Formation of Styrene

Carbonate from Styrene

Oxide and CO2
Honors Organic Chemistry Lab
Spring Semester 2017
Dr. Deborah Lieberman & Dr. Allan Pinhas
Background to Honors Organic Lab Projects
Synthesis of cyclic carbonates from epoxides and CO2 provides tremendous
promise for converting this hazardous waste into industrially useful raw
materials
Engineering plastics
Cosmetics
Polar solvents
Honors Organic Lab investigates this synthesis of cyclic carbonates using
variously substituted oxiranes and various catalysts
Significant findings
Tetrabutylammonium iodide as simple salt catalyst provides the highest product yields
High speed ball mill (HSBM) or on the bench reactions make fancy, expensive catalysts
unnecessary
H2O > THF > No solvent
Our Research Goal
The goal of our research is to further determine optimal conditions and
components to provide the highest yields of styrene carbonate using relatively
inexpensive materials.

General Mechanism of Intended Reaction

Areas We Investigated
Which iodide catalysts produce the highest yield of product
Which bromide catalysts produce the highest yield of product
How temperature is related to product formation
Which proportions of reactants produce the highest yields
Which solvent between THF, H2O, and no solvent works the best
Which method of adding CO2 works the best
Methods: GCMS Sample Preparation
1.) Open steel vial noting if there is a hiss heard.
2.) Run IR
3.) Wash with diethyl ether until sample being retrieved is clear (about 3 pipets).
4.) Remove bottom layer.
a.) If water, use pipet
b.) If salt, gravity filter
5.) Place 3-5 drops of sample into GCMS vial.
6.) Fill GCMS vial to top line with isopropyl alcohol.
7.) Label and place in GCMS.
Which Iodide catalysts will produce the
highest yield of product with and
without H2O as a solvent?
Erica Fastnacht and Sarah Han
Methods
Each reaction was run under controlled conditions. The components were added to
a steel vial in the following order:

- Salt catalyst (0.15 mmol) - ammonium iodide (NH4), tetrabutylammonium iodide

(TBAI), tetramethylammonium iodide (TMAI)
- Either 1.0 mL of solvent (water) or no solvent
- Styrene oxide (1 mmol)
- 0.1 g or 2.27 mmol of CO2 (dry ice)

Vials (w/ O-rings) were capped tightly and left at room temperature for one week,
unless otherwise noted.
NH4I as the Catalyst

91 107 121 164

g/mol g/mol g/mol g/mol
(8 min) (11 min) (13 min) (13.8 min)

With H2O 12% 78% 4% 5%

No Solvent 79% 0% 9% 8%
TMAI as the Catalyst

91 107 121 164

g/mol g/mol g/mol g/mol
(8 min) (11 min) (13 min) (13.8 min)

With H2O 51% 8% 22% 16%

With H2O 10% 43% 18% 21%

No Solvent 60% 21% 0% 9%

TBAI as the Catalyst - Product Yields
Trial 1 Trial 2 Trial 3

With Water 73% 92%* 80%

Without Water 97%* 42% 91%

*reaction time: 2 weeks instead of 1

TBAI as the Catalyst

164
91 107 121 g/mol
g/mol g/mol g/mol (13.8
(8 min) (11 min) (13 min) min)

With H2O (1) 4% 11% 9% 73%

With H2O (2) 1% 4% 3% 92%

With H2O (3) 3% 3% 0% 80%

No Solvent (1) 1% 0% 0% 97%

No Solvent (2) 11% 37% 0% 42%

No Solvent (3) 7% 1% 0% 91%

Conclusion
TBAI worked the best as a catalyst for the formation of styrene carbonate from
styrene oxide and CO2 for the given reaction conditions, followed by TMAI and
NH4I
Results from the GCMS showed that the carbonate was the major product only
when TBAI was used as the catalyst
There is not enough data to conclude whether using water as a solvent has an
effect on the yield of product
Possible Explanations - Solubility

TBAI was visibly more

soluble in styrene oxide
than water
NH4I was visibly more
soluble in the water than
the styrene oxide
Possible Explanation - Solubility
Possible Explanation - Solubility
Since TBAI is the salt that is the most soluble in styrene oxide, it makes sense
that it is the catalyst that produces the best yield, regardless of whether water
is used
NH4I and TMAI did not work as well because they are not as soluble in styrene
oxide
When run in water, the salts dissolve in the water and do not come in
contact with the styrene oxide, where the reaction is taking place
When run with no solvent, the salts still do not incorporate into the
reaction because they do not become homogenous in the styrene oxide
Investigation of the Effects of Various
Iodide Catalysts on Styrene
Carbonate Formation in
Tetrahydrofuran (THF) & Water (H2O)
Alaina Werling and Andrew (Scottie) Emmert
 Experimental Approach
Research Question: What combination of iodide salt catalyst and solvent leads
to the optimal yield of styrene carbonate from styrene oxide & CO2?
Experimental Timeline:

Week 1: NaI & THF Week 3: LiI & THF Week 5: NH4I & THF Week 7: TBAI & THF
Week 2: NaI & H2O Week 4: LiI & H2O Week 6: NH4I & H2O Week 8: TBAI & H2O
Methods
Reaction Preparation:
All reactions were performed under controlled conditions in a steel vial
containing the following reagents:
Iodide salt (in 1:1 molar equivalent with styrene oxide)
NaI, LiI, NH4I, C16H36NI (TBAI)
Styrene Oxide (100 uL)
Solvent (THF or H2O, 1000 uL)
CO2 (extreme excess, stuffed)
Insert O-ring into cap, tighten with vice grip, and allow to sit in bench for 1
week (168 hours*) until next lab period
*TBAI/THF sample in bench for 2 weeks (336 hours)
Conditions 120 g/mol
121 g/mol 164 g/mol 136 g/mol

(8 minutes) (13 minutes) (13.8 minutes) (11 minutes)

NaI/THF 21 63 0 0

NaI/H2O 27 16 16 38

LiI/THF 0 47 7 0

LiI/H2O 35 55 5 4

NH4I/THF 30 43 19 8

NH4I/H2O 6 21 32 0

TBAI/THF* 79 0 5 0

TBAI/H2O 7 5 5 83
NaI as Catalyst
In THF - 0% product
In H2O- 16% product

120 g/mol 121 g/mol 164 g/mol 136 g/mol

Conditions
(8 minutes) (13 minutes) (13.8 minutes) (11 minutes)

NaI/THF 21 63 0 0

NaI/H2O 27 16 16 38
LiI as Catalyst
In THF - 7% product
In H2O- 5% product

(8 minutes) (13 minutes) (13.8 minutes) (11 minutes)

Conditions
120 g/mol 121 g/mol 164 g/mol 136 g/mol

LiI/THF 0 47 7 0

LiI/H2O 35 55 5 4
NH4I as Catalyst
In THF - 19% product
In H2O- 32% product

Conditions 120 g/mol 121 g/mol 164 g/mol 136 g/mol

(8 minutes) (13 minutes) (13.8 minutes) (11 minutes)

NH4I/THF 30 43 19 8

NH4I/H2O 6 21 32 0
C16H36NI (TBAI) as Catalyst
In THF - 5% product
In H2O- 5% product

(8 minutes) (13 minutes) (13.8 minutes) (11 minutes)

Conditions
120 g/mol 121 g/mol 164 g/mol 136 g/mol

TBAI/THF 79 0 5 0

TBAI/H2O 7 5 5 83
Conclusions
Extreme excess of CO2 (i.e., packing vial with dry ice) possible culprit of low
styrene carbonate yields for time-tested salts
TBAI/H2O reaction yields
Erica & Sarah: 80% yield
Alberta & Divya: 71%
Alaina & Scottie: 5%
Iodide salts involving alkali and alkali earth cations (e.g., Na+ and Li2+) prevent
ring closure due to strong, covalent character of oxygen-cation bond
Ring opens, but then sits there unable to react.
Our results affirmed the idea that H2O is a better solvent than THF for this
reaction.
Some low yields could be due to CO2 gas escape. Some weeks we did not
hear a hiss upon opening the steel vial (LiI/THF, LiI/H2O, TEAI/THF).
Covalent Character of Na+-O- & Li+-O- Bond Prevents
Ring Closure in Formation of Styrene Carbonate
Does THF as a solvent
improve product yield?
Alberta Negri and Divya Takkellapati
Methods
Reaction Preparation:
Wash and dry steel vial, making sure to replace o-ring for each trial
Add reagents
1 mmol of salt (TBAI or TEAI)
114 uL of styrene oxide
Approximately .5 g of dry ice
If applicable, 1 mL of solvent (H2O, THF, or dry THF)
Close vial immediately, using vice grip to ensure tightest seal
Allow reaction to sit for 1 week at room temperature
Carry out product analysis (GCMS and IR readings)
Results TBAI as Catalyst (1:1 molar ratio)

Solvent Percentage of Product

None 2.84%

None 32.39%

Dry THF 15.45%

H2O 70.55%

Wet THF 77.28%

TEAI as Catalyst (1:1 molar ratio)

Solvent Percentage of Product

H2O 55.85%
Conclusions
Initial results hinted THF might be an effective solvent (wet THF trial)
Further trials with dry THF and H2O support that THF alone does not noticeably increase
product yield
Product yields were highest for reactions with H2O
as solvent
TBAI is more effective salt than TEAI
Bulkiness of catalyst may play a role

Important to replace O-rings after every trial

Glass vials should not be stuffed with dry ice
Role of Carbon Dioxides
Method of Addition in
Styrene Carbonate Formation
Kyle Necamp and Nate Ranly
Baseline Experiments (dry ice directly added)
All of the experiments used: One mL of solvent, 114 microliters(0.996 mmol) of styrene oxide,
Tetrabutylammonium Iodide as the catalyst, and were run for one week.

Type of Vial Dry Ice Solvent Catalyst Percent of Notable Peaks

(mmol) (mmol) Product

Glass 65.89 water 0.2897 66.36 Styrene Oxide

(15.04%)

Steel 22.72 water 0.277 84.21 Diol (7.76%)

Steel 0 water 0.145 0.36 Styrene Oxide

(97.93%)

Steel 2.73 water 0.135 69.85 Diol (17.86%)

Steel 22.72 none 0.179 74.6 Styrene Oxide

(23.41%)
Experimental Set Ups
Single 50 mL Erlenmeyer Flask System Data
All experiments run with tetrabutylammonium iodide, 114 microliters (0.996 mmol) of styrene oxide, and for
one week in a single Erlenmeyer Flask system with the reaction vial separate from the dry ice.

Catalyst Solvent Volume First CO2 Second CO2 Percentage Other Peaks
(mmol) (mL) Addition Addition of Product
(mmol) (mmol)
*Unknown
present in
Styrene
0.133 None None 67.7 97.7 3.7 Styrene Oxide (57%) Oxide
Unknown* (28%) Spectra

0.137 THF 1.00 71.1 95.5 10.2 Sty. Ox. (72%)

0.135 Water 1.00 93.2 None 12.0 Sty. Ox. (80%) Parafilm
Seal
Added
0.14 Water 1.00 118 90.9 23.5 Sty. Ox. (67%)

0.14 Water 1.00 70.9 102 53.5 Unknown* (22%)

Two 50 mL Erlenmeyer Flask System Data
All experiments run with tetrabutylammonium iodide, 114 microliters (0.996 mmol) of styrene oxide, and for
one week in a two Erlenmeyer Flask system with the reaction vial in a separate flask, connected by tubing
from sidearm to sidearm, from the dry ice.

Catalyst Solvent Volume First CO2 Second CO2 Percentage Other Peaks
(mmol) (mL) Addition Addition of Product
(mmol) (mmol)

0.148 Water 1.00 104 0 43.5 Styrene Oxide (46%)

0.120 Water 1.00 68.2 182 57.1 Sty. Ox. (20%)

0.14 Water 1.00 68.2 102 57.7 Unknown* (23%)

CO2 bubbled into
solution throughout
reaction runtime
Two Round-Bottom Flask System Data
All experiments run with tetrabutylammonium iodide and 114 microliters (0.996 mmol) of styrene oxide in a
two round-bottom flask system with the reaction vial in a separate flask, connected by tubing from spigot to
spigot, from the dry ice.

Catalyst Solvent Volume First CO2 Second CO2 Percentage Other Peaks
(mmol) (mL) Addition Addition of Product
(mmol) (mmol)

0.14 Water 1.00 114 125 10.7 Styrene Oxide (42%)

Unknown* (35%)

0.14 Water 1.00 127 0 87.5 None of Significance

Reaction ran for two

weeks instead of one
Conclusions
Adding dry ice directly seems to be more effective.
The length of time the reaction is run should be investigated further.
The biggest problem was possible leaks in the set up.
Bubbling carbon dioxide directly into the reactants could be further
investigated.
Effects of Bromide Catalysts on
Styrene Carbonate Formation
Sam Blizzard and Jumee Park
Setup
Except where noted, all reactions:
Used 13.75mmol (250microL) of water as solvent
Used 1mmol (.44g) o f CO2
Used 1mmol (114microL) of styrene oxide
Conducted at room temperature (293K)
Conducted in steel vial
Conducted for one week
Preparation for GCMS same as other groups and mentioned
previously
Non-TEAB catalysts
Catalyst Amount of Catalyst % of Product Notes

None 0 0

NaBr 1.75mmol (.18g) 15

CuBr2 .62mmol (.139g) 3

LiBr .4mmol (.036g) 20 Conducted over two

weeks (Spring
Break)

Tetrabutylammoniu .47mmol (.15g) 44

m Bromide

NH4Br 2mmol (.196g) 57 Conducted in glass

vial
TEAB Catalysts

Conditions Amount of Catalyst Percent of Product Notes

Standard 3.3mmol (.7g) 82

Standard 3.3mmol (.7g) 29

Catalytic Amount of .1mmol (.021g) 0 No hiss observed

TEAB when opening vial

Temperature 3.3mmol (.7g) 82 .09g lost after week-

Increased to 333K possible leak of
CO2

THF used as solvent 3.3mmol (.7g) 26 .06g lost after week-

instead of H2O possible leak of
CO2
Conclusions
Amount of salt
Positive linear trend noticed, so standardize across experiments and use catalytic amounts for
practical purposes
Loss of CO2 noticed on some trials
Look for avenues of experimentation that guarantee tighter seals
TEAB generally stronger than other catalysts
More experimentation with catalytic amounts
Examine role of solubility of salts in water vs. styrene oxide
Temperature could have effect
More trials at more temperatures needed
Test multiple identical trials at same time
May need to test other catalysts again, as initial results determined whether to follow up with
further trials
Addition of CO2 may add variability to process
Effects of Temperature on
Styrene Carbonate Formation
Dean Hayes and Jordan Hill
Background
Question:

Does temperature of the system significantly alter the amount of product

obtained in a styrene oxide to styrene carbonate reaction?

Experimental set-up

Salt: TBAI (0.27 mmol)

CO2: 1.2 grams (27mmol, excess)
Starting material: 100 uL (0.87mmol)
Solvent: water (55mmol, 1mL)
Results
Results (Cont.)

10% of salt
Results (Cont.)

Less
Salt
Conclusions
Temperature has a significant effect on the amount of product obtained
Increasing temperature increased desired product up to 333K
At 333K and above, results were inconsistent and undesired products
increased in prevalence
Parabolic pattern of product formation possible with temperature
change
Decreasing the amount of salt appeared to inhibit product formation
In order to obtain more concrete conclusions, all the experiments should
be repeated several times
Overall Conclusions
Concentration of CO2 used is not linearly correlated (the more you use does
not mean the more yield you will get), but an optimal concentration does exist
for this reaction.
Water is a more effective solvent than THF
Varying results for no solvent - could be due to different quantities of salt or CO2
TBAI was frequently found to be the most effective catalyst
The procedure used led to inconsistent results in some cases
Same exact conditions led to different product yield
Future Directions
Determine optimal amount of CO2 and catalyst to be used for maximum yields.
Further investigate relationship between solubility of catalyst in styrene
oxide/solvent and product yield
Standardize reaction preparation amounts for all materials amongst groups
participating in study.
Quantify product yields beyond GCMS percentages.
Test how reaction runtime affects yield.
Modify experiment methods to increase the reproducibility of trials.
Measure the mass of the entire vial at the start and end of the reaction so the
amount of CO2 lost can be determined