Synthesis and Identification of Macrocycles and Complexes with (Cd2+)

 

Miad. Hassan. Jebur.

Lecturer, Chemistry Department, Science College, Kufa University, Najaf, Iraq

*Corresponding Author E-mail: mead.h@yahoo.com

 

ABSTRACT:

The novel macrocycles ligands were synthesized by reacting of various amine compounds such as (ethylene diamine, methylene diamine, Glycine–amino acid , hydrazine ) with di ketone compounds to produce five ligands [(DAP), (MAH), (PIP), (MCP), (MHD)] of macro cycles and their complexes with cadmium ion (II) . The synthesized compounds were confirmed by (I.R, UV –Vis, (C.H.N) –analysis), molar conductance and melting points.

 

KEYWORDS: Complex of cd , big ligands, ligand of imine.

 

 


INTRODUCTION:

Macro cycles ligands have a long history of application in analytical and inorganic chemistry , the literature is flooded with reports of variety of biological activities of these compounds represented (anticancer, antibacterial anti–inflammatory, antiviral, anti malarial), other pharmacological synthesis of these compounds were prepared by condensation reaction with catalysis to give good yields from macro cyclic compounds(1,2) .

 

These compounds included Schiff basses – bi molecular at same time and some of them included Azo- group with Schiff base(3-9) which give it ability to act as multi dentate ligands for transition metal ions , most of these compounds used are chelating ligands in coordination chemistry.

 

EXPERIMENTAL:

Melting points were determined in open capillary tube and were uncorrected. The I.R-spectra were recorder in KBr–disc, Shimadzu (8300), (C.H.N)–elemental analysis, Atomic absorption, UV–Visspectra  photometer, molar conductance (DMSO –solvent ).

 

Synthesis of ligand (DAP):

1,3 –(diphenyl ) -1,3 –bis (acetic imine ) propyl.

They compound was synthesized according procedure(10), 1,3 –diphenyl –propane -1,3 –dione(0.01mole) and (0.02mole) from glycine were refluxed in presence of absolute ethanol with drops of glacial acetic acid for (3hrs) , the precipitate was filtered and dried , then re crystallized with absolute ethanol to yield 87% of ligand (DAP) .

Synthesis of ligand (PIP) :

2,6bis (phenyl iminemethylene imine ) phenol .

2,6di formal phenol (0.01mole) was refluxed with (0.02mole) of methylene di amine in presence of absolute ethanol for (4hrs) with mechanical stir ,the precipitate was filtered and re crystallized , which refluxed with (0.02mole) of benzaldeehyde to produce 84% of ligand (PIP) .

 

Synthesis of ligand (MAH) and ligand (MCP) :

3–(4-methyl benzene azo )-2,4- bis(2-hydroxyl benzyl imine methylene imine )-pentyl

3-(4-methyl benzene azo)-2,4–bis(2-carboxy benzene–ethylene di imine) pentyl .

(0.01mole) of 4- methyl aniline was dissolved in (3ml) of hydro chloric acid and (0.6gm) of sodium nitrite in temperature (0-5) oC then ethanolic solution of acetyl acetone (0.01mole) added , after (48hrs), the precipitate was filtered and dried , which (0.01mole) refluxed with (0.02mole) of (methylene di amine or ethylene di amine) respectively. According to procedure(10,11) , the precipitate were filtered and dried , which (0.01mole) refluxed with (0.02mole) of (salicyldehyde, or 2- formal benzoic acid) respectively to yield (85%, 83%  ) from ligands (MAH) and (MCP) respectively.

 

Synthesis of ligand (MHD) :

2-(4–methyl benzyl azo ) -1,3- bis (2- hydroxyl benzyl hydrazo imine ) propane -1,3 –dione .4- methyl aniline (0.01mole) was dissolved in (3ml) of hydrochloric acid and (0.7gm) of sodium nitrite at (0-5)̊ C, then ethanolic solution of diethyl malonate (0.01mole), after (48hrs), the precipitate was filtered and dried, which (0.01mole) refluxed with (0.02mole) of hydrazine to produce compound, which (0.01mole) refluxed with (0.02mole) of salicyldehyde for (4hrs), the precipitate was filtered ,re crystallized from ethanol to produce 86% of ligand (MHD) .


Synthesis of complexes with (cd2+):

According to procedure(11), the hot ethanolic solution of ligand [(DAP), or (MAH) or (PIP) or (MCP)] respectively was added to solution of cadmium chloride (CdCl2) in mole ratio (metal:ligand) (1:1) respectively after stirring (1hrs), precipitates formed , dried and recrystallized to yield (80%, 83%, 81%, 84%) respectively from complexes of [(DAP), (MAH), (MCP), (PIP)] respectively.


 

RESULTS AND DISCUSSION:

All ligands and complexes were studied by many methods:

 

Study of optimal condition of complexes:

The optimal conditions for formation of complexes with cadmium ion(II) were studied in this paper like calibration curves of optimal concentration of Cd2+= (0.65X10-4m), while concentration of ligands [1X10-3M of ligand (DAP)., 0.5X10-3M of ligand (PIP)., 0.35X10-3M of ligand (MAH)., 0.40X10-3Mof ligand (MCP )]., while optimal (PH=8) was base medium to formation of complexes by job method and mole ratio method through series solutions were prepared having a constant concentration (1X10-3M) of Cd salt (CdCl2) and ligand., the (M:L) ratio was determined from relationship between the absorption of observed light and mole ratio (M:L) found to be (1:1) for all complexes. Other studies of these complexes in table (1) and  figs (1-5).

 

Other measurements:

The elemental analysis shown in the Table (1) indicates that the Cd–complexes [(DAP), (PIP), (MAH), (MCP)] have stoichiometry (Metal: Ligand) (1:1) from results of mole ratio method.

 

The molar conductance values (0.76 -1.64) ohm-1. mol-1.cm2 of (1X10-3m) solution in DMSO indicate that the Cd–complexes are non–electrolytic in nature .I.R – spectra shown absorption  bands in ligands [(DAP), (PIP) ,(MAH) ,(MCP) ] at  (3410 -3480) cm-1 due to phenolic hydroxyl groups(12) and hydroxyl groups of carboxylic group respectively in free ligands which disappeared in spectra of their complexes indicating the coordination through phenolic oxygen moiety and oxygen of carboxyl group at bond (M–O) are (509 -582) cm-1. The I.R –spectra of( Schiff bases CH=N, Azo group-N=N-)(13-16) respectively in ligands exhibit  bands  at (1643-1652 and 1486-1490 )cm-1respectively ,which have been  shifted towards lower frequencies at (1628-1640 and 1433-1436) cm-1 respectively in complexes to coordination with (Cd2+) –ion.

The coordination through nitrogen of imine group (CH=N) and Nitrogen of (-N=N-) azo group and oxygen of hydroxyl group of phenol or hydroxyl group of carboxyl in complexes, table (2) and figs (6-9).


Figures of Complexes

 


 

Table (1): physical properties and Elemental Analysis:

Ligands and Complexes

M.P (C)0

λmax

-1.Cm2.mole-1 Conductance

Calc./ Found

C%

H%

N%

Ni%

(DAP)

C19H18N2O4

160

355

/

67.45

67.39

5.32

5.27

8.28

8.17

/

/

(MAH)

C28H30N6O2

190

390

/

69.70

69.58

6.22

6.18

17.42

17.40

/

/

(PIP)

C24H22N4O

182

382

/

75.39

75.27

5.75

5.68

14.65

14.59

/

/

(MCP)

C32H34N6O4

198

398

/

67.84

67.72

6.00

5.92

14.84

14.79

/

/

(MHD)

C24H22N6O4

195

370

/

62.88

62.73

4.80

4.71

18.34

18.27

/

/

[Cd(DAP)]

218

408

0.76

50.84

50.71

3.56

3.48

6.24

6.18

25.06

25.00

[Cd(MAH)]

230

430

0.98

56.71

56.60

4.72

4.65

14.17

14.08

18.97

18.90

[Cd(PIP)Cl]

>250

418

1.64

54.45

54.36

3.97

3.88

10.58

10.44

21.25

21.16

[Cd(MCP)]

>250

445

1.23

56.77

56.64

4.73

4.60

12.41

12.32

16.61

16.53

 

Table (2): FT.IR data (cm-1) of ligands with complexes .

Ligands and Complexes

(CH=N) imine group

(-N=N-) azogroup

(-OH)

(M-N)

(M-O)

(DAP)

1652

/

3480

     /

      /

(PIP)

1643

/

3410

     /

     /

(MAH)

1645

1486

3425

     /

     /

(MCP)

1646

1490

3450

     /

     /

(MHD)

1630

1495

3415

     /

     /

[Cd(DAP)]

1640

/

    /

495

582

[Cd(PIP)Cl]

1628

/

    /

482

509

[Cd(MAH)]

1631

1436

    /

470

557

[Cd(MCP)]

1634

1433

    /

465

575

 

Fig(1) :Mole ratio of Complex [Cd(MAH)]

Fig(2): Mole ratio of Complex [Cd(MCP)]

Fig(3): Mole ratio of Complex [Cd(DAP)]

Fig(4): Mole ratio of Complex [Cd(PIP)CL]


 

PHFig(5): Variation of PH of Complexes

Fig 6

Fig 7

Fig 8

 

Fig 9


 

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Received on 22.03.2014          Accepted on 27.03.2014        

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Asian J. Pharm. Tech.  2014; Vol. 4: Issue 2, Pg 53-58