S2 Exp 7 Report

Synthesis of Methyl 5-phenylpent-2,4-dienoate
Name: Alejandro Fernandez Zaitsev

Student number: S5678862
Assistants: David Grantz, Vasilis Koutsogiannopoulos
Date: 3-10-2024
Reaction Overview:
Figure 1: Overview of of the steps involved in the formation of 3,3-dimethylpent-4-enoic acid
Abstract:
A Ireland-Claisen rearrangement was performed using prenyl acetate, to form
3,3-dimethylpent-4-enoic acid, which was purified through an acid-base extraction.
The product was analyzed using 1H-NMR spectroscopy, to find that indeed
3,3-dimethylpent-4-enoic acid was the major product, but that there were
substantial impurities, making the yield inaccurate.
Introduction:
The reaction performed in this experiment is quite specific, a Ireland-Claisen
rearrangement, which needs two C=C bonds in an arrangement where it can form a
stable ring intermediate with both double bonds next to each other. This happens
when they are in a chain with 6 atoms, additionally an ester group is needed, to make
one of the C=C bonds as an enolate, but also to break the ring intermediate, which in
the end forms a carboxylic acid. Hence the purpose of this experiment is to analyze
whether indeed 3,3-dimethylpent-4-enoic acid is formed.
Theory:
Figure 2: Mechanism of the Ireland-Claisen rearrangement forming 3,3-dimethylpent-4-enoic acid
In Figure 2, the mechanism first shows how the base used, LDA, is formed using
diisopropylamine and n-BuLi, where n-BuLi deprotonates diisopropylamine, forming
a cathode, which is stabilized by the lithium ion. In Step 1 of the mechanism, LDA
deprotonates the acidic hydrogen, forming an enolate. Then in Step 2 the enolate is
stabilized, and made relatively stable by forming a Si-O bond. Afterwards in Step 3,
the Ireland-Claisen rearrangement occurs, using the oxygen with two C-O bonds. And
finally, the carboxylic acid group is formed, through protonation, and the Si bonding
to a more electronegative oxygen, giving the final product.
Experimental:
Diisopropylamine (1.0 mL, 7.5 mmol, 1.25 eq) and THF (10 mL) were stirred in an ice
bath under nitrogen, and shortly after n-BuLi (4.4 mL, 7.0 mmol, 1.4 eq) was added
carefully. The mixture was then stirred for 10 min, after which the mixture was cooled
using an ethanol bath and prenyl acetate (0.70 mL, 5 mmol, 1 eq) was added and after
5 min, chlorotrimethylsilane (0.9 mL, 1 mmol, 1.4 eq) was also added, and the solution
was heated to room temperature and stirred for 1 h. Afterwards the solution was
heated to reflux for 90 min as a yellow solution was observed. The mixture was then
cooled to room temperature and MeOH (3 mL) was added. Now exposed to
atmospheric air, NaOH (0.1 M, 50 mL, 5 mmol, 1 eq) was added and washed with
diethyl ether (2 × 20 mL), then after bringing the solution to pH 1 using HCl (11 M)
the product was extracted using diethyl ether (3 × 20 mL), washed with brine (
1 × 20 mL), dried using magnesium sulfate and concentrated in vacuo. The product
was then analyzed using 1-H NMR spectroscopy, and a yield was found as 109 %,
which is not possible, hence the product is impure and the yield is inaccurate.
1H-NMR (100 MHz, CDCl3): δ 10.88 (s, 1H), 7.32 (s), 5.97 (dd, 1H, J = 10 Hz, 7 Hz, 9 Hz),
5.05 (m, 2H), 2.38 (s, 2H), 1.81 (s), 1.21 (s, 6H).
Analysis & Discussion:

The expected results for the 1H-NMR are 4 different peaks, with a possible fifth. The
one that could not be seen is the H-O peak above 10 ppm, then two multiplets are
expected between 4.8 and 6.2 ppm, one which integrates to 1H and the other to 2H.
Finally the last peaks, both singlets, the first one integrates to 2H and is between 3.5
and 4.5 ppm, and the second one integrates to 6H and is between 1 and 2 ppm.
Figure 3: 1H-NMR of the final product at 100 MHz and using CDCl3 as solvent
The results shown in Figure 3 show all the expected peaks, including the O-H peak at
10.88 ppm. There is also the solvent peak, CDCl3 at 7.32 ppm, but also a small water
peak at 1.81 ppm, which means the product was not dried completely. The singlet at
1.21 ppm that integrates to 6H, is due to the two methyl groups 8 and 9 shown on the
molecule in Figure 3, and the other singlet at 2.38 ppm that integrates to 2H is due to
the hydrogens on carbon 4. The doublet of doublets that is at 5.97 ppm and integrates
to 1H is due to hydrogen 2, and this splitting pattern occurs due to the two hydrogens
on carbon 1 not being equivalent due to the lack of rotation in the double bond. The
final expected peak, at 5.05 ppm and integrates to 2H is caused by hydrogens 1, but
due to them not being equivalent they are split by each other and also hydrogen 2,
causing a multiplet. Lastly there are the small peaks scattered on the spectrum, which
indicates that there are a large amount of impurities, but that the product
3,3-dimethylpent-4-enoic acid was the major product. This implies that the
purification was not thorough enough, but that the methods do work.
Some improvements to be made in this experiment are, to use bigger volumes to wash
the product, potentially also increase the number of washes, and also a more thorough
drying using magnesium sulfate. With these, the product should be pure and the yield,
therefore, obtainable.
Conclusion:
The experiment was successful in making 3,3-dimethylpent-4-enoic acid, but the
product was too impure, with water and other reagents to make the yield viable. This
was observed using 1H-NMR spectroscopy, and using bigger volumes for washing and
extracting would have most likely made the product purer.

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Synthesis of Methyl 5-phenylpent-2,4-dienoate

Name: Alejandro Fernandez Zaitsev

Figure 1: Overview of of the steps involved in the formation of 3,3-dimethylpent-4-enoic acid

Figure 2: Mechanism of the Ireland-Claisen rearrangement forming 3,3-dimethylpent-4-enoic acid

Analysis & Discussion:

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