Bromination of Trans-stilbene

Aim:
Synthesise 1,2-dibromo-1,2-diphenylethane from trans-stilbene.
Determine the purity of the sample product via melting point determination.
Evaluate the validity of the procedure from the % yield.

180 159.8 339.8

Theory:
Alkenes readily
undergo
electrophilic
addition
reactions in the
presence of a
halogen, such as
bromine. In this
reaction, if
stereoisomers
are used in the
reactant, the
product formed
will be a
stereoisomeric
mixture. This is
because bromine
will attack
double bonded carbons from the opposite angle of the phenyl group, due to steric repulsion forces.
The phenyl groups are very large, and the bromine groups are also larger than the hydrogen groups,
so repulse from each other. These groups will not remain in the same angle as each other. The
reactant is trans, meaning the product will also be trans, therefore a mesocompound. A
mesocompound has two identical chiral carbons with opposing orientations, meaning it is optically
inactive as they counteract each other. This is the same effect seen in racemic mixtures of
enantiomers.
The double bond is electron rich and acts as a nucleophile, and the bromine acts as an electrophile in
this reaction. Therefor the electrophile attacks the nucleophilic site, causing an addition reaction.
The electrons on the electron-rich site polarise the Br-Br and push the charge to the further -Br.
Either side of the Br-Br can attack the double bond. The attacking -Br attaches to one carbon,
forming a remaining carbo-cation site which can be readily attacked by the Br - ion. 1,2-dibromo-1,2-
diphenylethane is formed.

Stereoisomer: Isomer with different dimensional orientation.

Diastereomers: A stereoisomer of a compound having two or more chiral carbon centres, which are
non-optically identical.
Meso Compound: Non-optically active diastereomer.
Enantiomers: Pairs of molecules that are mirror images of each other, and optically opposed.

Procedure:
5 grams of trans-stilbene was weighed Accurately Approximately using a 2 place balance, and added
to a 250cm3 conical flask. 40cm3 of dichloromethane, measured with a glass measuring cylinder, was
added to the same conical flask. Solution was swirled until no solids remained undissolved. 15cm 3 of
10% bromine-dichloromethane was measured in a glass measuring cylinder. 5cm 3 of bromine-
dichloromethane was added, then swirled until red/brown colour disappeared. Then repeated. 5cm 3
remaining bromine-dichloromethane was added until the colour remained. Conical flask was swirled
for several minutes to confirm the colour of solution. Cyclohexene was added dropwise until
bromine colour disappeared. Then cooled in an ice bath. Empty Petri-dish was weighed at 72.43g,
then crystalised solution was added to a Buchner Funnel. After emptied, Conical flask was washed
with 15cm3 of cold dichloromethane to collect remaining residue. Petri-dish crystals were placed in a
50⁰c oven to dry. Dried crystals in petri-dish were weighed at 79.207g for percentage-yield
calculation. Melting point analysis carried out on portion of product.

Results:
Mass of trans-stilbene: 4.93g
Mass of petri-dish: 72.43g
Mass (Theoretical) of 1,2-dibromo-1,2-diphenylethane: 9.29316g
Mass of Dried Product: 6.807g
Mass of Petri-dish and product: 79.24g
Melting Point of 1,2-dibromo-1,2-diphenylethane: 235°C-241°C
Melting Point of product: 231.9-232.4⁰c
% Yield: 73.247%
Observable Peaks: Aromatic C=C(alkene and aromatic), C-Cl, C-H, C-C.

Calculations:
Molar ratio of Trans-stilbene to 1,2-dibromo-1,2-diphenylethane is 1:1. Therefore no adjustment for
molar ratios required.

Number of Moles = Mass/Gram Theoretical

% Yield = Actual MassMass = Moles
/ Ideal Mass x
Formula Mass Gram Formula Mass
= (6.807/9.29316) x 100
= 4.93/180 = 0.0273489 moles x 339.9
= 73.247%
= 0.0273489 moles. = 9.29316 grams
Conclusion:
6.807g of 1,2-dibromo-1,2-diphenylethane was synthesised from 4.93g of trans-stilbene.

Systematic Error:
%error = (tolerance/measurement) x 100 Total Error for Determination of Theoretical Mass:

= 0.20284% + 0.14691%
Trans-stilbene: = 0.34975%
%error = (0.01/4.93) x 100 = 0.20284%

Product:
%error = (0.01/6.807g) x 100 = 0.14691%

More crystals would have formed and given a higher % yield if product in conical flask had been
allowed to remain in ice-bath for longer.

Discussion:
The peaks along >3000cm-1 correlate to the =C-H aromatic bonds, present in the phenyl groups of
both reactant and product. As well as the 1600cm -1 peaks, which can be ascribed to the C=C
aromatic bonds in the phenyl group.

The C-Cl bond present in the product can be shown in the 500-750cm -1 peaks, shown in the results
and IR Spectroscopy Table.

Cyclohexene was used as a solvent because organic compounds are extremely soluble in hot
cyclohexene, however poorly soluble at colder temperatures. Meaning that it is good for extracting
product in re-crystallisation.

Transfer Error:
A small amount of product is lost in cooled conical flask during transferring. This would be rectified
by double washing the flask and using more than 15cm 3 of dichloromethane.

More crystalised product is lost in transference of Buchner Flask to petri-dish. More time could be
used to scrape the smaller amounts of residue product from the Buchner Flask.

Measuring Error:
Ideally, the reactant, petri-dish and product would be measured in an isolated room without other
people performing the same experiment, to increase the accuracy of mass-balance.

Melting Point Error:

The melting point range is fairly small at 0.5°C in 231.9-232.4°C. Compared to the melting point of
241°C. This discrepancy could be ascribed to remaining trans-stilbene, which has a lower melting
point of 122°C.
Referring to the HN Data booklet, the multiple mini-peaks along 1500-2000 indicate additional bi-
products reducing the percentage yield. As the C=C alkene bond shown at 1700cm -1 would not be
present in a pure product.

The range in melting point can only be reduced to a certain extent, as the reaction produces
different enantiomers. Enantiomers can cause a difference in melting point, and there is no way to
dictate a reaction pathway to exclusively produce one enantiomer.

References:
http://www.chemspider.com/Chemical-Structure.553649.html

http://www.chemspider.com/Chemical-Structure.83963.html