Experiment No.
04
Wittig Synthesis of 1,4-Diphenyl-1,3-butadiene
(Post-Lab Report)
CHEM – 5301 – 08
Modern Laboratory Practices (Dr. Nguyen)
Department of Chemistry & Biochemistry
Lamar University
Submitted by: Md Arif Rafid
Student ID: L20338972
Lab Group: 10
Date: Oct-17-2014
Abstract
The reaction of phosphonium ylide obtained from benzyltriphenylphosphonium
chloride with cinnamaldehyde was carried out to yield 1,4-diphenyl-1,3-butadiene
by the Wittig reaction. The Wittig salt (benzyl triphenyl phosphonium chloride)
was synthesized by nucleophilic substitution reaction of triphenyl phosphine with
benzyl chloride. The final product, 1,4-diphenyl-1,3-butadiene, was obtained as a
solid form with 35.36% yield. The melting point was 140°C which is close to the
melting point of pure (E,E) isomer.
Introduction
Cinnamaldehyde can be naturally obtained from the bark of tree Cinnamomam
zeylanicum. Cinnamon bark contains 1-2 percent of an aldehyde-rich essential oil
of which about 70% is cinnamaldehyde. Cinnamon bark is used for various
purposes like flavoring agent and even as spices. The bark is peeled and sundried.
These are formed as quills, but are broken down to pieces for the sake of
convenience. Sometimes it is powdered. These plants are mainly grown for their
oil.
Like aldol condensation, which is used in the synthesis of synthetic
cinnamaldehyde, Wittig developed a reaction known as Wittig Reaction for which
he was awarded noble prize in 1979. The Wittig reaction is a chemical reaction of
an aldehyde or ketone with a triphenyl phosphonium ylide (often called a Wittig
reagent) to give an alkene and triphenylphosphine oxide. It includes several small
steps which at the final stage yield larger molecules. Here, we see construction of
larger molecules from smaller ones, connecting the components of the smaller
molecules with carbon- carbon double bond. In both the reactions given below, it
can be observed, the attack of nucleophilic carbon atom stabilized by a neighboring
electron withdrawing group at the carbonyl carbon atom of an aldehyde or ketone.
Principle
1,4-diphenyl-1,3-butadiene is an important novel diene which can be converted
into interesting products such as p-terphenyl using Diels-Alders reaction.
Benzyltriphosphonium chloride is formed by nucleophilic reaction of triphenyl
phosphine with benzyl chloride.
On addition of concentrated sodium hydroxide to benzyltriphenylphosphonium
chloride ylide is formed which gets reacted with the cinnamaldehyde to form 1,4-
diphenyl-1,3-butadiene.
benzyltriphenylphosphonium chloride ylide
(E,E)-1,4-diphenyl-
1,3-butadiene
(E,Z)-1,4-diphenyl-
1,3-butadiene
cinnamaldehyde 1,4-diphenyl-1,3-butadiene
Fig: Preparation of 1,4-Diphenyl-1,3-butadiene from cinnamaldehyde
The melting point of (E,E) 1,4-diphenyl-1,3-butadiene is 1530C which is to be a
major product.
Experimental Section
Equipments
Round bottomed flask, Erlenmeyer flask, Magnetic stir bar, Reflux condenser, Ice
bath, Vacuum filter, Separating funnel, Measuring cylinder, Boiling chips.
Chemicals Used
2ml benzyl chloride, 6gm triphenylphosphine, 30ml p-cymene, Petroleum ether,
10mmol trans-cinnamaldehyde, 30ml dichloromethane, 5ml aqueous sodium
hydroxide (NaOH), 35ml aqueous ethanol, Distilled water
Table
Physical properties
Sample Molecular Melting Boiling Density
weight point point
(gm/ml)
(gms) (0C) ( 0C)
Trans-cinnamaldehyde 132.2 -7.5 246 1.050
Dichloromethane 84.9 -97 40.5 1.326
(E,E)-1,4-diphenyl-1,3- 206.3 153
butadiene
(E,Z)-1,4-diphenyl-1,3- 206.3 88
butadiene
Safety Measurements
Trans-Cinnamaldehyde is skin irritant, contact was avoided. Dichloromethane may
be harmful if ingested, inhaled or absorbed through the skin. Contact with the
liquid was minimized and breathing its vapors was avoided. Sodium hydroxide is
toxic and corrosive. Cautions was taken when handling sodium hydroxide.
Procedure
Preparation of benzyltriphosphonium chloride
Under the hood 2ml of benzylchloride was added to 6gm of triphenylphosphine
and 30ml p-cymene in round bottom flask. Reaction mixture was heated and stirred
under reflux for 2 hours. The mixture was then cooled by placing in ice bath for 15
minutes and the product collected by vacuum filtration. The product was washed
using low boiling petroleum ether and dried. Resulted product was washed and
3.90gm is taken for further procedure.
Preparation of 1,4-Diphenyl-1,3-butadiene
3.90gm of benzyltriphosphonium chloride was taken in 50ml Erlenmeyer flask.
10mmol of cinnamaldehyde and 10ml of dichloromethane was added. To the
mixture, 5ml of aq.NaOH was added and stirred vigorously at room temperature
for 30 minutes.
Separation: The reaction mixture was transferred into separating funnel using 20ml
dichloromethane and 15ml water. The mixture was shaken to extract the product
into dichloromethane layer and the layer is poured into the flask. The
dichloromethane solution was dried by using anhydrous magnesium sulfate and
after than was evaporated under vacuum. The residue was collected which was
soon solidified.
Purification: 35ml of aqueous ethanol was added to solidified residue to remove
impurities. The solid was washed with several portions of cold ethanol and the
product was collected by vacuum filtration. The crude product was recrystallized
from ethanol and its mass and melting point were measured.
Calculation
Amount of cinnamaldehyde for reaction
10 mmol = 10 x 10-3 x 132.2 gm = 1.32 gm = 1.32gm/1.050(gm/ml) = 1.26 ml
Required amount of MgSO4
For 25ml of product 1gm of MgSO4
For 32ml of product 32x1/25=1.28gms of MgSO4
Percentage yield calculation:
Practical yield = 0.73 gm
Theoretical yield = 10 mmol = 10 x 10-3 x 206.3 gm = 2.063 gm
Percentage yield = 0.73/2.063 * 100 = 35.36%
Result
The weight of the product was 0.73 gm which gave a percentage yield of 35.36%.
The melting point is determined by Capillary method and was found to be 140°C.
Discussion
In the experiment, some sample was lost during filtration and transfers. Moreover,
some portion of reactants may not be converted into products. This explains why
the experimental yield was less than the theoretical value. The melting point of the
product was close to that of the (E,E) isomer. The variation was due to the fact that
the product may contain a mixture of both isomers, some impurities may also be
present; therefore, the melting point was lower than the pure (E,E)-1,4-diphenyl-
1,3-butadiene.
Conclusion
The melting point of the product was 140°C. Percentage yield was 35.36%.
Reference:
1. Dr. Nguyen’s protocol, 2. http://www.organic-chemistry.org, 3. J. of Advanced
Engineering and Technology Vol. 2, No. 2 (2009) pp. 345-347
