Chemical Organic Technology II.

Report of Laboratory Practice #1. - Phase Transfer Catalysis.

Belongs to. - Jose Alejandro Martiz Chalen.
Student of MSc. In Chemical Engineering at BME.

Phase Transfer Catalysis

Introduction
There are many chemical reactions, which by their nature (immiscible phases) need a
mechanism for the transport exclusively of ion through the interfaces. Throughout the
time many compounds were used as transport agents like ethanol, acetone, and dipolar
aprotic solvents. However, due to their affinity to one of the phases or its high
hydrophilicity or even toxicity were replaced for the method of Phase Transfer Catalysis
(PTC). In PTC reactions, the catalyst facilitates the passage of one of the reagents
through the phase boundary into the other phase. The most commonly used phase
transfer catalysts are quaternary ammonium and phosphonium salts such as benzyl
triethylammonium chloride (TEBAC). Crown ethers, polyamine- and polyethylene
glycol derivatives having complex forming abilities are other groups of phase transfer
catalysts.
Crown ethers are often applied in solid-liquid systems. For this, the catin is also
transported into the organic phase, where the reaction occurs and the crown ether
applied recovers.
One of the most important phase transfer catalysis reaction are the Darzens
condensation, in this group, there is a set of possible combination of functional group
and can be carried out in both homogeneous and heterogeneous media. In the
heterogeneous media case, PTC can be applied to accelerate the reaction and to
influence the stereochemistry in this kind of reactions.
Finally, the system of control in the practice is a TLC equipment, it allows to study the
progress of the reaction. It is carried out in few minutes, with a good methodology can
estimate the rate of disintegration and formation of the components in the reaction.

Procedure
The practice have as aim carried out the Darzens condensation of -chloroacetophenone
and benzaldehyde in a liquid-liquid system (toluene, 30% NaOH solution) in the
presence of a
phase transfer catalyst at room temperature. It was using two different types of
catalysts:18-crown-6 and tetrabutylammonium bromide, the chemical structure of both
compounds are shown in figure 1. Finally, the progress of the reaction is monitored by
TLC (thin layer chromatography).
 Figure 1.- Catalysts for PTC (i)18-crown-6 and (d) tetrabutylammonium bromide.

As part of the procedure shows a table with a Brief list of properties for materials used
in the practice.
compound Formula M(g/mol) (g/ml) MP (C) BP (C)
Benzaldehyde C7H6O 106.12 1.045 178-179
- C8H7ClO 154.59 1.324 54-56 244-245
Chloroacetophenon
e
Sodium hydroxide NaOH 40 1,33(30%) 318
toluene C7H8 92.14 0,865 110-111
18-Crown-6 C12H24O6 264.32 1.237 37-40 116
Tetrabutylamonium C16H36BrN 322.37 103
bromide (TBAB)
Phenyl-(3- C15H12O2 224.25 88-90
phenyloxiran-2-
yl)methanone

For practice, 0,1mmol of catalyst, in our particular case 0, 02643g. of 18-crown-6, were
added to 0,15g. of -Chloroacetophenone and 0,15ml benzaldehyde equivalent to 0,1
and 1,5mmol correspondingly. The complex is dissolved in 3ml of toluene. The reaction
starts with the addition of 1 ml of NaOH in solution at 30%. Samples were taken
throughout the time, first each five minutes and then each 10 minutes to be deposit with
a capillar tube over the TLC layer. Then of 30 minutes the layer was revealed being
introduced in a mixture of hexane and methyl acetate with a proportion of five to one
and for the detection, the film was put under UV light showing the profiles of figure 5.
A scheme of the reaction shows in figure 2.

Figure 2.- from left to right; -Chloroacetophenone, Benzaldehyde forming

Phenyl-(3-phenyloxiran-2-yl)methanone.
Results
In the present section are described the details observed during the practice. As first
point show, a pick taken then of 20 minutes started the reaction. In the left and up side
once can observe the container of reaction using as catalyst Tetrabutylammonium
bromide, while, to the right and down side is the container which reaction use as
catalyst 18-Crown-6. Comparing both with initial state one can think that left reaction
has a high rate of reaction due to their faster change of color and uniformity than the
right side.

Figure 3. - Container with the same reactant using a different catalyst to the reaction.

A closer view of the container which reaction is using crown catalyst shows two
different phases, indicating the presence of aqueous and organic media.

Interfa
se

Figure 4.- a close view of container with crown catalyst

Finally, figure 5 shows the TLC images revealed under the incidence of UV light, one
per each reaction using different catalyst, it describes in the left side of each reaction
one single dot equivalent to the presence of reactant without a catalyst. Later, that pint is
losing giving the chance to the formation of new compounds, the baseline describes the
times in which were taken the samples.

TBAB Crown

0 point
Final state
Timeline of Product+secund
reaction aries

Figure 5.- TLCs film under UV light revealed the advance of reaction in the time

The reaction carried out with TBAB shows a faster formation of products than crown
reaction. However, last show less formation of secondary products, important for a
process which requires a high purity. Considering that Crown catalyst is more expensive
that TBAB could be necessary a balance between the economy of catalyst and the purity
necessary for final products.

Conclusions
Undoubtedly, TBAB catalyst was the cheaper and the more efficiency in time catalyst
using for the practice, if one would be interested in the implementation of this process to
high scale and the purity of the results is less relevant than normal, this catalyst offers a
big opportunity.

In opposite, if the product will be use in for example pharmaceutical industry, the purity
of the product is important because of the high cost of refining the products from
secondaries products.

Unfortunately, TLC not give us a qualitative nor quantitative results, all the possible
conclusions are done in base of zero point, considerations about the rate of reaction
have a medium accurate only if the time interval to take the samples if short enough and
the estimation of secondary product is estimate having the displacement from the
reference zero point and the number of dots present in the film. However, TLC offers a
fast, easy and confidence result under many conditions of works.