Synthesis of Trans-9-(2-phenylethyenyl) anthracene via Wittig Reaction

Mitchell Cardow

Chem 213W, Spring 2018

Introduction

Ylide wittig reactions are most commonly used to produce unsaturated alkene molecules from

aldehydes or reactive ketone molecules with the ylide active reagent of phosphonium chloride.4 The

Wittig reaction always make an alkene in the same location of the carbon to oxygen double bond in the

aldehyde or ketone group on the starting material.5 The carbon carbon bond made in wittig reactions are

important because it allows for the making of larger molecules from two smaller molecules being stitched

together where the carbon oxygen bond was on the aldehyde or ketone functional group. 4 The reaction is

always started by a covalent bond which comes from the basic sodium hydroxide and a phosphonium

chloride hyrdogen which causes a nucleophilic attack on the ketone or aldehyde group on the starting

material.

The reaction is useful to create alkene products, this product, trans-9-(2-phenylethenyl) anthracene

is important because it emits a flourecent blue light in a chemical reaction that produces little to no heat.1

This process is called Chemiluminescence which is when the excited state of the molecule cools back

down to its grown state and this is what is inside glow sticks and allows them to glow. 5

Chemiluminescence is caused when a fluorescence molecule and small intermediate molecule under goes

an electron transfer to the flourescer through a charge transfer complex intermediate which then goes back

to its ground state which emites light and also produces carbon dioxide gas as a byproduct in this

experiment the flourescer was trans-9-(2-phenylethenyl) anthracene.5

Scheme 1. Synthesis of trans-9-(2-phenylethenyl) anthracene (3) from 9-anthracene-carboxyaldehyde (1)

and benzyltriphenyl-phosphonium chloride (2)

The mechanism for the formation of trans-9-(2-phenylethenyl) (3) is intiated when the hydroxide

ion deprotonates one of the sp3 hybridized hydrogen on the starting material 2, this then acts as a

nucleophile and attacks the aldehyde group on molecule 1 which kicks the electrons on to the oxygen

making it negatively charged. The positively charged phosphorus and negative charged oxygen form a

bond. This transition state then leads to the formation of oxyphosphenate 4 when the oxygen claims

electrons from the tetrahedral carbon which causes the electrons bonded to the phoshorus to collapse

back on to the carbon carbon bond forming the alkene product 3.3

Scheme 2. Wittig mechanism to form trans-9-(2-phenylethyenyl) anthracene

Purpose

The purpose of this experiment was to synthesize trans-9-(2-phenylethyenyl) anthracene via a

Ylide Wittig reaction. The reaction was monitored using thin layer chromatography (TLC) and the solid

product was isolated and purified with column chromatography which was monitored by TLC as well.

Column chromatography is used in organic chemistry to separate and purify solid or liquid substances

from large or small-scale experiments using polarity. The product of the Wittig reaction was then

characterized

Results and Discussion

The reaction between 9-anthracene and the ylide molecule, benzyltriphenylphosphonium chloride

was refluxed and monitored with TLC and the crude product was then purified and isolated with column

chromatography. In this experiment the trans product 3 was synthesized via ylide wittig reaction between

1 containing and aldehyde group and 2 a phosphonium chloride molecule, this was done under basic

conditions in the presence of sodium hydroxide. The ylide molecule used has an aromatic ring functional

group which allows the molecule to be resonance stabilized and stabilized ylide reagents result in trans

alkene products instead of a destabilized ylide molecule which producess a cis alkene product.1 TLC was

used to monitor the reaction since both the limiting reagent 1 and the product 3 were both UV active and

non-volatile. Product 3 was less polar so it traveled a greater distance and spot had an Rf value of .54

where the polar starting material 1 only had an Rf value of .30 and once the that spot had disappeared the

reaction was complete since no starting material was left in the reaction mixture.

The product 3 of this reaction was isolated and purified using column chromatography because it

is the most useful purification technique in organic synthesis, it uses the same method as TLC to separate

molecules in a mixture based on the polarities of each molecule. The column chromatography was

successful in obtaining a pure product 3 since it was monitored with TLC and there were no over lapping

spots in the fractions. Only one product was present in fractions 1-13 which showed a bright blue

fluorescent spot and there were no other spots that eluted out from the column.
 The purification afforded a shiny yellow powder with a yield of 76% which was above the

expected yield of 60%.1 The percent recovery from column chromatography of pure 3 product from the

crude product of the reaction was 89% recovery, this suggests that trace amounts of impurities were

present in the crude product. Although the yield is high the melting point of trans-9-(2-phenylethyenyl)

anthracene had a range of 131.5-133.4oC which was accurate compared to the expected melting point

which was 132 oC which suggests a pure product because if there was any starting material still present

the melting point range would be depressed since the melting point of the starting material was 104oC.8

The 400 MHz 1HNMR graph (Figure 2) the TMS peak is at 0 ppm and both the acetone peak at

2.18 ppm and water peak at 1.54 ppm are still present, and the peak at 7.24 ppm represents the solvent

CDCL3. The most up field singlet peak at 8.40 ppm with an integration value of 1.04 represents the lone

proton in the middle of the three aromatic rings because the electron density is the most withdrawn from

the aromaticity making it desheilded causing it to be the most down field. The doublet peak at 8.40 ppm

with an integration value of 1.88 represents the two protons on the three aromatic rings closest to the

alkene bond. The doublet peak at 8.02 ppm with an integration value of 1.90 ppm represents the two

symmetric protons on the single aromatic ring furthest from the alkene bond which would be more

downfield then the other two symmetric protons because they are further from electron density. These

doublet peaks show that the trans product was formed since the doublets are far away from each other, if

the cis product was formed their locations would be closer together do to the protons having a more similar

environment the trans product makes the J values higher which shows the two protons separated by three

bonds are further away which would have a lower J value if it was cis and the protons were closer together.

The doublet peak with a range of 7.94-7.89 ppm and an integration value of 1.04 represents the proton on

the alkene closest to the single aromatic ring. The other proton on the alkene closest to the three aromatic

rings is represented by the doublet peak with a range of 6.98-6.93 ppm and an integration value of 0.99.

The double peak at 7.68 ppm with an integration value of 2.01 ppm represents the two protons on the

single aromatic ring closest to the alkene and they are more up field than the other two protons on the ring
because they are closer to electron density making them more shielded. The largest peak is a multiplet at

7.46 ppm with an integration value of 5.79, this represents the 6 symmetrical protons on outside edges of

the three aromatic rings. The triplet peak at 7.36 ppm with an integration value of 1.02 represents the

proton furthest from the alkene on top of the single aromatic ring because it is a distinct triplet proton on

an aromatic ring. If starting material 1 was still present, there would be a singlet peak in the range of 9-10

ppm representing the single proton on the aldehyde functional group on 1. The 1HNMR analyses of trans-

9-(2-phenylethyenyl) anthracene shows a highly pure product other than the acetone that could have been

present in NMR tube and water that was not fully evaporated from the product.

The IR analysis (Figure 3) also provided evidence that a pure product was obtained since there is

a peak at 3055 cm-1 which represents the carbon hydrogen bond on the aromatic rings. The two signals at

3025 cm-1 and 3010 cm-1 both represent the carbon hydrogen bond on the alkene section of the molecule

and the peak at 2926 cm-1 represents the aliphatic carbon hydrogens bonds that are present in all IR spectra.

The signal at 1945 cm-1 represents the carbon double bonded to carbon on the aromatic rings of the

molecule. The last peak that can be identified on the IR spectra is at 1621 cm-1 and this represents the

alkene carbon double bond to carbon section in the molecule and this provides sufficient evidence that a

trans product was formed because if there was a peak at 1675 cm-1 or 1658 cm-1 that peak would represent

a cis alkene which would show a product of cis-9-(2-phenylethyenyl) anthracene. The two products that

could be possible during this reaction would be either the cis- or trans-9-(2-phenylethyenyl) anthracene

product seen in Scheme 3 but trans is highly favorable during the mechanism because of the steric

hindrance with the phosphonium chloride molecule during the unstable transition state.5 If there was any

starting material still present there would be a key peak at 2720 cm-1 and this would have represented the

aldehyde functional group on 1 which shows that the reaction went to completion and the starting material

was all consumed. Therefore, the IR analysis proves that a pure trans-9-(2-phenylethyenyl) anthracene

was obtained.
Scheme 3. Isomers of 9-(2-phenylethyeyl) anthracene

In conclusion, the Wittig reaction successfully produced a highly pure desired product 3 with a

yield of 76%, and the IR and 60 MHz and 400 MHz 1HNMR show that the product had a high purity

which was suggested by the narrow range of the melting point, 131.5-133.4oC. The IR only had peaks that

represented carbon carbon and carbon hydrogen bond, and the NMR data showed the correct number of

protons present in 3 as well as no peak that would have represented the aldehyde on starting material 1,

showing that a pure product was obtained. Error in this experiment could have occurred from the escape

of vapors during reflux which could lower the yield of product. So, in future experiments could have used

a better ylide molecule with a different halogen molecule which would be more reactive causing a better

nucleophilic attack on the carbonyl to improve yield of the product. Since the product only had trace

amounts of impurities based off of the percent recovery being 89% a more suitable method of purification

could have been utilized like recrystallization to purify the solid product.

Experimental

Trans-9-(2-phenylethyenyl) anthracene. 50% Sodium Hydroxide (1 mL) was added dropwise

to a mixture of 9-anthracenecaboxaldehyde (.206g, 1 mmol), benzyltriphenylphosphonium chloride (.777,

2 mmol), and Dimethylformamide (10 mL) which was stirred and refluxed (50oC) until completion. The

reaction was monitored using TLC (40% ethyl acetate, 60% hexanes). Upon completion the 1-propanol

and water (50% 1-propanol, 50% water, 10 mL) was added to the reaction mixture and cooled. The product

was isolated and purified by column chromatography on silica gel (98% hexanes, 2% dichloromethane to

95% hexanes, 5% dichloromethane), which afforded Trans-9-(2-phenylethyenyl) anthracene as a shiny

solid yellow powder (214 mg, 76%). MP 131.5-133.4oC. 1HNMR (400 MHz, CDCL3)  (ppm) 8.40

(s,1H), 8.35 (d, 2H), 8.02 (d,2H), 7.94-7.89 (d, 1H), 7.68 (d, 2H), 7.46 (m, 6H), 7.36 (t, 1H), 6.98-6.93

(d,1H); IR max (cm-1) 3055, 3025, 3010, 2926, 1945, 1621.

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