Experiment #8

Green Bromination of Trans-stilbene

Tyler Edwards

Lab Partner: Allicyn Cole

Organic Chemistry I Lab 233L

Date of experiment: November 10, 2017

Date of submission: December 1,2017

Abstract:

The purpose of the experiment was to brominate trans stilbene using a “green” process, as a

result decreasing the usage of harmful reagents, instead opting for more environmentally

friendly ones. The product was then tested to determine its nature, whether Syn or Anti.

Introduction:

Bromine may be added across the double bond of trans-stilbene to synthesize 1,2-dibromo-

1,2- diphenylethene. The product may then be characterized for conformation with the use of

melting point and IR spectroscopy. The addition of bromine to trans stilbene results in the

formation of two new chirality centers, consequently, four stereoisomeric products may be

formed depending on the mechanism of the addition reaction. As the reaction involves achiral

reagents, there is no control of the absolute stereochemistry of the product as only one relative

stereochemistry of the product may be formed. As a result, R and S configuration are not

known, but the nature of the product, in terms of Syn (groups on the same face of the

molecule) or Anti (groups on opposite faces of the molecule) configuration may be determined.

In this reaction, the groups governing the relative stereochemistry are the bromine atoms.

It is possible to differentiate these diastereometric dibromides die to the fact that the
melting points of the varying products differ by over 100 ᵒC: The anti-diastereomer has a

melting point of ~241 ᵒC (generally decomposes before the melting point) whilst the syn

diastereomer has a melting point of ~112 ᵒC. A mixture of both would correspond in a broad

melting range separate from the two extremes.

Ordinarily, the addition of bromine to an alkene involves the use of elemental bromine (Br₂)

in a chlorinated hydrocarbon solvent, e.g. dichloromethane (CH₂Cl₂) or a tetrachloride,

however, elemental bromine is volatile and highly corrosive, alongside being an irritant, whilst

both CH₂Cl₂ and CCl₄ are known carcinogens. As such, a “greener” alternative was formulated.

This alternative reaction relies on the generation of molecular bromine (by the oxidation of

sodium bromide by hypochlorite/bleach solution in acidic solution) rather than the elemental

form. The solvent used, ethanol, is a much more environmentally friendly reagent than the

tetrachloride and dichloromethane solvents.

Labcoats, goggles and gloves were worn to limit contact with the reagents used. Sodium

hypochlorite is corrosive while glacial acetic acid is both corrosive and dehydrating agent. Trans

stilbene and the products of the reaction are also corrosive and irritants, as such the reactions

were don in the fume hood. Acetone was kept away from the reagents and apparatus as it may

easily react with the bromine and interfere with the reaction, as well as produce a powerful eye

irritant: α bromoacetone.
Procedure:

A small water was prepared and set ~60 ᵒC. Two- three mmol of trans stilbene was then

added to a 50 ml round bottom flask, followed by an addition of 5.8 mmol of sodium bromide,

10 ml of ethanol, 50 ml of glacial acetic acid and a magnetic stir bar. The flask was then fit with

a water cooled reflux condenser and secured with a Keck clip. The water condenser itself was

secured to a stand using a clamp attached between the water inlet and outlet of the condenser

before lowering the flask into the water bath. The mixture was then stirred until the majority

of the solid dissolved. About 2.7 ml of ~8.25% bleach was then added through the top of the

condenser dropwise over a period of 2-3 mins whilst continuously stirring and heating the

mixture until the solution became cloudy white.

After the evolution of the cloudy white solution the flask was removed from the bath and

allowed to cool to room temperature, the pH of the solution was then verified with the use of

pH paper, if still acidic, a small amount of sodium bicarbonate solution was added until neutral

(pH 5-7). The mixture was then further cooled in an ice bath, after which the crystals formed

were collected by the use of vacuum filtration and rinsed with a cold water. Air was then drawn

through the product until dry. The mass, theoretical yield and percent yield were then

determined. The melting range and IR spectra were then collected and analyzed before placing

the product in a scintillation vial and given to the instructor.

Reaction Equation:
Trans-stilbene Syn-1,2-dibromo-1,2-diphenylethane AND/OR
Anti-1,2-dibromo-1,2-dephenylethane

Reagent Table:

Chemicals FW mp (℃) bp (℃) mmol mass (g) density volume

(g/mol) (g/mL) (mL)

Trans-stilbene 180.25 123 - 2.3 0.415 - -

 Sodium Bromide 102.894 - - 5.8 0.597 - -

Ethanol 46.07 - 78.37 - - - 10

Acetic acid, glacial 60.05 - 118.1 61.62 3.7 - 3.5

Sodium 74.44 - - 39.898 2.97 1.1 2.7

hypochlorite

Sodium 84.007 - 851 - - - 10

bicarbonate
(saturated)
Syn-1,2-dibromo- 340.058 112 - 2.3 0.78 - -
1,2diphenylethan
e
Anti-1,2-dibromo- 340.1 241 - 2.3 0.78 - -
1,2-
diphenylethane

Table 1: Table showing reagents used in the bromination of trans stilbene

Observations:

Trans stilbene was noted to be a white, crystalline solid. The solution, before addition of
bleach, was colorless. On addition of bleach a yellowish orange color evolved which eventually
faded to a cloudy white as time passed. A white solid was filtered out. Whilst testing the
melting point the product began turning brown.

Results:

Mass of Weigh Vessel: 1.829g

Mass of Product and Weigh vessel: 2.055g
Mass of Product: 0.226g
Melting Point: 235.7ᵒC - 241.2ᵒC

Theoretical Yield: 0.783g

Percent Yield: 28.9%

Discussion:

The melting point is the temperature at which a solid changes phase into a liquid (and vice

versa), and is generally specific for each compound. As such melting point analysis can give an

idea as to what compound is present (if it is pure) especially if a comparison sample is present.

In this experiment, the product was determined to have a melting point around 237-241
degrees celcius, this compares most closely to the melting point of the Anti diastereomer, of

241ᵒC rather than the Syn (112 ᵒC).

By the use of infrared spectroscopy, the functional groups comprising a compound may be

determined by analysis of the peaks and corresponding wavelengths. As such, it is extremely

useful in determining the nature of a compound. On the graph representing the IR spectra for

the starting material, trans-stilbene, a stretch from 3000-3078cm -1 was displayed with weak

intensity, and a short and narrow breadth, suggesting trans-stilbene is an alkene with

consistent peak range values.

IR spectra illustrating the product anti- 1,2 dibromo-1,2-diphenylethane, shows a broad peak at

~3370-3380cm-1 . It also showed a sharp peak with a short and narrow breadth at 3028 cm -1 .

Suggesting that the bromination of the trans stilbene was successful.

Conclusion:

From the results of the melting point range and IR spectra, the product was determined to be

anti- 1,2 dibromo-1,2-diphenylethane. The high melting point of 235ᵒC -241ᵒC corresponded

more to the known melting point of the Anti compound (241ᵒC) rather than the Syn (112 ᵒC).
Work Cited:

Ballard, C. E.; Henchey, L. K.; Leslie, J. M.; Struss, J. A.; Theodore, C. M. The University of

Tampa CHE 233L Organic Chemistry I Laboratory Fall 2017 Laboratory Manual; University of

Tampa: Tampa, FL, 2017.

Klein, David. Organic Chemistry: Second edition. John Wiley and Sons, Inc, 2015.