Analytical Application of Aminohydroxamic Acids
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SD0100031 Analytical Application of Aminohydroxamic Acids By atari \^Aibd (L*ud ^jradt L^l B. Sc. Chemistry A thesis submitted in fulfillment for the M. Sc. Degree in Chemistry Department of Chemistry Faculty of Science University of Khartoum November 2000 3 2 / 3 7 To The soul of my mother To my father, My children, My wife, My brothers, and sisters. DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document Ac It n o w I e d g m e n ts / I would like to express my deepest thanks and gratitude to my supervisor Dr. Taj Lilsir Abass for his directions, invaluable advice, encouragement and guidance throughout the course of this study. Thanks are also extended to the slalTof chemistry department for their permanent do-operation. My thanks also to my friends for their assistance and support. Last my special (hanks to my IViend Abdelhafe'ez and Abd El Latif for typing this thesis. Abstract Anlbranilic !|ydroxamic ^acad was {prepared by coupling of methylanthranilate! (prepared by esterification of anthranilic acid with methyl alcohol using the Fisher—Speir method)' with freshly prepared hydroxylamine. The ligand was characterized by the usual reaction of hydroxamic acid with acidic V( V) and Fe(III) solutions that gives' a blood-red colour in amyl alcohol and deep-violet colour in, aqueous solution, respectively. The absorbance of Fe(III)-hydro'xamic acids complexes increases with increase of pH. In this study, the effect of pH on the absorbance of Fe(lll)-anlhranilic hydroxamic acid was in accordance with this trend. The maximum absorbance was obtained at pH 5.0 at maximum wavelength of 482 HID. For Cu(II)—anthranilic hydroxamic acid complex, the use of acidic or basic pi I lead to the precipitation of Cu(II)-ligand complex. But when using buffer pi I (acetic acid/sodium acetate)a clear green colour of Cu(II)- Ligand complex was obtained. The maximum absorbance'was obtained at pi 1 6.0 at maximum wavelength of 390 nm. V(V)-anmranilic hydroxamic acid complex was extracted in acidic medium in amyl alcohol at pH 2.0 because in aqueous solution V(V)- anthianilic hydroxamic acid complex has not clear colour. It was observed that the maximum extraction in acidic medium decreases sharply with the Hi increasing' of pH yajue.. The maxi'mum; wavelength for maximum absorbance was recorded at 472 nm. V(V) interfered with deterrnination of Fe(III) above concentration of 2 pprn^ whereas Cu(II) interfers slightly with'the determination of Fe(III) ions even at a high concentration of the Cu(II) ions. i • Both Cu(ll) and Ni(II) do ridt interfer with the determination of V(V) ions even at high concentrations, Fe(III) ion produced slight interference, while Mo(VI) ions have a pronounced interference. Both. V(V) and Fe(III) iong ... interfered markedly with the deterniination of Cu(II) ions,and made impractical under these conditions. However, the calibration curves for the three metal ions produced a practical linear dynamic range. IV T^ble of Contents The Contents Page Dedication I Acknowledgment II Abstract in English III Abstract in Arabic V The Contents VI List of tables IX List of figures X Chapter One Introduction i , 1 1.1 Complexation reaction I 1.1.1. Complexation ability of metals 2 1.1.2 Complexation ability of ltgand . 3_ 1.2. Interference , 4 1.3. Masking and demasking of chemical reaction 5 1.4 Solvent extraction 8 1.4.1. The Distribution ratio 9 1.4.2. The percent of extraction 10 1.4.3 The extraction process ; 11 1.4.4. The separation efficiency of metal chelates 12 1.5. Hydroxamic acids 13 1.5.1. Structure of hydroxamic acid 14 1.5.2. Nomenclature 18 1.5.3. Acidity of hydroxamic acids 19 1.5.4. Preparation of hydroxamic acids 20 1.5.5. Reactions of hydroxamic acids 22 1.5.6. Detection of hydroxamic acids 29 1.5.7. 1. R. of hydroxamic acids 29 1.5.8. Monohydroxamic acids as a ligand , 30 1.5.9. Aminohydroxamic acid as ligands • 32 1.5.9.1. Acidity of aminohydroxamic acid ' 33 1.5.9.2. Complex formation and analytical application of 34 aminohydroxamic acids .5.9.2.1. Copper complexes 35 .5.9.2.2. Nickel complexes ' ' .37 .5.9.2.3. Zinc(II) and cobalt(II) complexes • 39 .5.9.2.4. lron(lll) Complexes ' 39 1.5.9.3. The effect of side chain donors on the coordination 43 of a-amino hydroxamic acid .1.5.9.4. Derivatives of p-aminohydroxamic acid 46 1.5.9.5. Complexes of 8-aminohydroxamic acids 50 VI 1.3.10. Th6 Biological activities' of ftydroxamic acids 5,0 Chapter "two 2. Experimental ' 53 2.1. Instruments, 53 2.2. Chemicals , 53 2.3. Synthesis of reagents. 53 213.1 Synthesis of anthranilic hydroxamic acid 53 2.3.1.1.. From the .coupling reaction of 54 N-hydroxyphthalimide anthranilic acid ester, and hydroxylamine 2.3.1.1.1. Preparation of N-hydroxyphthalimide • 54 2.3.1.1.2. Esterification of anthrahilic acid by N- . 54 hydroxyphthalimide \. 2.3.1.1.3. The coupling reaction between the N~ 55 hydroxyphthalimide and hydroxylamine 2.3.1.2.' Preparation of anthranilic hydroxamic acid from the 56 coupling reaction between methyl anthranilate and , hydroxylamine 2.3.1.2.1. Preparation of methyl anthranilate 56 2.3.1.2.1.1. Identification of methyl anthranilate . 57 2.3.1.2.1.1.1 Nitrogen contents (N%) .' 57 2.3.1.2.1.1.2 I.R spectra 58 2.3.1.2.2. The coupling reaction between methyl anthranilate 58 and the hydroxylamine 2.3.2. Characterization of the anthranilic hydroxamic acid 59 2.3.2.1. IR spectra ,.. 59 2.3.2.2. Nitrogen contents (N%) . , 60 2.4. Preparation of reagents : 60 2.4.1. Preparation of pH 1.0 to pH 10.0 buffer solutions 62 2,5. Analytical parameters for Fe(III),V(V) and Cu(II) 64 ions • 2.5.1. Determination of wavelength of the maximum 64 absorbance for 'Fe(III) 2.5.2. The effect of the ph on the absorbance using HC1, 64 HNO3 and H2SO4 acids , 2.5.3. Construction of calibration curve for Fe(III)- 65 anthranilic hydroxamic system ; 2.5.4. The effect of. foreign ions, on the absorbance of 68 Fe(lll) anthranilic hydroxamic acid 2.5.4.1. , The effect of V(V) on the absorbance or Fe(III)- 68 ligand 2.5.4.2. The effect of Cu(II) on the absorbance of Fe(III)- 69 anthranilic hydroxamic acid at pH5 and 482 nm. VII 2.6. Analytical parameters for V(V) 69 2.6.1. Determination of V(V) wavelength of the maximum 69: absorbance 2.6.2. The effect of thei>pH on the absorbance ofVCV)- 70 Ligarid complex using HC1, HNO3 and H2SO4 2.6.3. Construptioh of j calibration curve for V(V)- 71 anthraniHc hydrox^mic acid cpmplex 2.6.4. The effect of foreign |8ns {Mo(VI), Fe(III) Cu(II), 74 Ni(II)} I on the •absorbance of V(V)-anthranilic hydroxamic acid system at pH 2 and 472 nm 2.6.4.1. Effect of Fe(III) on the absorbance of V (V)-ligand 74 •..: complex • ; • . , . ' ' 2.6.4.2. The effect k>f Mo(VI) on. the absorbance of V(V)- 75 ligand complex at pH2 and 472 nm 2.6.4.3. The effect of Ni(II) on the absorbance of V(V)- 75 ligand complex at pH2 and 472 nm 2.6.4.4. Theyeffect of Cu(II) on^the absorban.ce of V(V)- 76 ligand complex at?pfH2 and 472vnm • 2.7. Analytical parameters for Cu(II) ion 77 2.7.1. Determination of Cu(II) wavelength of the maximum 77 absorbance 2.7.2. -The effect of the*;:buffer: pH on the absorbance of 77t , ' Cu(II)-ligand complex : 2.8. Construction of calibration curve for Cu(II)- 78 anthranilic hydroxamic acid complex 2.9. The, effect of foreign ions Fe(III), V(V) on the '81 absorbances of Cu (II)-anthranilic hydroxamic acid at buffer pH6 and 390 nm 2.9.1. The effect of Fe(III) on the absorbance of Cu(II)- 81 ligand complex 2.9.2. The effect ofV(V) on the absorbance of Cu(II)- 82 ligand complex 1 Chapter three : , , T Discussion ' 83 References 87 VIII List of tables Table 1 N%'o£methylanthranilate 58 Table 2 '.' :• The!I,R spectra for methyl anthranilate 58 Table 3 The IR spectra of anthranilic hydroxamic acid • 60 Table 4 N% of anthranilic hydroxamic acid 60 Table5 The effect of pH of an absorbance of Fe(III)-ligand with 65 different adijds at 482 nm Table 6 Calibration for Fe'(III) at 482 nm 66 Table7 The effect of V(V) on the absorbance of Fe(III) at pH5, 68 and482nm Table 8 The effect of Cu(II) on the absorbance of Fe(III)- 69 anthraru'lic hydroxamic acid at pH5 and 482 nm Table 9 ,• The effect of pH oh the absorbance of V(V)-ligand with 70 effect acids at 472 nm Table :10 Calibration for V(V) at 472 nm pH2 71 Table 11 The effect of Fe(III) on the absorbance of V(V) at pH2 74 and 472 nm Table !12 The effect of Mo(VI) on the absorbance of V(V)-ligand 75 Table 1 The effect of Ni(II) on the absorbance of V(V)- • 76 anthranilic hydroxamic acid at pH2 and 472 nm Tablet 4 The effect of Cu(II) on the absorbance of V(V)-ligand 77 complex at pH2 and 472 nm Tablel 5 The effect of pH on the absorbance of Cu(II)-ligand 78 complex Table 116 Calibration of Cu(Il)-Hgand complex at pH6 and 390 nm 79 Tablel 7 The effect of Fe(III) on the absorbance of Cu(II) 81 anthranilic hydroxamic acid at pH6 and 390 nm Table 18 The effect of V(V) on the absorbance of Cu-ligand 82 complex at pH6 and 390 nm IX List of figures Fig.