Synthesis and characterization of new Schiff bases and amides derived from N (1)‎ substituted isatin with 2-aminobenzothiazole, 2-aminopyrimidine and dithiooxamide and some of their metal complexes

Other Title(s)

تحضير و تشخيص قواعد شيف واميدات جديدة مشتقة من الايساتين المعوض في N (1)‎ مع 2-امينوبنزوثايازول، 2-امينو بيريميدين و ثنائي كبريتيدو اوكساميد و بعض معقداتها الفلزية

Dissertant

Khalil, Asma Muhammad Nuri

Thesis advisor

Abd al-Ghani, Ahlam Jamil

University

University of Baghdad

Faculty

College of Science

Department

Chemistry Department

University Country

Iraq

Degree

Ph.D.

Degree Date

2008

English Abstract

First- Six new ligands were synthesized two amides (LI, LII) and four Schiff bases (LIII-LVI) by reacting isatin derivatives with three types of amines in the following manner: 1- The amide ligand LI was prepared from heating N-acetylisatin with 2-aminobenzothiazole in acetic acid in a mole ratio of 1:2 respectively.

2- The second amide ligand LII was prepared by heating N-acetylisatin and 2-aminopyrimidine in acetic acid in a mole ratio of 1:2 respectively.

3- The Schiff base LIII was prepared by heating a homogenized powdered mixture of N-acetylisatin and dithiooxamide (dto) in a sealed tube at (160-170°C) in a mole ratio of 2:1 respectively.

4- The Schiff base LIV was prepared by heating a homogenized powdered mixture of N-benzylisatin and 2-aminobenzothiazole in a sealed tube at (110-120°C) in a mole ratio of 1:2 respectively.

5- The Schiff base LV was prepared by heating a homogenized powdered mixture of N-benzylisatin and dto at (140°C) in a mole ratio of 1:2 respectively.

XIV 6- The Schiff base LVI has been prepared by heating N-benzoylisatin with dto in butanol in a mole ratio 1:1 respectively.

Second- The ligands were characterized and their chemical structures were elucidated depending upon elemental microanalyses, IR, UVVisible, 1H, 13C NMR spectra and by mass spectrometry.

Third- The following series of metal complexes have been synthesized from heating the studied ligands with metal ions using various ratios of L:M to form the expected complexes in the following manner: 1- Complexes of LI with Co(II), Ni(II), Cu(II), Zn(II), Ir(III), Pd(II) and Pt(IV) ions in mole ratios (M:L) of (1:1), (1:1), (1:1), (2:1), (1:2), (1:2) and (1:2) respectively in ethanol gave instead the following formula: [LICoCl2].EtOH , [LINiCl2].0.1EtOH , [LICuCl2], [(LI)2Zn(OAc)2] , [(LI)2IrCl2].Cl.0.5EtOH, [(LI)2PdCl2].0.5EtOH and [(LI)2.5PtCl3].Cl.2EtOH respectively.

2- Complexes of LII with Co(II), Ni(II), Cu(II), Zn(II), Ir(III), Pd(II), Pt(IV) and In(III) ions in mole ratios (M:L) of (1:1), (1:1), (1:1), (2:1), (1:2), (1:2), (1:2) and (1:1) respectively in ethanol gave instead the following formula: [(LII)1.5CoCl2].1.3H2O , [(LII)1.5NiCl2].1.3H2O , [(LII)1.5CuCl2].2H2O , [(LII)2Zn(OAc)2].3.4H2O , [(LII)3IrCl3].2H2O , [(LII)3PdCl].Cl.0.1H2O , [(LII)2PtCl2]Cl2.0.1H2O and [(LII)1.5InCl3].0.1H2O respectively.

3- Complexes of LIII with Co(II) ion in DMF, Ni(II), Cu(II), Pd(II) in butanol and Pt(IV) ions in DMSO in mole ratios (M:L) of (1:1), (1:1), (1:1), (1:2), and (1:2) respectively gave instead the following formula: [(LIII)2Co2Cl2]Cl2 , [(LIII)2NiCl2].4BuOH , [LIIICuCl(H2O)]Cl.0.5BuOH, [(LIII)2PdCl]Cl and [(LIII)2PtCl2]Cl2.1.8EtOH.H2O respectively.

XV 4- Complexes of LIV with Co(II) and Pd(II) ions in butanol, Ni(II) in ethanol and Pt(IV) in DMSO in mole ratios (M:L) of (1:1), (1:2), (1:2), and (1:2) respectively gave instead the following formula: [LIVCoCl]Cl , [(LIV)2PdCl2] , [LIVNiCl2] and [(LIV)2.5PtCl3]Cl respectively.

5- Complexes of LV with Co(II) and Ni(II) ions in DMSO, Cu(II), Pd(II) and Pt(IV) ions in butanol in mole ratios (M:L) of (1:1), (1:1), (1:1), (1:2) and (1:2) respectively gave instead the following formula: [LVCoCl]Cl.0.4H2O.0.3DMSO , [LVNiCl2] , [LVCu]Cl2.H2O , [(LV)2Pd]Cl2 and [(LV)2.5PtCl]Cl3 respectively.

6- Complexes of LVI with Co(II), Ni(II) and Pd(II) ions in DMSO in mole ratios (M:L) of (1:1), (1:1) and (1:2) respectively gave instead the following formula: [LVICo]Cl2.H2O , [(LVI)2Ni]Cl2 and [(LVI)2Pd]Cl2 respectively.

7- Template synthesis of Co(II) complexes for all ligands was carried out by heating the starting materials used for the preparation of the ligand with Co(II) chloride in the specified solvent and molar ratio as follows: I- N-acetylisatin, 2-aminobenzothiazole and cobalt(II) chloride (1:2:1 respectively) in butanol gave the formal [LICoCl2].0.4BuOH.

II- N-acetylisatin, 2-aminopyrimidine and cobalt(II) chloride (1:2:1 respectively) in butanol gave the formula [(LII)1.5CoCl2].0.5H2O.

III- N-acetylisatin, dto and cobalt(II) chloride (2:1:2 respectively) in butanol gave the formula [(LIII)2Co2Cl2]Cl2.

IV- N-benzylisatin, 2-aminobenzothiazole and cobalt(II) chloride (1:2:1 respectively) in ethanol gave the formula [LIVCoCl]Cl.

XVI V- N-benzylisatin, dto and cobalt(II) chloride (1:2:1 respectively) in butanol gave the formula [LVCoCl].Cl.0.3H2O.0.1BuOH.

VI- N-benzoylisatin, dto and cobalt(II) chloride (1:1:1 respectively) in butanol gave the formula [LVICo]Cl2.0.2H2O.

Fourth- The metal complexes were characterized and their sterochemical structures and geometries were suggested depending upon data of microelemental analysis (CHN), spectral studies (FTIR, UV-Vis), magnetic moments, flame atomic absorption, chloride content and electrical conductivity as well as the thermogravimetric analyses (TG, DTG).

The coordination chemistry and bonding behaviours of ligands and metal ions were studied depending on electronic spectra of metal complexes in solution in the visible and near IR regions.

Ligand field transition were determined from observed absorption band positions.

Band energies and Racah parameters were calculated by applying observed data on Tanaba Saugano diagram of metal complexes.

Octahedral geometries were suggested for Pt(IV), Ir(III), Zn(II) and In(III) complexes, Co(II) complexes of LII, Ni(II) and Cu(II) complexes of LII and LIII.

The tetrahedral geometry was suggested for Co(II) complex of LI, LIII-LVI, Ni(II) complex of LI, LIV-LVI.

Square planar geometry was suggested for all Pd(II) complexes and Cu(II) complex with LI and LV.

Fifth- Complex formation by molar ratio method was studied in ethanol.

Results were comparable to those obtained in solid complexes.

Sixth- Biological activity of ligands LI, LIII LIV and LVI and some of their selected metal complexes were evaluated in comparison with isatin and its substituted derivatives as follows: 1- Studying the growth inhibition against two types of pathogenic bacteria (Staphylococcus Aureus and Proteus Vulgris).

The four ligands exhibited activity against both types except LI which was XVII inactive against Staphylococcus Aureus whereas most metal complexes showed various growth inhibition activities.

2- Studying of the growth inhibition against the two types of pathogenic fungi (Aspergillus Niger and Candida Albecans).

The four ligands showed no activity against Candida Albecans whereas metal complexes especially those of LVI were active.

Various degrees of growth inhibition against Aspergillus Niger were recoded by the ligands and some of their metal complexes.

Highest inhibition was recorded by LIII and LVI, Co(II) complexes of LI and LVI and Pd(II) complex of LIII.

Main Subjects

Chemistry

No. of Pages

255

Table of Contents

• APA
• MLA
• AMA

Language

English

Data Type

Arab Theses

Record ID

BIM-600302