Im Ole-fin(ished) With This Reaction

The Wittig Reaction

Arvind Narayan
GSI: Luke Peterson
Section 216-133
Date: 11/26/13

Background:
The Wittig reaction utilizes a reagent called a ylide to quickly assemble smaller carbon units into
larger complex molecules by joining them with a carbon double bond[1]. The witting reaction is
the preferred alkene formation mechanism because there is no need for accommodation of
sterics, which is needed when considering double bonds made by E1 or E2 elimination
reactions[2]. The Wittig reaction utilizes either a ketone or an aldehyde to form the alkene.
Purpose:
The purpose of this lab is to form a Wittig product from one of three starting reagents: 2chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, and eliminate the unwanted
phospene oxide product.
Reaction Scheme:

Reagents Table:
Compound
2-chlorobenzaldehyde
3-chlorobenzaldehyde
4-chlorobenzaldehyde
dichloromethane
(carbethoxymethylene)
triphenylphosphorane
Procedure:

mol. wt. (g mol1

)
140.57
140.57
140.57
84.93

m.p. or b.p.
(C)
209215 (bp)
213214 (bp)
213214 (bp)
39.840 (bp)

348.37

128130 (mp)

SAFETY
corrosive
toxic
toxic
health
hazard
--

2-chlorobenzaldehyde. Dissolve 2-chlorobenzaldehyde (150 mg) in dichloromethane (8 mL) in

a stir vial. Add 1.5 mol equivalents ylide (348.38 g mol-1) and stir. Use Thin Layer
Chromatography to monitor the reaction and continue to stir the reaction vial. When the reaction
is complete, evaporate the dichloromethane solvent with air and dissolve the reaction mixture in
1:4 diethyl ether to hexanes (35 mL). The formation of a white precipitate is unwanted side
product. Transfer the solution to a clean vial and evaporate the majority of the solvent. Purify the
crude product using a microscale wet column. During the reaction, work to modify the
developing solution by increasing or decreasing the ratio of diethyl ether to hexane until the TLC
confirms the proper ratio. Rf values .74. IR peaks (film) 2956.54 cm-1 , 1712.88 cm-1, 1632 cm-1
Results and Discussion:
The actual amount of 2-chlorobenzaldehyde used was 0.1611g. The procedure uses 1.5 mol
equivalent of the ylide, thus the following calculation was made:

The actual amount of ylide used was 0.5919 g.

The reaction was continually monitored using TLC. Since the reaction only took about 1 hr to
complete, only two TLC plates were run. The first one was taken at 30 min with 80:10 hexanes
to ethyl acetate and did not show any distinct separation. Since the Rf values were slightly low
(around .5) the ratio of hexanes to ethyl acetate was changed to 90:10. The second TLC, taken at
1 hr shows more separation. The starting material has an Rf of .23 compared to the product
which has an Rf value of .74. There was however a noticeable blob on the TLC plate that showed
that all the material was starting to run together. A determination was made on which was
product and which was starting material by using DNP. The fractional collection showed which

vials contained product. The fractions that contained product were identified by a glowing dot in
UV light. The collected fractions gave a .2850 g yield of product. After evaporating the solvent
from the vial containing product, another measurement was not taken, so thefinal mass of solid
product is unknown. There for a percent yield cannot be calculated. The spots that did not appear
as bright on the TLC during the fractional collection were put on a TLC plate with the same
solution. If the spot did not run as high as normal, it could be concluded that there is unwanted
product (Ph3P=O) in the vial. An IR spectrum taken of the alkene product gives peaks at
2956.54cm-1, 1712.88cm-1, and 1635.5cm-1. This indicates the presence of C-H bonds in the
aromatic ring and on both sides of the C=C double bond the peak at 1632.5cm-1 confirms that
there is a C=C double bond in the product as a result of the Wittig reaction. It is important to
note that even in the IR of the starting material there are peaks at 1693.65 cm-1 and 1590.26 that
should not be confused with the peaks in the product.
Conclusion:
In conclusion, the IR peaks and the DNP test show that the aldehyde reacted with the ylide to
form an alkene product. The yield could be low because not all of aldehyde reacted and the
reaction was stopped too soon. Further tests that could be done to determine exactly how the
ylide added is to take an HNMR spec of the product to see if a trans or cis double bond was
formed.

Works Cited:
1. Georg Wittig, Ulrich Schllkopf (1954). "ber Triphenyl-phosphin-methylene als
olefinbildende Reagenzien I". Chemische Berichte 87 (9):
1318.doi:10.1002/cber.19540870919.
2. B. E. Maryanoff, A. B. Reitz, D. W. Graden, and H. R. Almond, Jr., "NMR Rate Study
on the Wittig Reaction of 2,2-Dimethylpropanal and Tributylbutylidene-phosphorane",
Tetrahedron Lett., 30, 13611364 (1989)