untitled European Journal of Chemistry 7 (2) (2016) 230‐237 European Journal of Chemistry ISSN 2153‐2249 (Print) / ISSN 2153‐2257 (Online)  2016 Atlanta Publishing House LLC ‐ All rights reserved ‐ Printed in the USA http://dx.doi.org/10.5155/eurjchem.7.2.230‐237.1432 European Journal of Chemistry Journal webpage: www.eurjchem.com Heteroaromatization with 4‐phenyldiazenyl‐1‐naphthol. Part I: Synthesis of some new naphthopyrans and naphthopyranopyrimidines Ibrahim Ali Radini 1 and Ashraf Hassan Fekry Abd El‐Wahab 1,2,* 1 Chemistry Department, Faculty of Science, Jazan University, 2097, Jazan, Kingdom of Saudi Arabia 2 Chemistry Department, Faculty of Science, Al‐Azhar University, 11884, Nasr City, Cairo, Egypt * Corresponding author at: Chemistry Department, Faculty of Science, Jazan University, 2097, Jazan, Kingdom of Saudi Arabia. Tel.: +966.054.0963753. Fax: +966.017.3230028. E‐mail address: ash_abdelwahab@yahoo.com (A.H.F. Abd El‐Wahab). ARTICLE INFORMATION ABSTRACT DOI: 10.5155/eurjchem.7.2.230‐237.1432 Received: 27 March 2016 Received in revised form: 27 April 2016 Accepted: 29 April 2016 Published online: 30 June 2016 Printed: 30 June 2016 Reaction of 4‐phenyldiazenyl /or 4‐(p‐tolyldiazenyl)‐1‐naphthol (1) with various substituted α‐cyanocinnamonitriles (2a‐h) and ethyl α‐cyanocinnamates (2i‐p) afforded 2‐amino‐4‐ (aryl)‐6‐(phenyldiazenyl /or p‐tolyldiazenyl)‐4H‐naphtho[1,2‐b]pyrano‐3‐carbonitrile (3a‐ h) and ethyl 2‐amino‐4‐(aryl)‐6‐(phenyldiazenyl /or p‐tolyldiazenyl)‐4H‐naphtho[1,2‐ b]pyrano‐3‐carboxylate (3i‐p). Reaction of compound 3a with Ac2O or PhCOCl and formic acid afforded N‐acetylamino or N,N‐dibenzoylamino and naphthopyranopyrimidine derivatives (4‐8), respectively. The structures of these compounds were established on the basis of IR, UV, 1H NMR, 13C NMR, and MS data. KEYWORDS Naphthopyran α‐Cyanocinnamonitriles Ethyl α‐cyanocinnamates Naphthopyranopyrimidines 4‐Phenyldiazenyl‐1‐naphthol 4‐(p‐Tolyldiazenyl)‐1‐naphthol Cite this: Eur. J. Chem. 2016, 7(2), 230‐237 1. Introduction Nowadays, synthetic azo compounds are widely used in different application and in many fields, such as medicines, cosmetics, food, paints, plastics, shipbuilding, automobile industry, cable manufacture [1‐12]. Moreover, azo compounds are known for their antineoplastics [13], antidiabetics [14], antiseptics [15], antibacterial [16] and antitumor activities [17]. Naphthopyrans are biologically interesting compounds with antimicrobial activities [18‐21], inhibitors of influenza virus sialidases [22,23], DNA stand‐breaking activity and mutagenicity [24], antiviral agent [25], antiproliferation agent [26], sex pheromone [27], antitumor [28,29] and central nervous system (CNS) activity [30]. As a continuation of our previous work for synthesis of naphthopyrans with arylidine skeleton [20,21,31‐35], we efficiently synthesized a series of new 4‐phenyldiazenyl or (p‐ tolyldiazenyl)‐4H‐naphthopyrans and 4‐phenyldiazenyl or (p‐ tolyldiazenyl)‐4H‐naphthopyranopyraimidin‐8‐ones which are expected to possess considerable chemical and pharma‐ cological activities. 2. Experimental 2.1. Instrumentation Melting points were determined with a Stuart Scientific Co., Ltd. apparatus. UV spectra were measured on a Shimadzu UV‐1601PC UV‐Vis spectrophotometer. FT‐IR spectra were determined as KBr pellets on a Jasco FT/IR 460 plus spectro‐ photometer. 1H and 13C NMR spectra were recorded using a Bruker AV 400 MHz spectrometer. Mass spectra were measured on a Shimadzu GC/MS‐QP5050A spectrometer. Elemental analyses were performed on a Perkin‐Elmer 240 microanalyzer in the Faculty of Science, Cairo University, Cairo, Egypt 2.2. Synthesis 2.2.1. Synthesis of 4H‐naphthopyran derivatives (3a‐p) A solution of 4‐phenyldiazenyl/or 4‐(p‐tolyldiazenyl)‐1‐ naphthol (10 mmol) in ethanol (30 mL) was treated with α‐ cyanocinnamonitriles (2a‐h) or ethyl α‐cyanocinnamates (2i‐ p) (10 mmol) and piperidine (0.5 mL). The reaction mixture was heated until complete precipitation occurred (reaction times: 2 h for compounds 2a‐h; 3 h for compounds 2i‐p). Radini and El‐Wahab / European Journal of Chemistry 7 (2) (2016) 230‐237 231 O Ar` N NH2 Y N OH N N Ar` H CN Y EtOH / Pip. + X X 3a-p 2a-p 1 a; Ar`= p‐Cl‐C6H4 b; Ar`= p‐Cl‐C6H4 c; Ar`= p‐OMe‐C6H4 d; Ar`= p‐OMe‐C6H4 e; Ar`= p‐OH‐C6H4 f; Ar`= p‐OH‐C6H4 g; Ar`= C6H5 h; Ar`= C6H5 X = H X = CH3 X = H X = CH3 X = H X = CH3 X = H X = CH3 Y = CN Y = CN Y = CN Y = CN Y = CN Y = CN Y = CN Y = CN i; Ar`= p‐Cl‐C6H4 j; Ar`= p‐Cl‐C6H4 k; Ar`= p‐OMe‐C6H4 l; Ar`= p‐OMe‐C6H4 m; Ar`= p‐OH‐C6H4 n; Ar`= p‐OH‐C6H4 o; Ar`= C6H5 p; Ar`= C6H5 X = H X = CH3 X = H X = CH3 X = H X = CH3 X = H X = CH3 Y = COOEt Y = COOEt Y = COOEt Y = COOEt Y = COOEt Y = COOEt Y = COOEt Y = COOEt Scheme 1 The solid product which formed was collected by filtration and recrystallized from dioxane and ethanol:benzene (1:1, v:v), respectively (Scheme 1). (E) 2‐Amino‐4‐(p‐chlorophenyl)‐6‐(phenyldiazenyl)‐4H‐ naphtho[1,2‐b]pyran‐3‐carbonitrile (3a): Color: Yellow crystals. Yield: 90 %. M.p.: 245‐246 °C. UV/Vis (CH3COCH3, λmax, nm): 268.80. FT‐IR (KBr, , cm‐1): 3417, 3327, 3207 (NH2), 3001, 2960, 2812 (CH stretching), 2196 (CN), 1666 (C=C), 1510 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.93‐ 7.24 (m, 14H, Ar‐H), 4.95 (s, 1H, CH‐pyran), 4.84 (bs, 2H, NH2, exchangeable by D2O). 13C NMR (100 MHz, CDCl3, δ, ppm): 158.59 (C‐2), 152.94 (C‐6), 116.98 (CN), 61.33(C‐3), 40.74 (C‐ 4), 144.70, 142.63, 133.44, 131.41, 133.29, 129.45, 129.20, 129.14, 127.82, 127.43, 123.75, 123.71, 123.28, 123.17, 120.90, 112.25 (aromatic). MS (EI, m/z (%)): 438 (M++2, 0.0), 436 (M+, 20.4), 325 (75.8), 220 (59.9), 77 (100), 51 (18.2). Anal. calcd. for C26H17ClN4O: C, 71.48; H, 3.92; N, 12.82. Found: C, 71.01; H, 3.40; N, 12.39%. (E) 2‐Amino‐4‐(p‐chlorophenyl)‐6‐(p‐tolyldiazenyl)‐4H‐ naphtho[1,2‐b]pyran‐3‐carbonitrile (3b): Color: Yellow crystals. Yield: 86 %. M.p.: 232‐233 °C. UV/Vis (CH3COCH3, λmax, nm): 269.75. FT‐IR (KBr, , cm‐1): 3410, 3330 (NH2), 3015, 3000, 2981 (CH stretching), 2200 (CN), 1680 (C=C), 1500 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.94‐7.21 (m, 13H, Ar‐H), 5.01 (s, 1H, CH‐pyran), 4.88 (bs, 2H, NH2, exchangeable by D2O), 1.42 (s, 3H, CH3). 13C NMR (100 MHz, CDCl3, δ, ppm): 158.63 (C‐2), 152.82 (C‐6), 116.97 (CN), 61.45 (C‐3), 40.70 (C‐4), 21.33 (CH3), 144.71, 142.66, 133.42, 131.40, 131.27, 129.46, 129.21, 129.15, 127.80, 127.41, 123.73, 123.71, 123.26, 123.18, 120.87, 112.23 (aromatic). MS (EI, m/z (%)): 452 (M++2, 40.40), 450 (M+, 100), 339 (57.6), 220 (42.3), 91(47.0), 77 (1.6), 51 (0.7), 75 (100), 50 (46). Anal. calcd. for C27H19ClN4O: C, 71.92; H, 4.25; N, 12.43. Found: C, 71.35; H, 3.81; N, 12.11 %. (E) 2‐Amino‐4‐(p‐methoxyphenyl)‐6‐(phenyldiazenyl)‐4H‐ naphtho[1,2‐b]pyran‐3‐carbonitrile (3c): Color: Pale red crystals. Yield: 85 %. M.p.: 248‐249 °C. UV/Vis (CH3COCH3, λmax, nm): 269.81. FT‐IR (KBr, , cm‐1): 3420, 3327, 3210 (NH2), 3076, 2938 (CH stretching), 2198 (CN), 1664 (C=C), 1515 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.90‐7.11 (m, 14H, Ar‐H), 5.12 (s, 1H, CH‐pyran), 4.90 (bs, 2H, NH2, exchangeable by D2O), 3.79 (s, 3H, OCH3). 13C NMR (100 MHz, CDCl3, δ, ppm): 159.01 (C‐2), 116.90 (CN), 61.77 (C‐3), 56.40 (OCH3), 41.15 (C‐4), 153.01, 144.67, 142.60, 133.45, 131.43, 131.26, 129.49, 129.23, 129.16, 127.76, 127.39, 123.77, 123.70, 123.29, 123.20, 120.87, 112.23 (aromatic). MS (EI, m/z (%)): 434 (M++2, 3.6), 433 (M++1, 21.5), 432 (M+, 69.6), 325 (100), 220 (30.5), 76 (47.3), 51 (6.0). Anal. calcd. for C27H20N4O2: C, 74.98; H, 4.66; N, 12.95. Found: C, 74.40; H, 4.25; N, 12.45 %. (E) 2‐Amino‐4‐(p‐methoxyphenyl)‐6‐(p‐tolyldiazenyl)‐ 4H‐naphtho[1,2‐b]pyran‐3‐carbonitrile (3d): Color: Pale red crystals. Yield: 84 %. M.p.: 230‐231 °C. UV/Vis (CH3COCH3, λmax, nm): 269.84. FT‐IR (KBr, , cm‐1): 3419, 3325, 3207 (NH2), 3030, 3009, 2981, 2940 (CH stretching), 2196 (CN), 1664 (C=C), 1510 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.84‐6.96 (m, 13H, Ar‐H), 5.09 (s, 1H, CH‐pyran), 4.89 (bs, 2H, NH2, exchangeable by D2O), 3.78 (s, 3H, OCH3), 1.37 (s, 3H, CH3). 13C NMR (100 MHz, CDCl3, δ, ppm): 159.31 (C‐2), 127.51 (C‐8), 127.51 (C‐9), 121.16 (C‐10), 121.16 (C‐4a), 117.01 (CN), 61.89 (C‐3), 56.87 (OCH3), 41.15 (C‐4), 21.40 (CH3), 144.80, 142.66, 133.45, 131.40, 131.27, 129.46, 129.22, 129.16, 127.88, 127.40, 123.72, 123.70, 123.28, 123.18, 120.91, 112.28 (aromatic). MS (EI, m/z (%)): 448 (M++2, 1.9), 447 (M++1, 10.5), 446 (M+, 34.4), 220 (32.4), 91 (86.0), 77 (6.3). Anal. calcd. for C28H22N4O2: C, 75.32; H, 4.97; N, 12.55. Found: C, 74.81; H, 4.41; N, 12.16 %. (E) 2‐Amino‐4‐(p‐hydroxyphenyl)‐6‐(phenyldiazenyl)‐4H‐ naphtho[1,2‐b]pyran‐3‐carbonitrile (3e): Color: Red crystals. Yield: 80 %. M.p.: 198‐199 °C. UV/Vis (CH3COCH3, λmax, nm): 271.20. FT‐IR (KBr, , cm‐1): 3423 (OH), 3319, 3246 (NH2), 3055, 3010 (CH stretching), 2193 (CN), 1624 (C=C), 1541 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 9.72 (bs, 1H, OH, exchangeable by D2O), 8.45‐7.01 (m, 14H, Ar‐H), 4.93 (s, 1H, CH‐pyran), 4.80 (bs, 2H, NH2, exchangeable by D2O). 13C NMR (100 MHz, CDCl3, δ, ppm): 159.12 (C‐2), 153.40 (C‐6), 117.23 (CN), 62.01 (C‐3), 41.11 (C‐4), 144.75, 142.60, 133.40, 131.37, 131.26, 129.40, 129.25, 129.16, 127.86, 127.45, 123.73, 123.70, 123.26, 123.19, 120.93, 112.30 (aromatic). MS (EI, m/z (%)): 419 (M++1, 3.5), 418 (M+, 16.2), 325 (100), 221 (15.1), 180 (25.3), 77 (62.1), 52 (10.5). Anal. calcd. for C26H18N4O2: C, 74.63; H, 4.34; N, 13.39. Found: C, 74.12; H, 4.04; N, 12.89 %. (E) 2‐Amino‐4‐(p‐hydroxyphenyl)‐6‐(p‐tolyldiazenyl)‐4H‐ naphtho[1,2‐b]pyran‐3‐carbonitrile (3f): Color: Red crystals. Yield: 87 %. M.p.: 207‐208 °C. UV/Vis (CH3COCH3, λmax, nm): 271.01. FT‐IR (KBr, , cm‐1): 3430 (OH), 3321, 3249 (NH2), 3041, 3012 (CH stretching), 2197 (CN), 1628 (C=C), 1539 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 9.70 (bs, 1H, OH, exchangeable by D2O), 8.51‐6.83 (m, 13H, Ar‐H), 5.10 (s, 1H, CH‐pyran), 4.91 (bs, 2H, NH2, exchangeable by D2O), 2.41 (s, 3H, CH3). 13C NMR (100 MHz, CDCl3, δ, ppm): 159.01 (C‐2), 153.41 (C‐6), 116.92 (CN), 61.80 (C‐3), 41.11 (C‐4), 21.65 232 Radini and El‐Wahab / European Journal of Chemistry 7 (2) (2016) 230‐237 (CH3), 144.71, 142.62, 133.42, 131.40, 133.27, 129.43, 129.22, 129.16, 127.84, 127.46, 123.76, 123.74, 123.27, 123.19, 120.88, 112.30 (aromatic). MS (EI, m/z (%)): 432 (M+, 14.40), 339 (12.07), 314 (20.10), 221 (1.1), 172 (35.26), 106 (100), 77 (6.4), 53 (14.4). Anal. calcd. for C27H20N4O2: C, 74.98; H, 4.66; N, 12.95. Found: C, 74.34; H, 4.20; N, 12.23 %. (E) 2‐Amino‐4‐phenyl‐6‐(phenyldiazenyl)‐4H‐naphtho[1,2‐ b]pyran‐3‐carbonitrile (3g): Color: Red crystals. Yield: 86 %. M.p.: 265‐266 °C. UV/Vis (CH3COCH3, λmax, nm): 270.80. FT‐IR (KBr, , cm‐1): 3466, 3327, 3198 (NH2), 3050, 3020, 2985 (CH stretching), 2196 (CN), 1664 (C=C), 1510 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.80‐7.20 (m, 15H, Ar‐H), 5.21 (s, 1H, CH‐ pyran), 4.99 (bs, 2H, NH2, exchangeable by D2O). 13C NMR (100 MHz, CDCl3, δ, ppm): 158.76 (C‐2), 152.78 (C‐6), 116.97 (CN), 62.03 (C‐3), 41.19 (C‐4), 144.74, 142.60, 133.42, 131.42, 131.27, 129.43, 129.22, 129.16, 127.81, 127.42, 127.81, 127.40, 123.72, 123.70, 123.26, 123.14, 120.78, 112.22 (aromatic). MS (EI, m/z (%)): 404 (M++2, 5.0), 403 (M++1, 27.0), 402 (M+, 100), 325 (66.5), 220 (36.8), 76 (18.0), 51 (1.75). Anal. calcd. for C26H18N4O: C, 77.59; H, 4.51; N, 13.92. Found: C, 77.08; H, 4.07; N, 13.46 %. (E) 2‐Amino‐4‐phenyl‐6‐(p‐tolyldiazenyl)‐4H‐naphtho[1,2‐ b]pyran‐3‐carbonitrile (3h): Color: Yellow crystals. Yield: 83 %. M.p.: 260‐261 °C. UV/Vis (CH3COCH3, λmax, nm): 270.64. FT‐IR (KBr, , cm‐1): 3468, 3300, 3188 (NH2), 3048, 3027, 2988 (CH stretching), 2191 (CN), 1664 (C=C), 1512 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.99‐7.10 (m, 14H, Ar‐H), 5.17 (s, 1H, CH‐ pyran), 4.91 (bs, 2H, NH2, exchangeable by D2O), 2.40 (s, 3H, CH3). 13C NMR (100 MHz, CDCl3, δ, ppm): 159.07 (C‐2), 153.05 (C‐6), 117.01 (CN), 61.53 (C‐3), 41.27 (C‐4), 144.66, 142.56, 133.41, 131.40, 131.27, 129.42, 129.21, 129.17, 127.81, 127.40, 123.73, 123.70, 123.26, 123.15, 120.91, 112.26 (aromatic). MS (EI, m/z (%)): 418 (M++2, 4.5), 417 (M++1, 13.7), 416 (M+, 45.1), 339 (100), 297 (33.9), 220 (81.8), 91 (84.2), 77 (10.3). Anal. calcd. for C27H20N4O: C, 77.87; H, 4.84; N, 13.45 %. Found: C, 77.48; H, 4.34; N, 13.02 %. (E) Ethyl 2‐amino‐4‐(p‐chlorophenyl)‐6‐(phenyldiazenyl)‐ 4H‐naphtho[1,2‐b]pyran‐3‐carboxylate (3i): Color: Yellow crystals. Yield: 75 %. M.p.: 208‐209 °C. UV/Vis (CH3COCH3, λmax, nm): 267.58. FT‐IR (KBr, , cm‐1): 3417, 3380, 3126 (NH2), 3060, 3010, 2960, (CH stretching), 1675 (CO), 1629 (C=C), 1539 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.92‐ 7.20 (m, 14H, Ar‐H), 6.54 (bs, 2H, NH2, exchangeable by D2O), 5.14 (s, 1H, CH‐pyran), 4.11 (q, 2H, CH2, J = 7.0 Hz), 1.21 (t, 3H, CH3, J = 7.0 Hz). 13C NMR (100 MHz, CDCl3, δ, ppm): 169.15 (CO), 159.62 (C‐2), 153.08 (C‐6), 79.01 (C‐3), 59.73 (CH2), 40.37 (C‐4), 14.37 (CH3), 145.81, 145.79, 145.68, 144.26, 132.05, 131.24, 131.02, 129.61, 129.37,129.13, 128.45, 128.36, 127.32, 127.00, 126.40, 123.79, 123.61, 123.11, 120.54, 112.76 (aromatic). MS (EI, m/z (%)): 485 (M++2, 5.41), 483 (M+, 9.22), 372 (35.2), 268 (18.5), 181 (6.7), 91 (100), 75 (60.1), 51 (9.3). Anal. calcd. for C28H22ClN3O3: C, 69.49; H, 4.58; N, 8.68. Found: C, 69.05; H, 4.12; N, 8.25 %. (E) Ethyl 2‐amino‐4‐(p‐chlorophenyl)‐6‐(p‐tolyldiazenyl)‐ 4H‐naphtho[1,2‐b]pyran‐3‐carboxylate (3j): Color: Yellow crystals. Yield: 71 %. M.p.: 222‐223 °C. UV/Vis (CH3COCH3, λmax, nm): 267.82. FT‐IR (KBr, , cm‐1): 3454, 3321, 3290 (NH2), 3020, 3001, 2980, (CH stretching), 1680 (CO), 1670 (C=C), 1521 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.90‐ 7.11 (m, 13H, Ar‐H), 6.41 (bs, 2H, NH2, exchangeable by D2O), 5.12 (s, 1H, CH‐pyran), 4.19 (q, 2H, CH2, J = 7.0 Hz), 2.40 (s, 3H, CH3), 1.23 (t, 3H, CH3, J = 7.0 Hz). 13C NMR (100 MHz, CDCl3, δ, ppm): 170.00 (CO), 160.10 (C‐2), 153.60 (C‐6), 80.00 (C‐3), 60.21 (CH2), 41.13 (C‐4), 21.58, (CH3), 14.37 (CH3), 145.80, 145.78, 145.70, 144.28, 132.10, 131.22, 131.08, 129.60, 129.36, 129.15, 128.43, 128.34, 127.30, 127.02, 126.42, 123.78, 123.60, 123.16, 120.56, 112.78 (aromatic). MS (EI, m/z (%)): 499 (M++2, 2.17), 497 (M+, 4.61), 386 (43.5), 221 (19.51), 220 (1.87), 91 (100), 75 (3.7), 51 (2.2). Anal. calcd. for C29H24ClN3O3: C, 69.95; H, 4.86; N, 8.44. Found: C, 69.51; H, 4.40; N, 8.02 %. (E) Ethyl 2‐amino‐4‐(p‐methoxyphenyl)‐6‐(phenyldiazenyl)‐ 4H‐naphtho[1,2‐b]pyran‐3‐carboxylate (3k): Color: Yellow crystals. Yield: 72 %. M.p.: 290‐291 °C. UV/Vis (CH3COCH3, λmax, nm): 268.30. FT‐IR (KBr, , cm‐1): 3383, 3259 (NH2), 3066, 3012, 2955, (CH stretching), 1672 (CO), 1618 (C=C), 1529 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 9.21‐7.42 (m, 14H, Ar‐H), 6.39 (bs, 2H, NH2, exchangeable by D2O), 5.06 (s, 1H, CH‐pyran), 4.25 (q, 2H, CH2, J = 7.0 Hz), 2.67 (s, 3H, CH3), 1.41 (t, 3H, CH3, J = 7.0 Hz). 13C NMR (100 MHz, CDCl3, δ, ppm): 170.20 (CO), 160.30 (C‐2), 154.77 (C‐6), 81.02 (C‐3), 60.25 (CH2), 58.10 (OCH3), 41.17 (C‐4), 14.39 (CH3), 145.84, 145.77, 145.69, 144.28, 132.08, 131.27, 131.09, 129.70, 129.36, 129.17, 128.46, 128.34, 127.30, 127.10, 126.38, 123.81, 123.62, 123.15, 120.55, 112.73 (aromatic). MS (EI, m/z (%)): 479 (M+, 0.7), 406 (0.8), 220 (1.63), 155 (27.6), 77 (100), 51 (45.1). Anal. calcd. for C29H25N3O4: C, 72.64; H, 5.26; N, 8.76. Found: C, 72.21; H, 4.83; N, 8.42 %. (E) Ethyl 2‐Amino‐4‐(p‐methoxyphenyl)‐6‐(p‐tolyldiazenyl)‐ 4H‐naphtho[1,2‐b]pyran‐3‐carboxylate (3l): Color: Yellow crystals. Yield: 87 %. M.p.: 268‐269 °C. UV/Vis (CH3COCH3, λmax, nm): 268.27. FT‐IR (KBr, , cm‐1): 3439, 3270 (NH2), 3060, 3017, 2986 (CH stretching), 1670 (CO), 1620 (C=C), 1531 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.39‐6.80 (m, 13H, Ar‐H), 6.15 (bs, 2H, NH2, exchangeable by D2O), 5.14 (s, 1H, CH‐pyran), 4.10 (q, 2H, CH2, J = 7.0 Hz), 3.59 (s, 3H,OCH3), 2.40 (s, 3H, CH3), 1.27 (t, 3H, CH3, J = 7.0 Hz). 13C NMR (100 MHz, CDCl3, δ, ppm): 170.08 (CO), 160.02 (C‐2), 153.06 (C‐6), 80.15 (C‐3), 61.79 (CH2), 56.15 (OCH3), 40.81 (C‐4), 21.15 (CH3), 14.20 (CH3), 145.80, 145.79, 145.68, 144.24, 132.10, 131.26, 131.02, 129.60, 129.37, 129.11, 128.52, 128.44, 127.25, 127.05, 126.42, 123.76, 123.63, 123.14, 120.80, 120.60, 112.69 (aromatic). MS (EI, m/z (%)): 493 (M+, 11.4), 386 (32.4), 221 (18.6), 155 (27.1), 77 (100), 51 (60.7). Anal. calcd. for C30H27N3O4: C, 73.01; H, 5.51; N, 8.51. Found: C, 72.64; H, 5.10; N, 8.14 %. (E) Ethyl 2‐amino‐4‐(p‐hydroxyphenyl)‐6‐(phenyldiazenyl)‐ 4H‐naphtho[1,2‐b]pyran‐3‐carboxylate (3m): Color: Red crystals. Yield: 69 %. M.p.: 190‐191 °C. UV/Vis (CH3COCH3, λmax, nm): 267.75. FT‐IR (KBr, , cm‐1): 3439 (OH), 3259, 3132 (NH2), 3033, 3012, 2950, (CH stretching), 1672 (CO), 1620 (C=C), 1510 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 9.70 (bs, 1H, OH), 8.76‐6.80 (m, 14H, Ar‐H), 6.25 (bs, 2H, NH2, exchangeable by D2O), 5.07 (s, 1H, CH‐pyran), 4.36 (q, 2H, CH2, J = 7.0 Hz), 1.29 (t, 3H, CH3, J = 7.0 Hz). 13C NMR (100 MHz, CDCl3, δ, ppm): 170.02 (CO), 160.61 (C‐2), 153.02 (C‐6), 80.20 (C‐3), 62.21 (CH2), 40.34 (C‐4), 14.15 (CH3), 145.90, 145.80, 145.78, 144.29, 132.15, 131.30, 131.10, 129.80, 129.40, 129.21, 128.56, 128.48, 127.29, 127.10, 126.44, 123.80, 123.65, 123.18, 120.85, 120.70, 112.70 (aromatic). MS (EI, m/z (%)): 465 (M+, 21.2), 372 (3.8), 262 (20.3), 220 (29.1), 142 (52.6), 115 (48.4), 65 (100), 50 (30.1). Anal. calcd. for C28H23N3O4: C, 72.25; H, 4.98; N, 9.03. Found: C, 71.80; H, 4.52; N, 8.66 %. (E) Ethyl 2‐amino‐4‐(p‐hydroxyphenyl)‐6‐(p‐tolyldiazenyl)‐ 4H‐naphtho[1,2‐b]pyran‐3‐carboxylate (3n): Color: Pale red crystals. Yield: 68 %. M.p.: 252‐253 °C. UV/Vis (CH3COCH3, λmax, nm): 267.64. FT‐IR (KBr, , cm‐1): 3423 (OH), 3256, 3136 (NH2), 3082, 3010, 2941 (CH stretching), 1670 (CO), 1614 (C=C), 1508 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 9.76 (bs, 1H, OH, exchangeable by D2O), 8.26‐6.98 (m, 13H, Ar‐H), 6.28 (bs, 2H, NH2, exchangeable by D2O), 4.96 (s, 1H, CH‐ pyran), 4.31 (q, 2H, CH2, J = 7.0 Hz), 2.30 (s, 3H, CH3), 1.27 (t, 3H, CH3, J = 7.0 Hz). 13C NMR (100 MHz, CDCl3, δ, ppm): 169.99 (CO), 159.50 (C‐2), 153.40 (C‐6), 80.77 (C‐3), 62.53 (CH2), 40.42 (C‐4), 21.17 (CH3), 14.18 (CH3), 145.92, 145.83, 145.76, 144.27, 132.16, 131.32, 131.15, 129.86, 129.42, 129.22, 128.58, 128.47, 127.28, 127.12, 126.43, 123.81, 123.66, 123.20, 120.83, 120.71, 112.65 (aromatic). MS (EI, m/z (%)): 479 (M+, 1.20), 386 (0.7), 262 (20.3), 219 (23.0), 143 (56.4), 115 (78.8), 65 (100), 50 (42.7). Anal. calcd. for C29H25N3O4: C, 72.64; H, 5.26; N, 8.76. Found: C, 72.20; H, 4.78; N, 8.32 %. Radini and El‐Wahab / European Journal of Chemistry 7 (2) (2016) 230‐237 233 Scheme 2 (E) Ethyl 2‐amino‐4‐phenyl‐6‐(phenyldiazenyl)‐4H‐ naphtho[1,2‐b]pyran‐3‐carboxylate (3o): Color: Pale red crystals. Yield: 65 %. M.p.: 206‐207 °C. UV/Vis (CH3COCH3, λmax, nm): 268.15. FT‐IR (KBr, , cm‐1): 3300, 3184, 3165, 3124 (NH2), 3026, 2999, 2982 (CH stretching), 1650 (CO), 1610 (C=C), 1533 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.88‐ 7.10 (m, 15H, Ar‐H), 6.40 (bs, 2H, NH2, exchangeable by D2O), 5.10 (s, 1H, CH‐pyran), 4.10 (q, 2H, CH2, J = 7.0 Hz), 1.28 (t, 3H, CH3, J = 7.0 Hz). 13C NMR (100 MHz, CDCl3, δ, ppm): 169.89 (CO), 159.30 (C‐2), 153.10 (C‐6), 80.30 (C‐3), 62.40 (CH2), 40.60 (C‐4), 14.75 (CH3), 145.87, 145.81, 145.79, 144.28, 132.17, 131.31, 131.17, 129.81, 129.42, 129.26, 128.58, 128.46, 127.27, 127.13, 126.45, 123.82, 123.60, 123.20, 120.82, 120.68, 112.63 (aromatic). MS (EI, m/z (%)): 449 (M+, 2.95), 374 (8.4), 271 (100), 104 (94.6), 48 (47.2). Anal. calcd. for C28H23N3O3: C, 74.82; H, 5.16; N, 9.35. Found: C, 74.43; H, 4.65; N, 8.84 %. (E) Ethyl 2‐amino‐4‐phenyl‐6‐(p‐tolyldiazenyl)‐4H‐ naphtho[1,2‐b]pyran‐3‐carboxylate (3p): Color: Pale red crystals. Yield: 63 %. M.p.: 240‐241 °C. UV/Vis (CH3COCH3, λmax, nm): 268.06. FT‐IR (KBr, , cm‐1): 3454, 3381, 3321 (NH2), 3027, 3010, 2933 (CH stretching), 1680 (CO), 1666 (C=C), 1520 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.73‐ 7.21 (m, 14H, Ar‐H), 6.45 (bs, 2H, NH2, exchangeable by D2O), 5.13 (s, 1H, CH‐pyran), 4.30 (q, 2H, CH2, J = 7.0 Hz), 2.39 (s, 3H, CH3), 1.24 (t, 3H, CH3, J = 7.0 Hz). 13C NMR (100 MHz, CDCl3, δ, ppm): 169.50 (CO), 159.10 (C‐2), 153.30 (C‐6), 80.60 (C‐3), 62.30 (CH2), 40.39 (C‐4), 21.28 (CH3), 14.19 (CH3), 145.86, 145.78, 145.80, 144.27, 132.15, 131.30, 131.16, 129.80, 129.40, 129.25, 128.56, 128.43, 127.25, 127.16, 126.46, 123.80, 123.64, 123.22, 120.81, 120.69, 112.60 (aromatic). MS (EI, m/z (%)): 463 (M+, 7.50), 387 (100), 244 (45.18), 143 (20.1), 99 (8.5), 57 (0.1), 55 (0.2). 2.2.2. Synthesis of 2‐acetylamino‐4‐(p‐chlorophenyl)‐6‐ (phenyldiazenyl)‐4H‐naphtho[1,2‐b]pyran‐3‐carbonitrile (4) A solution of compound 3a (0.43 g, 10 mmol) in Ac2O (20 mL) was heated under reflux for 30 min. The solid product formed was filtered off and washed with cold ethanol; the solid obtained was filtered off and recrystallized from ethanol (Scheme 2). Color: Yellow crystals. Yield: 83 %. M.p.: 181‐182 °C. FT‐IR (KBr, , cm‐1): 3450 (NH), 3120, 2943 (CH‐ stretching), 2231 (CN), 1715 (CO), 1650 (C=C), 1541 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 10.29 (bs, 1H, NH, exchangeable by D2O), 8.83‐6.93 (m, 14H, Ar‐H), 5.18 (s, 1H, pyran CH), 2.19 (s, 3H, CH3). 13C NMR (100 MHz, CDCl3, δ, ppm): 170.50 (CO), 160.41 (C‐2), 152.88 (C‐6), 116.43 (CN), 60.13 (C‐3), 41.12 (C‐4), 22.65 (CH3), 145.79, 145.71, 145.68, 144.24, 132.11, 131.26, 131.02, 129.50, 129.37, 129.13, 128.40, 128.31, 127.24, 127.01, 126.40, 123.79, 123.61, 120.82, 120.68, 112.62 (aromatic). MS (EI, m/z (%)): 480 (M++2, 2.31), 478 (M+, 7.20), 367 (45.2), 308 (56.1), 179 (33.1), 77 (100), 50 (37.4). Anal. calcd. for C28H19ClN4O2: C, 70.22; H, 4.00; N, 11.70. Found: C, 69.85; H, 3.61; N, 11.42%. 2.2.3. Synthesis of 7‐(4‐chlorophenyl)‐10‐methyl‐5‐(phenyl diazenyl)‐7,9‐dihydro‐8H‐benzo[7,8]chromeno[2,3‐d] pyrimidin‐8‐one (5) Method A: A solution of compound 3a (0.43 g, 10 mmol) in Ac2O (20 mL) was heated under reflux for 3 h. The precipitate was filtered off, washed with cold ethanol. The solid obtained was filtered off and recrystallized from DMF. Method B: Gaseous dry HCl was bubbled through the mixture of compound 3i (0.48 g, 10 mmol) and CH3CN (30 mL) for 6 h. The reaction mixture was poured into ice water and alkalized with 10% aqueous ammonium hydroxide to give compound 5 (Scheme 2). Color: Yellow crystals. Yield: 85 %. M.p.: > 360 °C. FT‐IR (KBr, , cm‐1): 3456 (NH), 3020, 3005, 2920 (CH‐ stretching), 1680 (CO), 1643 (C=C), 1540 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.81‐7.71 (m, 15H, Ar‐H + NH), 5.37 (s, 1H, pyran CH), 2.40 (s, 3H, CH3). MS (EI, m/z (%)): 480 (M++2, 11.58), 478 (M+, 11.47), 433 (73.1), 328 (64.8), 293 (84.7), 77 (100), 51 (29.7). Anal. calcd. for C28H19ClN4O2: C, 70.22; H, 4.00; N, 11.70. Found: C, 69.80; H, 3.75; N, 11.53 %. 234 Radini and El‐Wahab / European Journal of Chemistry 7 (2) (2016) 230‐237 Scheme 3 2.2.4. Synthesis of 2‐N,N‐dibenzoylamino‐4‐(p‐chloro phenyl)‐6‐(phenyldiazenyl)‐4H‐naphtho[1,2‐b]pyran‐3‐ carbonitrile (6) A solution of compound 3a (0.43 g, 10 mmol) in benzoyl chloride (10 mL) in dry benzene (20 mL) was heated under reflux for 6 h. The excess of benzoyl chloride was removed under reduced pressure and the residue was poured into cold water. The precipitate was collected by filtration, washed with carbon tetrachloride (10 mL) to remove the formed benzoic acid and the residue was dried. The solid obtained was filtered off and recrystallized from DMF (Scheme 3). Color: Pale yellow crystals. Yield: 70 %. M.p.: >360 °C. FT‐IR (KBr, , cm‐1): 3076, 3015 (CH‐ stretching), 2231 (CN), 1735 (CO), 1641 (C=C), 1541 (N=N). 1H NMR (400 MHz, DMSO‐d6, δ, ppm): 8.99‐6.90 (m, 24H, Ar‐H), 5.20 (s, 1H, pyran CH). MS (EI, m/z (%)): 646 (M++2, 0.0), 644 (M+, 0.1), 435 (37.6), 330 (41.0), 302 (100), 238 (21.3), 77 (47.7). Anal. calcd. for C40H25ClN4O3: C, 74.47; H, 3.91; N, 8.68. Found: C, 74.02; H, 3.50; N, 8.24 %. 2.2.5. Synthesis of 7‐(4‐chlorophenyl)‐10‐phenyl‐5‐(phenyl diazenyl)‐7,9‐dihydro‐8H‐benzo[7,8]chromeno[2,3‐d] pyrimidin‐8‐one (7) A solution of compound 3a (0.43 g, 10 mmol) in benzoyl chloride (10 mL) in DMF (20 mL) was heated under reflux for 6 h. The excess of benzoyl chloride was removed under reduced pressure and the residue was poured into cold water. The precipitate was collected by filtration, washed with carbon tetrachloride (10 mL) to remove the formed benzoic acid and the residue was dried. The solid obtained was filtered off and recrystallized from DMF (Scheme 3). Color: Pale yellow crystals. Yield: 78 %. M.p.: >360 °C. FT‐IR (KBr, , cm‐1): 3452 (NH), 3041, 3023 (CH stretching), 1695 (CO), 1633 (C=C), 1542 (N=N). 1H NMR (400 MHz, DMSO‐d6, δ, ppm): 11.92 (br, 1H, NH, exchangeable by D2O), 8.78‐6.96 (m, 19 H, Ar‐H), 5.14 (s, 1H, pyran CH). MS (EI, m/z (%)): 542 (M++2, 4.21), 542 (M+, 9.31), 429 (46.3), 353 (100), 248 (37.5), 77 (16.4), 50 (7.3). Anal. calcd. for C33H21ClN4O2: C, 73.26; H, 3.91; N, 10.36. Found: C, 72.80; H, 3.56; N, 9.78 %. 2.2.6. Synthesis 7‐(4‐chlorophenyl)‐5‐(phenyldiazenyl)‐7,9‐ dihydro‐8H‐benzo[7,8]chromeno[2,3‐d]pyrimidin‐8‐one (8) Method A: A solution of compound 3a (0.43 g, 10 mmol) in formic acid (20 mL) was heated under reflux for 10 h. The solid obtained was filtered off and recrystallized from dioxane. Method B: A solution of compound 3i (0.48 g, 10 mmol) in formamide (20 mL) was heated under reflux for 6 h to give compound 8 (Scheme 3). Color: Pale yellow crystals. Yield: 84 %. M.p.: >190‐191 °C. FT‐IR (KBr, , cm‐1): 3433 (NH), 3064, 2911 (CH‐ stretching), 1718 (CO), 1662 (C=C), 1540 (N=N). 1H NMR (400 MHz, CDCl3, δ, ppm): 11.21 (br, 1H, NH, exchangeable by D2O), 8.42‐6.70 (m, 15H, Ar‐H + CH‐ pyrimidine), 5.15 (s, 1H, pyran CH). 13C NMR (100 MHz, CDCl3, δ, ppm): 165.70 (CO), 161.41 (C11a), 155.10 (C‐10), 41.65 (C‐ 7), 61.26 (C‐7a), 145.78 145.70, 145.67, 144.23, 132.10, 131.24, 131.01, 129.51, 129.36, 129.16, 128.41, 128.30, 127.33, 127.05, 126.41, 123.77, 123.60, 123.17, 120.40, 112.60 (aromatic). MS (EI, m/z (%)): 466 (M++2, 0.0), 464 (M+, 0.1), 265 (51.6), 202 (47.5), 133 (72.9), 108 (100), 76 (37.5), 51 (16.0). Anal. calcd. for C27H17ClN4O2: C, 69.75; H, 3.69; N, 12.05. Found: C, 69.35; H, 3.21; N, 11.74 %. 3. Results and discussion Condensation of various substituted α‐cyanocinnamo‐ nitriles (2a‐h) and ethyl α‐cyanocinnamates (2i‐p) with 4‐ phenyldiazenyl /or 4‐(p‐tolyldiazenyl)‐1‐naphthol (1) in ethanolic piperidine afforded the corresponding 2‐amino‐4‐ (aryl)‐6‐(phenyldiazenyl/or p‐tolyldiazenyl)‐4H‐naphtho[1,2‐ b]pyran‐3‐carbonitrile (3a‐h) and ethyl‐2‐amino‐4‐(aryl)‐6‐ (phenyldiazenyl /or p‐tolyldiazenyl)‐4H‐naphtho[1,2‐b]pyran‐ 3‐carboxylate (3i‐p), respectively (Scheme 1). The structures of compounds 3a‐p were established on the basis of 1H NMR and 13C NMR spectra, which showed 4H‐pyran at δ 4.85‐5.15 and C‐4 at δ 40.15‐41.27 ppm. The IR spectra of compounds 3a‐i showed v(NH2) stretch at 3440‐3405, 3327‐ 3307 and 3216‐3196 cm‐1; v(CN) stretch at 2200‐2191 cm‐1, and compounds 3g‐p showed v(CO) stretch at 1680‐1670 cm‐1. The UV spectrum of compound 3a‐p revealed a weak shoulder characteristic for 4H‐pyran [36] at λmax (CH3COCH3): 267.58‐ 271.20 nm (log ε = 4.82‐4.81). The mass spectra of compounds 3a‐p showed, the corresponding molecular ion peaks at m/z 436 (M+, 20.4), 450 (M+, 100), 432 (M+, 69.6), 446 (M+, 33.4), 418 (M+, 16.2), 432 (M+, 14.40), 402 (M+, 100), 416 (M+, 45.1), 483 (M+, 9.22), 497 (M+, 4.61), 479 (M+, 0.79), 493 (M+, 11.44), Radini and El‐Wahab / European Journal of Chemistry 7 (2) (2016) 230‐237 235 Scheme 4 465 (M+, 20.23), 479 (M+, 1.20), 449 (M+, 0.90), 463 (M+, 7.50). The fragmentation patterns of compounds 3a‐p, respectively (Scheme 4). The formation of compound 3a‐p indicates that the naphtholate anion (C‐2) of compound 1 attack at the β‐carbon of compound 2 to yield an acyclic Michael adduct [37], which underwent cyclization as shown in Scheme 5. 236 Radini and El‐Wahab / European Journal of Chemistry 7 (2) (2016) 230‐237 Scheme 5 Interaction of 2‐amino‐4‐(p‐chlorophenyl)‐6‐(phenyl‐ diazenyl)‐4H‐naphtho[1,2‐b]pyran‐3‐carbonitrile (3a) with acetic anhydride for 30 min afforded the N‐acetylamino derivative 4 while heating of compound 3a with acetic anhydride for 6 h afforded 8,9‐dihydro‐10‐methyl‐5‐(phenyl‐ diazenyl)‐ 7‐(p‐chlorophenyl)‐7H‐naphtho [1,2‐b]pyrano[2,3‐ d]pyrimidin‐8‐one (5) (Scheme 2). The structure of compound 4 was established on the basis of IR which showed the presence of CN group stretch at 2225 cm‐1 and CO of acetyl stretch at 1715 cm‐1, while for compound 5 the absence of CN, the presence of NH stretch at 3450 and CO of amide stretch at 1655 cm‐1. 1H NMR spectra for compound 4 revealed the presence of signal at δ 2.19 ppm (s, 3H, COCH3) and δ 10.29 ppm (br, 1H, NH), while for compound 5 showed δ 2.40 (s, 3H, CH3) and δ 8.81‐7.10 ppm (m, 15H, Ar‐ H + NH). The structure of compound 5 was also supported by an independent synthesis of the same products from compound 3i and acetonitrile in the presence of HCl gas [38] (M.p. and mixed m.p.) (Scheme 5). Interaction of compound 3a with benzoyl chloride in benzene for 6 h afforded N,N‐ dibenzoylamino derivatives 6, while heating of compound 3a with benzoyl chloride in DMF for 6 h afforded 7‐(4‐ chlorophenyl)‐10‐phenyl‐5‐(phenyldiazenyl)‐7,9‐dihydro‐8H‐ benzo[7,8]chromeno[2,3‐d]pyrimidin‐8‐one (7). Treatment of compound 3a with formic acid for 10 h afforded naphtha‐ pyranopyrimidine‐8‐one derivative 8, the structure of compound 8 was supported by an independent synthesis from compound 3i and formamide (Scheme 3). The structures of compounds 6‐8 were confirmed by IR, 1H NMR and MS. The IR spectrum of compound 6 showed v(CN) stretch at 2214 cm‐1 and (CO of benzoyl) group stretch at 1735 cm‐1, while for compound 7, (CO of amide) group stretch at 1659 cm‐1 and compound 8 showed v(NH) stretch at 3433 cm‐1 and v(CO) stretch at 1718 cm‐1. 1H NMR of spectra for compound 7 revealed the presence of signal at δ 11.89 ppm (br, 1H, NH, D2O exchangeable), while for compound 8 showed δ 8.45 ppm (s, 1H, CH‐Pyimidine), 11.21 ppm (br, 1H, NH D2O exchan‐geable). The mass spectra of compounds 6‐8 showed the corresponding molecular ion peaks m/z 540 (M+, 10.5), m/z 644 (0.01) and 464 (M+, 0.17), respectively. 4. 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