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Synthesis and Biological Studies of Some Sulfur, Selenium and Tellurium Organic Compounds Based on Diethanolamine

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Synthesis and Biological Studies of Some Sulfur, Selenium and Tellurium Organic Compounds Based on Diethanolamine International Journal of Scientific & Engineering Research, Volume 5, Issue 8,August-2014 145 ISSN 2229-5518 Synthesis and Biological Studies of Some Sulfur, Selenium and Tellurium Organic Compounds Based on Diethanolamine Ali Z. Al-Rubaie*1, Shaker A. S. Al-Jadaan2, Salah K. Muslim2, Eman T. Ali2, Sabaa. A. M. Al-Fadal2, Ali K. Suad2, Hussien N. K. Al-Salman2 and Eman A. Saeed2 1Department of Chemistry, College of Science, University of Basrah, Basrah, Iraq 2Department of Chemistry, College of Pharmacy, University of Basrah, Basrah, Iraq Abstract— Several new and known bis(2-(arylchalcogeno)ethyl)amines (i.e. HN(CH 2CH2 EAr) 2; where E= S, Se and Te, Ar = C6H 5, 4- CH3C6H 4, 4-CH 3OC6H 4, 4-CH 3CH2OC 6H4, 4-BrC 6H4, 4-ClC6H 4 and 4-PhC 6H4) were prepared by the reaction of bis(chloroethyl)amine - with lithium arylthiolate or with the corresponding sodium arylchalcogenate (generated in situ by borohydride reduction of R2Ee2; i.e. ArE Na+; E= Se and Te). All compounds were obtained in good yield and characterized by elemental analysis, IR, 1H and 13C NMR and mass spectroscopic data. Antibacterial activity study of these compounds showed some promising activity against S. aureus, P. aeruginosa and E. coli. Key words— Diethanolamine, organotellurium, selenium, sodium arylchalcogenate, diaryl dichalcogenides, biological activity. —————————— —————————— 1 INTRODUCTION IETHANOLAMINE has been used as surfactants for de- spectrometer at 400 (1H NMR) MHz and 100 (13C NMR) MHz D tergents and cleaning agent formulations and as a gas using CDCl3 solution with TMS as internal standard. Ele- purification agent to remove carbon dioxide or hydrogen mental analyses were determined on an MT-3 elemental ana- sulfide gas. Furthermore, diethanolamine was also used as an lyzer within ±5 % of the theoretical values. Mass spectra were anticorrosion agent in metalworking fluids, and in prepara- recorded on a HP-598 8A MS instrument at 70 eV. tions of agricultural chemicals. In addition, diethanolamine is raw materials to synthesize drugs and it is also a cross linking 2.2 Synthesis agent for production of highIJSER elasticity polyurethane foam [1- All reactions were carried out under nitrogen or ar- 3]. gon atmosphere and monitored by conventional TLC method. Selenium and tellurium compounds were considered a poi- All organic solvents were dried prior to use according to son for many years, until non-toxic selenium and tellurium standard methods. Diphenyl diselenide[13], bis(4- compounds with high biological activity were found [4–10]. A methylphenyl) diselenide [14] , bis(4-methoxyphenyl) variety of organoselenium compounds with potential antioxi- diselenide [14], bis(4-ethoxyphenyl) diselenide [14], bis(4- dant activity, including ebselen analogues, benzoselenazoli- bromophenyl) diselenide [14], bis(4-chlorophenyl) diselenide nones, diaryl diselenides, selenamide and related derivatives [14] and bis(4-phenlphenyl) diselenide[14] were prepared have been reported in a variety of pathological situations [8- according to literature methods. Diphenyl ditelluride[15], 12]. Like organoselenium compounds, a number of or- bis(4-methoxyphenyl) ditelluride[15], bis(4-ethoxyphenyl) ganotellurium compounds exhibited high glutathione peroxi- ditelluride[16] , bis(4-bromophenyl) ditelluride[16], bis(4- dase-like activity [2–5]. The literature [4–12] indicates that chlorophenyl) ditelluride[16] , bis(4-phenlphenyl) ditellu- among organotellurium compounds, mainly telluranes (four- ride[16], Bis(2-chloroethyl)amine was prepared by chlorina- valent tellurium compounds), showed high biological activity. tion of diethanolamine with thionyl chloride in CHCl3 as de- Thus, the present work describes the synthesis of some new scribed in a literature method[17]. All the above compounds and knows organosulfur, organoselenium and organotelluri- were characterized according to their mp’s and IR spectra. um compounds based on diethanolamine in order to study Diphenyl) disulfide and bis(4-methoxyphenyl) disulfide were their biological activity. obtained from Aldrich-Sigma company and used without fur- ther purification. 2 EXPERIMENTAL 2.2.1 Bis(2-(phenylthio)ethyl)amine (1) To 0.18 mole of phenyllithium in 100 cm3 THF was added 2.1 Physical measurements cautiously sulfur(5.77 g; 0.18 g. atom) . The reaction was exo- All melting points were determined on a Gallenkamp melt- thermic; the stirring was continued until all the sulfur had ing point apparatus and are uncorrected. FT-IR spectra were been disappeared. The resulting solution was stirred for addi- recorded on FT-IR spectrophotometer -8400s Shimadza as KBr tional 1 h at room temperature. The solution was cooled in ice- disc. The 1H and 13C NMR spectra were measured on a Bruker IJSER © 2014 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 5, Issue 8,August-2014 146 ISSN 2229-5518 bath and a solution of bis(2-chloroethyl)amine (12.07g; 1H, NH), 2.01 (t, 4H, J = 6.4 Hz), 3.32 (t, 4H, J = 6.6 Hz), 7.08 (d, 3 13 0.085mol) in dry THF(100 cm ) was added drop wise to the 6H, J = 5.6 Hz),7.22 (d, 4H, J= 6.4 Hz) ; P CP NMR (CDCl R3R): + rapidly stirred solution of PhSLi. After the addition was com- 21.3, 28.4, 38.8, 127.5, 131.2, 134.7, 138.2. EI MS: m/z [M]P P = plete, the reaction mixture was stirred for 12h at room temper- 413 ature. The resulting solution was hydrolyzed with distilled 2.2.5 Bis(2-(4-methoxyphenylseleno)ethyl)amine (5) 3 o water and the extracted with dichloromethane (5 x 50 cm ). White solid. Yield: 88%, m.p.65-67P C.P The organic layer was dried over anhydrous calcium chlo- Anal. Calcd. for CR18RHR23RNOR2RSeR2R: C, 48.77 ; H, 5.23; N, 3.16%; 1 ride. Solvent was removed by rotary evaporator, to give a Found: C, 48.49; H, 5.24; N 3.13%. P HP NMR(CDCl R3R): 1.72(sb, yellow solid product. Recrystallization of the product from a 1H, NH), 1.92(t, 4H, CHR2RSe), 2.03(t, 4H, CHR2RN), 4.30(s, 6H, mixture of ethyl acetate-CH2Cl2gave compound 1 as a pale- OCHR3R), 6.62(d, 4H, J= 6.4 Hz, Ar-H), 7.21(d, 4H, , J= 6.4 Hz, o 13 yellow solid in 56% yield. M.p. 54-55 C. Ar-H); P CP NMR (CDCl R3R):28.3, 27.5, 55.4. 112.4, 121.7, 131.6, + Anal. Calcd. for CR16RHR19RNSR2R: C, 66.39; H, 6.62; N, 4.84%; 159.7. EI MS: m/z [M]P P = 445. 1 Found: C, 66.09; H, 6.44; N 4.53%. P HP NMR(CDCl R3R): 1.62 (s, 2.2.6 Bis(2-(4-ethoxyphenylseleno)ethyl)amine(6) o 1H), 2.77 (d, 4H, J = 6.4 Hz), 2.98 (d, 4H, J = 6.5 Hz), 7.09 (d, White solid. Yield: 84%, m.p.95-96P C.P 13 13 6H, J = 6.6 Hz), 7.33 (d, 4H, J= 6.4 Hz); P CP NMR (CDCl R3R), P CP Anal. Calcd. for CR20RHR27RNOR2RSeR2R: C, 50.96 ; H, 5.77; N, 2.97%; 1 NMR (CDCl R3R): 31.8, 49.6, 124.8, 128.7, 129.6, 139.7 EI MS: m/z Found: C, 50.78; H, 5.64; N 2.73%. P HP NMR(CDCl R3R): 1.68(sb, + [M]P P = 289. 1H, NH), 1.81-1.95(m, 10H, CH R3 R+ CHR2RSe), 2.11(t, 4H, CH R2RN), 4.82(q, 4H, OCH R2R), 6.82(d, 4H, J= 6.8 Hz, Ar-H), 7.21(d, 4H, , 13 2.2.2 Bis(2-(4-methoxyphenylthio)ethyl)amine(2). J= 6.6 Hz, Ar-H); P CP NMR (CDCl R3R): 13.7, 26.2, 38.2, 63.8, + Synthesis of 2 is similar to the method used for compounds 1, 113.5, 120.9, 132.1, 160.2 . EI MS: m/z [M]P P = 473. except that 4-MeOPhSLi was used instead of PhSLi. A pale 2.2.7 Bis(2-(4-bromophenylseleno)ethyl)amine(7) o o yellow solid was obtained in 45% yield. M.p. 63-64P C.P White solid. Yield: 89%, m.p.70-72P CP Anal. Calcd. for CR18RHR23RNOR2RSR2R: C, 61.86 ; H, 6.63; N, 4.01%; Anal. Calcd. for C R16RHR17 RNBr R2RSeR2R: C, 35.52 ; H, 3.17; N, 2.59%; 1 1 Found: C, 61.59; H, 6.24; N 4.13%. P HP NMR(CDCl R3R): 1.64(sb, Found: C, 34.98; H, 2.96; N 2.33%. P HP NMR(CDCl R3R): 1.61(sb, 1H, NH), 2.82(t, 4H, CHR2RSe), 3.11(t, 4H, CHR2RN), 3.82(s, 6H, 1H, NH), 1.82 (t, 4H, CHR2RSe), 2.11(t, 4H, CHR2RN), 7.18(d, 4H, J= 13 OCHR3R), 7.12(d, 4H, J= 6.4 Hz, Ar-H), 7.33(d, 4H, , J= 6.4 Hz, 6.6 Hz, Ar-H), 7.51(d, 4H, , J= 6.6 Hz, Ar-H); P CP NMR 13 + Ar-H); P CP NMR (CDCl R3R): 31.4, 49.8, 114.8, 124.7, 128.8, 159.1. (CDCl R3R): 32.6, 49.7, 119.2, 128.6, 131.6, 134.8. EI MS: m/z [M]P P + EI MS: m/z [M]P P = 349. = 545. 2.2.8 Bis(2-(4-chlorophenylseleno)ethyl)amine (8) o Synthesis of bis(2-(arylseleno)ethyl)amine (3-9) White solid. Yield: 75%, m.p.100-102P CP Compounds 3-9 were prepared according to the previously Anal. Calcd. for C R16RHR17 RNCl R2RSeR2R: C, 42.50 ; H, 3.79; N, 3.10%; 1 reported method [19] and as follow: Found: C, 42.47; H, 2.97; N 2.86%.
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