Lab 3 Amar PDF

Stereoisomeric Study of Wittig Product
Name: Ammar Hassan Jiskani

Contribution from Department of Chemistry, Syed Baber Ali School of Science and Engineering,
Opposite U Block, 54792, DHA, Lahore, Pakistan.
Received February 28, 2022; Email: 21130005@lums.edu.pk
Abstract: The Wittig reaction is a technique for synthesis of alkenes by reacting ylide (a neutral
specie with a carbanion connected hetero atom bearing a positive charge) with ketones or
aldehydes. Cis and trans stilbenes (stereoisomers) were isolated in ethanol and ether throughout
the experiment. The yield of cis was (24%) and trans (46.54%). Both products were analyzed
using FTIR and NMR methods. The acquired results were close to the published values, indicating
the generation of stereoisomers.
INTRODUCTION materials, liquid crystals, optical brighteners,

gels, medicinal agents, DNA binding agents,
The Wittig reaction is one of the most well-
sensors, and other applications. Such
known reactions in organic chemistry, so
compounds' characteristics are mostly
much so that its discoverer, Georg Wittig,
influenced by the nature of substitution and
who published the reaction in 1954, was
the length of conjugation.3 Stilbenes are
awarded the Nobel Prize in Chemistry in
employed in dyes, paper and textile
1979. It is one of the simplest and least
whiteners, dye-lasers, organic solid lasers,
expensive methods of producing alkenes
radiation detectors, and other applications.
from ketones and aldehydes.1 The Wittig
They are also utilized as anti-cancer drugs.
reaction is excellent because various cheap
Regio- and stereo selectivity are critical
carbonyl compounds, phosphonium salts,
factors to consider while developing a
and phosphonium ylides are available, and it
chemical route, particularly for natural
produces high yields in a reasonable amount
compounds.
of time. Because of its unique mechanism,
stereoselectivity, and potential for green
reactions, the Wittig reaction has been used
in numerous studies.2 Because of their uses in
material chemistry, conjugated molecules are Scheme 1. General Wittig Reaction
an important class of chemicals. Because of
The reactive species in this reaction, as well
structural and orbital configurations,
as in similar methods such as the Horner-
molecules with p-conjugation can allow
Wadsworth-Emmons reaction, is a one-of-a-
electron mobility through continual
kind intermediate known as the ylide. An
delocalization. Most of these compounds are
ylide is an overall neutral species with nearby
used as photovoltaic materials in solar cells,
atoms with opposing charges, which is
organic light emitting diodes, conducting
Ammar Hassan Jiskani, Syed Baber Ali School of Science and Engineering
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generally enabled by one of those atoms
having an extended valence shell.
Phosphorus and Sulphur, for example,
frequently produce ylides due to the presence
of d orbitals, which may stabilize nearby
negative charges. In terms of reactivity, the
ylide is nucleophilic because it works like a
carbanion. In general, a phosphorous ylide
combines with an aldehyde or ketone to form
an alkene.1
Scheme 3. Wittig Reaction (General Mechanism)
Scheme 2. Formation of Phosphorus Ylide
The Wittig reaction process is depicted

below. The phosphorus ylide is formed via
deprotonation of a phosphonium salt.
Because the ylide is nucleophilic at carbon, it
will add to the carbonyl's * orbital to form a
betaine intermediate in the presence of an
aldehyde. Because phosphorus is oxophilic,
the betaine undergoes cyclization, yielding
cyclo oxa-phosphetane, a four-membered
ring containing both oxygen and phosphorus.
Alternatively, a concerted [2+2]
cycloaddition between the ylide and the
carbonyl group of the ketone or aldehyde
results in the cyclo oxa-phosphatane. This
latter route is thought to be active in most
carbonyl olefination reactions nowadays. The Scheme 4. Specific Reaction Mechanism
alkene and the byproduct triphenylphosphine
oxide are formed because of cyclo reversion. The first significant difference between prior
Because the nucleophilic addition of the ylide versions of the Wittig reaction was the
to the carbonyl can be reversible depending substitution of water for the reaction solvent
on the specific composition of the ylide, the (diethyl ether,2 dichloromethane,3,4 or
reaction can be thermodynamically DMF). By employing water instead of
controlled, and the trans-isomer is the organic solvents, this clearly shows the
predominate product. In other circumstances, principle of "using safer solvents." Another
the reaction conditions may produce the Z- advantage of performing the reaction in water
isomer, which is the kinetic product.1 is that there is no need to remove the product
from the solution when the reaction is suggests that the Z isomer will be the
complete since the product alkenes are not preferable final alkene product.5
water-soluble. This also cuts down on solvent
The Z isomer is the kinetic product, not the
waste. The second area of improvement was
thermodynamic product. The key to
to replace propanol as the recrystallization
obtaining a high yield of the kinetic Z isomer
solvent with ethanol. The use of ethanol
is to exclude anything that could equilibrate
rather than propanol for recrystallization
the betaine and thus the following
addresses the "use of renewable feedstocks"
oxaphosphetane ring. Low temperature
criterion, as ethanol is generally generated
reaction aids in stabilization of charged
from grains rather than petroleum products,
intermediates, as does limiting extraneous
which is the most common source of
salts.5
propanol. Recrystallization considerably
lowers the volume of solvent waste generated
by conventional organic processes that
involve liquid-liquid extraction or column
chromatography. The reaction also
demonstrates "design for energy efficiency"
because it is carried out at ambient
temperature (without heating). The entire Scheme 5. Two Possible Products (Cis and Trans Stilbene)
process tackles the notion that it is preferable
to "avoid waste" rather than clean it up after
a reaction, as well as the fact that "inherently
safer chemistry" exists.4 The amazing feature
is that the reaction is Z selective for simple
molecules. The reaction is governed by
kinetics. The initial step in the reaction
between the ylide and the carbonyl is the
creation of a betaine intermediate. The
carbonyl approaches the ylide carbon at a
right angle to the C-P bond. This is the best
steric approach, and it is also compatible with
a full molecular orbital study of the problem.
Figure 1. Structure of Ylide & PPh3
When the betaine is created, the oxygen atom
may swing around and make a new covalent One drawback of the Wittig reaction is that
link with the phosphorous atom. phosphorous ylides with stabilizing groups
Phosphorous prefers to make five bonds and close to the negatively charged carbon are not
exceptionally strong bonds with oxygen. This reactive enough to perform the required
new bond produces a four-membered ring reaction with a carbonyl.5 The stabilizing
complex known as oxa phosphetane.5 groups can spread out the negative charge via
resonance, reducing the nucleophilicity of the
The stereochemistry of the substituents is cis
carbon atom. The solution is to create the
when the oxaphosphatane forms. This is
yilide with a more reactive phosphorous
because of the carbonyl's choice of route
molecule. The most common approach is the
when the betaine was produced. This
Horner-Wadsworth-Emmons (HWE) was dissolved in 30 mL of ethanol. A thick,
reaction, which begins with triethyl cloudy residue resulted. This solution was
phosphate to create a phosphonate ester.5 chilled for 15 minutes in an ice bath.
Because of the flexibility to adjust several Filtration was used to capture the trans
reaction variables and examine a range of product. The filtrate was evaporated, and
projected trends, such as alkene 40mL of low boiling petroleum ether was
stereoselectivity, ylide reactivity, and base added to precipitate triphenyl phosphine
strength, the Wittig reaction seemed suitable oxide. On a rotary evaporator, the filtrate was
for a collaborative guided-inquiry evaporated. The liquid residue (cis stilbene)
2
experiment. that formed was collected. The yield was
computed, and the product was analyzed.
EXPERIMENTAL SECTION
TLC Analysis.
Chemicals and materials. Benzaldehyde,
dichloromethane, petroleum ether, ethanol
and benzyltriphosphonium chloride.
Glassware and Equipment. Round bottom
flask (100mL), reflux condenser, hot plate,
stir bar, beakers, watch glass, ice bath,
melting point capillaries, oil bath, extension
clamp and fasteners, grease, and Buchner
funnel etc.
Procedure. Figure 2. TLC of the Product
In a 100 mL two neck round bottom flask, 1 The TLC analysis after regular intervals of 15
mL of benzaldehyde, 3.875 g of min shows that the product has been
benzyltriphosphonium chloride, and 10Ml of synthesized.
methylene chloride were added. It was then
equipped with a condenser and an additional
funnel. To keep the temperature stable, a RESULT AND DISCUSSION
thermometer was placed in an oil bath. A
Table 1. Physical data of reactants
magnet bar was used to vigorously stir the
mixture. Through an addition funnel, 10 mL Reagent Benz- Benzyltri DCM
aldehyde phosphonium
of 50% (by weight) aq. NaOH was added. chloride
With vigorous stirring, the temperature was
kept at 50°C for 30 minutes. After 5 minutes, Mol. C7H6O C25H22ClP CH2Cl2
the mixture had become turbid and yellow. Formula
After separating the organic phase, it was Mol. 106.12 388.8 84.93
Mass
rinsed with 30mL of water. The pH was then
(g/mol)
adjusted with HCl until it was neutral. The Melting -26 337 -96.7
organic phase was dried for 15- 20 minutes point
(◦C)
with anhydrous sodium sulphate before being
Density 1.04 - 1.33
filtered and dried. After that, the dry product
(g/cm3)
Percentage yield of Product. Spectral Analysis.
Table 2. Percentage yield calculations
Table 3. Literature IR values of the cis and trans
stilbene
Moles of Benzaldehydeused 0.00906 𝑚𝑜𝑙 Type of Cis stilbene Trans-
(limiting reactant) vibration stilbene
Moles of product expected
0.00906 𝑚𝑜𝑙
Aromatic C-H 3069cm-1 3079cm-1
stretching
0.00906 𝑚𝑜𝑙
Mass of product expected
× 180.25g/𝑚𝑜𝑙 Aromatic C=C 1600- 1679cm-1
= 1.633g doublebond 1575cm-1
Mass of trans product
obtained 0.76 g The peak of the alkene C=C bond is generally
Mass of cis product 0.4 g stronger for the cis isomer, but it appears at a
obtained
0.76 g lower wavenumber than the trans isomer.
Percentage yield (trans)
× 100
𝐴𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 1.633 g
× 100 = 46.54 %
%
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙d
0.4 g
Percentage yield (cis) × 100
1.633 g
= 24.49 %
Melting Point.
The trans-stilbene had a melting
temperature of 123 degrees Celsius and was
decomposed upon melting. The melting
Figure 4. IR spectrum of trans stilbene from literature
point of trans-stilbene described in the
literature was 122-125 degrees Celsius. The
variation in value might be due to an error
in observation.
80
Transmittance [%]
60 50
40 70
3096.98
3057.12
3019.33
1493.79
1450.81
1071.13
960.52
761.35
689.23
539.58
523.38
4000 3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1
Figure 5. Obtained IR spectrum of trans product.

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The aromatic C-H stretching was observed at
3019cm-1 in the IR spectra of trans-stilbene,
while the other main peak was observed at
Figure 3.Trans Product 1493cm-1. The OOP region at 960.52cm-1
indicates the presence of trans-stilbene.
These IR peaks match the ranges described in
the literature. Because the molecule is The peak(singlet) at 6.95ppm mainly indicate
symmetric, the absence of an alkene C=C these protons belongs to C=C, and it is
double bond peak is due to a net zero dipole evident from the integration factor that these
moment. It signifies the purity of trans- signals correspond to the 2H+ as they are in
stilbene. the same environment. Another (complex)
peak shows signals at 7.72ppm, which are
100
mainly the protons of aromatic rings, (ortho

position) that’s why they are de-shielded, the
80
Transmittance [%]
protons of benzene ring are not equivalent as

60
they are directly attached to the C=C, so due

40
to resonance effect they have different peaks.

The peak at 7.45ppm (complex) indicate the
20
presence of distinct aromatic protons at meta

position. Another main peak (complex) at
3078.33
3023.71
2957.29
2870.19
1599.62
1575.43
1493.57
1444.09
1118.52
923.62
778.66
721.05
692.27
539.33
4000 3500 3000 2500 2000
Wavenumber cm-1
1500 1000 500
7.30ppm indicate the presence of aromatic
Figure 6. IR spectrum of cis stilbene
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proton at the meta position of the benzene
ring, and its value is less than the
The IR spectrum of cis stilbene shows very Page 1/1
crossponding protons, the reason is the

distinct peak at 3023.71cm-1which indicate
resonance effect lowers with the lengthening
the presence of aromatic C-H stretch. The
of the bond.
peaks 1575.43 and 1599.62 indicate the
presence of aromatic C=C ring, the OOP
region appeared at 692.27cm-1 conformed
that the product formed is cis-stilbene.
Figure 8. 1H-NMR of Cis-Stilbene
Figure 7. 1H-NMR of Trans-Stilbene
The figure 10 shows the 1H-NMR spectra of

(Z)- Cis-stilbene. The standard used for this
spectrum is TMS, whose value is 0ppm. The
peak(singlet) at 6.56ppm mainly indicate
these protons belongs to C=C, and it is
The figure 10 shows the 1H-NMR spectra of
evident from the integration factor that these
(E)- Trans-stilbene. The standard used for
signals correspond to the 2H+ as they are in
this spectrum is TMS, whose value is 0ppm.
the same environment. Another (complex) indicate the presence of 4-CH- aromatic
peak shows signals at 7.72ppm, which are carbon atoms at the meta position. The peak
mainly the protons of aromatic rings, (ortho at 127.9ppm also indicate the presence of two
position) that’s why they are de-shielded, the aromatic -CH- group, which is at para
protons of benzene ring are not equivalent as position.
they are directly attached to the C=C, so due
to resonance effect they have different peaks.
The peak at 7.45ppm (complex) indicate the
presence of distinct aromatic protons at meta
position. Another main peak (complex) at
7.30ppm indicate the presence of aromatic
proton at the meta position of the benzene
ring, and its value is less than the
crossponding protons, the reason is the
Figure 10. C13-NMR of Trans-Stilbene
resonance effect lowers with the lengthening
of the bond.
Figure 13 shows the spectrum of C-13-NMR

of product Trans-Stilbene . The spectrum
shows that the peak at 127.4ppm indicate the
Figure 9. C13-NMR of Cis-Stilbene presences of two -CH- carbons which are
directly attached with the benzene ring, and
are in conjugation with the rings, that’s why
they are deshielded. The peak at 137.5ppm
indicate the presence of two-C atoms of
aromatic ring which are substituted with the
sp2 carbon. The peak at 128.5ppm indicate
Figure 13 shows the spectrum of C-13-NMR the presence of 4-aromatic carbons at the
of product Cis-Stilbene . The spectrum shows ortho position. The peak at 128.6ppm also
that the peak at 127.4ppm indicate the indicate the presence of 4-CH- aromatic
presences of two -CH- carbons which are carbon atoms at the meta position. The peak
directly attached with the benzene ring, and at 127.9ppm also indicate the presence of two
are in conjugation with the rings, that’s why aromatic -CH- group, which is at para
they are deshielded. The peak at 137.5ppm position.
indicate the presence of two-C atoms of
aromatic ring which are substituted with the
sp2 carbon. The peak at 128.5ppm indicate
the presence of 4-aromatic carbons at the
ortho position. The peak at 128.6ppm also
CONCLUSION 1599.62cm-1, the decrease in wavenumber of
the C=C doble bond is lower than usual
The Wittig reaction is used to introduce a
aliphatic C=C bond, which appears at
double bond to a molecule, and it was applied
1650cm-1. This is due to extended
here to synthesize stilbene through the
conjugation in the molecule. In case of trans
reaction of benzaldehyde with phosphorus
IR spectrum, the peak of C=C bond not
ylide, yielding cis (24%) and trans (46.54%)
appeared because the molecule is
yields. The observed melting point was
symmetrical and the net dipole moment is
somewhat higher than the typical range. The
zero, so it is IR inactive. This is the major
product was characterised using FTIR, which
difference in IR spectrum of both products.
revealed the difference between the cis and
trans isomers (stereoisomers). Trans and cis stilbene can be distinguished
from OOP region. Trans isomers give peak in
Post Lab Question
OOP region at 960cm-1, which do not appear
• Discussion of lab report related to this for cis isomer.
experiment should comprehend that
how one can use IR, 1H-NMR, and
13C- NMR spectroscopy to 80
Transmittance [%]
70
distinguish between the two products

60
formed in this experiment.

50
There are two possible products which can be

40
obtained from Wittig reaction when

3096.98
3057.12
3019.33
1493.79
1450.81
1071.13
benzaldehyde reacts with phosphorus ylide.
960.52
761.35
689.23
539.58
523.38
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber cm-1
The two stereoisomers cis and trans stilbene
Figure 11. Obtained IR spectrum of trans product.
are possible products. C:\PROGRAM FILES\OPUS_65\MEAS\27-28-31(Trans Product).0 27-28-31(Trans Product) ATR platinum Diamond 1 Refl 17/02/2021
Page 1/1
100 80
Transmittance [%]
40 60 20
The Z-isomer (cis) is a kinetic product which

3078.33
3023.71
2957.29
2870.19
1599.62
1575.43
1493.57
1444.09
1118.52
923.62
778.66
721.05
692.27
539.33
can be obtained at lower temperature. But in 4000 3500 3000 2500 2000 1500 1000 500
this experiment, we obtained trans product Wavenumber cm-1
(thermodynamic) by heating the reaction Figure 12. IR spectrum of cis stilbene

C:\PROGRAM FILES\OPUS_65\MEAS\27-28-31(Cis Product).0 27-28-31(Cis Product) ATR platinum Diamond 1 Refl 17/02/2021
mixture, which is thermodynamic product. Page 1/1
The stereochemical isomers can also be

Then cis product was obtained later.
differentiated using 1H-NMR. The cis and
By using IR spectrum of these two products trans isomers have different coupling
can be distinguished. The intensity of alkene constants. Cis isomers have lower coupling
C=C bond peak is more for cis isomer and constant (6-15Hz) than trans isomer(11-
this peak appears in IR spectrum near 18Hz)7, so the chemical shift of both the
isomers is also different. In trans stilbene The spectrum of cis stilbene shows that color
hydrogens on C=C bond are deshielded by red showed at 7.30ppm, green at 7.45ppm
two phenyl rings. Therefore, its signal sky blue at 7.72ppm and blue at 6.56ppm.
appears downfield than cis isomer on the
The 13C-NMR spectrum also indicates
NMR spectrum. The chemical shifts of cis
different chemical shifts for cis and trans
and trans isomers are 6.56ppm and 6.95ppm,
isomers, but there is a minor
respectively. This pattern also helps in
difference; unambiguous information cannot
differentiation of both products.
be acquired only from carbon NMR. Along
with IR data, 1H-NMR data provide further
details regarding geometrical isomerism.
References.
1. Guthrie, R. D., Introduction to
Spectroscopy (Pavia, Donald;
Lampman, Gary M.; Kriz, George S.,
Jr.). ACS Publications: 1979.
Figure 12. 1H-NMR of Trans-Stilbene 2. Patel, K. N.; Kamath, B. V.; Bedekar,
A. V., Synthesis of alkyloxy stilbenes
by one-pot O-alkylation-Wittig and
O-alkylation-Wittig– Heck reaction
sequence. Tetrahedron Letters 2013,
54 (1), 80-84.
3. Morsch, L. A.; Deak, L.; Tiburzi, D.;
The 1H-NMR spectrum of trans stilbene Schuster, H.; Meyer, B., Green
show that protons showed in red color aqueous Wittig reaction: Teaching
appears at 7.30ppm, yellow at 7.43ppm, green chemistry in organic teaching
laboratories. Journal of Chemical
green at 7.72ppm and blue at 6.95ppm.
Education 2014, 91 (4), 611-614.
4. Likhtenshtein, G. I., Stilbenes
synthesis and applications. Kirk‐
Othmer Encyclopedia of Chemical
Technology 2000, 1-24.
5. A Bisceglia, J.; R Orelli, L., Recent
progress in the Horner-Wadsworth-
Emmons reaction. Current Organic
Chemistry 2015, 19 (9), 744-775.
Figure 13. 1H-NMR of Cis-Stilbene
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Stereoisomeric Study of Wittig Product

Name: Ammar Hassan Jiskani

INTRODUCTION materials, liquid crystals, optical brighteners,

Scheme 3. Wittig Reaction (General Mechanism)

Scheme 2. Formation of Phosphorus Ylide

The Wittig reaction process is depicted

4000 3500 3000 2500 2000 1500 1000 500

Figure 5. Obtained IR spectrum of trans product.

mainly the protons of aromatic rings, (ortho

protons of benzene ring are not equivalent as

they are directly attached to the C=C, so due

to resonance effect they have different peaks.

presence of distinct aromatic protons at meta

crossponding protons, the reason is the

Figure 8. 1H-NMR of Cis-Stilbene

Figure 7. 1H-NMR of Trans-Stilbene

The figure 10 shows the 1H-NMR spectra of

Figure 13 shows the spectrum of C-13-NMR

distinguish between the two products

formed in this experiment.

There are two possible products which can be

obtained from Wittig reaction when

The Z-isomer (cis) is a kinetic product which

this experiment, we obtained trans product Wavenumber cm-1

(thermodynamic) by heating the reaction Figure 12. IR spectrum of cis stilbene

mixture, which is thermodynamic product. Page 1/1

The stereochemical isomers can also be

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