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Josh Lomonaco

Sec: 104
3/17/10

The Wittig Reaction of Ester Stabilizing Ylides


Purpose:
A Wittig reaction was used to synthesize cis- and trans-3-(4methylphenyl)-2-propenoic acid ethyl ester from ylide and p-tolualdehyde in
methanol solvent. The ylide was synthesized from phosphonium salt,
triphenylphosphonium bromide, and aqueous sodium hydroxide. The
techniques involved included reflux, rotoevaporation, liquid-liquid extraction,
and NMR preparation. The product was identified by H NMR.

Chemical Equation:

Procedure:
A reflux was setup in a 100 mL round bottom flask with, a reflux
condenser, and a magnetic stir bar. In this set up 2.527g (0.00725 mol) of

triphenylphosphorane, and 25 mL (0.617 mol) methanol were combined and


this reaction was stirred. In a separate graduated cylinder 0.638 g (0.00531
mol) was measured out and mixed with 2 mL (0.0494 mol) of methanol which
was then added to the round bottom flask and this reaction was heated at
reflux, while stirring. The reaction was then refluxed for fifteen minutes. After
that the reaction was stopped and poured into a separatory funnel with 25
mL (1.388 mol) of water and the resulting solution was mixed. Then the
aqueous layer was extracted from the solution using two 15 mL (0.114 mol)
of hexane. That was then added to an Erlenmeyer flask and dried with
anhydrous sodium sulfate. The hexane solution was decanted into a
preweighed round bottom flask, rotoevaporated and reweighed. After that 5
drops of CDCl3 was added to the round bottom flask and one drop of the
resulting solution was placed in an NMR tube along with 0.75 mL (0.00935
mol) CDCl3 and capped. H NMR (CDCl3, ppm): cis- 7.396, 7.119, 6.871,
5.865, 4.156, 2.329, 1.236; trans- 7.640, 7.396, 7.160, 6.369, 4.233, 2.342,
1.309; Percent yield: 83.1%

Results:
Calculation of limiting reagent
Triphenylphosphorane- 2.527 g / 348.38 g/mol = 0.007254 mol
p-tolualdehyde- 0.638 g / 120.15 g/mol = 0.00531 mol
Theoretical yield
0.638 g / 120.15 g/mol = 0.00531 mol x 190.24 g/mol = 1.01 g

Percent yield
0.839 g / 1.01 g x 100 = 83.1%

Conclusion:
cis-3-(4-methylphenyl)-2-propenoic acid ethyl ester
Hydrogen

Zgem

Zcis

Ztrans

Chemical Shift
()

HA

1.35

0.00

0.56

7.16

HB

0.84

0.00

-0.10

5.99

trans-3-(4-methylphenyl)-2-propenoic acid ethyl ester


Hydrogen

Zgem

Zcis

Ztrans

Chemical Shift
()

HA

1.35

0.00

0.56

7.75

HB

0.84

0.00

-0.10

6.46

cis-3-(4-methylphenyl)-2-propenoic acid ethyl ester

Hydroge

Chemical Shift

Type of

Splitting

Integratio

()

Hydrogen

Pattern

2.329

Saturated Methyl

7.119

Aromatic

7.396

Aromatic

6.871

Vinylic

5.865

Vinylic

4.156

Alkoxy

1.236

Saturated Methyl

trans-3-(4-methylphenyl)-2-propenoic acid ethyl ester

Hydrogen

Chemical

Type of

Splitting

Integratio

Shift ()

Hydrogen

Pattern

2.342

Saturated

Methyl
2

7.160

Aromatic

7.396

Aromatic

7.640

Vinylic

6.369

Vinylic

4.233

Alkoxy

1.309

Saturated

Methyl

The H NMR spectrum for the cis- and trans-3-(4-methylphenyl)-2propenoic acid ethyl ester was consistent with its structures. There is
evidence that shows there were two products because the H NMR has
multiple sets of peaks that are very close. The differences in the two sets of
peaks can be calculated using the equations for splitting pattern and
chemical shift. These calculations show that there is a cis- and trans- product
and proves that the cis- and trans-3-(4-methylphenyl)-2-propenoic acid ethyl
ester product was successfully created. There are a few peaks that dont
correlate because of contamination from hexane and triphenylphosphorane.
Hexane has normal carbon to hydrogen bonds so it appeared upfield, and
triphenylphosphorane had phenyl rings so it appeared downfield. There was a
ratio based on integration of cis and trans products which was calculated to
be 1:3.7, which means the trans product was the major product.