1. BROMINATION OF STILBENE: A GREEN SYNTHESIS
Experiment 8:
BROMINATION OF STILBENE:
A GREEN SYNTHESIS

2. Objectives
To perform a Green Chemistry synthesis and determine chemical yield.
To purify and isolate the product by recrystallization and vacuum filtration.
To determine the degree of product purity using TLC analysis.

3. Before coming to lab…
Review the techniques of:
TLC
Suction filtration

4. Introduction to Green Chemistry
Green Chemistry: the design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances.
A “PERFECT” chemical reaction would be one that is:
Selective: forming the desired product ONLY.
Efficient: converting all atoms of starting materials and reagents to product.
Non-hazardous: is safer to the chemist and the environment.

5. Typical Bromination Reaction
Elemental bromine (Br2) and chlorinated solvents are used!
Both are extremely hazardous!

6. “Greener” Bromination Reaction
We use ethanol, a much safer solvent.
The Br2 will be generated “in situ”, through the oxidation of HBr with H2O2.

7. Bromination Mechanism
p electrons form bond to d+ bromine atom…
… to form bromonium ion intermediate.
… d- bromine atom forms bond to carbon on opposite side of bromonium ion…
… to result in trans addition product.

8. Bromination Mechanism
The following link will allow you to view an animation of this mechanism:

9. OVERVIEW
Heat alkene, acid, and peroxide under reflux to synthesize products.
Neutralize acid, then suction filter to isolate solid product from unreacted starting materials.
Analyze product to determine identity and purity using TLC analysis.

10. Experimental Procedure (Synthesis)
Add Stilbene and ethanol to the flask.
Begin water flow and heating with 20. Heat solution until it refluxes.
Add 48% HBr during the reflux, followed by 30% H2O2. This should result in the appearance of a yellow color. LOWER SASH TO HOOD.
As the reflux proceeds, the solution will return to colorless.
Neutralize excess HBr using NaOH.

11. Experimental Procedure (Product Isolation)
Set up a suction filtration apparatus to isolate the solid.
Remember to clamp the filter flask to the ring stand and connect the red hose to the vacuum line!
Once isolated, determine the purity of the solid using TLC Analysis.
Prior to calculating percent yield, the solid must then be dried in a warm oven for several minutes.

12. Experimental Procedure (TLC Analysis)
Prepare TLC plate and TLC chamber.
Apply standard solutions and sample solution to plate.
Develop TLC plate in chamber.
Visualize plate using UV lamp!
Circle spots.
Calculate TLC Rf value for each spot.
If all of the stilbene has reacted, there will be no evidence of it in the product lane. This indicates a successful reaction!

13. Theoretical Yield
In order to determine the theoretical yield, one must first determine which reactant is the limiting reagent by converting the amount of each reactant used to moles of product that can be produced.
A simple analogy is the synthesis of a cheese sandwich.
You have six slices of bread and four slices of cheese. The recipe for a cheese sandwich is:
bread
cheese
sandwich

14. Theoretical Yield
Question: How many sandwiches can you make, and which ingredient runs out first?
Answer: You can make three sandwiches and the bread runs out first:
6 slices of bread * sandwich = 3 sandwiches
2 slices of bread
4 slices of cheese * sandwich = 4 sandwiches
1 slice of cheese
The bread is the limiting reagent. The number of slices of bread or cheese is analogous to the number of moles of each of the reactants in a chemical equation.

15. Limiting Reagent If you used 0.8 mL of H2O2 and 1.2 mL of HBr:
Stilbene = 0.50g x 1 mol stilbene x 1 mol dibromostilbene = 2.78 x 10-3 mol g 1 mol stilbene dibromostilbene
If you used 0.8 mL of H2O2 and 1.2 mL of HBr:
H2O2:
(0.8 mL) x 1.11 g x 0.30 g x 1 mol x 1 mol dibromostilbene= 7.8 x 10-3 mol mL g g mol H2O2 dibromostilbene
HBr:
(1.2 mL) x 1.49 g x 0.48 g x 1 mol x 1 mol dibromostilbene = 5.3 x mol
mL g g 2 mol HBr dibromostilbene
The reactant which produces the least amount of the product is the LIMITING REAGENT! We now calculate the theoretical yield based on it!

16. Theoretical Yield
The last step is to convert the number of moles of product based on the limiting reagent to a mass in grams of product. This is your THEORETICAL YIELD!
2.78 x 10-3 mol X 340 g = ? g product
mol

17. Table 8.1 Final Mass of product (g) Obtained at end of this lab!
Theoretical Yield (g)
Calculated
% Yield
Actual mass/theoretical yield
Product Appearance
Physical state & color

18. Table 8.2 2 decimal places ONLY! Rf values are UNITLESS! Compound
TLC Rf values
Standard
Sample
Stilbene
Dibromostilbene
Rf values are UNITLESS!
2 decimal places ONLY!

19. SAFETY CONCERNS Goggles are required at all times during the lab!
30 % Hydrogen peroxide is a very strong oxidizer and will burn your skin if you get any on yourself. One person per group should handle the H2O2 using gloves

20. WASTE MANAGEMENT
Place all liquid waste from recrystallization and TLC analysis in container labeled “ORGANIC WASTE”.
Place all solid waste in container labeled “SOLID ORGANIC WASTE”.
Place used TLC capillaries in broken glass container.
Place TLC plates in yellow trashcan under supply hood.

21. LABORATORY NOTEBOOK (Pre-lab)
OBJECTIVE (Must clearly state…)
What compound you will make and how
How you will purify the compound
How you will determine the purity of your compound
CHEMICAL EQUATION
Include the chemical equation from the top of p. 67
TABLE OF PHYSICAL DATA (Complete the following table using MSDS sheets from a site on WWW Links ONLY. Wikipedia is unacceptable)
REFERENCE TO PROCEDURE (Must include…)
full title, including edition and authors
page numbers where actual procedure can be found
Compound
MW (g/mol)
bp (Co)
d (g/mL)
Mp (Co)
HAZARDS
trans-stilbene
XXX
dibromostilbene
48% hydrobromic acid
30% hydrogen peroxide
ethanol
acetone
hexane
diethyl ether

22. LABORATORY NOTEBOOK (In-lab)
DATA/CALCULATIONS
Initial weight of trans-stilbene used
small filter paper weight
watch glass weights
watch glass+ filter+ product weight
final product weight
Physical state and color of product
Theoretical yield calculation
% yield calculation
TLC diagram
give an example of an Rf calculation
EXPERIMENTAL PROCEDURE
In paragraph form, briefly describe the procedure that you actually followed during the lab.
Paragraph must be written in PAST TENSE, PASSIVE VOICE.
Include any volumes or weights of chemicals used during the experiment.
Include any mistakes, accidents, or observations if necessary.