1. Honors Organic Chemistry Lab Presentation
Spring 2016

2. The Significance of Carbon Dioxide
-There has been much attention surrounding catalytic processes utilizing CO2, especially with reactions involving epoxides.
-Carbon dioxide in efficient catalytic reactions has been particularly important due to the fact that CO2 is a naturally abundant, nontoxic, greenhouse gas.
In this lab we used CO2, in the form of dry ice, and inserted it into an epoxides with a salt catalyst which produced a cyclic carbonates.
100 percent atom efficiency
Solvent-free reaction

3. Significance of Cyclic Carbonates
Cyclic carbonates are especially important due to the wide usage of these compounds.
Applications range from: lithium ions in batteries, usage as chiral auxiliaries, and aprotic solvents in organic synthesis, pharmaceutical applications.
THF
cyclic carbonate
Oxazolidinone

4. General Mehanism
The method by which CO2 will be added to epoxides in this lab is by the High speed ball mill. The contact of the ball on the walls of the vial as shown in the video creates microstates with enough activation energy to push the reaction forward.
For this lab the salts that were tested as catalysts during the semester was Li, Na, K, and NH4 for the cation and Cl, Br, and I as the anion. Other salts that were tested were Zinc and Copper as cations.

5. Related Research lated Research
This graph is a depiction of the effects of Silicon dioxide catalysts and how pressure from carbon dioxide in the reactor affects the yield. The optimum pressure for the reaction using SiO2 – Br was 4 atm.1 It was inferred that higher pressure of carbon dioxide may cause for low styrene oxide concentration in the vicinity of the catalyst, ultimately resulting in a lower yield of the styrene carbonate product.
lated Research
94%
69%
1Hajipour, Abdol et. al. “Silica grafted ammonium salts based on DABCO as heteregenous catlysts for cyclic carbonate synthesis from carbon dioxide and eoxides.” RSC Advances. 23 February 2015: Print.

6. Related Research
Another test was conducted to examine how silicon dioxide bromide catalysts, influences the reaction time on the yield of the styrene carbonate. It was found that the optimal reaction time was 24 hours. Resulted in a 94% yield.
94%
32%
Other Interesting Applications
-Usage of amino acids as green catalysts for cycloaddition reactions
-reusability of catalysts under optimum reaction conditions
1Hajipour, Abdol et. al. “Silica grafted ammonium salts based on DABCO as heteregenous catlysts for cyclic carbonate synthesis from carbon dioxide and eoxides.” RSC Advances. 23 February 2015: Print.

7. Bobby Buse & Austin Songer

8. Setting the Controls Two reactions:
200mg styrene oxide, 3 small stainless steel balls, packed with dry ice.
IR showed only styrene oxide
200mg styrene oxide, 3 small stainless steel balls, 100mg Tetrabutyl Ammonium Iodide, packed with dry ice.
IR showed great peak at 1786
Now that we know salt is needed in a steel vial, we set out to find a way to to use copper, and no salt.

9. I have not failed. I've just found 10,000 ways that won't work.
---Thomas Edison

10. Testing our Hypothesis
Vial Type
Ball Bearings
Reagents
Results
copper
steel balls (3)
styrene oxide (200mg), packed with CO2
Test failed - Copper vials were not able to seal
Steel
styrene oxide (200mg), copper line vial (6.32g), CO2 packed
Copper wrapping torn up. IR results negative.
copper balls (4)
Copper balls torn up. IR results negative.
copper wrapped steel (1 lg.)

11. Background
Research showed that Zn, Al, and Fe catalyze the reaction for Carbon fixation in heterocycles.
The stock room had Zinc balls, and Zinc powder
Aluminum was too soft
Fe is the main component in steel, and we already know this does not work.
Ema, Tadashi, et al. "Bifunctional porphyrin catalysts for the synthesis of cyclic carbonates from epoxides and CO2: Structural optimization and mechanistic study." Journal of the American Chemical Society (2014):

12. Results Vial Type Ball Bearings Reagents Results Steel
3 Zinc (1.15g/ball)
styrene oxide (200mg), packed with CO2
No carbonyl
3 steel balls
styrene oxide (200mg), packed with CO2, Zinc Powder (2:1 zinc:styr.)
styrene oxide (200mg), packed with CO2, Zinc Powder (1:1)
styrene oxide (200mg), packed with CO2, Zinc Powder (1:2)

13. New Information Came to Light
MOF compound (nitrogen rich triazole groups, Cu(II) ions) - catalyzes CO2 fixation in small epoxides.
Although, we did not have the Metal Organic Framework, we had Copper salts to work with.
Cupric Acetate, Copper (II) Sulfate, Copper (II) Chloride, Copper (II) Carbonate
Li, Pei-Zhou, et al. "A Triazole-Containing Metal–Organic Framework as a Highly Effective and Substrate Size-Dependent Catalyst for CO2 Conversion." Journal of the American Chemical Society (2016):

14. Results Vial Type Ball Bearings Reagents Results Steel 3 steel balls
styrene oxide (200mg), packed with CO2, CuSO4*5H2O
No Carbonyl. Alcohol group.
These four reactions were run at 2:1, 1:1, and 1:2 molar ratios
styrene oxide (200mg), packed with CO2, Cu(CH3CO2)2
No Carbonyl. No alcohol.
styrene oxide (200mg), packed with CO2, CuCl2 * 2H2O
No carbonyl. Alcohol.
styrene oxide (200mg), packed with CO2, CuCO3

15. Why?
The -OH groups in the IR analyses could be due to the above mechanism.
Weak Nucleophiles, except for Cl (hydrated)
-OH possibly due to the hydrated copper salts.

16. Promising Update CuBr Anhydrous was obtained
Zirconyl chloride is a catalyst in an aziridine reaction
Wu, Ying, et al. "Zirconyl chloride: an efficient recyclable catalyst for synthesis of 5-aryl-2-oxazolidinones from aziridines and CO 2 under solvent-free conditions." Tetrahedron (2009):

17. Reactions Vial Type Ball Bearings Reagents Results Steel 4 steel balls
styrene oxide (200mg), packed with CO2, zirconium chloride*8H2O
No Carbonyl. Large -OH peak.
styrene oxide (200mg), packed with CO2, 75mg CuBr (anhydrous)
No carbonyl. Very small -OH peak.
Wu, Ying, et al. "Zirconyl chloride: an efficient recyclable catalyst for synthesis of 5-aryl-2-oxazolidinones from aziridines and CO 2 under solvent-free conditions." Tetrahedron (2009):