جامعة قناة السويس suez canal university...faculty of science port-said university...

Faculty of Science Port-Said University

Chemistry Department

Cu and Ni complexes of 2,3 Dihydroxybenzaldehyde

semicarbazon

A Thesis Submitted by

norhan rammdan Elsayed Ahmed

Supervisors

Dr.

Nader Youssri Hassan Lecturer of Inorganic Chemistry


Faculty of Science Portsaid University

Submitted to


Faculty of Science

Portsaid University

(2016)



Acknowledgment

In the name of Allah, the Most Gracious and the Most

Merciful Alhamdulillah, all praises to Allah for the strengths

and His blessing in completing this research.

I would like to express my deepest gratitude and sincere appreciation to Dr. Nader Yousri Hassan, Teacher of Inorganic Chemistry,Faculty of Science, Portsaid Unversity for his assistance, guidance, care and encouragement Last but not least, Sincere thanks to my parents and my brother for their endless love, prayers and encouragement



content -1 introduction..................................................................1

-1-1 general introduction....................................................2

-1-2 schiff base...................................................................3

-1-2-1 synthsis of schiff base...............................................4

-1-2-2 schiff base as catalyst..............................................8

-1-2-3 Application in medicine and pharmacy ...................10

-1-3 semicarbazon............................................................18

-1-3-1 nature of coordination of carbazon...........................21

-1-3-2 application of thio/semicarbazon and

their complexes................................................................23

-2 Aim of work.........................................................................28

-3 Abstract...............................................................................29

-4experiment..............................................................................30

-5 resultes and discussion..........................................................34

referance...................................................................................41



1.1. General introduction

Coordination compounds have been a challenge to the inorganic chemist since

they were identified in the nineteenth century. After the profound studies done

by Alfred Werner, inorganic chemistry witnessed a great outflow of coordination

compounds, with unique structural characteristics and diverse applications. The

stereochemistry of coordination compounds is one of the major interests of the

coordination chemist. The development of instrumental techniques provides

methods of investigating thermal, spectral and magnetic properties of metal

complexes. Coordination compounds can have a wide variety of structures

depending on the metal ion, coordination number and denticity of the ligands

used. The presence of more electronegative nitrogen,

oxygen or sulfur atoms on the ligand structure is established to enhance the

coordination possibilities of ligands. Coordination compounds are widely used as

potential drugs, in the field of catalysis and in biological fields. This includes a

number of important biological materials such as

vitamin B12 and haemoglobin



1-2 schiff base

Schiff bases are condensation products of primary amines and carbonyl

compounds and they were discovered by a German chemist, Nobel Prize winner,

Hugo Schiff in 1864 [1] Structurally, Schiff base (also known as imine or

azomethine) is

an analogue of a ketone or aldehyde in which the carbonyl group (C=O) has been

replaced by an imine or azomethine group (Fig. 1) [2].

Schiff base ligands are essential in the field of coordination chemistry, especially

in the development of complexes of Schiff bases because these compounds are

potentially capable of forming stable complexes with metal ions [3].

figure 1 General structure of Schiff bases [4]



I.2.1) Preparations of Imines

1) Methods of Preparation of N-Aryl or Alkyl Substituted

Imines

a) Reaction of Aldehydes and Ketones with Amines: The most common method for preparing imines is the original

reaction discovered by Schiff [ 5,6,7 ] Basically it consists in the reaction of an

aldehyde (respectively a ketone) with a primary amine and elimination of one

water molecule. This reaction can be accelerated by acid catalysis and is

generally carried out by refluxing a mixture of a carbonyl compound 1and an

amine 2, in a Dean Stark apparatus in order to remove the water. This removal

is important as the conversion of aminal 3 into the imine 4 is reversible. From

this point several dehydrating agents have been successfully used including

sodium sulphate and molecular sieves

Alternatively, some in situ methods, involving dehydrating solvents

such as tetramethyl orthosilicate or trimethyl orthoformate, have been reported

as well [8,9] As far as the use of acid catalyst is required , mineral acids, like

H2SO4or HCl, organic acids such as p-toluene sulphonic acids or pyridinium p-

toluenesulphonate, acid resin, montmorillonite or even Lewis acids like ZnCl2,

TiCl4, SnCl4, BF3Et2O, MgSO4, Mg(ClO4)2, etc., have been reported.



figure 2 In the course of the preparation of imines, if aliphatic aldehydes are

used, a known competitive reaction, due to the formation of a condensation

product arising from an aldol type reaction, can occur as well.

figure 3



Aliphatic ketones react with amines to form imines more slowly

than aldehydes; therefore, higher reaction temperatures and longer reaction

time are required. Acid catalysts and water removal from the reaction mixture

can significantly increase the reaction yields, which can reach 80%–95% values

Aromatic ketones are less reactive than aliphatic ones and require

harsh conditions to be converted into imines. Recently, several new techniques to

produce imines have been published, including solvent-free, clay, microwave

irradiation, water suspension medium, liquid crystals, molecular sieves, infrared

and ultrasound irradiation [10-15]



2)Synthesis of Some Salicylaldehyde-Based Schiff Bases in

Aqueous Media:

A new efficient and environmental friendly procedure for the

synthesis of a series of salicylaldehyde-based Schiff bases under microwave

irradiation is described. The method is compared with the conventional method

also. The present work involves condensation of salicylaldehyde with various

aromatic amines in water under microwave irradiation. A judicious choice of the

solvent and reaction conditions allowed the final products to be generated in

excellent yields in a one-step procedure, whereas experiments under thermal

conditions led to lower yields with tedious work-up. Microwave irradiation

method gives advantages like reduction in reaction time, increase in conversion,

reduced wastes, and good yields. The structures of synthesized compounds were

confirmed by IR, 1HNMR, and Mass Spectra data [16]



figure 4



1.2.2 -schiff base as catalyst

A large number of Schiff base complexes are characterized by an excellent

catalytic activity in a variety of reactions at high temperature (>100ºC) and in

the presence of moisture. In recent years, there have been numerous reports of

their use in homogeneous and heterogeneous catalysis [17,18].

Schiff bases and their metal complexes are increasingly being used as catalysts

in various biological systems, polymers and dyes. Moreover, it is confirmed that

these compounds can act as enzyme preparations [19]. Due to the excellent

selectivity, sensitivity and stability of Schiff bases for specific metal ions such as

Ag(II), Al(III), Co(II), Cu(II), Gd(III), Hg(II), Ni(II), Pb(II), Y(III) and Zn(II), a

large number of different Schiff base ligands have been used as cation carriers in

potentiometric sensors. Studies in terms of catalytic properties of Schiff bases

exhibit the catalytic activity in the hydrogenation of olefins. One of the more

interesting applications of these compounds is the possibility to use them as

effective corrosion inhibitors. This phenomenon is the spontaneous formation of

a monolayer on the surface to be protected [1]

.



The interest in metal complexes in which the Schiff bases play a role as the

ligands are increasing as evidenced by the number of publications appearing

annually (approximately 500) [20]. So much interest in imines can be explained

by the fact that they are widely distributed in many biological systems and they

are used in organic synthesis and chemical catalysis, medicine, pharmacy and

chemical analysis, as well as new technologies [21].



1.2.3 -Application in medicine and pharmacy

Imine complexes have a broad range of biological properties:

antitumor, antiviral, antifungal, antibacterial [22]. They are also used in the

treatment for diabetes and AIDS. As biological models, they help in

understanding the structure of biomolecules and biological processes occurring

in living organisms. They participate, inter alia, in photosynthesis and oxygen

transport in organisms. They are involved in the treatment of cancer drug

resistance, and often tested as antimalarials. It also could be used for the

immobilization of enzymes [23,24].

Biological activity

Schiff bases are characterized by an imine group –N=CH-, which

helps to clarify the mechanism of transamination and racemization

reaction in biological system [1]. It exhibits antibacterial and antifungal effect in

their biological properties [25,26]. Metal-imine complexes have been widely

investigated due to antitumor and herbicidal use. They can work as models for

biologically important species [25].



Antibacterial properties

Mortality increase caused by infectious diseases is directly related to the bacteria

that have multiple resistance to antibiotics. The development of new

antibacterial drugs enriched by innovatory and more effective mechanisms of

action is clearly an urgent medical need [27].

Schiff bases are identified as promising antibacterial agents. For example, N-

(Salicylidene)-2-hydroxyaniline [Fig.5] is active against

Mycobacterium tuberculosis [4].



figure 5 N-(Salicylidene)-2-hydroxyaniline as the example of

bioactive Schiff base



Isatin derived Schiff bases present anti-HIV and antibacterial activity. Other

Schiff bases derivatives, which possess antibacterial activity are: benzimidazole,

thiazole, pyridine, glucosamine, pyrazolone, hydrazide, thiazolidiones, indole,

thiosemicarbazone, p-fluorobenzaldehyde [19]

Antifungal properties

Fungal infections usually are not only limited to the contamination

of surface tissues. Recently, there was a considerable increase in the incidence of

systemic fungal infections, which are potentially lifethreatening [28]. Exploration

and development of more effective antifungal agents is necessity, and the

individual Schiff bases are considered to be promising antifungal medicines [29].

Some of them, such as imine derivatives of quinazolinones possess antifungal

properties against Candida albicans, Trichophyton rubrum, T. mentagrophytes,

Aspergillus niger and Microsporum gypseum Schiff bases and their metal

complexes formed between furan or furylglycoxal with various amines exhibit

antifungal activity against Helminthosporium gramineum – causing leaf stripe in

barley, Syncephalostrum racemosus – contributing to fruit rot in tomato and



Colletotrichum capsici – causing anthracnose in chillies [19].



Biocidal properties

Schiff bases obtained by the synthesis of o-aminobenzoic acid and β-keto esters

have found biocidal use against S. epidermidis, E. coli, B. cinerea and A. niger [2].

By contrast, Schiff bases of isatin derivatives are used in the destruction of

protozoa and parasites [30]

Antiviral properties

The use of vaccines may lead to the eradication of pathogens known viruses, such

as smallpox, poliomyelitis (polio), whether rubella. Although there are many

therapeutic ways to work against viral infections, currently available antiviral

agents are not fully effective, which is likely to cause a high rate of mutation of

viruses and the possibility of side effects. Salicylaldehyde Schiff bases derived

from 1-amino-3-hydroxyguanidine tosylate are good material for the design

of new antiviral agents [4].

Isatin Schiff base ligands are marked by antiviral activity, and this

fact is very useful in the treatment of HIV [30]. In addition, it was also

found that these compounds have anticonvulsant activity and may be



included in the anti-epileptic drugs [31].

Gossypol derivatives also present high antiviral activity. Increasingly,

gossypol, often used in medical therapy is replaced by its derivatives,

because of their much lower toxicity [32]. Schiff bases have obtained

acceptable results for Cucumber mosaic virus, whose effectiveness was

estimated at 74.7% [19]

Antimalarial properties

Malaria is a disease which when is neglected causes serious health problems.

Human malaria is largely caused by four species of the genus Plasmodium (P.

falciparum, P. vivax, P. ovale and P. malariae).

The search for new drugs, vaccines and insecticides for the prevention or

treatment of this disease is a priority. Schiff bases are interesting compounds,

which could be part of antimalarial drugs. For example, the compound with such

effect is Ancistrocladidine (Fig.6), which is a secondary metabolite produced by



plants of the family Ancistrocladaceae and Dioncophyllaceae, and presenting an

imine group in a molecular chain [4].



figure 6. Ancistrocladaceae – antimalarial activity of bioactive Schiff

base [4]

Cryptolepine, valid indolchinoline alkaloid, isolated from African plant

Cryptolepis sanguinolenta, also used in the treatment of malaria, is the product

of multi-stage reaction, in which Schiff base is involved [33].

Anticancer properties

Some Schiff bases have a high antitumor activity. Imine derivatives

of N-hydroxy-N’-aminoguanidine block ribonucleotide reductase in

tumor cells, so that they are used in the treatment of leukemia [34].

Schiff bases of PDH [N-(1-phenyl-2-hydroxy-2-phenyl ethylidine)- 2′,4′-

dinitrophenyl hydrazine], PHP [N-(1-phenyl-2-hydroxy-2-phenyl ethylidine)-2′-

hydroxy phenyl imine] and HHP [N-(2-hydroxy benzylidine)-2′-hydroxy phenyl

imine]



reduce the average tumor weight (reduction in tumor growth increases with

increasing dose) and decrease the growth of cancer cells in mice EAC cells. In

addition, they have ability to rebuild depleted haematological parameters, such

as hemoglobin, red blood cells (RBC) and white blood cells (WBC) towards the

right content. They also show protective effect on hematopoietic system [35].

Application in modern technologies

Photo- and thermochromic properties of Schiff bases as well as their biological

activity make them applicable in modern technology. Among others, they are

used in optical computers, to measure and control the intensity of the radiation,

in imaging systems, as well as in the molecular memory storage, as organic

materials in reversible optical memories and photodetectors in biological systems

[36,37].

Due to photochromic properties, Schiff compounds could behave as

photostabilizers, dyes for solar collectors, solar filters. They are also exerted in

optical sound recording technology [37].



Among others, worthy of interest in the properties associated with Schiff rules

include: properties of liquid crystal [38], chelating ability [39], thermal stability

[40], optical nonlinearity [41] and the ability to create the structure of a new type

of molecular conductors using electrical properties to proton transfer [42].

Because of its thermal stability Schiff bases can be used as stationery phase in

gas chromatography [40]. The optical nonlinearity of these compounds allows us

to use them as electronic materials, opto-electronic (in optical switches) and

photonic components [41].

Imine derivatives can be exerted to obtain conductive polymers. Schiff bases as

an electrical conductor possess a variety range of uses: as catalysts in

photoelectrochemical processes, electrode materials and micro-electronic

equipment, organic batteries or electrochromic display device (graphical output

devices) [18].



Due to the presence of the imine group, the electron cloud of the aromatic ring

and electronegative nitrogen, oxygen and sulfur atoms in the Schiff bases

molecules, these compounds effectively prevent corrosion of mild steel, copper,

aluminium and zinc in acidic medium [43].



Application in synthesis and chemical analysis

Schiff bases are a group of organic intermediates, which are very often used in

the synthesis and chemical analysis. They are exerted in the production of

pharmaceutical and agrochemical industry. In the reaction with hydrogen

cyanide Schiff bases may form α-amino acid precursors (Strecker synthesis).

Moreover, chiral Schiff bases are used as initial substrates for the asymmetric

synthesis of α-amino acids, and as catalysts in asymmetric synthesis.

Furthermore, the imines obtained by the condensation reaction of arylamines

and carbonyl compounds have determined a group of intermediates used in the

preparation of important compounds (arenediazonium nitrates, N-arylarene

carboxamides, the appropriate amines and cyanamides, β-lactams) [24].

Otherwise, Schiff bases are precursors of reaction of polycyclic derivatives of

quinoline and isoquinoline receiving by oxidative ring closure under the

influence of ultraviolet light. They are also used for the preparation of acyclic

and macrocyclic compounds, such as: cryptats, coronates and podates [36].

These compounds lead to the formation of Ruhemann’s purple (reaction between

an amino acid and ninhydrin), which allows to detect and assist in the

identification of fingerprints [44].



1- 3 semicarbazon

Semicarbazones are the Schiff bases, usually obtained by the condenzation of

semicarbazide with suitable aldehydes and ketones [45]

f igure 7 Method of synthesis of the semicarbazone

The conversion of aldehydes and ketones into imine like derivatives is an

exothermic and pH dependent reaction

General method for the synthesis of semicarbazone analogues:

The general method for the synthesis of semicarbazone analogues is presented in

Scheme 1.



An interesting attribute of the semicarbazones is that in the solid state, they

predominantly exist in the keto form, whereas in solution state, they exhibit a

keto-enol tautomerism Figure[.8]. Keto form acts as a neutral bidentate ligand

and the enol form can deprotonate and serve as monoanionic bidentate ligand in

metal complexes. Thus semicarbazones are versatile ligands in both neutral and

anionic forms.



Figure.8 Keto-enol tautomerism of semicarbazones.

Both tautomeric forms have an efficient electron delocalization along the

semicarbazone moiety. Aromatic substituents on the semicarbazone skeleton can

further enhance the delocalization of electron charge density. These classes of

compounds usually react with metallic cations giving complexes in which the

semicarbazones behave as chelating ligands. Upon coordination to a metal

center, the delocalization is further increased through the metal chelate rings.

The coordination possibilities are further increased if the substituent has



additional donor atoms



1.3.1- nature of coordination of semicarbazon

semicarbazones show a variety of coordination modes with transition metals.

The coordination mode is influenced by the number and type of substituents.

This is because the active donor sites of the ligand vary depending upon the

substituents .

The coordination possibilities in semicarbazones are increased if the substituents

of the aldehyde or ketone include additional donor atoms. The π-delocalization

and the configurational flexibility of their molecular chain can give rise to a

great variety of coordination modes [46] the coordination mode of the

semicarbazone is very sensitive towards minor variations in the experimental

conditions, the nature of the substituents on the carbonyl compound and the

metal salt [47]

The coordination mode of the N4-substituted semicarbazones [48] is given

figure[9] The different coordination modes of the substituted benzaldehyde

semicarbazone [49]. are given figures[ 4,5,6]



figure 9

figure 10



figure 11

figure 12



/ semicarbazones and their complexesApplications of thio-1.3.2

There are a large number of works on the coordination chemistry, analytical

applications and biological activity of thiosemicarbazones and

semicarbazones.[50 -52] The chemistry of transition metal complexes of the

semicarbazone ligands has been receiving considerable attention because of their

biological relevance [53-59]

The synthesis and structural investigations of thiosemicarbazone and their metal

complexes are of considerable centre of attention because of their potentially

beneficial pharmacological properties and a wide variation in their modes of

bonding and stereochemistry.[60-62]

Thiosemicarbazones and their metal complexes have received considerable

attention because of their antibacterial, antifungal, antitumor, antiamoebic,

antimalarial, antiviral, radioprotective, trypanocidal and anti-inflammatory

activities.[63-73]

The biological activity is considered to involve three kinds of mechanisms:

(a) inhibition of enzyme ribonucleoside diphosphate reductase (essential for

DNA synthesis);

(b) creation of lesions in DNA strand by oxidative rupture;



(c) binding to the nitrogen bases of DNA or RNA, hindering or blocking base

replication.

In addition of this, they have been screened for their medical properties because

they possess some cytotoxic effect. They also stabilize uncommon oxidation

states, generate a different coordination number in transition metal complexes in

order to participate in various redox reactions.[74-75]

Much attention has been drawn towards the chemistry of transition metals[76-

77] indifferent coordination spheres.

As regards biological implications, thiosemicarbazone complexes of copper(II)

have been intensively investigated for antiviral, antibacterial, antitumour, and

antifungal activity and inhibitory action is attributed to their chelating

properties While structural chemistry of copper(II) has been well investigated

corresponding complexes of copper(I) are limited [78-92]..

Semicarbazones present a wide range of bioactivities, and their chemistry and

pharmacological applications have been extensively investigated. The biological

properties of semicarbazones are often related to metal ion coordination. Firstly,

lipophilicity, which controls the rate of entry in to the cell, is modified by

coordination [93]. Also, the metal complex can be more active than the free

ligand. The mechanism of action can involve binding to a metal in vivo or the



metal complex may be a vehicle for activation of the ligand as the cytotoxic

agent. Moreover, coordination may lead to significant reduction of drug-

resistance [94].

A variety of 5-nitrofuryl semicarbazone derivatives have been developed for the

therapy of Chagas disease, a major problem in the Central and the South

America [95]. 4-Bromobenzaldehyde semicarbazone has been used as

anticonvulsant. Recently, a review reported on the anticonvulsant activity of

thiosemicarbazones, semicarbazones and hydrazones derived from aromatic and

unsaturated carbonyl compounds as well as from other precursors [96].

In contrast to thiosemicarbazones, literature records fewer examples of

semicarbazones presenting significant anticancer and cytotoxic activity but some

nitroso, naphtopyran, and fluorine derivatives showed anti-leukemia

effect in mice [97].

Several N4-substituted semicarbazone derivatives of o- and p-

chlorobenzaldehyde and 2,6-dichlorobenzaldehyde exhibit potent anti-

hypertensive effects [98]. The orally administered drug naftazone (1,2-

naphtoquinone semicarbazone) protects the vascular system through an

inhibitory effect on nitric oxide synthesis [99].

Many other bioactivities of semicarbazones have been reported, such as

their antimicrobial [100], pesticide [101], herbicide [102], and hypnotic [103]



properties or the ability of some of their Cu(II) complexes to mimic superoxide

dismutase activity [104]. Semicarbazones are widely used as spectrophotometric

agents for the analysis of metal ions [105]. Semicarbazones are frequently used in

the qualitative organic analysis of carbonyl compounds [106].



2-Aim of work

The coordination compound of the metals with Schiff base

compounds will be prepared and characterized by elemental analysis, Infrared

spectroscopy and NMR spectroscopy

3-Abstract

Schiff base based on organic compound are synthesized as potential

medicinal preparations. Biological activities such as bactericidal, pesticidal,

fungicidal and tuberculostatic have been found to be associated with the

compound derivatives. The Schiff base derivatives of compounds are capable of

forming chelates with a large number of metal ions. one of this compound is

simcarbazon compounds



Reagent :

all chemicals and solvent that were used

2,3dihydroxy

benzaldehyde

semicarbazide

hydrochlorid

ethanol,

Ni ions as (NiCl₂

.6H₂O) hydrated nickel chloride

Cu ions as ( CuSO₄

.5H₂O) hydrated copper sulfates

methanol

amonia solution

instrument: Elemental analysis

Infrared spectroscopy

NMR spectroscopy



2,3dihydroxy benzaldehyde semicarbazon synthesis

A mixture of 2,3dihydroxy benzaldehyde (0.01mole), semicarbazide

hydrochloride (0.01mole) and fused sodium acetate(0.03mole) in ethanol (50ml)

was heated for 3hr .

the reaction mixture was cooled and poured into water. the solid obtained was

filtered off , washed and recrystliztion from ethanol to give 2,3dihydroxy

benazldehyde semicarbazon az yellow crystal.

procedure 1) take weight (0.194 gram) of ligand in 2 beakers

2) add 20 ml of mixture ( methanol/H₂=50/50) to ligand



3) add drops of ammonia to make the ligand completely dissolve

notice : after addition of ammonia to ligand , its color change to yellow

4) dissolve 0.2395 gram of Ni salt and 0.2495 gram of Cu both of them in

20 ml of mixture ( methanol /H₂O)

5) add soln. of Ni ions drop by drop to ligand , then the color change to

yollewish green

6) when add soln. of Cu ions drop by drop to ligand , the color change to

dark green

7) after 3 days filter the ppt. then washing with 10ml methanol and 10ml

DW. (hot)



Analytical Techniques:

Elemental Analysis: The elemental analyses (e.g., carbon, hydrogen and nitrogen)

L :2,3DIHYDROXY BENZALDEHYDE SEMICARBZON

C₈H₉O₃N₃ M.wt=195 gram

N% H%

C%

Sample

20.84

4.40

48.93

L

14.30 3.95

33.46

Cu

12.74

4.45

28.68

Ni



H-NMR:

HNMR OF 2,3DITDROXYBENZALIDENE SEMICARBAZON



L-Cu

peak of NH and OH groups in HNMR of ligand disappared in complexe this mean



that complexe formed with this groups



IR: 2,3DITDROXYBENZALIDENE SEMICARBAZON

3459.67 NH

3243.68 OH

1693.19 C=O

3186.79 Ar-H



L-Ni

3427.85 NH

1654.62 C=O



L-Cu



EXPECTED COMPLEXE



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