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Thioxopyrimidinecarbonitriles As Precursors for Linked and Fused Available online a t www.scholarsresearchlibrary.com Scholars Research Library Archives of Applied Science Research, 2014, 6 (2):122-135 (http://scholarsresearchlibrary.com/archive.html) ISSN 0975-508X CODEN (USA) AASRC9 Thioxopyrimidinecarbonitriles as precursors for linked and fused pyrimidine derivatives: synthesis of imidazo-, pyrazoloimidazo-, triazoloimidazopyrimidines and pyrimidoimidazotriazepines aAbdelmoneim A. Makhlouf, bRasha A. M. Faty* and aAsmaa K. Mourad aFayoum University, Faculty of Science, Fayoum, Egypt bChemistry Department, Faculty of Science, Cairo University, Giza, Egypt _____________________________________________________________________________________________ ABSTRACT Alkylation of 6-aryl-4-oxo-2-thioxopyrimidine-5-carbonitriles ( 1a-c) afforded the key intermediates 2a-e, which underwent further alkylation at N-3 nitrogen atom, upon treatment with α-halofunctionalized compounds, namely: ethyl bromoacetate, chloroacetone, chloroacetylacetone, chloroacetonirile, or monobromomalononitrile to perform 2-alkylthio-6-aryl-5-cyano-4-oxo-3-substituted-3,4-dihydropyrimidines 7-9. Heating 7-9 with hydrazine hydrate produced imidazo[1,2-a]pyrimidine derivatives 10-15. Treatment of 10a with each of ethyl cyanoacetate, ethyl acetoacetate, or acetylacetone gave pyrazoloimidazopyrimidine derivatives 18a,b, 19 , respectively. Compound 10a reacted with carbon disulphide to give oxazoloimidazopyrimidine 20 . Reaction of the imidazopyrimidine derivative 15a with glacial acetic acid or thiourea afforded triazoloimidazopyrimidines 21,22 . Also, compound 15a underwent cycloaddition reaction upon treatment with either of phthalic anhydride or acrylonitrile to give 2-phenyl-4,12- dioxopyrimidino[2``,1``:2`,3`]imidazo[1`,5`:2,3][1,2,4]triazolo[1,5-b]isoindole-3-carbonitrile ( 23 ) or 8-amino-2- phenyl-4-oxo-7H-pyrimido[2`,1`:2,3]imidazo[1,5-b][1,2,4]triazepine-3-carbonitrile (24 ), respectively. Imidazo pyrimidines 15d,e underwent cyclocondensation upon heating with each of formic acid, formamide/ formic acid or ammonium thiocyanate to produce the pyrimido[2,1-f]purine derivatives 25a,b, 26,and 27 ,respectively. Keywords: ImidazoPyrimidine; pyrazoloimidazopyrimidine; pyrimidoimidazotriazepine. _____________________________________________________________________________________________ INTRODUCTION Pyrimidine and fused heterocyclic pyrimidine derivatives have received significant attention over the past few years owing to their therapeutic and pharmacological properties[1-6].Imidazopyrimidines are used as anti-HIV [7], antifungustic [8], anticoccdial agents [9], and as modulators of key biological targets [10], also a novel series of imidazopyrimidines have been discovered that potently inhibit p38 and suppress the production of TNF-alpha in vivo [11] . Many fused triazolopyrimidines and tetrazolopyrimidines are well known for their antibacterial [12] and antifungal activities [13]. Furthermore, some series of thiazolo[3,2-a]pyrimidine derivatives have been prepared and investigated for their anti-inflammatory [14] and anticancer[15] activities. On the other hand, functionalized 4-oxo-2-thioxopyrimidines are of considerable importance as excellent precursors for the synthesis of fused pyrimidines. They have been extensively utilized to prepare different fused heterocycles including thiazolo-[16], triazolo-[17], tetrazolo-[18], pyrazolo-[19], and imidazopyrimidines [10,16]. In continuation 122 Scholars Research Library Abdelmoneim A. Makhlouf et al Arch. Appl. Sci. Res., 2014, 6 (2):122-135 ______________________________________________________________________________ of the work directed to synthesis of different heterocyclic compounds [20-23], we herein report on the synthesis and utilization of some 2-substituted alkylmercapto-pyrimidines to attach and annelate a variety of heterocycles to the pyrimidine nucleus. MATERIALS AND METHODS All melting points are uncorrected and were taken in open capillaries on a Gallen Kamp apparatus. Microanalysis was carried out at the Microanalytical units, Faculty of science, Cairo University. IR spectra were recorded as potassium bromide pellets on Perken Elmer FT/ IR system 2000 spectrophotometer. 1H-NMR and 13 C-NMR spectra were measured in DMSO-d6, using JEOL-JNM-EX 270 NMR Spectrometer. Chemical shifts are expressed in δ ppm using TMS as the internal standard. MS were recorded on a HP model MS-5988 spectrometer at electron ionizing energy 70ev. Synthesis of 6-aryl-5-cyano-4-oxo-2-thioxo(alkylthio)-1,2,3,4-tetrahydropyrimidines 1a-c and 2a-e. The starting compounds 1a-cand 2a-e have been synthesized according to reported procedures [17,24]. Synthesis of pyrimidinonehydrazidederivative 3. To a solution of 2e (3.15 g, 0.01mole) in dioxane (25ml) hydrazine hydrate (2.5g, 0.05 mole) was added and the reaction mixture was heated, under reflux, for 0.5 h then evaporated under reduced pressure. The solid product thus obtained was crystallized from ethanol as white crystals. Yield 61%, m.p. 238-240 °C. IR (KBr); 3282 (NH), 2204 -1 1 (CN), and 1683cm (CO).H -NMR; (DMSO-d6) δ1.70 (br,s, 2H, NH 2, D2O-exchangeable), 3.81 (s,2H, CH 2), 7.14- 7.51(m,5H, Ar), 8.0 (s,1H, NH D2O-exchangeable), and 8.21 ppm(s, 1H, NH, D2O-exchangeable). Anal .Calcd for C13 H11 N5O2S (301.32): C, 51.82; H, 3.68; N, 23.24; S,10.64.Found: C, 51.46; H, 3.46; N, 23.12; S, 10.30. Arylmethylidinehydrazino derivatives 4a,b. A solution of the hydrazide derivative 3 (3.01g, 0.01mole) in ethanol (20 ml) containing few drops of piperidine was treated with p-chlorobenzaldehyde or p-methoxybenzaldehyde (0.01mole). The reaction mixture was heated under reflux for 3 h, left to cool, then poured into cold water and acidified with HCl. The solid formed was filtered off and recrystallized from the proper solvent. Compound 4a , was obtained as yellow crystals recrystallized from ethanol. Yield 78%, m.p. 280-281 °C. IR (KBr); 3208 (NH), 2212 (CN), and 1653 cm -1 (CO). MS; m/z (%): M +-Ph; 347 (4.0), 238(73), 212(52.2), 184(71.9), 141(14.5), 127(28.8), 104(52.4), 89(100), 77(37.3), and 51(32.1). Anal .Calcd for C 20 H14 ClN 5O2S (423.88): C, 56.67; H, 3.33; N, 16.52; S, 7.56; Cl, 8.36. Found: C, 56.60; H, 3.19; N, 16.34; S, 7.23; Cl, 7.61. Compound 4b was recrystallized from dimethylformamide as pale yellow crystals. Yield 70%, m.p. 301-303°C.IR -1 1 (KBr); 3157 (NH), 2208 (CN), and 1658cm (CO).H -NMR; (DMSO-d6) δ 3.78 (s, 3H, CH 3), 3.82 (s,2H, CH 2), 6.90-7.81 (m, 10H, Ar+CH), 8.0 (s,1H, NH D2O-exchangeable), and 8.21 ppm(s, 1H, NH, D2O-exchangeable). MS; + m/z (%): M 419 (32). Anal .Calcd for C 21 H17 N5O3S (419.46): C, 60.31; H, 4.09; N, 16.70; S, 7.64. Found: C, 60.22; H, 3.98; N, 16.54; S, 7.34. 2-(5-Thioxo-4,5-dihydro-1H-[1,2,4]triazol-3-ylmethylthio)-4-oxo-6-phenyl-3,4-dihydro-pyrimidine-5-carbonitrile (5): To a solution of 3 (3.01g, 0.01mole) in ethanol (15ml), potassium thiocyanate (0.97g, 0.01mole) was added and the reaction mixture was heated, under reflux, for 3 h allowed to cool and poured into cold water then acidified with HCl. The formed precipitate was filtered off and recrystallized from ethanol giving yellow crystals. Yield 65%,m.p. -1 1 259-260 °C. IR (KBr); 3190 (NH), 2199 (CN), and 1686 cm (CO). H-NMR; (DMSO-d6) δ 2.30(s, 1H, NH, D2O- exchangeable),3.12(s, 2H, CH 2), 7.15-7.68(m,6H,ArH+NHD2O-exchangeable) and 8.21ppm(s,1H,NH D2O- + exchangeable). MS; m/z (%): M ; 342(85.4). Anal. Calcd for C 14 H10 N6OS 2 (342.40): C, 49.11; H, 2.94; N, 24.54; S, 18.72. Found: C, 49.31; H, 2.75; N, 24.42; S, 17.86. 2-(5-Thioxo-4,5-dihydro-1H-[1,3,4]oxadiazol-3ylmethyl-thio)-4-oxo-6-phenyl-3,4-dihydro-pyrimidine-5- carbonitrile (6). To a stirred mixture of 3 (3.01g, 0.01mole) and potassium hydroxide (1.38g, 0.01mole) in ethanol (25ml), carbon disulfide (3.8g, 0.05mole) was added dropwisely. The reaction mixture was allowed to stir for 5 h, heated under reflux for another 8 h, then left to cool and poured into cold water. Acidification with HCl gave a pale yellow precipitate which was filtered off and recrystallized from dilute dimethylformamide.Yield 64%, m.p. 280- -1 1 282°C.IR (KBr); 3127 (NH), 2218 (CN), 1444(CS), and 1676 cm (CO). H-NMR; (DMSO-d6) δ3.96(s, 2H, CH 2), 123 Scholars Research Library Abdelmoneim A. Makhlouf et al Arch. Appl. Sci. Res., 2014, 6 (2):122-135 ______________________________________________________________________________ 7.42-7.90 (m, 5H, ArH), 10.03(s, 1H, NH D2O-exchangeable), and 10.65ppm(s, 1H, NH, D2O exchangeable). Anal. Calcd for C 14 H9N5O2S2 (343.38): C, 48.97; H, 2.64; N, 20.40; S, 18.67. Found: C, 48.67; H, 2.39; N, 20.23; S, 18.21. 6-Aryl-3-carboethoxymethyl-5-cyano-2-methylthio-4-oxo-3,4-dihydropyrimidines7a-c Ethyl bromoacetate (1.67g, 0.01 mole) was added to a stirred refluxing mixture of 2a-c(0.01 mole) and potassium carbonate (1.38 g, 0.01 mole) in ethanol (25 ml) for 2h. The reaction mixture was left to cool, poured into cold water and acidified with HCl. The solid product formed was filtered off and recrystallized from the proper solvent. (Tables 1,2). Synthesis of 8a-e and 9d,e. Alkylation of 2a-d with chloroacetone, chloroacetylacetone, or monobromomalononitrile according to the previous method but using acetone as a solvent in place of ethanol. (Tables 1,2). 6-Aryl-5-cyano-3-cyanomethyl-2-methylthio-4-oxo-3,4-dihydropyrimidines 9a-c. A mixture of 2a-c (0.01 mole), potassium carbonate (1.38g, 0.01mole) and chloroacetonitrile (0.76g, 0.01mole) in dimethylformamide (20 ml) was stirred over night at room temperature then poured into cold water and acidified with HCl .
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