My thesis is named “A sustainable access to coumarin-3-carboxylic esters”

Theoretical part of thesis was revolving around coumarins. I described groups of coumarins and focused on
theirs biological activities such as antiviral, antifungal, antineurodegenerative. Next section involved describing
synthesizing coumarins and their ester derivatives through various methods such as Perkin reaction, Wittig reaction,
Pechmann reaction and Knoevenagel condensation.

Main goal of my experimental part was to find a method that could be used in synthesizing substituted
coumarin-3-carboxylic esters with possible , optimizing conditions of chosen reaction and then synthesizing planned
derivatives.

Coumarin derivatives are important to the pharmaceutical industry, so the development of simple,
environmentally friendly, low-cost methods for their synthesis remains desirable. Searching for a universal and
convenient method of synthesizing coumarins, i turned mine attention to the traditional method of their
preparation by Knoevenagel condensation. I also decided to use L-proline in this reaction because it's an efficient
bifunctional catalyst that is inexpensive and commercially available. It has two functional groups that can act as
both acid or base which can facilitate chemical transformations and has already been widely used in numerous
organic syntheses.

Before I started optimization, I had to prepare one of the main ingredients for my desired reaction. For
my reaction i needed two main chemical compounds. Salicylaldehyde and its derivatives and the most important
one was malonate esters. Salicylaldehyde and its derivatives were available in laboratory but I had to obtain
malonic esters as there weren’t any to start from. I synthesized them in a simple esterification reaction using
malonic acid and 5 alcohols (methanol, ethanol, isopropanol, allyl and benzyl alcohol).

When I had all needed substrates I started process of optimization. Firstly I used 0.5 mol% of L-proline but it
wasn’t enough to get good yield. Than using 1 and 5 mol% resulted in achieving two times better yield than before. I
tried to use other solvents than ethanol and to my delight it worked aswell. When I used room temperature instead of
80 C results were dissapointing. It meant that high temperature was a determining factor for this reaction. When I have
chosen to use 10 mol% of L-proline, ethanol as solvent and heating everything in 80 C I proceeded to perform planned
syntheses.

Last part of my experimental process was synthesizing some of coumarin-3-carboxylic esters via method that
I’ve optimized before. The corresponding pure reaction products were obtained by crystallization omitting additional
purification by column chromatography. Most of the products were achieved with satisfying efiiciency. In conclusion
I have developed an efficient method that could be used for the large scale synthesis without using expensive and toxic
catalyst.

Based on results obtained from experimental part of my masters degree together with my supervisor we
wrote a publication that was published in Biomedical Journal of Scientific & Technical Research. Besides that they
will presented tomorrow in a form of poster and short speech at symposium NPMS – Nauka I Przemysł that takes
place in Lublin from 27-29 of June this year.