Microsoft Word - 215-244 Chemistry | 217 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 Preparation, Characterization and Study of Biological Activities of New Organozinc Compounds Drived from Cytosine Alyaa K. Abbas Dept. of Chemistry/ College of Science/ University of Baghdad Received in:17/November/2015,Accepted in:31/January/2016 Abstract The novel heterocyclic organozinc compounds were prepared from the reaction of diazonum salt cytosine zinc chloride with thymol and vanilin as coupler components. The prepared compounds were characterized by elemental analysis and UV-Vis, FTIR and 1HMNR spectroscopic techniques. The biological activity was also studied for all prepared compounds. Keyword: Organzic, Azo cytosine, Perparation, Identification ,Biological activity. Chemistry | 218 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 Introduction Now day, organozinc compound represents the largest and is an indispensable part of synthetic chemist's knowledge [1]. It has received much attention due to the fact that almost every synthesis of natural product has at least one step which contains the use of this type of compounds. So, there is constant need for the development of new method for a simple and effective synthesis organozinc compound [2]. For organozinc bivalent two basic types (R2Zn and R Zn X) where R being hydrocarbon groups or more generally groups attached to zinc via a zinc-carbon bond and X being a halogen or groups being attached to zinc( oxygen, nitrogen, sulphar, phosphorus and the like). Furthermore organozinc compounds are strongly electron- deficient since four low-lying orbitals are available for bonding and only two valance electrons are supplied by zinc [3]. Zinc (ΙΙ) compounds have been adopted several coordination geometries commonly octahedral, tetrahedral and various penta coordinate geometries, so these structural flexibility can be attributed to zinc's electronic configuration [Ar] 3d104s2. The 3d subshell is filled and therefore, ligand field effects, it does not exist [4]. Thus the coordination geometry is determined largely by electrostatic and steric interactions [5]. This type of compounds have been widely employed in many applications such as in clinical, biological and industrial [6,7]. In addition the rich chemistry of the azo compounds are associated with several applications, e.g. industrial, dyeing and biological reactions [8,10] with histochemical detection of compounds containing cytosine moiety. This paper describes the synthesis organozinc compounds include azo moiety. Identification and biological activity were studied for prepared compounds. Experimental Materials and Instrument All solvent and chemicals were used directly as purchased. UV-Vis spectra were recorded on a (shimadzn uv-160 A) Ultra Videt-Visible spectrophotometer. FTIR-Spectra were taken on a (shimadzn, FTIR-8400s Fourier Transfor, Infrared) Spectrophotometer (200- 4000) cm-1 with samples prepared as CsI discs. The 1HNMR spectra were recorded on (Brucker-300 MHz Ultra shield) using DMSO as a solvent and TMS as a reference. Melting points were obtained by using (Stuart Melting Point Apparatus). Microelemental analysis (C, H ,N) were performed by using (Euro vector EA 3000A Elemental Analyser). The percentage of (Zn) was determined by A.A using a (GBC 933) Flame Atomic Absorption Spectrophotometer.The Cl% was determined by Mohr method. Preparation Method Cytosine zinc chloride was prepared from the reaction of cytosine with zinc chloride according to literature [11] as was shown below: N N NH2 O H + ZnCl2 N N NH2 O H ZnCl Preparation of (C1 & C2) ( 0.01 mole) of cytosine zinc chloride was dissolved in a mixture of 2 ml H2SO4 (conc.), 10ml ethanol and 10ml distilled water. After that this solution diazotized at (0-5)C with 2.5% sodium nitrite solution. The diazo solution was added dropwise with stirring to a cooled alkaline ethanolic solution of (0.01 mole) of vanilin and thymol . Color precipitate was Chemistry | 219 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 filtered and washed several times with (1:1) EtOH:H2O, mixture then left to dry. The reaction is shown below Result and Discussion The two color compounds (C1and C2) were prepared by coupling thymol and vanillin respectively with diazonium solution of cytosinezinc(ΙΙ) chloride. They are not soluble in water but soluble in most organic solvent (ethanol , chloroform, carbontetrachloride ,DMF, … etc) and are stable in air, moisture and light. The elemental analysis data and physical properties are included in Table (1). The synthesized compounds (C1 and C2) were characterized by UV-Vis, FTIR and 1HNMR spectroscopy. UV-Vis Spectra The prepared compounds (C1 and C2) were characterized by UV-Vis spectroscopic technique in ethanol (10-3 M) as shown in Figure (1 and 2) which were mainly showed two peaks, the first peak at (365,420nm) for (C1 and C2) respectively were assigned to a (π→π*) transition of benzene ring and substituted functional group, so they cause a very pronounced shift and a greatly intensified absorption [12]. The second band which was observed in the region (612nm and517nm) (Table1) for (C1 and C2) respectively, due to (π→π*) transition of intermolecular charge transfer involving the whole electronic system through azo moiety [13]. FTIR Spectra The important vibrational bands have been determined on the basis of t he reported assignments of IR spectral bonds in the literature [14-16].The FTIR spectrum for (C1) (Figure 3) exhibited a strong and sharp band at (3498 cm -1) with shoulder at (3479 cm -1), which is assignable to ν(OH) on the thymol ring while in the spectrum of (C2) (Figure 4) was observed a broad medium intensity band in the region (3581-3400 cm-1) and centered at (3490 cm -1)that attributed to the (O-H) stretching vibration of internally hydrogen bonded enolic group[17]. Thus, the FTIR spectrum strongly supports the existence of an intra molecular hydrogen bond azo-enol form. The (N-H) in the pyrimidyl moiety was observed at (3402 and 3303 cm-1) in the spectra for (C1and C2) respectively, the changes in shape and position of this band were presumably due to formation of new azo compound boarding of the band in (C2). The (C1 and C2) were exhibited a medium duplet band at (1604, 1585cm-1) and (1676, 1649) cm-1respectively which were assignable to (C=O)ald.+pym. and (C N)pym.. The band for the Chemistry | 220 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 (N=N) appeared with broading and shifted to low wave number in the spectrum of (C1 and C2) at (1483, 1450 cm-1) and (1455, 1404 cm-1) respectively may be due to the intramolecular interaction between nitrogen atom for azo moiety and zinc atom (N‒Zn) in the solid state [18]. At (1311 cm-1) in the spectrum for (C2) referred to the (C‒O) for the aldehyde group the vanillin moiety. Intermolecular interaction for (N–Zn) at (459 and 452 cm-1) and (Zn‒ Cl) at (229 and 230 cm-1) for (C1 and C2) respectively [14, 18]. The characteristic bands for (C1 and C2) are given in Table (2). These data are in agreement with these earlier reported. Some bands were noticeable at low frequency that attributed 1HNMR Spectra Figure (5) showed the 1HNMR spectrum for the compound (C1), it was observed different peaks. A singlet signal at (9.18, 1H)ppm referred to the (‒NH) for the proton of pyrimidine moiety and multiplet signal at (7.9- 7.1, 3H)ppm. The singlet signal also appeared at (4-6, 1H)ppm and (3.13, 9H)ppm which corresponded to the phenolic proton (OH) and methyl protons respectively. However the 1HNMR spectrum for compound (C2) (Figure 6) showed a singlet signal at (9.93, 1H)ppm, (9.11, 1H)ppm, (6.7, 1H)ppm and (4.78, 3H)ppm for (CHO), (N‒H)pyr., (O‒H)ph. and (O‒CH3) respectively. The benzene ring was observed multiplet signal at (7.9-7.2) ppm [15,19]. Antibacterial Activity Due to well known antibiotic properties for these kinds of compounds [20,21], they exhibit a variety biological activities. The antibacterial activities of the prepared compounds (C1 and C2) have been studied against three selected types of bacteria Escherichia Coli, Staphylococcus Aursea and Bacillus. The paper disc diffusion method has been used and the activity was determined by measuring the diameter of the zone of inhibition in mm. Tetracycline was used as standard material in order to make a comparison of it's effectiveness with that at the prepared compounds (C1 and C2) and ethanol was used as a solvent, while the concentration of solution was (10-4M). Table(3) shows that the (C1) has high activity against selected bacteria while (C2) appeared different activity which was recorded. Conclusion The obtained from elemental analysis, UV-Vis, FTIR and 1HNMR spectroscopy indicated and characterized two new hetrocyclicorgan zinc compounds that prepared by coupling reaction of vaniline and thymol with diazonium salt of cytosine zinc chloride. References 1- Rapport, Z. and Marek, I.(2006) "the Chemistry of Organic Zinc Compounds", John Wiley and Sons,New York. 2- Knochel, N. and Jones,P. (1999)"Organic Reagents-A Practical approach",Oxford Medical Publication, Oxford. 3- Sattler, W.; Ruccolo, S. and Parkin, G.(2013) "Synthesis, Structure, and Reactivity of a Terminal OrganozincFluride Compound: Hydrogen Bonding,and Donor-Acceptor Interaction" J. Am.Chem. Soc., 135(5):18714-18717. 4- Miessler, G.L. and Tarr,D.A. (2011)"Inorganic Chemistry" 4th Ed.,Pearson/Prentice Hall Publisher. Chemistry | 221 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 5- Landies,C. R. and Weinhold, F. (2007) "Valence and Extra-Valance Orbitals in Main Group and Transition Metal Bonding",Journal of Computational Chemistry,28(1):128- 203. 6- Grevy, J. M.(2011) "Encyclopedia of Inorganic and Bioinorganic Chemistry", John Wiley. 7- Belhany, A.;Fernando, P. and Veglia,G.(2006)"Biological Chemistry of Organotin Compounds: Interactions andDealkylation by Dithiols", Journal of Organometallic Chemistry,691:1748-1755. 8- Manuela,M.R. M.;Ferreira, A. M. and Pereira,M.N. (2009) "The Synthesis and Characterization of HetrocyclicAzo Dyes Derived from 5-N,N-dialkylamino-2,2- bithiophene Couplers", Dyes and Pigments, 83:59-65. 9- Khalid, A. and Arshad, M. (2008) "Accelerated Decolonization of Structurally Different Azo Dyes by Newly IsolatedStrains",APPL. Microbiol. Biotech., 78:361-369. 10- Towns, A.D. (1999) "Developments in AzoDisperese Dyes Derived from Heterocyclic Diazo Components", Dyes and Pigment,42:3-28. 11- Ali,A. and Osama,K.(2003) "Synthesis and Characterization of New Azo Pyrimidine Complexes", J.Cood.Chem.,56(8):725-742. 12- Sarkar,D.;Kumar, A. and Tapan,K.(2013) "Synthesis, Crystal Structure and Spectral Properties of 2-[(1-methyl-2-benzimidazolyl)azo]-P-Cresol: An experimental and Theoretical Study" SpectrochimicaActa Part A :Molecular and Biomolecular Spectroscopy,115:421-425. 13- Youssef, N. and Hegab, K.(1999) "Synthesis and Characterization of some Transion Metal Chelates of5-(1-hydroxy-6-naphthylazo-3-sodium Sulphonate) Thiobarbituric(L1) and Barbituric (L2) Acids", J.Mater.Sci.Technol.,15(3):263-266. 14- Sliverstein,R.M.;Bassler,G.C. and Morrill, T.C.(1996), 6th Ed., John Wiley and Sons, New York. 15- Dyes,R.(1969)"Application of absorption Spectroscopy of Organic Compounds, Prentice.Hall., Englewood cliffs, N, J. London. 16- Asniza, M. and Abdul Khallil, H.(2011) "Synthesis and Characterization of a new Hetero cyclic Azo Pigment",SainsMalaysiana,40(7):765-770. 17- Sanap,S.V. and Patil, R.M.(2013) "Synthesis, Characterization and Biological Activity of Chiral Mixed Ligand Ni(ΙΙ) Complexes", Research Journal of Pharmaceutical Sciences, 2(1):1-10. 18- Fahad, T.(2014) "Synthesis, Characterization and Thermal Studies of Novel Organomercury Driven from Sulfa Drugs" Journal of Advances in Chemistry, 7(2);1338- 1347. 19- Masoud, M. and Alaa, E. (2004) "Specrtoscopic Studies on someAzo Compounds and their Cobalt, Copper and nickel Complexes",SpectrochimicaActa part A , 60:2807-2817. 20- Patil, R. M.,(2007) "Synthesis,Structural and biological properties of binuclear complexes with Som Schiff bases",ActaPoloniaePharmaceutca-Drug Research., 64(4):345-353. 21- Cobir, B.;Avar, B. and Gulcan, M. (2013) "Synthesis, Spectroscopic Characterization and Genotoxicity of New Group Azo-Oxime Metal Chelates", Turk. J. Chem.,37;422-438. Chemistry | 222 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 Table (1): Physical properties and elemental analysis for C1and C2 Eemental analysis (Cal.) M.P. Yiel d% MWt. Color ( max)nm Compound Cl% M% N% H% C% 9.34 (9.44) 17.32 (17.38) 14.87 (14.89) 3.701 (3.72) 44.66 (44.67) 295 86 374.1 2 Blue(612 ) C1 9.43 (9.44) 17.36 (17.38) 14.87 (14.89) 2.36 (2.39) 40.88 (40.95) 310 83 376.0 3 Red(517)C2 Table (2): The main FTIR bands (200-4000) cm-1 for (C1 and C2) Compounds compounds (OH) (N–H) (C– H)arm.+alk. (C=O)ald.=im (C=N)im (N=N) (C– O) (N– Zn) (Zn– Cl) C1 3498st, sh 3479vw,shl 3402 vw 3099 w 2954 w 1604m 1585m 1483 sh,st 1450 sh,m – 459 w 229 m C2 3581 3400 3303 w,br 3064 vw 2883 vw 1676m 1649m 1455m 1404m 1311 w 452 w 230 m vw=very weak, w=weak; m=medium, st=strong; sh=sharp, br=broad, shl=shoulder, d=dublet Table (3): Antibacterial activity for (C1 and C2) compounds E.Coli S.auerus Bacillus C1 +++ +++ +++ C2 ++ +++ ++ Tetracycline +++ +++ +++ ++ (7-9)mm, +++ (10-12)mm Figure (1): The electronic spectrum of C1 compound Chemistry | 223 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 Figure (2): The electronic spectrum of C2 compound Figure (3): FTIR spectrum for (C1) compound Chemistry | 224 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 Figure (4): FTIR spectrum for (C2) compound Figure (5): The HNMR spectrum for C1 compound Chemistry | 225 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 Figure (6): The 1HNMR spectrum for C2 compound Chemistry | 226 2016) عام 2(العدد 29المجلد مجلة إبن الهيثم للعلوم الصرفة و التطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 29 (2) 2016 ة جديدة عضوي –تحضير وتشخيص ودراسة الفعالية البايولوجية لمركبات زنك مشتقة من السايتوسين علياء خضير عباس الكيمياء/كلية العلوم/جامعة بغدادقسم 2016/كانون الثاني/31،قبل في: 2015 /تشرين الثاني/17استلم في: الخالصة ع ين م ك سيتوس د الزن دايزونيوم لكلوري ح ال ل مل ن تفاع ك م دة و ذل ك جدي ة للزن وية فلزي ات عض رت مركب حض اطة ت بوس رة شخص ات المحض ة ازدواج المركب انيلين مكون ايمول و الف جية الث وق البنفس عة ف اف االش ة اطي ة -دراس المرئي ن ة م واع منتخب د ان ة ض ة بايولوجي ات فعالي ذه المركب رت ه ي. اظه ووي المغناطيس رنين الن راء و ال ت الحم عة التح واالش البكتريا. زنك عضوية, آزو سايتوسين , تحضير , تشخيص , فعالية بايولوجية : الكلمات المفتاحية