Experiment 4

SCH 213 02

Hannah Judy

3-17-2020
Abstract:

This experiment was conducted by using the Wittig reaction to synthesize trans-Stilbene

from benzaldehyde and benzyltriphenylphosphonium chloride, as shown in scheme 1. This

reaction practiced green chemistry principles by utilizing safer chemicals. The melting point

range analysis determined the purity of the product (128-130oC). The structure was determined

by analyzing the Infrared Spectroscopy (IR) and the proton nuclear magnetic resonance (1H-

NMR) data. The percent yield of the trans-Stilbene product was 77%.
Scheme 1. Synthesis of trans-Stilbene using Benzaldehyde and

Benzyltriphenylphosphonium

Introduction:

The Wittig reactions are known for being the most effective way of forming alkenes from

aldehydes or ketones. Georg Wittig, winner of the 1976 Nobel Prize in Chemistry, showed the

importance of utilizing this reaction in order to synthesize organic compounds. The reaction uses

the Wittig reagent, phosphorous ylide in order to make an alkene from aldehydes and ketones.

Since yildes have a phosphorus that is positively charged and a carbon that is negatively charged,

the opposing charges make for a neutral molecule. The neutral ylide used in this experiment is

benzyltriphenylphosphonium chloride, shown in scheme 1. The ylide carbon is able to react with

the aldehyde or ketone carbonyl by being present as a nucleophile. The highly polarized electron

distribution causes the carbon to be electron rich. An oxaphosphetane is then synthesized from

the combination of the carbonyl compound a ylide, as shown in scheme 2.

Scheme 2. General Mechanism of Wittig Reaction

Wittig reactions have numerous important applications to the world. These reactions can

be utilized in synthesizing pharmaceuticals such as Vitamin A. This reaction is also used in

synthesizing beta-carotene, which is found in carrots, sweet potatoes, and mangoes2. The Wittig
reaction is also known for following the Green Chemistry techniques. The Green Chemistry

techniques focuses on practicing ways to benefit our environment by creating more efficient way

to conduct chemistry experiments. The goals of these techniques are to develop ways to conserve

energy, reduce waste, and replace harmful chemicals in order to protect the planet and its living

organisms. By replacing organic solvents such as tetrahydrofuran, diethyl ether, and

dichloromethane with water, the Wittig reaction is following the principles of Green Chemistry.

In this experiment, a Wittig reaction was conducted by synthesizing and examining trans-

Stilbene.

Results and Discussion:

The goal of this experiment was to conduct the synthesis of trans-Stilbene by reacting a

benzaldehyde with benzyltriphenylphosphonium chloride. IR and 1H-NMR were then used to

analyze the product and validate the known structure, which was determined to be trans-Stilbene.
Figure 1. IR of trans-Stilbene

Table 1. IR Peaks and Functional Groups of trans-Stilbene

Peaks Functional Groups

3018.28 cm-1 C-H Stretch, aromatics
1596.63 cm-1 C-C Stretch (in-ring), aromatics
1494.00 cm-1 C-C Stretch (in-ring), aromatics
1450.46 cm-1 C-C Stretch (in-ring), aromatics
1365.60 cm-1 C-H rock alkanes

The structure of trans-Stilbene was determined by analyzing the IR peaks. The peaks,

depicted in figure 1, were the used find the corresponding functional groups. The data that

resulted, as shown in table 1, included a C-H Stretch, aromatics at 3018.28 cm-1, a C-C Stretch

(in-ring), aromatics at 1596.63 cm-1, a C-C Stretch (in-ring), aromatics at 1494.00 cm-1, a C-C

Stretch (in-ring), aromatics at 1450.46 cm-1, and a C-H rock, alkanes at 1365.60 cm-1. The data

was then analyzed to piece together the structure of trans- Stilbene structure. The C-H Stretch,

aromatics at 3018.28 cm-1 was used to determine there was an aromatic ring in the structure,
symbolized as A in figure 3. The C-C Stretch (in-ring), aromatics at 1596.63 cm-1, 1494.00 cm-1,

1450.46 cm-1, and 1365.60 cm-1 were used to determine the structure contained an aromatic ring,

symbolized as A in figure 3. The C-H rock, alkanes at 1365.60 cm-1 was used to determine there

was an alkane present in the structure, symbolized as B, in figure 3. This analysis of the IR

enabled the known structure of the product to be verified.

Figure 2. 1HNMR of trans-Stilbene

Table 2. 1HNMR Analysis of trans-Stilbene

Chemical Shift Integration Splitting Pattern

(ppm)
 A 7.25-7.60 4.74 Multiplet
B 7.00-7.25 1.00 Doublet

The 1H-NMR analysis depicted in figure 2, was used to verify the known structure of

Stilbene. The integration, chemical shift, and splitting pattern of the labeled peaks, A and B

presented in figure 2, were used to determine the structure. The resulting data shown in table 2,

included a chemical shift of 7.25-7.60 ppm, integration of 4.74, and a multiplet splitting pattern

for A, and a chemical shift of 7.00-7.25 ppm, integration of 1.00, and a doublet splitting pattern

for B. The aromatic ring that was present in the structure was due to the chemical shift of 7.25-

7.60 ppm for A. The doublet splitting pattern symbolized by B, indicated that there was 1

hydrogen that would be attached to the carbon. In order for B to exist as a carbon attached to 1

hydrogen, it was determined to be the alkene carbons attached to two aromatic rings symbolized

as A. Thus, the known structure was verified as trans-Stilbene.

Figure 3. 1HNMR of trans-Stilbene Labeled Analysis

Table 3. Melting Point Range of trans-Stilbene

Initial Temperature C Final Temperature C

 Stilbene 128 130

The melting point range of the Stilbene was obtained in order to determine the level of

purity the product obtained. The melting point range of the Stilbene product was determined to

be 128-130C. The known melting point range that was expected of Stilbene is 122-125C,

which was near the resulting experimental range3. Based on the experimental 2-degree melting

point range, the product was determined to be relatively pure.

This experiment practiced the green chemistry principles by utilizing safer chemicals that

have less harm on the environment, such as water. The percent yield obtained in this experiment

by synthesizing trans-Stilbene from reacting a benzaldehyde with benzyltriphenylphosphonium

chloride, was determined to be 77%. This percent yield could have been a result from possible

error throughout this experiment. For future experiments, in order to obtain a higher percent

yield, limiting to amount of error while performing the experiment would be beneficial. By

practicing better efficiency while conducting the experiment, such as maintaining precise

measurements, would result in less error. Sources of error could have included, not allowing the

solution to stir for the full duration of time needed due to a stir bar malfunction. Another factor

that could have resulted in the percent yield could be that the product was not basic enough

before adding the boiling ethanol. Therefore, affecting the overall reaction and percent yield.

Calculations:

By using the reagent’s molecular weight and density, the calculations were completed in

order to determine the amounts used in mmol and grams. The theoretical yield and percent yield

were then found after obtaining the trans-Stilbene product.

 Benzaldehyde:

1g 1 mol
mmol of Benzaldehyde=amount ∈mg x x
1000 mg MW

1g 1 mol
¿ 500 mg x x
1000 mg 106.1 g

¿ 4.71 mmol

Benzyltriphenylphosphonium:

1 mol MW
grams of Benzyltriphenylphosphonium=amount ∈mmol x x
1000 mmol 1 mol

1 mol 388.9 g
¿ 5.18 mmol x x
1000 mmol 1mol

¿ 2.01 g

NaOH:

Density 1 mol
mmol of NaOH=amount ∈mL x x x 1000
1 m ol MW

1.515 g 1 mol
¿ 5.00 mL x x x 1000
1 m ol 39.997 g

¿ 189 mmol

Theoretical yield:

1 mol
Theorctical yeild of Stilbene=mmol of limiting reagent x x MW
1000 mmol

1 mol g
¿ 4.71 mmol x x 180 ¿ 0.18 g
1000 mmol mol

Percent yield:
 actual yield
Percent yield of Stilbene= x 100 %
theoretical yeild

0.14 g
Percent yeild of Stilbene= x 100 %¿ 77 %
0.18 g

Experimental:

Benzaldehyde (0.500 g, 4.71 mmol) and benzyltriphenylphosphonium chloride

(2.01 g, 5.18 mmol) were obtained in a 25-mL Erlenmeyer flask with a magnetic stir bar. 10M

NaOH (5 mL) was then added to the reaction flask, which was then placed on a stir plate and

stirred for 30 minutes. Once the solution was finished stirring, the resulting clumpy, cream

colored product was suction filtered. The crude solid product was washed with water until it was

no longer basic and transferred to a 25-mL Erlenmeyer flask. A minimum amount of boiling

ethanol was added until the product was completely dissolved. The solution was cooled to room

temperature and then placed in an ice bath for 30 minutes. The product was vacuum filtered and

the crystalline product then weighed (0.14 g, 0.77 mmol, 77.1%): IR (ATR) 3018.28, 1596.63,

1494.00, 1450.46, 1365.60 cm-1, 1HNMR (60MHz, CDCL3) 7.25- 7.60 (m, 5H), 7.00-7.25 (s,

1H).
References:

1. Morsch, L. A., Deak, L., Tiburzi, D., Schuster, H., & Meyer, B. (2014). Green Aqueous

Wittig Reaction: Teaching Green Chemistry in Organic Teaching Laboratories. Journal

of Chemical Education, 91(4), 611–614. doi: 10.1021/ed400408k (accessed March 24,

2020)

2. Pommer, H., & Thieme, P. C. (n.d.). Industrial applications of the wittig reaction. Wittig

Chemistry Topics in Current Chemistry, 165–188. doi: 10.1007/bfb0018058 (accessed

March 24, 2020)

3. Trans-Stilbene, National Center for Biotechnology Information. PubChem Compound

Database. U.S. National Library of Medicine.

https://pubchem.ncbi.nlm.nih.gov/compound/trans-Stilbene (accessed March 24, 2020)