste If conversion is not 100% Sheldon, R. A. Green Chem. 2007, 9,

12 E (Environmental) Factor (108*0.1) = 10.8 N Cr Cl 90% Conversion DCM 95.4 Cr N Cl eqs Na (aq) NaCl 2 N Atom Economy = 33% E factor = ( ) / 95.4 = 2.8 Nature vs. quantity of waste Final fate of the waste can it be recycled? Sheldon, R. A. Green Chem. 2007, 9,

13 E-Factors and Solvents E-Factors in the Chemical Industry Industry Product Tonnage E- Factor (kg waste / Kg Product Bulk Chemicals <1-5 Fine Chemicals >50 Pharmaceutical >100 Product Tonnage = Annual Production of the product world wide or at a specific plant igh E-Factors (inorganic salts) Incorporate 2, 2, 2 2, C, C 2 and N 3 Best solvent is no solvent Sheldon, R. A. Green Chem. 2007, 9,

14 Ideal xidation 2 Cat 2 R 2 2 R 2 2 R Cat R R Radical Side Products Sheldon, R. A. Green Chem. 2007, 9,

15 Catalysts in Green xidations Si Si Ti Si Si Titanium Silicate M Mn 3 Fe 3 Porphyrins Re, Pd, Mo, W have been studied in Green oxidation Na 2 W 4 forms homogenous species in water with hydrogen peroxide ave to Use Phase Transfer Catalysts R 1 R 2 N R 4 R 3 X

16 ydrogen Peroxide as an xidant with Transition Metal Catalysts Cat. 2 2 W X Cat. Catalyst stability to oxygen, water, and hydrogen peroxide Lewis Acidity Catalyst Turnover Catalyst Turnover Frequency Sheldon, R. A. Catalysis Today. 2000, 57,

17 Lipophilicity Effect 1 mol% Na 2 W 4 1 mol% PTC 30% eqs 2,90 C,4hrs 31% N S N S 81% 86% N S W Na C 4, 16C's C 6, 24C's C 6, 19C's N S N S C 16 12% 97% C 8, 25C's Noyori, R.; Sato, K.; Aoki, M.; Takagi, J.; Zimmermann, K. Bull. Chem. Soc. Jpn. 1999, 72,

18 Counter Ion Effect 30% eqs 1 mol% Na 2 W 4 1 mol% PTC 2,90 C,4hrs Entry Counter Ion of PTC Additive equivalents relative to Catalyst 1 No PTC None 0 2 Cl - None 0 3 S 4 - None 97 4 S 4-5 NaCl 59 5 S 4-5 Na 2 S 4 95 % Yield W Na Aqueous Phase W (C 8 17 ) 3 NC 3 X Cation Exchange Na PTC Cation = Q W Q rganic Phase Noyori, R.; Sato, K.; Aoki, M.; Takagi, J.; Zimmermann, K. Bull. Chem. Soc. Jpn. 1999, 72,

19 p Effect with 2 W 4 1 mol% 2 W 4 30% eqs 1 mol% PTC 2, 90 C Entry Counter Ion of PTC Additive equivalents relative to Catalyst Initial p Final p 1 No PTC None Cl - None S 4 None S 4 None < S Na S 4 2 Na S Na S 4 3 Na % Yield Na W (C 8 17 ) 3 NC 3 S 4 Noyori, R.; Sato, K.; Aoki, M.; Takagi, J.; Zimmermann, K. Bull. Chem. Soc. Jpn. 1999, 72,

20 Mechanism of Alcohol xidation 2-2Na Na W - W - W A B C Dominant At p>4 Dominant from p pka = 0.1 S S Na Na S Na Noyori, R.; Sato, K.; Aoki, M.; Takagi, J.; Zimmermann, K. Bull. Chem. Soc. Jpn. 1999, 72,

21 Mechanism of Alcohol xidation 2 2 R 1 R 2 W Q W Q R 1 R 2 W Q R 1 R 2 R R 2 1 W Q rganic Phase Aqueous Phase W Na 2 W Na Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003,

22 Aqueous xidation of Secondary Alcohols with Sodium Tungstate R 1 R 2 30% eqs 0.2 mol% Na 2 W mol% PTC 2, 90 C, 4hrs Substrate/Cat = 500 R 1 R 2 2 C 9 19 W Na 92% 96% 84% 93% (C 8 17 ) 3 NC 3 S 4 78% 83% 96% 89% Noyori, R.; Sato, K.; Aoki, M.; Takagi, J.; Zimmermann, K. Bull. Chem. Soc. Jpn. 1999, 72,

23 Aqueous xidation of Primary Alcohols to Aldehydes R 1.1 eqs mol% Na 2 W mol% PTC 2, 90 C, 4-17hrs Substrate:cat = 200 R 2 3 C 3 C 90% 91% Br Cl 81% 82% W Na C 3 88% 59% (C 8 17 ) 3 NC 3 S 4 2 N 87% 82% Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003,

24 E-Factor and Atom Economy N Cr Cl 90% Conversion DCM Cr N Cl 2 E-Factor = 2.8 (including Neutralization) Atom Economy 33% PTC = 449 g/mol 0.5 mol% Na 2 W mol% PTC 1.1 eqs 2 2 2, 90 C, 4-17hrs 2 Substrate:cat = % Atom Economy = 85% E-factor = 0.39 Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003, *0.87 = *1.1 = 19.8

25 xidation of Alcohols to Acids R 30% eqs 2 mol% Na 2 W 4 2 mol% PTC 2, 90 C, 4-12hrs R 2 2 C % 68% 52% C % 3 C 5% 80% Cl 81% 86% 2 N 87% 91% Br W Na Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003, (C 8 17 ) 3 NC 3 S 4

26 E-Factor and Atom Economy 1 2 Cr 2 S 4 / Acetone 2 Cr Atom Economy =37% E-Factor mol% Na 2 W 4 2 mol% PTC 30% eqs 2, 90 C, 4-12hrs % 117*0.81 = *2.5 = 45 Atom Economy = 76% E-Factor = 0.7 Noyori, R.; Sato, K.; Aoki, M.; Takagi, J.; Zimmermann, K. Bull. Chem. Soc. Jpn. 1999, 72,

27 xidation of Aldehydes to Carboxylic acids without Tungsten R 30% eqs 0.5 mol% PTC 2, 90 C, 2-3hrs Substrate/Catalyst 200 R 2 3 C( 2 C) 6 85% 85% (C 8 17 ) 3 NC 3 S 4 65% 8 85% 9 75% 79% Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003,

28 Isolation of Ketones, Aldehydes,, and Carboxylic Acids 100g Scale 2 2 Addition 3hrs Dropping Funnel 1) Seperation 2) Washed 50ml sat. Na 2 S 2 3 3) Distillation 87% 2 2 Addition 5hrs Dropping Funnel 1) Filtration 100g Scale 81% Noyori, R.; Sato, K.; Aoki, M.; Takagi, J.; Zimmermann, K. Bull. Chem. Soc. Jpn. 1999, 72,

29 Determination of Catalyst Turnover 1) Seperation 2) Washed 50ml sat. Na 2 S 2 3 Aqueous Phase 1st reaction 0.2 mol% PTC g Scale 3) Distillation Aqueous Phase 1st reaction 0.2 mol% PTC % Repeat Workup 86% Repeat Workup 92% Catalyst Turnover = 77, mol 127.8g 5.07 umol Na 2 W mmol PTC 1.5 mol hrs 90 C, 1000 rpm 40.1% Noyori, R.; Sato, K.; Aoki, M.; Takagi, J.; Zimmermann, K. Bull. Chem. Soc. Jpn. 1999, 72,

30 Epoxidation vs. PTC Anion (C 2 ) 5 C 3 30% eqs 2 mol% Na 2 W mol% PTC 2, 90 C, 2hrs Substrate/ Catalyst =100 (C 2 ) 5 C 3 2 Entry Counter Ion of PTC 1 No PTC Cl S S4-86 % Yield Na W (C 8 17 ) 3 NC 3 X Noyori, R.; Sato, K.; Aoki, M.; gawa, M.; ashimoto, T.; Panyella, D. Bull. Chem. Soc. Jpn. 1997, 70,

31 Epoxidation vs. Additive 30% eqs (C 2 ) 5 C 3 2 mol% Na 2 W mol% [C 3 (C 8 17 ) 3 N]S 4 (C 2 ) 5 C 3 2, 1000 rpm, 90 C, 2hrs Substrate/ Catalyst =100 Entry Additive 1 mol% % Yield Entry Additive 1 mol% % Yield 1 None N P 11 2 P 3 P 4 2 N P 63 6 P 52 7 P 3 2 N 2 N 5 mol% NaCl N P 5 mol% Na 2 S Na W (C 8 17 ) 3 NC 3 S 4 Noyori, R.; Sato, K.; Aoki, M.; gawa, M.; ashimoto, T.; Panyella, D. Bull. Chem. Soc. Jpn. 1997, 70,

32 Mechanism of Catalytic Epoxidation R 1 R 2 R 1 R 2 Q 2 N P W I Cation Exchange Q 2 N P W rganic Phase R 1 R 2 2 N P W J Cation Exchange 2 N P W Na Aqueous Phase 2 N P W K Na L 2 Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003,

33 Epoxidation of Simple lefins R 30% eqs 2 mol% Na 2 W mol% PTC 1mol% N 2 C 2 P 3 2 2, 70 C, 1-12hrs Substrate/ Catalyst = 100 R 2 Na 2 N P W (C 8 17 ) 3 NC 3 S 4 86% 98% 99% 95% 6 99% 73% 85% (C2 ) 7 C 3 64% 61% Noyori, R.; Sato, K.; Aoki, M.; Takagi, J.; Zimmermann, K. Bull. Chem. Soc. Jpn. 1999, 72,

34 Epoxidation of lefins Containing Functional Groups 2 mol% Na 2 W mol% P TC R 1 R 2 1 mol% N 2 C 2 P 3 2 R 1 R 2 30% eqs 2, 90 C, 0.5-4hrs S ubst rate/ Catalyst = 50 Reagent Pr oducts 2 N P W Na (C 8 17 ) 3 NC 3 S % % 95% Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003,

35 Atom Economy and E-Factor Cl CCl 3 Atom Economy = 45% E-Factor = 1.5 (including Neutralization) 128 Cl mol% Na 2 W mol% P TC 30% eqs Atom Economy = 83% E-Factor = mol% N 2 C 2 P 3 2 2, 70 C, 1-12h rs 86% 128*0.86= *1.5=27 Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003,

36 Aqueous xidative Cleavage of lefins 1 mol% Na 2 W 4. 2 N=1,2 30% eqs 2 mol% PTC 2, C, 8hrs Substrate/ Catalyst = 100 N=1, 2 Reagents Products Reagents Products C 2 90% C 2 C 2 59% 2 C 2 C 2 C 2 C 2 C 2 C C 2 C 2 C 2 C 2 96% 91% C 2 C 2 41% W Na (C 8 17 ) 3 NC 3 S 4 Noyori, R,; Sato, K.; Aoki, M.. Science. 1998, 281,

37 xidation Pathway of lefin Cleavage 2 2 aq Na 2 W 4 PTC aq Na 2 W 4 PTC 2 2 aq Na 2 W 4 PTC 2 2 aq Na 2 W 4 PTC 3 C 2 C 2 Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003,

38 Adipic Acid and Nylon 6-6 Significance 2 N N N 2 N - 2 Manufactured into: Carpet fiber, Airbags, Apparel, Tires, Ropes, Conveyor Belts, oses Global Annual Production: 2.8 billion kg Ni-Al 2 3 2, psi C Co, psi C n Cu, N 4 V 3 60% N 3, C igh Temp 2 N 2 igh Pressure 2 N 2 2 Cat. N 2 Thiemens,. M.; Trogler, W. C. Science, 1999, 251,

39 Atom Economy and E-Factor Cu, N 4 V 3 N 3 60 C - 80 C N Atom Economy = 77% E-Factor = mol% Na 2 W % eqs 2 mol% PTC 2, C,8hrs 90% C 2 C 2 4.4eqs 2 Atom Economy = 65% E-Factor = *0.9= *4.4=79.2 Thiemens,. M.; Trogler, W. C. Science, 1999, 251,

40 Problems with Current Industrial Process Using hazardous inputs Are not Minimizing complexity ard not to over engineer the process Are not Limiting reagent and product diversity Using a depleting resource instead of a renewable one N 2 decomposition not efficient

41 Green Synthesis of Adipic Acid or or 30% eqs 1 mol% Na 2 W mol% PTC 2, C, 8hrs Substrate/ Catalyst = 100 Reaction 1 = 400 cat turnovers, 90% Reaction 2 = 400 cat turnovers,78% verall yield 84%, 99% pure W Na (C 8 17 ) 3 NC 3 S 4 Noyori, R.; Aoki, M.; Sato, K. Green xidation with Aqueous ydrogen Peroxide. Chem. Comm. 2003,

42 Recent Advances in Adipic Acid 2 50% eqs N C mol% Catalyst 2, 85 C, 5hrs W 3 Soluble 83% P 4 [W() 2 ( 2 )] N W C P 4 [W() 3 ] 4 3 Insoluble Chen,.; Dai, W. L.; Gao, R.; Cao, Y.; Li,.; Fan, K. Applied Catalysis: A General. 2007, 328,

43 Recent Advances in Adipic Acid When Reaction done isolate adipic acid by filtration Quench excess hydrogen peroxide to isolate catalyst Can be reused Don t have to use more phase transfer catalyst New trend for oxidations igher Substrate / Catalyst Ratio Chen,.; Dai, W. L.; Gao, R.; Cao, Y.; Li,.; Fan, K. Applied Catalysis: A General. 2007, 328,

44 Benefits of Noyori s Green Process Don t use benign reagents igh Atom Economy, Low E-Factor Great Separation Efficient Minimized Complexity Don t have to over engineer the process incase of hazards Minimizing reagent and product diversity

45 Conclusion Environmental regulation Greenhouse Gases Volatile organic solvents New technology replacing older technology Adipic Acid Green Process Recyclable Catalyst with igh Catalyst Turnovers Safe, Simple, Environmentally Friendly Chemical Process Economical