مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Synthesis of Some New Metal Complexes of 5,6-O- Isopropylidene-2,3,-O,O Acetic Acid-L-Ascorbic Acid and Evaluation their Biological Activity J. S. Sultan, A. A. Mukhlus, F. H. Musa Department of Chemistry, College of Education, Ibn Al- Haitham, University of Baghdad Received in : 3 April 2011 Accepted in : 16 November 2011 Abstract Stable new derivative of L-ascorbic acid, 5,6-O-iso propylidene 2,3-O,O acetic acid-L- ascorbic acid (L) was synthesized in good yield by the reaction of 5,6-O-isopropylidene-L- ascorbic acid with chloroacetic acid in presence of potassium hydroxide. The new product (L) was characterized by 1H, 13C–NM R, mass spectrum and fourier transform infrared (FTIR). The reaction of the ligand (L) with metal bivalent ion., M+2 = (Co, Ni, Cu, Cd, Hg, Mg, Ca, Pb) synthesized and characterized by FTIR, UV-Visible, Molar conductance, Atomic absorp tion and the molar ratio (Ni+2, Cd+2) complexes. Spectroscopic evidence showed that the binding of the M(II) ions with (L) are through the (C–I=O) Lacton and O-2-CH2COO – as a bidentate manar resulting in a six– coordinated metal ion; the values of , KF, G were estimated for Cd +2 , Ni +2 complexes and , B value, for Co +2, Ni+2 complexes were calculated too. The study of biological activity of the ligand (L) and (Cd+2, Cu+2, Ca+2) complexes showed various activities toward staphylococcus aureu and Escherichia coli, except Ca- complex didn't show any effect. Key word: synthesis, spectroscopic, Biological studies Introduction The most synthetically useful and well studied class of modified L-ascorbic acid is the 5,6-O-isopropylidene-L-ascorbic acid derivatives (Ketal of L-ascorbic aicd). These derivatives (5,6-O-Ketal & 5,6-O-acetal) are significant in organic synthesis for protection of the 5,6- hydroxyl functions, which makes them more soluble in organic solvents and also limits the interference of the protected hydroxyl group from reactions involving the C2- and C3- enol hydroxyls[1-3], consequently, most synthesis began with 5,6-O-isopropylidene- L-ascorbic acid as the starting material, which is cheaply and easily made from L-ascorbic acid[4]. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Metal complexes of ascorbic acid have been prepared and characterized. Synthesis of ascorbate complexes of some metals of the first transition series (e.g., TiO+2, Cr+3, Mn+2, Co+2, Ni+2, and Zn+2) have been achieved and they showed biochemical mechanism of metal ion catalyzed autooxidation of pharmaceutical and naturally occurring vitamin C[5]. The Vis, FTIR and 1 H–NMR spectral characterization of titanyl ascorbates has been done by Jabs et.al.,[6]. Tajimir– Riahi[7] reported the FTIR and 13C–NM R analysis of Al(III), La(VI) and Pb(II) ascorbates as solids and in solutions. The biological importance of the ascorbic acid and its complexes are well known[5,6,8-12]. Recently, we reported some new metal complexes with 2,3,5,6-O,O,O,O-tetra acetic acid-L-ascorbic acid and showed various activities toward staphylococcus aureu and Escherichia coli, except Ca-complex didn't show any effect[13]. The main target of the present article is to prepare new derivatives of 5,6-O-iso propylidene-L-ascorbic acid and its metal complexes and evaluate their activity toward staphylococcus aureu and Escherichia coli. Experimental Materials All chemicals were purchased from BDH, and used without further purifications. Instrumentation 1. FTIR spectra were recorded in KBr on Shimadzu- 8300 Spectrophotometer in the range of (4000-400 cm–1). 2. The electronic spectra in H2O were recorded using the UV-Visible spectrophotometer type (spectra 190-900 nm) CECIL, England, with quartz cell of (1 cm) path length. 3. The melting point was recorded on "Gallen kamp melting point apparatus". 4. The conductance measurements were recorded on W. T. W. conductivity meter. 5. The characterize of new ligand (L) is achieved by: A: 1 H- and 13 C NM R spectra were recorded by using a bruker 300 MHZ (Switzerland). Chemical shift of all 1 H- and 13 C-NM R spectra were recorded in  (ppm) unit downfield from internal reference tetramethylsilane (TMS), using D2O solvent. B: GCM S spectrum was performed GCM S solution/ Msc/ Msc-DI- unk, 9gm, company a Shimadzu model carried out QP 505 A, orgin: Japan. C: All these analysis were done in at AL-al-Bayt University , Al- Mafrag, Jordan. 6. Thin layer chromatography (TLC): The (TLC) was performed on aluminum plates coated with (0.25 mm) layer of silica gel F254 (Fluka), and were detected by iodine. 1. Synthesis of 5,6-O-iso propylidene-2,3,O,O-acetic acid -L-ascorbic acid (L) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 O O O O O O O O HO OH O O 2 KOH H3C H 3C H3C H3 C H 2C OH C 2 Cl CH 2COOH O H 2C C OH O 2KCl.xH2O 5,6-O-iso propylidene-L-ascorbic acid (0.216 gm, 1 m mole) was dissolved in (15 ml) ethanol. Potassium hydroxide (0.112 gm, 2 m mole) in ethanol (10 ml) solution was then added. Stirring was continued for (30) minutes. The chloroacetic acid (0.190 gm, 2 m mole) in ethanol (15 ml) solution was then added drop wise, stirring was continued for one hour. The resulting mixture precipitate was filtered, recrystallized from (15 ml ethanol + 5 ml water) gave pale brown crystalline residue, melting point (109- 110 C), yield 92%), RF  0.581, (Methanol: Benzene), (5:5). 2. Synthesis of 5,6-O-iso propylidene 2,3-O,O-acetic acid-L- ascorbic acid metal complexes, (M II =Co, Ni, Cu, Cd, Pb, Hg, Ca and Mg) All complexes were prepared as follows: To a solution of the L (0.332 gm 1 m mole) in ethanol (20 ml) was added a solution of potassium hydroxide (0.056 gm, 1 m mole) in ethanol (5 ml). The mixture was stirred at room temperature for hour. To this mixture was added solution of (1 m mole) of metal chloride in (20 ml) of ethanol. (0.170 gm CuCl2.2H2O), (0.238 gm NiCl2.6H2O), (0.238 gm CoCl2.6H2O), (0.202 gm CdCl2.H2O), (0.331 gm Pb(NO3)2), (0.271 gm HgCl2), (0.204 gm MgCl2.6H2O) and (0.219 gm CaCl2.6H2O). Then the solution was stirring for one hour. The solution was evaporated slowly to bring down the complex. The complex was recrystallized from ethanol. The physical properties for synthesized ligand L and its complexes are shown in Table (1). Results and Discussion 5,6-O-iso propylidene-2,3-O,O-acetic acid L-ascorbic acid (L) was prepared in one step from reactions 5,6-O-iso propylidene-L-ascorbic acid with chloroacetic acid in presence of potassium hydroxide, scheme (1): Scheme (1): The reaction of 5-6-iso propylidene-L-ascorbic acid with chloro acetic acid in presence of potassium hydroxide 1 2 مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 The I.R spectrum of 5,6-O-iso propylidene-L-ascorbic acid Fig. (1) as starting material is compared with the new ligand (L) Fig. (2), the results are summarized in Table (2). 5,6-O-iso propylidene-L-ascorbic acid exhibits two bands at 3240 cm –1 and 3078 cm –1 assigned to (OH) positions (C–3) and (C–2) respectively[14-15]. These are disappeared in the spectrum of the new liagnd (L) accompanied by the appearance of bands in the (3402 cm –1) (OH of water); (3244– 2789 cm–1), 2596 cm–1 are characteristic strongly H–bonded O–H of carboxylic acid[16-17]. Stretching bands at (2993, 2943 cm–1) and bending bands at (1431 cm–1) are assigned for C–H aliphatic respectively. (C–I=O) stetching vibration appeared at (1755 cm–1). The bands at (1662, 1652 cm–1) in starting material are due to the (C=C) + (C=O) appeared as one symmetric band at (1662cm–1) in the new ligand (L). The new ligand exhibits additional two peaks at (1600, 1381cm–1) due to the stretching vibration of asymmetric and symmetric of (COO–), (=219 cm–1)[18,19]. The mass spectrum of the ligand (L) Fig. (3) gave the fragments as shown in scheme (2): Scheme (2): The fragmentation sequence of (L) with relative bundance O O O O H C 4 H 4 O 2 1 1 6 ( 8 % ) O O H 3 C H 3 C H 3 C O C - C 9 H 1 2 O 8 1 0 1 ( 2 % ) H H H C H 2 O O O H H H H C O 2 4 (100%) C H 2 C O O H H O O C C 8 H 8 O 8 C 1 3 H 1 6 O 1 0 M . W = 3 3 2 H 3 C C H C H C 5 H 8 O 2 - C 3 H 4 O 2 -C4H8 مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 NMR Spectral (1H, 13C) The 1H, 13C–NM R spectra of ligand (L) in D2O are shown in Figs. (4 and 5). The following signals were distinguished: 1. The 1H–NMR for the Lacton ring 4–H was displayed as doublet (4.5–4.6) ppm[21,22]. 2. The CH3 appeared at = 1.27 ppm. 3. The CH2–6, CH–5 appeared at (4.1, 4.2) ppm. 4. The CH2–7 showed at (4.7–4.8) ppm. The 13 C–NMR 1. The signal at =22 ppm is due to the CH3. 2. The signal at 176.7 ppm is assigned to C–1 Lactone. 3. The signal at 169.8 ppm is due to carboxylic group. 4. The signals at (121), (153), (76), (65), (110) are due to (C–2, C–3, C–4, C–5, C–6). The results were compared with those obtained by chem. office program. IR spectra of the complexes The I.R. spectrum of 5,6-O-isopropylidene-2,3-O,O-acetic acid as a ligand (L) comprised with its complexes, the results are summarized in Table (3). A broad band centered at 3402 cm –1 is related to (OH of water), bands at (3244– 2789 cm–1) are due to the presence of (H– bonded OH of carboxylic acid) in free ligand[23]. The free ligand (L) carbonyl C–I=O stretching vibration was observed as a band with medium intensity at 1755 cm –1 and shifted towards a lower frequency at 1739 cm –1 in (Cd II ), 1732 cm–1 (HgII, CoII), and 1735 cm–1 (NiII, CuII, MgII, CaII, PbII) due to coordinate with metal ions. Similarly, the slightly broad band concerned at 1662 cm –1 is due to couple C=O and C=C stretching of free ligand (L) were observed as two bands (1639, 1620 cm –1) (HgII), (1670, 1612 cm–1) (CuII), (1645, 1604 cm–1) (NiII), broaden peak center at 1620 cm–1 (CoII) Fig. (7), 1635 cm –1 (Mg II ), 1610 cm –1 (Pb II ), 1627 cm –1 (Cd II , Ca II ). The observed spectral changes are due to the presence of unequivalent behavior of O–CH2COOH groups in C–2 and C–3 towards the metal ions[24,25]. The free ligand (L) exhibits a very strong absorption band with shoulder at 1600 cm –1 is due to the stretching vibration of carboxylic group. This group is present in the spectra of all complexes confirming that O–CH2COOH–C–3 is uncomplexed which is lower than expected, so this is related to the degree of hydrogen bonding which is lengthing and weaking the , Fig. (6)[26,27]. The appearance of two bands in the (1416, 1320, =96) cm–1 (CuII), (1408, 1315, =93) cm–1 (NiII), (1419, 1323, =96) cm–1 (CaII), (1404, 1311, =93) cm–1, (CdII), (1420, 1327, =93) cm–1, (MgII), (1390, 1370, =70) cm–1, (HgII) are due to the  asymm. (COO–),  symm. (COO–)[28,29]. The value of (96–70) cm–1 indicated that the carboxylate group in C–2 coordinate to metal ions as a bidentate fashions[29-30]. The C–O, C–C stretching vibrations of (L) were observed as sharp bands at 1100–900 cm–1 and exhibited major losses of intensities in the all complexes. (C=O) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 The absorption band at range (700–600) cm–1 is assigned to the coordinated water[22,31] conclusive evidence of the bonding is also shown by the observation that new bands in the spectra of all metal complexes appeared in the low frequency region at 555–516 cm–1 characteristic to M–O stretching vibration[16,19,32]. Electronic Spectra The electronic spectrum of (L) Fig. (8) under study in water solution was characterized mainly by two absorptions in the region (248.5) nm (40241) cm–1 (max=952 molar –1 cm –1 ) assigned to (–*) and (358.5) nm (27894) cm –1 (max=17 molar –1 cm –1 ) as tail assigned to (n–*) transition[33]. The electronic absorption of Co–complex red colour solution is shown in Fig. (9). Bands at 750 nm (13333) cm –1 is due to 4A2g  4T1g and at (650) nm (15380) cm–1 is due to 4T2g  4T1g. However most octahedral cobalt (II) complexes are pink or reddish brown and these two transitions are typical of the spectra of octahedral complexes[21,22,24,34]. The ligand field parameters (q, B an ) are calculated from Fig. (a) 1 2 cm740 18 13333 ΔqΔq18υ  1 = 8 q = 8  740 = 5920 cm–1 3= 6 q + 15 B 15385 = 6  740 + 15 B 75.0 971 66.729 B B 729.66B metal free comp. comp    The electronic absorption of Ni complex[35-36] Fig. (10) showed multiple bands centered at (700) nm (14286) cm –1 and another band at (430) nm (23256) cm–1 are due to 3T1g 3A2g and 3T1g(P) 3A2g respectively[37] parameters (q, B an ) are calculated from Fig. (b) 1.63 14286 23256 υ υ 2 3  861 27 23256 27 B υ E comp 3  compB 84.0 1030 861 B B metal free comp.  The spectrum of Cu– complex green colour is shown in fig. (11). The observed band (786.5) nm (12715) cm –1 is broad and clearly is due to 2 Eg 2 T2g contains several components. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 The ion is in fact tetragonal distorted presumably as a result of the operation of the Jan Teller effect[35,37]. The electronic of the metal complexes M II = Cd, Pb, Hg, Ca, Mg (Table 4) showed (–*) and tail transition are shifted to lower energy for (–*) and high energy for the tail (n –*) compared to the free ligand transition confirming of the ligand (L) to metal ion. Solutions chemistry Molar ratio The complexes of the ligand (L) with selected ions (Ni +2, Cd+2) were studied in solution using water as solvents, in order to determine (M:L) ratio in the prepared complexes, following molar ratio method[38]. A series of solutions were prepared having a constant concentration (C) 10 –3 M of the hydrated metal salts and the ligand (L). The (M:L) ratio was determined from the relationship between the absorption of the observed light and mole ratio (M:L) found to be (1:1). The result of complexes formation in solution is shown in Table (5), Table (6) and Table (7), Fig. (12) and Fig. (13). Molar conductivity for the complexes of ligand (L) The molar conductance of the complexes in (water), Table (8) lies in the (27.5–60) S.cm 2 molar–1 range, indicating their non–electrolyte nature, except for the complexes Hg, and Mg which their molar conductance lies in the (70.4–132.8) S.cm2 Molar–1 range, indicating their electrolytic nature with (1:1) ratio[39]. Biologcal effect of new ligand L and its complexes Indicating that the new ligand and its complexes exhibited antibacterial activity against both gram positive and gram negative bacteria[10-13], except Ca–complex has no effect on both bacteria. Table (9), Fig. (14) and Fig. (15). Conclusion A series of complexes of Co+2, Ni+2, Cu+2, Cd+2, Pb+2, Hg+2, Ca+2, Mg+2 with 5,6-O- isopropylidene 2,3-O,O acetic acid-L-ascorbic acid (L) have been prepared and characterized. The ligand (L); (C13H16O10) acts a tridentate via C–I Lactone and one bidentate carboxylate group giving general formula LM +2 (H2O)X,Y (EtOH)z (KCl)n(X – ). with octahedral structure the resulted carboxylate group were assigned by the infrared spectra. X = H2O coordinated Y = number of H2O hydrated z = number of EtOH n = number of KCl مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 X– = Cl, NO3 in Pb complex. The complexation between metal ions as (CoII, NiII, CuII, CdII, PbII, HgII, CaII and MgII ) with ligand (L, resulted in the formation (1:1) molar ratio (Metal: L). Fig (6). References 1. Ayodel, O. and Mathew, P. D. Mahindaratne and Kandateg wimalasena (2005) Aconvenient to C2 and C3– substituted Gulono -Lactone Derivatives from L–ascorbic acid, J. Org. Chem., 70 (17): 6782-6789. 2. Ayodel, O.; Olabisi, and Kandateg Wimalasena (2004) Rational Approach to selective and Direct 2-O-alkylation of 5,6-O-isopropylidene-L-ascorbic acid, J. Org. Chem., 69 (21): 7026-7032. 3. Hasan, T.and Hindsgaul, O. (2000) Regio Chemoselective Alkylation of L-ascorbic acid under mitsunobu condition, J. Org. Chem., 65: 911-913. 4. Salamon, L. L. (1963) 5,6-O-isopropylidene-L-ascorbic acid, Experientia, 19(12):6119. 5. Jabs, A. M. (1984) The synthesis of ascorbate complexes of some metals, Anorg. Allg. Chem. 514: 179-184. 6. Jabs, A. M.(1984) The electronic, infrared and 1H-NMR of titanyl ascorbates, Anorg. Allg. Chem., 514: 185-195. 7. Tajimair- Riahi. (1991) FT-IR and 13C-NM R of Al(III), La(VI) and Pb(II) ascorbates as solids and in solution, J. of Inorg. Biochem. 441: 39-45. 8. 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Accepted for puplication in Ibn-Haitham Jornal for pure and Applied Science's, 1881/2. 14. Silverstein M. R. G. C. Bassler and Morrill T. C. (1981), "Spectrometric Identification of Organic Compounds", 4 th ed., John Wiley and sons, New York. 15. Fleming and Williams, D. H. (1966) Spectroscopic methods in organic chemistry", Ed. McGraw Hill publishing company ltd, London. 16. Abd El- Wahab, Z. H. (2007) Mononuclear metal complexes of organic carboxylic acid derivatives, Spectrochimica Acta Part A, 67:25-38. 17. John, R. Dyer (1965) Application of Absorption Spectroscopy of Organic compound, Prentic– Hall, Inc. 18. Mesubi, M. A. (1982) An infrared study of Zinc, Cadmium and lead salts of some fatty acids Journal of Moleculular structure, vol. 81(1–2): 61–71. 19. Mohamed, G. G.and Abd El– Wahab, Z. H. (2005) Mononuclear metal complexes of organic carboxylic acid derivatives, Spectrochem. Acta A 61:1059. 20. Parikh, V. M. (1985) Absorption Spectroscopy of Organic Molecules. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 21. Tajmir- Riahi (1990) Coordination Chemistry of vitamin C. part I. Interaction of L- Ascorbic Acid with Alkaline Earth Metal Ions in the Crystalline Solid and Aqueous Solution, J. Inorg. Biochem, 40:181-188. 22. Tajmir- Riahi (1991) Coordination Chemistry of vitamin C. part (II). Interaction of L- Ascorbic Acid with Zn(II), Cd(II), Hg(II), and Mn(II) Ions in the solid state and in Aqueous solution, Int. J. Inorg. Biochem, 42:47-55. 23. Fodor, C.; Arnold, R. and Mohacsi, T. (1983) A new role for L-ascorbic acid Michael donor to alpha, beta-unsaturated carbonyl compounds. Tetrahedron 39: 2137-2145. 24. Malcolm, J. Arendse, Gordonk- Anderson and Nigam P. Rath (1999) Synthesis and characterization of Platinum (II) Complexes of L- Ascorbic Acid, Inorg. Chem. 38:5864- 5869. 25. Rajesh, S. B. and Vidyanand, K. R. (2006) Coordination diversity of new mononucleating hydrazone in 3d metal complexes, J. Serb. Chem. Soc. 71, 12, 1301- 1310. 26. El– Washed, M. G. A.; Refat, M. S. and El, Megharbel S. M. (2009) Synthesis spectroscopic and thermal characterization of some transition metal complexes of folic acid spectrochimia acta A, vol. 70(4): 916–922. 27. Nakamato, K. (1968) M ecarthy Spectroscopy and structure of metal chelate compounds, P. J. John Wiley & Sons, New York, NY, U.S.A. 28. Choi, K. Y.; Jeon, Y. M.;Lee, K. C.; Ryu, H.; Suh, M.; Park, H. S.; Kim, M. J. and Song, Y. H. (2004)Preparation and characterization of a bidentate carboxylate bridged dinuclear cadimium(II) complex with bis(2-pyridyl methyl) amino-3-propionic acid, Journal of Chemical Crystollography, vol. 34: No. 9. 29. Anacona, J. R. (2006) Synthesis and antibacterial activity of some metal complexes of –Lactams Antibiotics, J. Coord. Chem., 54: 355– 365. 30. Nakamoto, K. (1986)Infrared and Raman Spectra of Inorganic and Coordination compounds", 4th, ed., Wiley. New York. 31. Sutton, D. (1968) Electronic spectra of Transition Metal Complexes Mc GRAW-HILL., London. 32. Wang, Y. Y.; Shi, Q.; Gao, Y. C. and Zhou, Z. Y. (2009)preparation and characterization of a bidentate carboxylate bridge dinuclear, Polyhedron 1999, 18. 33. William Kemp. (1987) Organic spectroscopy 2 nd, Edition. 34. Orgel, L. (1966) "An Introduction to transition metal Chemistry", 2 nd ed, Wiley, New York. 35. Rakesh, K.; Sharma, Munirathnam N. and Ashoka, G. Sumuleson, (2008) Asymmetric allylic alkylation by palladium- bisphosphinites, Tetrahedron; Asymmetry , 19:555–663. 36. Khen, F. and khanam, A. (2008) Study of Complexes of cadmium with some L- amino acids and Vitamin-C by Voltammetric technique, Ecl. Quim, Saopaulo, 33 (2):29-36. 37. P. Lever A. B., (1968), "In organic electronic spectroscopy", New York, 6: 121. 38. Skoog, D.A. and Donald ,M. west (1974)Fundamentals of Analytical Chemistry Altoit London Edition. 39. Kettle, S. F. (1975), "Coordination Compounds", Thomas Nelson and Sons, London, P. 165. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Fig. (a): Energy level diagram (Tanabe- Sugano) for d7 ions in an octahedral field[37] (C=4.633B) Fig. (b): A2 and T1 ground states, transition energy ratios versus E(v3)/B (range 16-47). Note that the left-hand ordinate refers to E(v3)/B (16-24.6) and the right-hand ordinate to E(v3)/B (24.6-47) Co and Ni complexes[37] مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Table (1):The physical properties for synthesized lignad (L) and its complexes D = Decomposition, DMF = dimethyl formamide, DM SO = dimethyl sulfoxide Found (Calc.) % Empirical formula Yiel d % M.P.C Colour Metal Solubili ty L.2KCl.XH2O 77.9 109–110 Brown Water, DMF, DMSO LCoCl.2H2O 74 109–110 Red (12.20) 12.70 = LNiCl.2H2O 83 120D Golden (12.80) 12.70 = [LCuCl.2H2O].6H2O.4EtOH.3 KCl 80 130D Green (6.80) 6.60 = [LCdCl.2H2O]. 3KCl 75 210D Brown (14.00) 14.50 = [LPbNO3.2H2O].3KCl 68 210 Dark brown (24.45) 25.60 = [LHgCl.2H2O]. 5H2O.3EtOH.3KCl 83 205D Brown (18.30) 19.10 = LCaCl.2H2O 75 115D White (10.40) 9.50 = [LMgCl.2H2O].10H2O.8EtOH .3KCl 76.7 220D Dark brown (1.24) 1.92 = مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Table (2): infrared spectral data (wave number – ) cm –1 for the L and starting material Compoun d (OH) (C– H) aliph. (C= C) (C– O) (C= O) Lacto ne Additional peaks 5,6-O-iso propyliden e L- ascorbi c acid (3240)br (3078)m (2993 )w (1662 )s (1652 )s 1751( s) (1360–1220)cm –1 Strongly coupled O(2)–H,O(3)–H and C–H bending modes (1100–900)s due to C–O, C–C L (3402)m(OH– H2O) (3244, 2789, 2596) (OH– COOH) (2993 )w (2943 )w (1662 )s (1755 )s (1600,1381)cm–1 asymmetric and sym. COO – (1281–1219)cm–1shifting and splitting OH(C2-C3) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Table (3): Infrared spectral data (wave number  – ) cm –1 for the ligand L and its complexes. Compound (O–H) (C– H) (C =O)  c m –1 asy m.  sym . CO O –  c m – 1 ( M– O) Additional peaks L.2KCl.XH2O 3402(w) (OH water) (3244,2789, 2596) (OH– COOH) (2993– 2943) w (175 5)s (3093)w Due to OH of carboxylic acid C–2 (1662)s C=O, C=C (1100 – 900, for (C–O), C–C–C L complexes LCoCl.2H2O 3417 the OH water 2730-2500 (OH– COOH) 2920 173 2 2 3 (14 00) br (13 20) w 80 520 – 443 1620 C=O, C=C 779- 605 coordinated water LNiCl.2H2O 3396 3344 2650- 2560 OH–COOH 2730 173 5 2 0 140 8 131 5 93 590 - 516 1604(br) C=O, C=C 702-671 coordinated water [LCuCl.2H2O].6 H2O.4EtOH.3KC l 3414(w) 3475(w) 2680- 2580(OH– COOH) 2951 173 5 2 0 141 6 132 0 96 532 - 482 1612 C=O, C=C 661-609 coordinated water [LCdCl.2H2O].3 KCl 3487(br) OH water 2730- 2580 (OH– COOH) 2989(w ) 173 9(s) 1 6 140 4 131 1 93 590 - 524 1616(br) C=O, C=C 783-621 coordinated water OH water OH water مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 [LPbNO3.2H2O]. 3KCl 3410(s) OH water 2700- 2500 (OH– COOH) 2997(w ) 173 5(w) 2 0 (14 19)s (13 85) w 34 555 - 515 1593(w) C=O, C=C 775-605 coordinated water 1420, 1660 NO3 group [LHgCl.2H2O].5 H2O.3EtOH.3KC l 3421(br) OH water 2750- 2500 (OH– COOH) 2981(w ) 173 2(w) 2 3 (13 90) m (13 20) w 70 594 - 516 1639(s) C=O, C=C 771-632 coordinated water [LCaCl.2H2O] 3429(br) OH water 2790- 2660(OH– COOH) 2931(w ) 173 5 2 0 (14 19) (13 23) 96 555 - 493 1616(s) C=O, C=C 779-621 coordinated water [LMgCl.2H2O].1 0H2O.8EtOH.3K Cl 3429(br) OH water 2720- 2620 (OH– COOH) 2940 173 5 2 0 (14 20) (13 27) 93 578 - 540 1635(s) C=O, C=C 779-605 coordinated water Recorder as KBr disk br = broad, s = strong, w = weak, m = medium,  = bending, aliph. Aliphatic مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Table (4): Electronic spectral data of the ligand (L) and its metal complexes Compound n m – wave number cm –1 (max molar– 1 cm –1 ) Assignment s Proposed structure L.2KCl.XH2O 248. 5 358. 5 40241 27894 952 17  * n* LCoCl.2H2O 497. 5 650 20097 15380 770 270 4T1g(P) 4T1 g 4A2g(F) 4T1 g Distorted Octahedral LNiCl.2H2O 372. 9 655. 5 14266 15255.5 1500 240 3T2g 3A2g 3T1g(F) 3A2 g Distorted Octahedral [LCuCl.2H2O].6H2O.4EtO H.3KCl 786. 5 12715 844 2Eg2T2g Tetragonal [LCdCl.2H2O].3KCl 350 28571 350 L.F.C.T. Octahedral [LPbNO3.2H2O].3KCl 350 28571 425 L.F.C.T. Distorted Octahedral [LHgCl.2H2O].5H2O.4EtO H.3KCl 350 28571 1025 L.F.C.T. Octahedral [LCaCl.2H2O] 350 28571 875 L.F.C.T. Octahedral [LMgCl.2H2O].10H2O.8Et OH.3KCl 350 28571 525 L.F.C.T. Octahedral L.F.C.T. = Ligand Field Charge Transfer مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Table (5): VM, VL and Absorption of ligand L2, VM = volume of metal in ml, VL= volume of ligand in ml [L–NiCl.2H2O] [L–CdCl.H2O].3KCl VM VL Abs VM VL Abs 1 ml 0.25 1.654 1 ml 0.25 1.400 1 0.50 1.910 1 0.50 1.700 1 0.75 2.10 1 0.75 1.778 1 1 2.230 1 1 1.990 1 1.25 2.370 1 1.25 2.125 1 1.50 2.300 1 1.50 2.285 1 1.75 2.420 1 1.75 2.340 1 2.0 2.460 1 2 2.345 1 2.25 2.440 1 2.25 2.400 1 2.50 2.470 1 2.50 2.500 1 2.75 2.450 1 2.75 2.550 1 3.0 2.450 1 3 2.565 1 3.25 2.500 1 3.25 2.570 1 3.50 2.500 1 3.50 2.580 1 3.75 2.550 1 3.75 2.590 1 4 2.550 1 4 3.00 K= ML/ [M] [L] (1)  = (Am – As) / Am (2) K = The equation (1) is written to mole ratio (1:1) as the following KF = (1-)/ 2C (3)  = max.b.c (4) KF = stability constant  = Decomposition Degree M = Metal ion L = The ligand مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 [ ] = concentration As = The absorption at the equivalent point of mole ratio. Am = The maximum absorption of the mole ratio. C = The complex concentration (mole. L–1).  G = – 2.303 RT Log K. R = 8.303 T = 273 + 25 = 298 Compounds As Am  K Log K 1/K G [LCdCl.2H2O]3K Cl 1.990 2.345 0.15 3×109 9.5 0.11 –54.2 [LNiCl.2H2O] 2.230 2.460 0.0934 10×108 9 0.11 – 51 [LCdCl.2H2O].3KCl > [LNiCl.2H2O] Table (6): The absorbance values against mole– ratio values of complex [LCdCl.2H2O].3KCl in solution (1×10–3 mole.L–1) in water at  264.5 nm No. L: M absorbance 1 0.5:1 1.700 2 1:1 1.990 3 2:1 2.345 4 3:1 2.565 5 4:1 3.000 Table (7): The absorbance values against mole- ratio values of complex [LNiCl.2H2O] in solution (1×10 –3 mole.L –1 ) in water at  260 nm No. L: M absorbance 1 0.5:1 1.910 2 1:1 2.230 3 2:1 2.460 4 3:1 2.450 5 4:1 2.550 مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Table (8): The molar conductance of the complexes* Compound fragment ions m S.cm2 molar–1 ratio LCoCl.2H2O 28.6 Neutral LNiCl.2H2O 46 Neutral [LCuCl.2H2O].6H2O.4EtOH.3KCl 60 Neutral [LCdCl.2H2O].3KCl 45.4 Neutral [LPbNO3.2H2O].3KCl 27.5 Neutral [LHgCl.2H2O].5H2O.3EtOH.3KCl 70.4 1:1 LCaCl.2H2O 35.1 Neutral [LMgCl.2H2O].10H2O.8EtOH.3KCl 132.8 1:1 * Recorded in (water) solvent Where L=(C13H16O10).2KCl Table (9): Showed the inhibition circle diameter in millimeter for the bacteria after 24 hour in cubation paid and 37C. Compounds Staphylococcus aureu (gram positive) Escherichia coli (gram positive) L 14 12 L Cd 40 24 L Cu 28 25 L Ca 0 0 مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Fig. (1) The IR. Spectrum of the 5,6-O-isopropylidene-L-ascorbic acid Fig. (2) The IR. Spectrum of the ligand (L) Fig. (3) The GCMS spectrum of the ligand (L) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 4.5 4.6 1.27 4.1 4.2 4.7 4.8 30 65 153 76 110 121 176.7 169.8 C H 3C O O H 3C O C CH 2 H H O O O CH 2 C O O M OH 2 X OH 2 CH 2 C O O H Fig. (4) 1 H NMR of the ligand L (practical) Fig. (5) 13C NMR of the ligand L (practical) Fig.(6): Suggested structure of (LM II ) M II = Co, Ni, Cu, Cd, Hg, Pb, Ca and Mg. X= Cl, NO3 for Pb- Complex مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Fig. (7) The IR. spectrum of the (LCoCl.2H2O] complex Fig. (8) The electronic spectrum for the ligand (L) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 65 0.0 Fig. (9) The electronic spectrum for the [LCoCl.2H2O] complex Fig. (10) :The electronic spectrum for the [LNiCl.2H2O] complex مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 0 0.5 1 1.5 2 2.5 3 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 Mole Ratio Absorbtion Fig. (11) :The electronic spectrum for the [LCuCl.2H2O].3KCl complex Fig. (12): The mole ratio curve of complex [LNiCl.2H2O] in solution (1×10 -3 mole. l -1 ) at (=260 nm) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 0 0.5 1 1.5 2 2.5 3 3.5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 Mole Ratio A b s o rb ti o n Fig. (13): The mole ratio curve of complex [LCdCl.2H2O].3KCl in solution (1×10 -3 mole. l -1 ) at (=264.5 nm) Fig. (14): Effect of staphylococcus aureu gram positive 0 5 10 15 20 25 30 35 40 45 50 Cu Cd L Ca Concentration of ligand and its complexes (1mg/ml) D im e te r of in h ib it io n zo n e ( m m ) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 Fig. (15): Effect of Escherichia coli gram negative 0 5 10 15 20 25 30 35 40 45 50 Ca Cu Cd L D im e te r of in h ib it io n zo n e ( m m ) Concentration of ligand and its complexes (1mg/ml) مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012 ـ O,O-2,3-ایزوبروبلدین O-5,6تحضیر بعض المعقدات الفلزیة الجدیدة ل حامض االسكوربیك مع تقییم الفعالیة البایولجیة- L-حامض الخلیك جاسم شهاب سلطان، عبد الجبار عبد القادر مخلص، فالح حسن موسى الهیثم، جامعة بغداد ابن-قسم الكیمیاء، كلیة التربیة 2011 تشرین الثاني 16 قبل البحث في 2011 نیسان 3:استلم البحث في الخالصة اسكوربك اسید،-Lمشتق مستقر جدید لحامض حضر 5,6-O-iso propylidene-2,3,-O,O-acetic acid-L- ascorbic acid (L) O-iso propylidene-L-ascorbic acid-5,6بناتج جید بواسطة مفاعلة .حامض الخلیك وبوجود هیدروكسید البوتاسیوم رومع كلو اللكانـد الجدیــد شــخص بوســاطة الــرنین النــووي المغناطیــسي البروتــون 1 H ـاربون والكـ 13 C وطیــف الكتلــة، وطیــف ، ــة اللكانــد . األشــعة تحــت الحمــراء وطیـــف األشــعة فــوق البنفــسجیة افؤ الثنائیــة التكـــمــع أیونــات بعـــض العناصــر ) L(مفاعلـ )Co ،Ni ،Cu ،Cd ،Pb ،Hg ،Ca ،Mg ( ًمعطیا معقدات، حضرت وشخصت بواسطة األشعة تحت الحمراء، واألشعة ـادمیوم ـة لمعقـــدات النیكـــل والكـ واســـتنتج مـــن . فــوق البنفـــسجیة، والتوصــیلیة الكهربائیـــة، واالمتـــصاصیة الذریــة والنـــسبة المولیـ ً معطیــا ایــون –O-2-CH2COO، )الكتـون (C–I=O اللكانــد مـن خــالل التحلیـل ان تناســق ایـون الفلــز الثنـائي التكــافؤ مـع B ،كـذلك تـم حـساب قـیم . لمعقـدات النیكـل والكـادمیوم ثنائیـة التكـافؤ ،KF ،Gالفلز سداسي التناسق وقد حسبت قـیم ه ثنائیـ الكـادمیوم، والنحـاس (ة التكـافؤ لمعقدات الكوبلت والنیكل ثنائیة التكافؤ، كما دراست الفعالیـة البایولوجیـة للكانـد ومعقداتـ مـا عـدا معقـد الكالـسیوم الـذي Escherichia coli وStaphylococcus aureuوأظهرت فعالیة متباینـة تجـاه ). والكالسیوم .لم یظهر أي فعالیة تجاه البكتریا المذكورة أعاله .تحضیر، مطیافیة، الدراسات البایولوجیة: الكلمات المفتاحیة مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 1 Vol. 25 Year 2012