Honors Organic Chemistry Lab

2018
Andrei N. Savu, Cameron J. Bowman, Divya Vinod, Farhan Z.
Ilyas, Hanna H. Sorensen, Jessica R. Ventura, Maia H. Forman,
Maya Radić, Meaghan E. LaBarre, Megan A. Urbanic, Misha L.
Haq
Part I: Alkene to Epoxide
Objectives and Mechanism
Objectives
○ Understand the general reaction for epoxidations
○ Learn spectroscopic techniques
■ IR, H-NMR, C-NMR, GCMS
○ Synthesis for further reaction to generate cyclic carbonate
Alkene ---> Epoxide (Epoxidation)
○ MCPBA
■ Used in the electrophilic addition of oxygen to the double bond of alkene
■ Ring will have the same stereochemistry as the starting alkene (concerted)
Methods
1. Obtain .1g of alkene and dissolve in 2mL of dichloromethane
2. Add carefully .828g of MCPBA in a round bottom flask
3. Attach a jacketed condenser and reflux for 1 hour
a. Do not let solvent evaporate
4. Obtain 2.5mL aliquot of NaOH into a conical vial
5. Transfer mCPBA and alkene to ice bath to cool before adding to the conical vial
6. Cap, shake, and vent vial 2X
7. Prepare a drying column and pass organic layer through
8. Evaporate remaining dichloromethane
9. Run an IR
 Alkene Product?
Results 4-chlorostyrene No

IR 4-vinylanisole Likely

● 3010-3100 cm-1 indicated alkene (sp2 Carbon) 3- nitrostyrene No

● C-O single bond stretch 1050-1150 cm-1 in 2-vinylnaphthalene Likely

epoxide trans-4-octene Likely
● Results were dependent on the disappearance
of the peak at 3010-3100 cm-1
● Normally would further confirm with GCMS
○ GCMS could more accurately demonstrate
addition of oxygen across the alkene
Cyclohexene IR
Cyclohexene Oxide
IR
Part II: Epoxide to Cyclic Carbonates
Background
● Why make a cyclic carbonate?
○ Reaction that utilizes CO2
○ Is theoretically a “clean” reaction
○ Certain oxirane reactions can be used to form polymers
○ “The future” of oxirane synthesis as CO2 fixation
● Why test different catalysts?
○ Objective: Prove/Disprove theoretical paper by Ping, et al.
○ Their hypothesis: Based on relative nucleophilicities of anions Cl, Br, and I in the catalysts
used, the reaction rates, from fastest to shortest, will be Cl>Br>I.
○ We sought out to test this hypothesis and compare our results to their hypothesis by using the
same methods and amounts of catalyst, CO2, etc. and comparing our yields each week

Ping, et al., Organometallics, 2018, 406-414.

 Objectives
● Determine which oxirane to use

● Observe effects of CO2 on reaction

● Optimize amount of solvent and which solvent to use

● Determine if solvent or no solvent works best

● Determine amount of and which catalyst: Ammonium tetra-butyl Iodide,

Ammonium tetra-butyl Bromide, & Ammonium tetra-butyl Chloride would

produce the best yield of cyclic carbonate in a one week period

○ The yields determined the reaction rates of each catalyzed reaction

 Oxirane Determination
● Each group chose a certain oxirane, all different from each other. The objective was to see

which oxiranes formed the cyclic carbonate the best (through carbonyl presence).

● Combining the oxirane with carbon dioxide, tetra-butyl ammonium iodide, without the

presence of a solvent, the yields and presence of a carbonyl are shown below:

● In conclusion, there were a few oxiranes to choose from, but styrene oxide was chosen

because the difference in success was small between them and styrene oxide was present in

abundance.
Oxirane Carbonyl? % yield

Styrene Oxide Yes 85%

1,2-epoxy-2-methylpropane Yes 87%

1,2 epoxybutane Yes 63%

3,4-epoxy-1-butene No N/A

2-(4-bromophenyl) oxirane Yes 48%

Optimize CO2
● Does the amount of Carbon Dioxide matter?
○ No - there were substantial differences between each group, where the amount of carbon
dioxide did not matter, most likely because styrene oxide would be the limiting reagent
○ Similar results were gained whether or not there was a 27:1 ratio of CO2 or 1:1 ratio of CO2
● Started with a 5:1 ratio of CO2 to regulate among groups
● CO2 is in excess, so the amount did not need to be regulated, only for the fact
that it should be larger than the amount of styrene oxide
● Increased the amount of CO2 to a 10:1 ratio in further experimenting
● In the future, more experiments should be conducted with various CO2
amounts to determine any substantial effects
 Solvent
Solvents Tested with iodide catalyst:
Solvent Carbonyl present?

Water Present

Dichloromethane Absent

Toluene Absent

Ether Absent

No solvent Present

● Solvent chosen: Water

● Why: Only solvent group with carbonyls present in IR
 Solvent
● Problems with using water as a solvent:
○ -OH group present in IR spectra
○ Only worked with iodide catalyst
■ When used with chloride & bromide there were limited yields
& lack of carbonyls

● How we fixed the problems:

○ Eliminated solvent from last experiment for more comparable
results
○ No solvent for chloride & bromide lead to higher yields & more
carbonyls present in IR spectra
 Solvent

69 % 71%

50%

38%
30.65%

6.6%
Catalyst
● How was the Catalyst affecting the results?
○ Began with one catalyst: tetra-butyl ammonium Iodide at a 1:1 ratio
○ Without regulation, most groups found copious amounts of catalyst in their GC-MS results.
○ Started extractions with dichloromethane and water, instead of ether and water, which
reduced the amount of catalyst in the GC-MS
○ Started testing with two other catalysts: tetra-butyl ammonium Chloride and tetra-butyl
ammonium Bromide
○ Once the two other catalysts were obtained, the ratio went from 1:1 styrene oxide to catalyst
to 1:1/10 styrene oxide to catalyst
○ Tetra-butyl ammonium Iodide with water made the final product have a yellow color, which
did not happen with any other combination of water and catalyst
○ The results that were obtained showed that Cl>I>Br, however more testing should be done
since some of the data were scattered
 Time
● Investigating effects of
time on the reaction
● Experimental procedure:
Reactions proceed for 1
week versus 2 weeks
● More data for two weeks
must be collected in order
to form a conclusion
● IRs were taken to confirm
presence of product
Heat
● Investigating effects of heat on the reaction
● Experimental Setup:
○ 2 Vials, both containing
tetrabutylammonium chloride as catalyst,
no solvent
○ Heated in sand bath for approx. 90 hours at
50 deg. C, then removed and set for 60
hours before opening and extracting
product
● IR, GC-MS Report taken to interpret results
Vial Number Carbonyl % Yield
Present?

Vial 1 Yes 61% *Lower yield is believed to be a result of technical issues in the
experiment setup process.
Vial 2 Yes 24% *
Spectra from Heated Setup
Spectra from Heated Setup
 Future Directions
● Further investigate time and heat
○ Test lengths of time shorter than 1 week
● Utilize GC-mass spec data to determine more accurate yields
● Groups perform each catalyst reaction
○ Increases generalizability of conclusions
■ Removes error from differences in individual technique
○ Enables each group to investigate their own factor
● Show presentation to new Honors Lab students
 Acknowledgments
We would love to thank Dr. Lieberman, Dr. Pinhas, as well as the entire Chemistry
Department for facilitating our learning and allowing us to participate this semester!
This experience has been an invaluable asset to forming our creativity in the research
process, as well as deepening our understanding of Organic Chemistry as a whole. We
are so grateful for this opportunity and cannot wait to continue our love for learning
and questioning!

Additionally, special thanks go to PJ for being the most supportive and wonderful TA
we could have asked for!
 The Team

Maia H. Forman Cameron J. Bowman Misha Haq Andrei Savu

Second Year
Second Year Second Year Second Year
Health Sciences Major
Biology Major Neuroscience & Medical Sciences Major
Medical Sciences Minor
Psychology Major. Spanish Minor
Maumee, OH
Cincinnati, OH
Cincinnati, OH
Louisville, KY
 The Team

Farhan Ilyas Jessica Ventura Maya Radić Meaghan E. LaBarre

Second Year Third Year Second Year Second Year

Medical Sciences Major Biology Major Biochemistry Major Chemistry Major

Mason, OH Cincinnati, OH Independence, KY Marietta, OH

 The Team

Hanna Sorensen Divya Vinod Megan Urbanic

Second Year Second Year Second Year

Chemistry Major, Pre-med Medical Sciences Major Biology Major

Spanish Minor
Hudson, OH
Mason, OH