Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 5(6), 5-8, June (2015) Res. J. Chem. Sci. International Science Congress Association 5 Synthesis of New Seleno-Nitrone Compounds Haddad Batool S., Majeed Nisreen N. and Al-Rubaie Ali Z. Department of chemistry, college of Science, University of Basrah, Basrah, IRAQAvailable online at: www.isca.in, www.isca.me Received 9th May 2015, revised 23rd May 2015, accepted 13th June 2015 AbstractThe 1,1-Diiodo-1-seleno-4-cyclohexanone were synthesized from the reaction of 1,1-Dibromo-3-penta-none with selenium and then converted to nitrones by the condensation of carbonyl group with substituted N-phenylhydroxylamine. The resulting products were identified by physical properties such as melting poin (m.p.), retardation factor (Rf) and color. Also compounds showed the expected data in identification techniques such as FTIR, HNMR, mass spectroscopy and Elemental analysis (CHN). The results proved the validity of the expected chemical structures of synthesized compounds.Keywords: Nitrone, seleninium, seleno-nitrone. Introduction Nitrone has been extensively investigated, because of their utility as versatile synthetic intermediates and their relative stability. Nitrone has been considered as a promising group of anti-cancer agents by intercalating DNA with higher affinity and found it was easily metabolized with low toxicityNitrones were synthesized by the condansation of carbonyl group in 1,1-diiodo-1-seleno-4-cy-cloheanone with N-phenylhydroxyl amine, as shown in scheme-1. Scheme-1 CaCl was used as a drying agent in the synthesis of nitrones to remove the water that obtained during the reversible reaction and because of that the reaction can be shifted to the right direction to obtain the nitrones in a good yield. 3 drops of benzene sulfonic acid was added to protonated the ketocarbonyl groups, this will increase the reaction rate. Material and MethodsA series of substituted (1, 1-diiodo-1-seleno-4-cyclohex anone) were synthesized to condensation with synthesi- zed N-phenylhydroxylamine in order to synthesize the corresponding nitrone compounds. The general structu- res of 1, 1-diiodo-1-seleno- 4-cycloheanone), N-phen- yl h-ydroxylamine and nitrones are illustrated below in figure-1. General method of Preparation 1, 1-Di iodo-1-seleno-4-cyclohexaneone: 1,5-dibromo-3-pentanone (5.78 gm ,0.04gm) was used in a mixing with Selenium powder (5.1 g 0.04 mol) and Sodium Iodide (23 g, 0.16mol) in 2-butoxy ethanol (100 ml) (was refluxed for 1 hr, after that cooled and added water the precipitated was filtered off and washed with water and reclystalizdtion from DMF. The m.p (153-155) 0C, (160-162)C and (159-161) 0C , and the yield 80%, 71% and 69%, for compounds (R=H,Br and Cl) respecticvely. The six member ring, selenapyran, can be obt-ained by the reaction shown in scheme-2. Figure-1 The general structures of Preparation 1, 1-Di iodo-1-seleno-4-cyclohexaneone, N- phenylhydroxylamine and nitrones Scheme-2 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(6), 5-8, June (2015) Res. J. Chem. Sci. International Science Congress Association 6 The substituted (1-seleno-4-cyclohexanone) was easily decomposed10, because of that it used as an intermediate to synthesize the corresponding substituted (1,1-diiodo-1-seleno-4-cycloheanone). Three derivatives of 5-Dibromo-3-pentanone were prepared and studied in this research. These compounds were formed by the nucle-ophilic attack of selenium metal at the carbon atom of carbon-halide. The mechanism of the reaction, as illustrated in scheme-3 Scheme-3 The mechanism of the formation of (1, 1-Diiodo- 1-seleno-4-cyclohexanone) Synthesis of nitrone: In a 250ml one- necked round bottomed flask 15gm of CaCl and 0.02mol of (1,1-diiodo-1-seleno-4-cyclohexanone) was placed with addition 30ml of absolute ethanol. This solution was stirred and a solution of N-benzyl hydroxyl amine (0.02mol) in 30ml of absolute ethanol was added, 3 drops of benzene sulfuric acid was added to the mixture. After the addition was completed, the reaction mixture was refluxed with stirring in dark place for several hours according to the type of substituents. The reaction mixture was filtered by suction filteration and the product was recrystallized by abs. ethanol11. Nitrone structures are represented in table-1. Table-1 The Structures of nitronescompound Structures Ba1 Ba2 Ba3        Ba4 Ba A series of nitrone compounds have been synthesized and studied in our research. These reactions were monitored by thin layer chromatography TLC. The mechanism of the reaction, as illustrated in scheme-4. Scheme-4 The mechanism of the formation of nitrone Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(6), 5-8, June (2015) Res. J. Chem. Sci. International Science Congress Association 7 The synthesized nitrone compounds were first purified by recrystallization in abs. ethanol and tested by thin layer chromatography TLC using different eluents. The best separation was obtained in mixture of (n-Hexane: DCM) having a ratio (6:4), respectively as eluent. The compounds were second purifiedcolumn chromatography using the above eluent. Results and Discussion The resulting data were obtained for the synthesised compounds from analysis data as following: N-1,1Diiodo-1-seleno-4-cyclohexylidene ph- enyl N-oxide (N1) melting point (m.p.) 169-170 C, orange Needles yield 76%, TLC,n-hex- ane: ethylacetate 6:4, retardation factor Rf =0.52, FTIR /cm-1 : 1600 (C=N), 1198 (N-O), 1343(C-N) and 579 (C-Se). HNMR(500 MHz, dimethyl sulfoxide(DMSO); :8.00 (AA`BB`Harom), 6.65-7.70 (m,Harom) and 1.29,1.68(t,t selenopyran). Mass (m/z): 522 [M], 508,399, 147, 91, 53. For C11H13NOSeI (found): 25.79 % C, 2.85 % H, and 2.90 % N -1,1-Diiodo-1-seleno-4-cyclohexylidene (2-chloro) benzyl-N-oxide, (N2), melting point (m.p.) 47.87-49.21C, orange, yield 55%, TLC, n-hexane: ethylacetate 8:2, retardation factor Rf =0.50, FTIR /cm-1: 1604 (C=N), 1187 (N-O), 1345(C-N) and 581 (C-Se). HNMR (500) MHz, dimethylsulfoxide (DMSO); : 8.06 (AA`BB` Harom), 6.9-7.81 (m, Harom) and 1.27, 1.98 (t,t selenopyran). Mass (m/z):[M], 542,399, 147, 125, 53. For C11H12NOSeClI (found): 24.16 % C, 2.28 % H, and 2.67% N. N-1, 1-Diiodo-1-seleno-4-cyclohexylidene (3-chloro) phenyl-N-oxide, (N3), melting point (m.p.) 64.8-63.9C, orange, yield 61%, TLC, Diethylether:chloroform 6.5:3.5, retardation factor Rf =0.58, FTIR /cm-1: 1635 (C=N), 1190 (N-O), 1348 (C-N) and 588 (C-Se). HNMR(500)MHz, dimethylsulfoxide(DMSO); :7.9 8.08 (AA`BB` Harom), 7.0-7.81 (m, Harom) and 1.31,1.52 (d, t selenopyran). Mass (m/z): [M], 542,399, 147, 125, 53. For C11H12NOSeClI (found): 24.80 % C, 2.38 % H, and 2.61% N. N-1, 1-Diiodo-1-seleno-3,5-dibromo-4-cycloh-exylidene-phenyl -N-oxide, (N4), melting point (m.p.) 243-244C, Pale yellow crystals yield 75%, TLC, n-hexane: chloroform 5:.5, retard-ation factor Rf =0.5, FTIR /cm-1: 1587 (C=N), 1200 (N-O), 1340(C-N) and 571 (C- Se HNMR (500) MHz, dimethylsulfoxide (DMSO); : 8.08 (AA`BB` Harom), 7.2-7.91 (m, Harom) and 2.05, 2.30 (d, t selenopyran). Mass (m/z): [M], 566,557, 305, 91, 211. For C11H11NOSeBr (found): 19.82 % C, 1.71 % H, and 1.98% N. N-1, 1-Diiodo-1-seleno-3,5-dichloro-4-cyclohexylidene benzyl-N-oxide, (N5), melting point (m.p.) 67-65C, orange yield 64%, TLC, n-hexane:ethylacetate 5.7:4.3, retardation factor Rf =0.6, FTIR /cm-1: 1599 (C=N), 1220 (N-O), 1329 (C-N) and 579 (C-Se). HNMR(500)MHz, dimethylsulfoxide  \n \r (AA`BB` Harom), 7.5-7.9 (m, Harom) and 2.21,2.50 (d, t selenopyran). Mass (m/z):[M], 576,467, 305, 91, 121. For C11H13NOSeCl (found): 22.83% C, 1.83 % H, and 2.51% N. The relevant IR spectra of nitrone compounds showed the disappearance of (C=O) band and the appearance of (C=N), (N-O) and (C-N) bands in the region (1599-1635) cm-1, (1195-1198) cm-1and (1334-1379) cm-1 respectively. In HNMR the spectra of nitrones which they have (R= H) showed two triplet signals 12 at (1.31-2.21) ppm and (1.28-2.50) ppm which belonged to the protons of (C3 and C5) and (C2 and C6) position respectively in the selenopyrans ring, while which have (R= Br or Cl) at 3-position and 5-position, showed two signals with (doublet and triplet) 13 in the region (1.37-1.41) ppm and (1.50-1.53) ppm, due to the interaction between one proton at 3-position with the two protons at 2-position, and the same case for 5 and 6 position, respectively. Mass spectrscopy give the molecular ion and other fragments which indicated the stracture of prepared nitrones. The elemental analysis fond resemble to theoretical values. Conclusion New nitrone were obtained from the condensation between carbonyl group in selenopyran ring and N-phenylhydroxylamine. This method was easier than other methods to produce nitrone. The chemical structures of new sulfaselenonitrone compounds were characterized by identification methods. References 1. Breuer E., Aurich H.G. and Nielsen A., Nitrones, Nitronates and nitroxides, chapter 3, New Jersey, John Wiley and Sons, (1989) 2.Al-Jassem M.A. and Majeed N.N., Synthesis, Characterization and Conformation of Some New Macromolecules Containing Nitrone Moieties, Chemistryand Materials Research., 6(10), 100-108 (2014) 3.Floyd R.A., Hensley K., Forster M.J. and Kelleher Andersoon J.A., For reviews dealing with biological activity of nitrones, (2002) 4.Green A.R., Ashwood T., Odergren T. and Jackson D.M., Pharmacol., (2003)5.Wang Y., Larrik J.W., Antioxidant Nitroxides and Nitrones as Therapeutic Agents, US Patent No.6852889, February 08, (2005)6.Zink M., Kramer A. and Nesvadba P., Macromolecules,33, 8106-8108 (2000)7.JasiŽnski R., Ciezkowska A., Lyubimtsev A. and BaraŽnski A., Chem. Heterocycl.Comp., 40, 206-210 (2004) Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(6), 5-8, June (2015) Res. J. Chem. Sci. International Science Congress Association 8 8.Mottley C. and Mason R, In: Biological Magnetic Resonance, Berliner LJ, ReuberV (Ed.), Plenum Press, New York, 490-546, (1989)9.AL-Rubaie A.Z., Shirayda H. and Chazelle S., J. Org. Chem., 287, 321-327 (1985)10.Keiko N.A., Funtikova E.A., Larina L.I., Sarapulova G.I. and Mazhukin D.G., Russ. J. Org. Chem., 41, 1421-1429 (2005)11.Voinov M.A., Shevelev T.G., Rybalova T.V., Gatilov Y.V., Pervukhina N.V., BurdukovA.B. and Grigor I.A., Organometallics, 26, 1607-1615 (2007)12.Witanowski M., Stefaniak L. and Januszewski H., Nitrogen Chemical Shifts in Organic Compounds in Nitrogen NMR, Witanowski M, Webb GA (Eds.), Plenum Press London, New York, 164, (1973)13.Varlamov A.V., Grudinin D.G. and Chernyshev A.I., Chem. Heterocycl. Compd., 40, 622-630. (2004)