OBJECTIVE

1. To prepare 4-vinylbenzoic acid by a Wittig reaction in aqueous medium

2. To obtain the yield and melting point for product and analyse the product
using IR and NMR spectroscopy.

INTRODUCTION
The Wittig reaction is one of the methods for the synthesis of alkenes. It uses
a carbonyl compound as an electrophile, which attacked by witting reagent which is
a phosphorus ylide. An ylide is a compound with opposite charges on adjacent
atoms both of which have complete octets. The geometry of the resulting alkene
depends on the reactivity of the ylide. If R is an electron withdrawing group, then the
ylide is stabilized and is not as reactive as when R is alkyl. Stabilized ylide give
predominantly (E)-alkenes whereas non-stabilized lead to (Z)-alkenes. Wittig
reaction are more general in the product carbonyl that do not need to have an
attached carbonyl.

Wittig reaction

The suitable bases in Wittig reaction are, for example NaOH, NaOMe, Net .3

EQUIPMENTS AND INSTRUMENTS

Magnetic stirrer, Reflux apparatus, suction filtration, IR spectroscopy

MATERIALS
1. Preparation of phosphonium salt
4-Bromomethylbenzoic acid (FW 215.1) 4.30 g (20 mmol)
Triphenylphosphine (FW 262.3) 5.20 g (20 mmol)
Acetone
Diethyl ether
2. Preparation of 4-vinylbenzoic acid
Formaldehyde (37 wt % solution) (FW 30.0) 32 mL
Sodium hydroxide pellets 2.5 g
Ethanol
Hydrochloric acid (concentrated)

PROCEDURE
1. Preparation of 4-carboxybenzyltriphenylphosphonium bromide
The bromomethyl benzoic acid and the triphenylphosphine were dissolved in 60
mL acetone in a 100 mL round bottomed flask. The mixture was refluxed for 45
min. After this time, the reaction mixture was cooled and the precipitated
phosphonium salt was filtered off with suction. The solid was washed with diethyl
ether (2 x 20 mL) on the sinter and dried with suction. Record the yield and
melting point of the product which is sufficiently pure were recorded and to be
used directly in the next stage.

2. Preparation of 4-vinylbenzoic acid

4-carboxybenzylphenylphosphonium bromide (3.76 g, 8 mmol), the aqueous
formaldehyde and 15 mL water were placed in a 250 mL Erlenmeyer flask
equipped with a magnetic stirrer bar. The solution was stirred vigorously and a
solution of the sodium hydroxide in 15 mL water was added over approximately 10
min. The mixture was stirred for an additional 45 min and the precipitate was
filtered off with suction and washed with water. Combined filtrate was acidified and
washed with concentrated hydrochloric acid. The residual precipitate of crude
product was filtered off with suction. The product was recrystallized from aqueous
ethanol. The purified material was analysed using NMR and IR spectroscopy.
RESULT AND OBSERVATON

1. Preparation of 4-caboxybenzyltriphenylphosphonium bromide. (Predicted

results)

Mass 7.1888 g

Melting points 2350C

Percentage yield 75.35 %

2. Preparation of 4-vinylbenzoic acid. (Predicted results)

Mass 1.1133 g

Melting points 1410C

Percentage yield 93.93%

3. IR spectroscopy analysed. (Predicted results)

Peak Wavenumber (cm-1) Type of bond Intensity

1. 3363.03 O-H broad Medium

2. 1678.47 C=O stretch Strong
3. 1425.94 CH2 bend Medium
4. 1291.16 C=C aromatic Medium-weak
5. 1183.05 =C-H vinyl Medium
6. 858.49 Para- Out-of-plane
substituted
DISCUSSION

The purpose of this experiment is to synthesis 4-vinylbenzoic acid by using an

ylide that was created to generate a Wittig reaction to form the alkene product. The
advantage of alkene synthesis by the Wittig reaction is that the location of the double
bond is absolutely fixed, whereas the mixtures often produced by alcohol
dehydration. In this experiment, three essential parts to synthesis 4-vinylbenzoic
acid. The first part to form 4-bromomethylbenzoic acid by radical substitution. The
product found was then utilized in next part of the lab to form phosphonium salt to
generate the product via Wittig reaction. Third part, the salt used, and the product
formed was 4-carboxybezyltriphenylphosphonium bromide to form 4-vinylbenzoic
acid as the final product. By performing Wittig reaction, major reagent should be
prepared in order to complete the reaction mechanism. Phosphonium salt is one of
the intermediate reactions to ensure the Wittig reaction can be achieved. In this
experiment, 4-bromomethylbenzoic acid and triphenylphosphine is used as the
reaction mechanism to produce the salt yield. Cloudy solution is formed when both of
the materials is added within acetone on it. The mixture is then heated by reflux to
dissolve all the solid formed of the materials.

Then, the mixture was heated for 45 minutes and after the time, the colour of
the solution turrns from cloudy to bright orange and the smelly gas was present. The
step was proceeded to suction the mixture in order to filter the solid and the
unwanted solution is removed which is by product. Phosphonium salt is suspended
in a solvent which used is diethyl ether. In addition, diethyl ether has limited solubility
in water, non-polar solvent and has lower density than the water to form the Wittig
reagent. As a result, the mass of filtered solid yield is about 7.1888 g. Therefore, the
percentage (%) of the product was calculate and its resulted is 75.35 %. This
evidence can be concluding where the product of the experiment is mostly pure due
to exceed from the half of the percent. The melting point of the yield is taken where
its approach about 2070C.

According to the research, 4-carboxybenzyltriphenylphosphonium bromide

has boiling points approximately 258 0C to 2600C. Experimentally, the melting point is
different with the theoretical due to the amount of material used which 4.30 g and
5.20 g for 4-bromomethylbenzoic acid and triphenylphosphine respectively. Wittig
synthesis of 4-vinylbenzoic acid is shown below,

The method of experiment continues with 3.76 g of 4-

carboxybenzylphenylphosphonium bromide where it mixed with formaldehyde and
water as to prepare the 4-vinylbenzoic acid. It observed that the colour of solution
change from colourless to milky white when the phosphonium yield is added to the
formaldehyde. 2.5 g of sodium hydroxide that dissolved in water is mixed within the
solution that acts as bases in the reaction mechanism. The bromine will left from the
4-bromobenzoic acid and bonded to the sodium to become sodium bromide.
Therefore, radical carbon will bind with the phosphonium salt as electropositive.

Concentrated hydrochloric acid (HCl) is added when the precipitate is filtered

off and smoke start to appear and present of smell. HCl is used to protonate the
organic product, causing a salt to form which would then dissolve in the aqueous
layer. The crude product was recrystallized from ethanol-water as white plates. A
melting point determination provided evidence that the desired product was formed.
The predicted experimental melting range was 140ºC-141ºC. This range is relatively
close to the literature value of 151ºC. This melting range also speaks on the relative
purity of the compound, suggesting that it’s have a relatively pure product. The mass
of yield produce after treat by vacuum suction is 1.1133 g. Thus percentage yield of
the product obtain are 93.93 %.

The crude yield was analyzed by using IR spectroscopy and the result
obtained from the peak is tabulated. It is important to note that the IR spectra show
an increase in purity from the crude spectrum to the pure spectrum. The O-H broad
and C=O stretching with peaks at 3363.03 cm -1 and 1678.47 cm-1 respectively. It
shows that the crude has functional group of carboxylic acid. The other evidence
provided is the peaks at 1183.05 cm-1 and 1425.94 cm-1 show for vinyl group.

The result that we predicted in this experiment is where the product must
have a double bond which is an alkene and it is proven. In this experiment, the
phosphonium salt was slow to crystalize. The colour of the mixture was brightly
orange, and we need to filter it until it turns into colourless liquid. Specific filter funnel
must be used to avoid the solution become contaminant with filter paper that been
degenerate by acidify solution. The error that might occurred during the experiment
is that the filter paper use has larger pore hence the phosphonium salt can easily
pass through. The student should wear gloves and handling the concentrated acid
carefully while conducting the experiment as safety precaution.

CONCLUSION
In conclusion, the reaction did synthesize 4-vinylbenzoic acid and undergo a
Wittig reaction. The preparation of phosphonium salt was effectively due to evidence
on melting point and the reaction mechanism. 4-vinylbenzoic acid was successfully
isolated with high purity as is evidenced by the melting point determination which is
141oC. Thus, the product obtained in this experiment is 1.1133 g for 4-vinylbenzoic
acid.

QUESTIONS
1. Assign the main absorption in the IR spectrum of 4-vinylbenzoic acid.

Peak Wavenumber (cm-1) Type of bond Intensity

 1. 3363.03 O-H broad Medium
2. 1678.47 C=O stretch Strong
3. 1425.94 CH2 bend Medium
4. 1291.16 C=C Medium-weak
aromatic
5. 1183.05 =C-H vinyl Medium

2. Explain why it possible to generate the ylides with aqueous sodium hydroxide
in this experiment.
It is possible to generate the ylides with aqueous sodium hydroxide because
common ylides include a carbanion attached to a phosphonium. These kinds
of reagents are required in Wittig reaction that forms alkenes from carbonyls.
In this experiment, to form a phosphorous ylides you need to get a carbanion.
However, in substitution and elimination reactions carbons atoms more
commonly form carbocation that are usually unstable. Bonded phosphonium
cation present makes the alpha carbon acidic. Then, the presence of a strong
base such as sodium hydroxide make the molecule to be deprotonated to
form stable ylide.

3. If an aldehyde other than formaldehyde were to be used, what would be the

geometry at the double bond in the major product? Why?
The double bond at vinyl will be different which not sp 2 hybrid anymore. For
example, the other aldehyde use is methanal, the geometry could be change
also due to structure of cis- and trans- vinyl.

REFERENCES
 4-Vinylbenzoic acid. (2017). Retrieved April 16, 2020, from
https://www.chemicalbook.com/ProductChemicalPropertiesCB1227893_EN.ht
m
Andrew P. Dicks (2009) A review of aqueous organic reactions for the
undergraduate teaching laboratory, Green Chemistry Letters and Reviews, 2:1,
9-21, DOI: 10.1080/1751825090282018
Hummel, H. E., & Miller, T. A. (Eds.). (2012). Techniques in pheromone research.
Libretexts. (2019, June 5). The Wittig Reaction. Retrieved April 18, 2020, from
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Mod
ules_(Organic_Chemistry)/Aldehydes_and_Ketones/Reactivity_of_Aldehydes_
and_Ketones/The_Wittig_Reaction
Mayzatulhusnazabar. (n.d.). EXP 1 - OBJECTIVES a to prepare the phosphonium
salt as Wittig reaction reagent b to prepare 4-vinylbenzoic acid in a aqueous
medium by a Wittig. Retrieved April 18, 2020, from
https://www.coursehero.com/u/file/23690111/EXP-1/#doc/qa
Wittig Reaction. (n.d.). Retrieved April 18, 2020, from https://www.organic-
chemistry.org/namedreactions/wittig-reaction.shtm

APPENDIX
CALCULATIONS
1. Percentage yield of 4-Carboxybenzyltriphenylphosphonium bromide
Number of moles for 4-Bromomethyl benzoic acid:
= mass/molar mass
=4.3013 g/ 215.1 g/mol
= 0.02 mol

1 mol of 4-Bromomethyl benzoic acid = 1 mol of 4-

Carboxybenzyltriphenylphosphonium bromide,
therefore, mol of 4-Carboxybenzyltriphenylphosphonium bromide = 0.02 mol

Molecular weight of 4-Carboxybenzyltriphenylphosphonium bromide = 477.338 g/mol

Theoretical mass of 4-Carboxybenzyltriphenylphosphonium bromide

= mole X molecular weight
 = 0.02 mol X 477.338 g/mol
= 9.54 g

Thus, % yield = (actual mass/ theoretical mass) X 100%

= (7.1888 g/9.54 g) X 100%
= 75.35 %

2. Percentage yield of 4-Vinylbenzoic acid

Number of moles for 4-Carboxybenzyltriphenylphosphonium bromide:
= mass/molar mass
=3.7610g/ 477.338 g/mol
= 0.008 mol

1 mol of 4-Carboxybenzyltriphenylphosphonium bromide = 1 mol of 4-Vinylbenzoic

acid,
therefore, mol of 4-Vinylbenzoic acid = 0.008 mol

Molecular weight of 4-Vinylbenzoic acid 148.161 g/mol

Theoretical mass of 4-Vinylbenzoic acid
= mole X molecular weight
= 0.008 mol X 148.161 g/mol
= 1.1853 g

Thus, % yield = (actual mass/ theoretical mass) X 100%

= (1.1133g/1.1853) X 100%
= 93.93 %

PRE-LABORATORY PREPARATION