PROJECT NO.

#01
Synthesis of Schiff Base ligand using 2-
hydroxybebzaldehyde and 2-bromoaniline.
This project consists of two phases.
Phase 1: Synthesis of 2-hydroxybenzaldehyde (salicylaldehyde).
Phase 2: Synthesis of Schiff Base ligands using 2-hydroxy benzaldehyde and
2-bromoaniline.

Submitted by: Group 04

Submitted to: Dr. Muhammad Tariq
Semester: BS 8th

Institute of Chemical Sciences, BZU,

MULTAN.
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Phase 1:
Synthesis of 2-hydroxybenzaldehyde
(salicylaldehyde).
1. Abstract
2-hydroxybenzaldehyde or salicylaldehyde is an organic compound with numerous uses in
organic industry and pharmaceutical industry. Its role as chelating agent is much of importance.
The present study investigates the easy, improved and inexpensive method of synthesis of 2-
hydroxybezaldehyde. This compound was prepared by using phenol and sodium hydroxide to form
phenoxide which acts as nucleophile to attack on dichlorocarbene generated by the action of base
and chloroform. The resultant intermediate species undergoes hydrolysis to give final product.

2. Introduction
2-hydroxybenzaldehyde or salicylaldehyde is an organic compound with formula
(C7H6O2). It is widely used in the organic industry and pharmaceutical industry. It is the main
precursor for the synthesis of variety of chelating agents. This piece of paper aims at the synthesis
of 2 hydroxy benzaldehyde by the Reimer Tiemann reaction. Reimer Tiemann reaction involves
the deprotonation of chloroform by a strong base to form a chloroform carbanion. Alpha
elimination occurred at chloroform carbanion to give dichlorocarbene. It is the principle reactive
species aqueous solution of sodium hydroxide deprotonates the phenol reactant to produce
negatively charged phenoxide. Benzene ring becomes nucleophilic due to delocalization of
negative charge. Phenoxide ring does nucleophilic attack on the dichlorocarbene to form
intermediate dichloromethyl substituted phenol. This intermediate undergoes hydrolysis by mild
acidification to yield desired ortho hydroxybenzaldehyde.

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 Salicylaldehyde is prepared by refluxing phenol and solution of sodium hydroxide with
small amount of ethyl alcohol and chloroform at 60-70°C temperature for 1.45h. Product mixture
recovered after cooling of 3h is filtered and then acidified with dil. HCl. The liquid product
obtained is extracted with organic solvent.

3. Experimental Work
Phenol (0.1mol, 24g) and sodium hydroxide (77g in 70ml water) with 7.5ml ethyl alcohol
was refluxed to 65-70°C for 45min. (37.5ml, 0.19mol) chloroform was added over 45min of
refluxing. The reaction mixture was again refluxed for 1h. It was then cooled for 3h at 20-25°C.
Solid that precipitated out was filtered and washed with ethyl alcohol. Solid obtained after filtration
was dissolved in 15 ml water and acidified with dil HCl until its pH reached below 4. The liquid
product was separated and extracted by using dichloromethane using separatory funnel. On
evaporation of dichloromethane 2-hydroxybenzaldehyde was obtainedi.

4. Result
Boiling point of the obtained liquid product was determined 200C. The mentioned boiling
point of the salicylaldehyde in the literature is 197C. So, the determination of b.p of the liquid
product confirms that the desired product was prepared.

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Phase 2:
Synthesis of Schiff Base ligands using 2-hydroxy
benzaldehyde and 2-bromoaniline.
1. Abstract
Schiff base ligands and their complexes are very significant in medicinal and pharmaceutical
fields due to their great biological activities such as antibacterial, antifungal, anti-malarial and
antiviral etc. In this research project, a Schiff base has been synthesized from condensation of 2-
bromoaniline with 2-hydroxybenzaldehyde or salicylaldehyde. Ethanol has been used as solvent
and the reaction mixture has been refluxed for few hours to get the Schiff base ligand.

2.Introduction
Coordination compounds of sulphur, oxygen and nitrogen have been reported for their
antimicrobial activities. Most of these compounds are formed from Schiff bases, which are
fundamental materials for synthesis of various Schiff base ligands used as chiral auxiliaries in
asymmetric synthesis. The development of these ligands resulted in an enhanced research activity
in the field of coordination chemistry. The chemistry of Schiff bases has led to important
discoveries in the chemical and medical industries. Multi-dentate complexes of Iron and Nickel
showed high activities of ethylene oligomerization and polymerization. Also, they are reported to
show a variety of biological activities including antibacterial, antifungal, anticancer and herbicidal
activities. Metal complex Schiff bases have also been used in oxidation reactions owing to their
ability to coordinate (as ligands), with various metals and stabilize them in various oxidation states,
enabling them as useful in catalytic transformations, catalytic activity in hydrogenation of olefins
and transfer of amino acids, their ability to form complexes with major metals. Schiff base ligand
is prepared by using 2-hydroxybenzaldehyde and 2-bromoanbiline.ii

3.Experimental Work
An ethanolic solution of salicyaldehyde was prepared by dissolving 0.59ml of

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 salicyaldehyde in 10 ml of ethanol and it was added to an ethanolic solution of aniline prepared
by dissolving about 1g of 2-bromoaniline in 5ml ethanol. The resulting solution was refluxed with
stirring for 4 hours, the solution turned yellow after about 30 min of stirring; it was cooled in an
ice bath and filtered to obtain a yellow solution which turned oily after concentration on water
bath. The oily yellow solution was left overnight to obtain crystals of the Schiff baseiii.

Results and Discussion

The Schiff base has been synthesized by the condensation between 2-bromoaniline and
2-hydroxybenzaldehyde or salicyladehyde according to the procedure discussed above. The
product is solid at room temperature and stable under air. Synthesized Schiff base can be used as
bidentate ligand as it has two donor atoms. Nitrogen atom of amide part of the Schiff base ligand
with lone pair and oxygen atom of hydroxyl group from salicylaldehyde part of the Schiff base,
are the two donor sites for the complex formation with any transition metal. Synthesized Schiff
can react with transition metal salts like salts of Co, Ni, Cu and Zn metals to yield transition metal
complexes of these metals.

Proposedivv complex structures of the transition metals with 2-bromoaniline-

salicylaldehyde Schiff base ligand are given below:

Hybridization state sp3 sp3 sp3:

Geometry: Tetrahedral Tetrahedral Tetrahedral

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References
i
Mokle, S. S., Dawane, B. S., Sayyed, M. A., & Vibhute, Y. B. (2006). An improved procedure for the synthesis of
2-hydroxybenzaldehyde and 2-hydroxynaphthalene-1-carbaldehyde. Journal of Chemical Research, 2006(2), 101-
101.
ii
Ejelonu, B. C., Oyeneyin, O. E., Olagboye, S. A., & Akele, O. E. (2018). Synthesis, Characterization and
Antimicrobial Properties of Transition Metal Complexes of Aniline and Sulphadiazine Schiff Bases as Mixed Ligands.
Journal of Chemical and Pharmaceutical Research, 10(5), 67-73.
iii
Ejelonu, B. C., Oyeneyin, O. E., Olagboye, S. A., & Akele, O. E. (2018). Synthesis, Characterization and
Antimicrobial Properties of Transition Metal Complexes of Aniline and Sulphadiazine Schiff Bases as Mixed
Ligands. Journal of Chemical and Pharmaceutical Research, 10(5), 67-73.
iv
Iftikhar, B., Javed, K., Khan, M.S.U., Akhter, Z., Mirza, B. and Mckee, V., 2018. Synthesis, characterization and
biological assay of Salicylaldehyde Schiff base Cu (II) complexes and their precursors. Journal of Molecular
Structure, 1155, pp.337-348.
v
Jaiswal, N., Kushwaha, A.K., Singh, A.P. and Dubey, R.K., 2019. Synthesis, spectroscopic characterization and
computational studies of Schiff base complexes of tin (IV) chloride. Main Group Metal Chemistry, 42(1), pp.28-36.

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