Lab Report PPLC

Synthesis and liquid crystalline properties of 4-

alkyloxibenzoic acids

1. Introduction

The core is one of the most important features a liquid crystalline material has. Tho it is
not easy to define the concept absolutely, the core is usually knows as the rigid unit constructed
from linearly linked ring units so it includes any linking groups or lateral substituents that are
connected to the ring. In terms of molecular structures, an important feature of a LC-forming
molecules is the anisotrophy meaning they have different proprieties on different directions.

The most common expression of this property is the overall shape of the molecules. It is
well known that spherical or ill-defined shape don’t tend to form LC phases, their most common
form being rod-like or disk-like shapes. In the current lab our goal is to synthesize 4-
alkoxybenzoic acids, a class of molecules having an overall rod like shape and to explore its
crystalline properties especially the tendency of some molecules to form larger, well-organized
architectures based solely on their design.

The acids in discussion have two ways of self-assembling: the first one is the hydrogen
bonding between the carboxylic acid groups with the formation of a dimer with a pronounced
rode-like shape, the second step being the formation of one or more liquid cristal phase using
those dimers. The analysis of these compounds are performed with two techniques, one called
differential scanning calorimetry (a very accurate and sensitive melting point apparatus) and the
other one polarized microscopy (a standard optical microscope fitted with polarizers for the light
entering and exiting the sample).

The advantage that our compounds own is presenting a unique liquid phase that is
temperature dependent leaving only the various chain lengths to have distinguishable liquid
crystal phase transitions.
 2. Experimental

The p-alkyloxybenzoic acids can be prepared using a three step process. First the 4-
hydroxybenzoic acid is converted to the coresponding esther using an acid as catalyst, then an
Williams o-alkylation takes place with the appropriate alkyl bromide analogue, the last step
being the hydrolysis of 4-alkyloxybenzoate to the correspoding acid in the presence of a base.

In this lab we will only perform the last step oh the synthesis. 1.5 g of methyl 4-
alkyloxybenzoate is disolved in a bottom round flask using 50 mL ethanol followed by heating
under the reflux using a hot plate with stirring. Taking in consideration that the boiling point of
ethanol is lower than the boiling temperature of water we can use a water bath to heat the bottom
round flask. If the solution after heating is clear, 2.5 of KOH dissolved in minimum amount of
water will be added. Heating will continue for another 2 hours.

After this time in which the reaction took place the excess of KOH is neutralised with
HCl 6N added in the hot mixture dropwise until a pH of 3-4 is reached. To complete a volume
sufficient for filtration 50 mL of deionised water will be added. The crude product will be
washed several times more with water or cold ethanol and will be left to dry. The recrystalisation
will be perfomed in hot ethanol of a mixture of ethanol:diclormethane=1:1 (v/v)

3. Experimental data and processing

If the final product was 4-dodecyloxybenzoate (M = 306 g/mole) we need to calculate the
quantity obtained if the weighted mass of p-hydroxybenzoic acid (M = 138 g/mole) is 2 grams of
and the overall yield is 50%.

As the reaction is happening mole to mole we transfomr the quantity given in moles.

2
υ p−hydroxybenzoic acid = =0.0145 moles
138

mt =0.0145 ×306=4.437 g 4−dodecyloxybenzoate

Considering the overall yield to be 50% we have the following result:

 4.437 × 50
m p= =2.2185 g 4−dodecyloxybenzoate
100

Using the information provided in annex regarding the transition temperatures and the
ehthalpies neded for the transition of the 6 different liquid cristals from a phase to another (Cr,
Smc, N and Iso) we can complete the table below. The data regarding the transitions caracteristic
for 4-dodecyloxybenzoate is obtained form the following graph.

50

40

30

20
Heat flow

10

0
0 20 40 60 80 100 120 140 160

-10

-20

Temperature (C)

Figure 3.1. Heatflow versus temperature for 4-dodecyloxybenzoic acid considering a heating and cooling process in
the 0−900 C at 100 C /min
Table 3.2. LC properties of 4-alkyloxybenzoic acids

Chain length (n) Transition Temperature(oC) ΔH(kJ.mol-1)

Cr-N 123 18.3872
5
N-I 150 1.9136
Cr-N 106 13.209
6
N-I 153 2.3754
Cr-SmC 91 24.4732
7 SmC-N 98 1.18
N-I 148 1.8408
Cr-SmC 100 10.325
8 SmC-N 106 0.8
N-I 147 1.975
Cr-SmC 92 18.4008
9 SmC-N 117 0.8712
N-I 141 1.2936
Cr-SmC 94 11.954
10 SmC-N 118 1.0842
N-I 140 2.363
Cr-SmC 96 21.84
12 SmC-N 133 1.33
N-I 139 1.46

Rewriting the table above by considering only the transition phases ( Cr-crystalline, Smc-
Smectic and Iso-isotropic) and the temperatures at which those transition are occuring we obtain
Table 3.2. below.

Chain Lenght (n) Cr SmC Iso

5 123 150
6 106 153
7 91 98 148
8 100 106 147
9 92 117 141
10 94 118 140
12 96 133 139
 180

160
Iso
140

120 SmC
Temperature (C)

100

80 Cr

60

40

20

0
4 5 6 7 8 9 10 11 12 13

Carbon lenght (n)

Figure 3.2. Temperature versus the carbon lenght of the chain attached to the ring for every phase (Crystalline,
Smectic and Isotropic)

Additional questions:

1. To what extent the alkyl chain length has an influence on mesophase type and stability?
We can see from the second table that a longer alkyl chain has a stabilising effect. As
observed from table 3.2. the longer the alkyl chain is, the more transitions the liquid crystal has
(maximul 3 transitions). If the first two compounds, having alkyl chains of 5 and of 6 carbons
have only one mesophase (the nematic one), the next compounds, having alkyl chaings made of
7-12 carbons present one more transition state (the smectic one) .

2. What is the possible explanation for liquid crystalline properties generation in the case of
such benzoic acid derivatives?
 3. Can you explain the necessity of the first esterification step required in the preparation
of 4-alkyloxybenzoic acids?
The esterification in the first step of the synthesis is requied as a protection for the
carboxilic group and to improve the yield in our desired compound. If this step wouldn’t take
place then the alkyl bromide analogue would react with both hydroxyles (the one from the
carboxilic acid and the phenolic one) lowering the quantity of desired product obtained. As soon
as the O-alkylation Williams type reaction takes place the carboxilic acid is unprotected to obtain
our 4-alkyloxybenzoate.