Supporting Information

Supporting Information Nano WO3-supported sulfonic acid: New, efficient and high recyclable heterogeneous nano catalyst Ali Amoozadeh* and Salman Rahmani* Department of Chemistry, Semnan University, Semnan, Zip Code: 35131-19111, Iran, Fax: +98 (233) 3354110, Tel.: +98 (233) 3366177, e-mail: aamozadeh@semnan.ac.ir, salmanrahmani64@yahoo.com 1

TABLE OF CONTENTS Contents Page Experimental. 4 Materials and Instruments... 4 Preparation of nano-wo3.. 4 Table 1. Reusability of n-wsa for the synthesis of octahydroxanthenes... 5 Table 2. Optimization of catalyst for the synthesis of tetrahydrobenzoxanthenes.. 5 Table 3. Reusability of n-wsa for the synthesis of tetrahydrobenzoxanthenes 5 Table 4. Optimization of catalyst for the synthesis of benzoimidazolo quinazolinones.. 6 Table 5. Reusability of n-wsa for the synthesis of benzoimidazolo quinazolinones. 6 Fig 1. 1 H NMR of (3a).. 7 Fig 2. 13 C NMR of (3a).... 8 Fig 3. 1 H NMR of (3c).. 9 Fig 4. 13 C NMR of (3c).... 10 Fig 5. 1 H NMR of (3d).. 11 Fig 6. 13 C NMR of (3d).... 12 Fig 7. 1 H NMR of (4a).. 13 Fig 8. 13 C NMR of (4a).... 14 Fig 9. 1 H NMR of (4c).. 15 Fig 10. 13 C NMR of (4c)...... 16 Fig 11. 1 H NMR of (4d).... 17 Fig 12. 13 C NMR of (4d)...... 18 Fig 13. 1 H NMR of (4e).... 19 Fig 14. 13 C NMR of (4e)...... 20 Fig 15. 1 H NMR of (4h).... 21 Fig 16. 1 H NMR of (4l).... 22 Fig 17. 13 C NMR of (4l)...... 23 Fig 18. 1 H NMR of (4m)...... 24 Fig 19. 13 C NMR of (4m)..... 25 Fig 20. 1 H NMR of (4n).... 26 Fig 21. 13 C NMR of (4n)...... 27 Fig 22. 1 H NMR of (5a).... 28 Fig 23. 13 C NMR of (5a)...... 29 Fig 24. 1 H NMR of (5b).... 30 Fig 25. 13 C NMR of (5b)...... 31 Fig 26. 1 H NMR of (5c).... 32 Fig 27. 13 C NMR of (5c)...... 33 Fig 28. 1 H NMR of (5d).... 34 Fig 29. 13 C NMR of (5d)...... 35 Fig 30. 1 H NMR of (7f).... 36 Fig 31. 13 C NMR of (7f)...... 37 Fig 32. 1 H NMR of (7j).... 38 Fig 33. 13 C NMR of (7j)...... 39 Fig 34. 1 H NMR of (8l).... 40 Fig 35. 13 C NMR of (8l)...... 41 2

Fig 36. 1 H NMR of (9a).... 42 Fig 37. 13 C NMR of (9a)...... 43 Fig 38. 1 H NMR of (9b).... 44 Fig 39. 13 C NMR of (9b)...... 45 Fig 40. 1 H NMR of (9c).... 46 Fig 41. 13 C NMR of (9c)...... 47 Fig 42. 1 H NMR of (9d).... 48 Fig 43. 13 C NMR of (9d)...... 49 Fig 44. 1 H NMR of (9e).... 50 Fig 45. 13 C NMR of (9e)...... 51 Fig 46. 1 H NMR of (9f).... 52 Fig 47. 13 C NMR of (9f)..... 53 Fig 48. 1 H NMR of (11a)...... 54 Fig 49. 13 C NMR of (11a)..... 55 Fig 50. 1 H NMR of (11e)...... 56 Fig 51. 13 C NMR of (11e)..... 57 Fig 52. 1 H NMR of (12).... 58 Fig 53. 13 C NMR of (12)...... 59 Fig 54. 1 H NMR of (13)...... 60 Fig 55. 13 C NMR of (13)...... 61 3

Experimental Materials and Instruments Chemicals were purchased from the Merck chemical companies. Thin-Layer Chromatography (TLC) on commercial plates of silica gel 60 F254 was used to monitor the progress of reactions. The products were characterized by FT-IR spectra, 1 HNMR, 13 CNMR and CHN analyzer. FT-IR spectra were recorded on Shimadzo FT-IR 8400 instrument. 1 H and 13 CNMR spectra were recorded on Bruker Advance Spectrometer 400 & 500 MHz using CDCl3-d and DMSO-d6 as solvent. The chemical shifts are expressed in parts per million (ppm) and tetramethylsilane (TMS) was used as an internal reference. Elemental analyses were performed by Perkin Elmer CHN analyzer, 2400 series II. Melting points were recorded on a THERMO SCIENTIFIC 9100 apparatus. X-ray diffraction analyses were conducted using a Siemens D5000 (Siemens AG, Munich, Germany) diffractometer using Cu-Ka radiation of wavelength 1.54 Å (Cu-Ka radiation, k = 1.54) were obtained for characterization of the heterogeneous catalyst. Field emission scanning electron microscopy (FE-SEM) was carried out with a Philips XL30 (Royal Philips Electronics, Amsterdam, The Netherlands) instrument. Thermo gravimetric analyses (TGA) were conducted on a Du Pont 2000 thermal analysis apparatus under air atmosphere at a heating rate of 5 C/min. Preparation of nano-wo3 10 ml of ammonia solution (25 wt%) was added to the CTAB solutions while stirring. After getting a homogenous solution, 0.117 mol of WCl6 1000 ml 1 of CTAB solution was added with vigorous stirring. After stirring for 4 h, the products were aged at ambient temperature for 72 h. The final product was filtered, washed with deionized water and absolute ethanol in order to remove surfactant, residual reactants and by products and then calcinated at 500 C for 2 h [1]. 4

Table 1. Reusability of n-wsa for the synthesis of octahodroxanthenes a. Number of Cycle Yield b (%) 1 93 2 93 3 93 4 92 5 92 6 92 7 91 8 91 9 91 10 90 a Reaction condition: para-chlorobenzaldehyde (1 mmol), dimedone (2 mmol), reaction time: 1 h at 100 ºC in solvent free condition. b Isolated yield. Table 2. Optimization of the catalyst for the synthesis of tetrahydrobenzoxanthenes a. Entry Catalyst (g) Yield b (%) 1 Catalyst Free 15 2 Nano WO 3 (0.019) 31 3 Nano-WO 3-SO3H (0.019) 91 a Reaction condition: benzaldehyde (1 mmol), dimedone (1 mmol), β-naphtole (1 mmol) at 100 ºC in solvent free condition. b Isolated yield. Table 3. Reusability of n-wsa for the synthesis of tetrahydrobenzoxanthenes a. Number of Cycle Yield b (%) 1 91 2 91 3 91 4 90 5 90 6 90 7 90 8 89 9 89 10 89 a Reaction condition: benzaldehyde (1 mmol), dimedone (1 mmol), β-naphtole (1 mmol), reaction time: 85 min at 100 ºC in solvent free condition. b Isolated yield. 5

Table 4. Optimization of catalyst for the synthesis of benzoimidazolo quinazolin a. Entry Catalyst (g) Yield b (%) 1 Catalyst Free 12 2 Nano WO 3 (0.019) 34 3 Nano-WO 3-SO 3H (0.019) 94 a Reaction condition: benzaldehyde (1 mmol), dimedone (1 mmol), β-naphtole (1 mmol) at 100 ºC in solvent free condition. b Isolated yield. Table 5. Reusability of n-wsa for the synthesis of benzoimidazolo quinazolin a. Number of Cycle Yield b (%) 1 94 2 94 3 94 4 94 5 93 6 93 7 92 8 92 9 92 10 91 a Reaction condition: benzaldehyde (1 mmol), dimedone (1 mmol), 2-amino benzimidazole (1 mmol), reaction time: 15 min at 100 ºC in solvent free condition. b Isolated yield. 6

Spectral data of some selected compound 9-phenyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione (3a) M. P.: 213-215 C; IR (KBr, Cm -1 ) ν max: 3001, 1661, 1532, 1367, 1332, 1221, 1160, 1134, 1091, 841, 739. 1 H NMR (400 MHz, DMSO): δ 1.90-2.09 (m, 4H), 2.26-2.28 (m, 2H), 2.30-2.38 (m, 2H), 2.51-2.64 (m, 4H), 4.79 (s, 1H), 7.05-7.09 (t, J= 7.6, 2H), 7.11-7.12 (d, J= 8.4 Hz, 1H), 7.23-7.31 (dd, J= 8, 24.2, 2H). 13 C NMR (100 MHz, DMSO-d 6 ): δ 20.42, 21.22, 27.19, 31.32, 37.08, 113.62, 117.13, 128.28, 128.93, 129.36, 135.97, 136.87, 141.76, 163.67, 196.62. Anal. Calcd for C19H18O3: C, 77.53; H, 6.16; O, 16.31; Found: C, 77.58; H, 6.19; O, 16.37. Fig. 1. 1 H NMR of 3a. 7

Fig. 2. 13 C NMR of 3a. 8

9-(4-bromophenyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione (3c) M. P.: 222-225 C; IR (KBr, Cm -1 ) ν max: 2976, 1662, 1518, 1375, 1329, 1226, 1159, 1138, 1089, 829, 737. 1 H NMR (400 MHz, DMSO): δ 1.92-2.08 (m, 4H), 2.28-2.32 (m, 2H), 2.34-2.40 (m, 2H), 2.53-2.65 (m, 4H), 4.76 (s, 1H), 7.13-7.27 (m, 2H), 7.33-7.43 (dd, J= 30.6, 8.4 Hz, 2H). 13 C NMR (100 MHz, DMSO-d 6 ): δ 20.10, 20.27, 27.13, 31.39, 36.76, 36.90, 116.41, 120.28, 129.43, 130.21, 131.17, 131.66, 131.83, 133.08, 143.47, 158.49, 164.12, 196.51. Anal. Calcd for C19H17BrO3: C, 61.14; H, 4.59; O, 12.86; Found: C, 61.19; H, 4.65; O, 12.93. Fig. 3. 1 H NMR of 3c. 9

Fig. 4. 13 C NMR of 3c. 10

9-(p-tolyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione (3d) M. P.: 244-246 C; IR (KBr, Cm -1 ) ν max: 2973, 1667, 1531, 1362, 1328, 1224, 1158, 1132, 1081, 832, 739. 1 H NMR (400 MHz, DMSO): δ 1.96-2.07 (m, 4H), 2.26 (s, 3H), 2.29-2.42 (m, 4H), 2.52-2.69 (m, 4H), 4.79 (s, 1H), 7.03-7.05 (d, J= 8 Hz, 2H), 7.12-7.21 (d, J= 7.6 Hz, 2H). 13 C NMR (100 MHz, DMSO-d 6 ): δ 20.31, 21.06, 27.15, 31.22, 36.98, 55.14, 113.52, 117.03, 128.25, 128.84, 129.33, 135.86, 136.88, 141.53, 163.77, 196.52. Anal. Calcd for C20H20O3: C, 77.90; H, 6.54; O, 15.57; Found: C, 77.97; H, 6.59; O, 15.64. Fig. 5. 1 H NMR of 3d. 11

Fig. 6. 13 C NMR of 3d. 12

3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-9-phenyl-2H-xanthene-1,8(5H,9H)-dione (4a) M. P.: 203-204 C; FT-IR (KBr, Cm -1 )νmax: 2950, 1660, 1648, 1360, 1200, 1162, 1141, 998, 694. 1 H NMR (500 MHz, DMSO-d 6 ): δ: 0.90 (s, 6H), 1.04 (s, 6H), 2.07-2.10 (d, J= 6.4 Hz, 2H), 2.25-2.28 (d, J= 6.5 Hz, 2H), 2.51-2.60 (m, 3H), 4.53 (s, 1H), 7.09-7.12 (t, J= 2.8 Hz, 1H), 7.17-7.18 (d, J= 2.8 Hz,1H), 7.20-7.23 (t, J= 2.9 Hz, 3H). 13 C NMR (DMSO, 125 MHz), δ: 26.45, 29.13, 32.14, 32.88, 50.24, 111.47, 125.46, 127.56, 127.63, 147.15, 149.32, 194.36. Anal. Calcd for C23H26O3: C, 78.83; H, 7.48; O, 13.70; Found: C, 78.92; H, 7.59; O, 13.83. Fig. 7. 1 H NMR of 4a. 13

Fig. 8. 13 C NMR of 4a. 14

3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-9-(3-nitrophenyl)-2H-xanthene-1,8(5H,9H)-dione (4c) M. P.: 168-169 C; FT-IR (KBr, Cm -1 )νmax: 2950, 1659, 1619, 1520, 1360, 1200, 1180, 1000. 1 H NMR (500 MHz, CDCl3): δ: 0.91 (s, 6H), 1.05 (s, 6H), 2.09-2.12 (d, J= 4.4 Hz, 2H), 2.27-2.30 (d, J= 6.4 Hz, 2H), 2.55-2.63 (dd, J= 7.2 Hz,4H), 4.64 (s, 1H), 7.55-7.58 (t, J= 3.1 Hz, 1H), 7.65-7.67 (d,j= 3 Hz, 1H), 7.99-8.02 (d, J= 5.1 Hz, 2H). 13 C NMR (125 MHz, CDCl3) δ: 27.24, 29.56, 32.03, 32.72, 50.02, 56.65, 60.77, 106.31, 115.13, 136.85, 140.75, 153.22, 163.89, 197.01. Anal. Calcd. for C23H25NO5: C, 69.86; H, 6.37; N, 3.54; O, 20.23; Found: C, 69.91; H, 6.49; N, 3.68; O, 20.35. Fig. 9. 1 H NMR of 4c. 15

Fig. 10. 13 C NMR of 4c. 16

3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-9-(4-nitrophenyl)-2H-xanthene-1,8(5H,9H)-dione (4d) M. P.: 222-224 C; FT-IR (KBr, Cm -1 )νmax: 2950, 1658, 1614, 1508, 1360, 1340, 1196, 1160, 1136. 1 H NMR (500 MHz, CDCl3) δ: 0.90 (s, 6H), 1.05 (s, 6H), 2.08-2.11 (d, J= 6.5 Hz, 2H), 2.27-2.30 (d, J= 6.5 Hz, 2H), 2.50-2.63 (m, 4H), 4.63 (s, 1H), 7.45-7.48 (m, 2H), 8.10-8.12 (m, 2H). 13 C NMR (125 MHz, CDCl3) δ: 27.24, 29.57, 32.13, 32.74, 50.96, 56.69, 60.80, 106.33, 115.15, 136.86, 140.77, 153.26, 163.89, 197.11. Anal. Calcd for C23H25NO5: C, 69.86; H, 6.37; N, 3.54; O, 20.23; Found: C, 69.91; H, 6.49; N, 3.68; O, 20.35. Fig. 11. 1 H NMR of 4d. 17

Fig. 12. 13 C NMR of 4d. 18

9-(4-fluorophenyl)-3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione (4e) M. P.: 222-224 C; FT-IR (KBr, Cm -1 )νmax: 2980, 1672, 1512, 1373, 1333, 1218, 1166, 1135, 1086, 835, 733. 1 H NMR (400 MHz, CDCl3) δ: 0.99 (s, 6H), 1.11 (s, 6H), 2.15-2.26 (dd, J= 16, 28.6 Hz, 4H), 2.46 (s, 4H), 4.73 (s, 1H), 6.88-6.92 (t, J- 8.8 Hz, 2H), 7.24-7.27 (d, J=10.8 Hz, 2H). 13 C NMR (125 MHz, CDCl3) δ: 27.22, 29.53, 32.00, 32.74, 50.05, 56.62, 60.79, 106.34, 115.16, 136.89, 140.71, 153.26, 163.56, 197.05. Anal. Calcd for C23H25FO3: C, 74.98; H, 6.84; O, 13.03; Found: C, 74.93; H, 6.82; O, 13.09. Fig. 13. 1 H NMR of 4e. 19

Fig. 14. 13 C NMR of 4e. 20

3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-9-o-tolyl-2H-xanthene-1,8(5H,9H)-dione (4h) M. P.: 230-232 C; FT-IR (KBr, Cm -1 )νmax: 2910, 1660, 1620, 1350, 1200, 1160, 1020, 853. 1 H NMR (500 MHz, CDCl3): δ: 0.88 (s, 6H), 1.04 (s, 6H), 2.03-2.06 (d, J= 6.5 Hz, 2H), 2.24-2.27 (d, J=6.5 Hz, 2H), 2.48-2.51 (d, J=6.5 Hz, 2H), 2.57-2.60 (d, J=7 Hz, 2H) 2.71 (s, 3H), 4.63 (s, 1H), 7.09-7.11 (t, J= 5.6 Hz, 1H), 7.17-718 (d, J= 2.8 Hz, 1H) 7.20-7.23 (t, J= 6.0 Hz, 2H). Anal. Calcd for C24H28O3: C, 79.09; H, 7.74; O, 13.17; Found: C, 79.18; H, 7.89; O, 13.31. Fig. 15. 1 H NMR of 4h. 21

3,3,6,6-tetramethyl-9-(naphthalen-2-yl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione (4l) M. P.: 234-235 C; FT-IR (KBr, Cm -1 )νmax: 3053, 2833, 1640, 1585, 1503, 1373, 1276, 1133, 813, 748. 1 H NMR (400 MHz, CDCl3): δ: 0.99 (s, 6H), 1.12 (s, 6H), 2.13-2.06 (d, J= 6.5 Hz, 2H), 2.24-2.27 (d, J=6.5 Hz, 2H), 2.48-2.51 (d, J=6.5 Hz, 2H), 2.57-2.60 (d, J=7 Hz, 2H) 2.71 (s, 3H), 4.63 (s, 1H), 7.09-7.11 (t, J= 5.6 Hz, 1H), 7.17-718 (d, J= 2.8 Hz, 1H) 7.20-7.23 (t, J= 6.0 Hz, 2H). 13 C NMR (125 MHz, CDCl3) δ: 21.47, 27.80, 29.69, 31.86, 32.62, 41.30, 51.20, 116.19, 128.66, 129.20, 136.17, 141.63, 162.51, 196.80. Anal. Calcd for C27H28O3: C, 80.97; H, 7.05; O, 11.98; Found: C, 80.91; H, 7.09; O, 12.05. Fig. 16. 1 H NMR of 4l. 22

Fig. 17. 13 C NMR of 4l. 23

9-(5-bromo-2-hydroxyphenyl)-3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-2H-xanthene- 1,8(5H,9H)-dione (4m) M. P.: 268-271 C; FT-IR (KBr, Cm -1 )νmax: 3000, 1660, 1510, 1415, 1356, 1340, 912. 1 H NMR (500 MHz, CDCl3) δ: 0.90 (s, 6H), 0.97 (s, 3H), 1.05 (s. 3H), 2.02-2.06 (d, J= 8.3 Hz, 2H), 2.23-2.35 (dd, J=6.3, 4H), 2.51-2.56 (t, J=3.9, 2H), 5.54 (s, 1H), 6.94-6.96 (d, J=3.4 Hz, 1H), 7.04 (s, 1H), 7.27-7.29 (d, J=3.4 Hz, 2H), 10.56 (OH, 1H). 13 C NMR (125 MHz, CDCl3) δ: 26.99, 28.41, 30.02, 32.48, 43.70, 51.22, 100.39, 111.30, 116.32, 118.61, 129.15, 130.56, 131.44, 149.83, 165.34, 196.05, 196.50. Anal. Calcd for C24H28O3: C, 79.09; H, 7.74; O, 13.17; Found: C, 79.18; H, 7.89; O, 13.31. Fig. 18. 1 H NMR of 4m. 24

Fig. 19. 13 C NMR of 4m. 25

(E)-3,3,6,6-tetramethyl-9-styryl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione (4n) M. P.: 256-258 C; FT-IR (KBr, Cm -1 )νmax: 3412, 3000, 1630, 1610, 1380, 1200, 1160, 1140, 1000, 958. 1 H NMR (500 MHz, CDCl3) δ: 1.04-1.06 (d, 12H), 2.23-2.26 (d, J= 16.17 Hz, 2H), 2.30-2.33 (d, J= 16.02 Hz, 2H), 2.52 (s, 4H), 4.15-4.16 (d, J= 5.29 Hz, 1H), 6.16-6.22 (m, 2H), 7.19-7.28 (m, ArH, 5H). 13 C NMR (125 MHz, CDCl3) δ: 27.68, 28.33, 29.41, 32.79, 50.98, 114.08, 126.82, 129.19, 129.45, 130.41, 132.21, 137.48, 164.38, 197.15. Anal. Calcd for C25H28O3: C, 79.75; H, 7.50; O, 12.75; Found: C, 79.82; H, 7.52; O, 12.78. Fig. 20. 1 H NMR of 4n. 26

Fig. 21. 13 C NMR of 4n. 27

3,4,6,7-tetrahydro-3,6,9-triphenyl-2H-xanthene-1,8(5H,9H)-dione (5a) M. P.: 196-198 C; FT-IR (KBr, Cm -1 )νmax: 3031, 1667, 1365, 1188, 1134, 995, 694. 1 H NMR (400 MHz, CDCl3) δ: 2.57-2.75 (m, 4H), 2.80-3.01 (m, 4H), 3.30-3.55 (d, J= 3.9 Hz, 2H), 4.92-4.95 (d, J=3.5 Hz, 1H), 7.18-7.45 (m, Ar-H, 15H). 13 C NMR (100 MHz, CDCl3) δ: 31.98, 34.74, 38.26, 38.82, 43.89, 116.73, 126.65, 127.25, 128.39, 128.89, 142.11, 143.859, 144.25, 162.94, 195.59. Anal. Calcd for C31H26O3: C, 83.38; H, 5.87; O, 10.75; Found: C, 83.47; H, 5.95; O, 10.83. Fig. 22. 1 H NMR of 5a. 28

Fig. 23. 13 C NMR of 5a. 29

9-(4-Methylphenyl)-3,4,6,7-tetrahydro-3,6-diphenyl-2H-xanthene-1,8(5H,9H)-dione (5b) M. P.: 204-208 C; FT-IR (KBr, Cm -1 )νmax: 2939, 1666, 1504, 1358, 1242, 1180, 1134, 1033, 987, 764, 702. 1 H NMR (400 MHz, CDCl3) δ: 2.56-2.73 (m, 4H), 2.79-2.95 (m, 4H), 3.30-3.53 (d, J= 3.2 Hz, 2H), 3.88 (s, 3H), 4.86-4.88 (d, J=3.2 Hz, 1H), 6.75-6.87 (m, Ar-H, 2H ), 7.17-7.40 (m, Ar-H, 12H). 13 C NMR (100 MHz, CDCl3) δ: 31.03, 34.70, 38.29, 38.83, 43.91, 113.56, 116.85, 126.72, 127.12, 128.88, 129.51, 136.39, 142.12, 158.20, 163.14, 195.78. Anal. Calcd. for C32H28O3: C, 83.45; H, 6.13; O, 10.42; Found: C, 83.52; H, 6.20; O, 10.51. Fig. 24. 1 H NMR of 5b. 30

Fig. 25. 13 C NMR of 5b. 31

9-(4-Methoxyphenyl)-3,4,6,7-tetrahydro-3,6-diphenyl-2H-xanthene-1,8(5H,9H)-dione (5c) M. P.: 212-215 C; FT-IR (KBr, Cm -1 )νmax: 3031, 1666, 1504, 1357, 1242, 1180, 1134, 987, 764, 702. 1 H NMR (400 MHz, CDCl3) δ: 2.60-2.75 (m, 4H), 2.79-2.99 (m, 4H), 3.32-3.54 (d, J= 3.4 Hz, 2H), 3.79-3.80 (d, J=2.5 Hz, 3H), 4.87-4.88 (d, J=3 Hz, 1H), 6.80-6.88 (m, Ar-H, 4H ), 7.19-7.40 (m, Ar-H, 10H). 13 C NMR (100 MHz, CDCl3) δ: 31.04, 34.71, 38.30, 38.81, 43.91, 113.64, 116.85, 126.72, 127.24, 128.88, 129.45, 136.40, 142.12, 158.21, 163.10, 195.77. Anal. Calcd for C32H28O4: C, 80.65; H, 5.92; O, 13.43; Found: C, 80.74; H, 6.02; O, 13.56. Fig. 26. 1 H NMR of 5c. 32

Fig. 27. 13 C NMR of 5c. 33

9-(4-chlorophenyl)-3,4,6,7-tetrahydro-3,6-diphenyl-2H-xanthene-1,8(5H,9H)-dione (5d) M. P.: 234-236 C; FT-IR (KBr, Cm -1 )νmax: 3031, 1666, 1357, 1188, 1134, 995, 756, 694. 1 H NMR (400 MHz, CDCl3) δ: 2.56-2.76 (m, 4H), 2.81-3.00 (m, 4H), 3.30-3.54 (d, J= 3.9 Hz, 2H), 4.88-4.89 (d, J=2.75 Hz, 1H), 7.17-7.40 (m, Ar-H, 14H). 13 C NMR (100 MHz, CDCl3) δ: 31.59, 34.69, 38.28, 38.61, 43.79, 116.33, 126.70, 127.31, 128.30, 128.91, 129.96, 132.29, 141.92, 142.36, 142.77, 195.61. Anal. Calcd. for C31H25ClO3: C, 77.41; H, 5.24; Cl, 7.37; O, 9.98; Found: C, 77.50; H, 5.33;Cl, 7.45; O, 10.08. Fig. 28. 1 H NMR of 5d. 34

Fig. 29. 13 C NMR of 5d. 35

12-(4-fluorophenyl)-9,10-dihydro-8H-benzo[a]xanthen-11(12H)-one (7f) M. P.: 209-211 C. FT-IR (KBr) ν cm -1 = 738, 835, 999, 1135, 1251, 1359, 1504, 1672, 2889, 2950. 1 H NMR (400 MHz, CDCl3): δ 7.92-6.84 (m, 13H), 5.73 (s, 1H), 2.78-2.69 (m, 2H), 2.64-2.55 (m, 2H), 2.49-2.30 (m, 1H), 2.07-1.99 (m, 1H). 13 C NMR (100 MHz, CDCl3): δ 21.42, 28.93, 36.01, 38.21, 116.53, 118.17, 118.72, 124.90, 126.07, 126.60, 126.93, 127.99, 128.20, 128.32, 128.61, 129.14, 129.19, 129.54, 130.14, 132.60, 132.69, 133.30, 134.48, 143.62, 149.02, 167.02, 198.18. Anal. Calc. for C23H17FO2: C, 80.22; H, 4.98; F, 5.52; O, 9.29. Found: C, 80.28; H, 4.92; F, 5.58; O, 9.25. Fig. 30. 1 H NMR of 7f. 36

Fig. 31. 13 C NMR of 7f. 37

9,10-dihydro-12-(naphthalen-2-yl)-8H-benzo[a]xanthen-11(12H)-one (7j) M. P.: 190-191 C. FT-IR (KBr) ν cm -1 = 748, 858, 954, 1193, 1373, 1508, 1650, 2875, 2933. 1 H NMR (400 MHz, CDCl3): δ 8.01-7.27 (m, 13H), 5.93 (s, 1H), 2.65-2.77 (m, 2H), 2.44-2.36 (m, 2H), 2.09-2.02 (m, 1H), 1.99-1.96 (m, 1H). 13 C NMR (100 MHz, CDCl3): δ 28.36, 30.44, 33.40, 36.04, 42.60, 52.06, 115.20, 118.21, 118.69, 124.85, 126.05, 126.54, 126.85, 127.87, 128.17, 128.28, 128.57, 129.15, 129.52, 130.10, 132.60, 133.27, 143.26, 148.97, 165.07, 198.01. Anal. Calc. for C27H20O2: C, 86.14; H, 5.36; O, 8.50. Found: C, 86.18; H, 5.41; O, 8.46. Fig. 32. 1 H NMR of 7j. 38

Fig. 33. 13 C NMR of 7j. 39

9,10-dihydro-9,9-dimethyl-12-(naphthalen-2-yl)-8H-benzo[a]xanthen-11(12H)-one (8l) M. P.: 228-230 C. FT-IR (KBr) ν cm -1 = 748, 825, 1110, 1218, 1342, 1512, 1650, 2989. 1 H NMR (400 MHz, CDCl3): δ 8.06-7.26 (m, 13H), 5.9 (s, 1H), 2.61 (s, 2H), 2.34-2.21 (quintet, J= 16 Hz, 2H), 1.13 (s, 3H), 0.94 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ 21.43, 28.27, 28.87, 32.19, 35.07, 38.08, 38.18, 115.91, 116.11, 116.30, 116.52, 117.89, 118.14, 118.52, 124.69, 126.12, 128.20, 129.60, 130.15, 130.98, 131.06, 131.15, 132.37, 132.65, 141.31, 141.95, 148.88, 161.35, 165.43, 166.57, 197.51, 198.05. Anal. Calc. for C29H24O2: C, 86.11; H, 5.98; O, 7.91. Found: C, 86.17; H, 5.92; O, 7.96. Fig. 34. 1 H NMR of 8l. 40

Fig. 35. 13 C NMR of 8l. 41

9,10-dihydro-9,12-diphenyl-8H-benzo[a]xanthen-11(12H)-one (9a) M. P.: 118-124 C. FT-IR (KBr) ν cm -1 = 732, 811, 1128, 1228, 1359, 1519, 1666, 2885, 2943. 1 H NMR (300 MHz, CDCl3): δ 7.40-7.17 (m, 32H), 4.91 (s, 1H), 4.92 (s, 1H), 3.49 (quintet, J= 5.57 Hz, 1H), 3.34 (quintet, J= 4.95 Hz, 1H), 3.00-2.81 (m, 4H), 2.74-2.53 (m, 4H). 13 C NMR (75 MHz, CDCl3): δ 31.77, 31.94, 34.62, 34.75, 38.22, 38.76, 43.70, 44.02, 126.63, 126.72, 126.75, 127.02, 127.16, 127.25, 127.99, 128.88, 128.14, 128.30, 128.39, 128.51, 128.59, 128.72, 128.80, 142.01, 142.10, 143.81, 162.43, 162.54, 163.21, 163.36, 195.51, 195.65. Anal. Calc. for C29H22O2: C, 86.54; H, 5.47. Found: C, 86.00; H, 6.01. Fig. 36. 1 H NMR of 9a. 42

Fig. 37. 1 H NMR of 9a. 43

9,10-dihydro-12-(4-fluorophenyl)-9-phenyl-8H-benzo[a]xanthen-11(12H)-one (9b) M. P.: 234-235 C. FT-IR (KBr) ν cm -1 = 738, 835, 958, 1135, 1207, 1359, 1504, 1650, 2889, 3024. 1 H NMR (400 MHz, CDCl3): δ 7.94-6.83 (m, 15H), 5.77 (s, 1H), 3.54 (s, 1H), 3.05-2.91 (m, 2H), 2.87-2.65 (m, 2H ). 13 C NMR (100 MHz, CDCl3): δ 35.21, 35.32, 39.35, 40.10, 44.95, 45.32, 116.04, 116.25, 116.36, 116.46, 118.15, 118.21, 118.54, 124.74, 126.19, 126.24, 127.87, 127.91, 128.19, 128.27, 128.34, 129.66, 129.88, 130.03, 130.27, 131.11, 131.19, 131.28, 132.36, 132.73, 132.76, 141.37, 141.40, 143.47, 143.55, 148.87, 149.00, 161.18, 163.72, 165.21, 166.12, 197.23. Anal. Calc. for C29H21FO2: C, 82.84; H, 5.03; F, 4.52; O, 7.61. Found: C, 82.86; H, 5.08; F, 4.48; O, 7.56. Fig. 38. 1 H NMR of 9b. 44

Fig. 39. 13 C NMR of 9b. 45

9,10-dihydro-12-(4-chlorophenyl)-9-phenyl-8H-benzo[a]xanthen-11(12H)-one (9c) M. P.: 181-183 C. FT-IR (KBr) ν cm -1 = 748, 819, 997, 1143, 1228, 1595, 1650, 2875, 2933. 1 H NMR (300 MHz, CDCl3): δ 7.93-7.79 (m, 6H), 7.43-7.13 (m, 24H), 5.78 (s, 1H), 5.76 (s, 1H), 3.52-3.49 (m, 1H), 3.35-3.33 (m, 1H), 3.00-2.81 (m, 4H) 2.79-2.54 (m, 4H). 13 C NMR (75 MHz, CDCl3): δ 34.24, 34.34, 35.12, 35.26, 38.29, 38.93, 43.98, 43.76, 114.91, 116.98, 123.51, 126.62, 126.70, 127.05, 127.17, 127.19, 128.35, 128.52, 128.54, 128.73, 128.87, 128.93, 129.20, 129.88, 129.95, 141.86, 142.32, 142.91, 147.70, 162.71, 163.52, 164.11, 165.09, 195.56, 196.06. Anal. Calc. for C29H21ClO2: C, 79.72; H, 4.81; Found: C, 78.43; H, 4.79. Fig. 40. 1 H NMR of 9c. 46

Fig. 41. 13 C NMR of 9c. 47

9,10-dihydro-12-(4-nitrophenyl)-9-phenyl-8H-benzo[a]xanthen-11(12H)-one (9d) M. P.: 191-192 C. FT-IR (KBr) ν cm -1 = 746, 771, 829, 1201, 1346, 1514, 1650, 2891, 2952. 1 H NMR (400 MHz, CDCl3): δ 8.09-7.16 (m, 15H), 5.88 (s, 1H), 3.56 (s, 1H), 3.04-3.02 (d, J= 5.6 Hz, 2H), 2.81-2.65 (m, 2H ). 13 C NMR (100 MHz, CDCl3): δ 115.26, 116.91, 117.21, 118.21, 124.33, 124.70, 124.92, 126.45, 126.50, 127.83, 128.30, 128.45, 128.58, 129.85, 129.90, 130.09, 130.60, 130.66, 130.88, 132.14, 132.78, 143.19, 147.49, 148.89, 149.04, 152.65, 153.19, 165.83, 197.13. Anal. Calc. for C29H21NO4: C, 77.84; H, 4.73; N, 3.13; O, 14.30. Found: C, 77.88; H, 4.70; N, 3.09; O, 14.35. Fig. 42. 1 H NMR of 9d. 48

Fig. 43. 13 C NMR of 9d. 49

9,10-dihydro-12-(4-methylphenyl)-9-phenyl-8H-benzo[a]xanthen-11(12H)-one (9e) M. P.: 183-186 C. FT-IR (KBr) ν cm -1 = 702, 763, 833, 987, 1033, 1134, 1180, 1242, 1357, 1504, 1666, 2893, 3031. 1 H NMR (300 MHz, CDCl3): δ 8.01-7.88 (d, J= 8,35 Hz, 1H), 7.80-7.75 (m, 2H), 7.42-7.25 (m, 9H), 7.24-7.20 (m, 1H), 6.77-6.70 (m, 2H), 5.75 (s, 1H), 5.73 (s, 1H), 3.72-3.71 (t, J= 1.74, 3H), 3.55-3.33 (m, 1H), 3.05-2.83 (m, 2H), 2.79-2.58 (m, 2H). 13 C NMR (75 MHz, CDCl3) δ: 30.94, 31.12, 33.87, 34.00, 35.14, 35.26, 38.31, 38.78, 39.20, 43.74, 43.96, 44.05, 44.20, 55.17, 113.56, 113,71, 115.49, 116.67, 116.94, 117.01, 117.50, 117.86, 126.67, 126.78, 127.01, 127.27, 128.42, 128.75, 128.91, 129.40, 129.55, 136.21, 137.39, 142.05, 142.57, 147.68, 147.80, 157.85, 158.24, 162.43, 163.22, 163.86, 164.77, 195.72, 195.84, 196.21, 196.35. Anal. Calc. for C30H24O2: C, 86.51; H, 5.81; Found: C, 86.43; H, 5.76. Fig. 44. 1 H NMR of 9e. 50

Fig. 45. 13 C NMR of 9e. 51

9,10-dihydro-12-(4-methoxyphenyl)-9-phenyl-8H-benzo[a]xanthen-11(12H)-one (9f) M. P.: 198-200 C. FT-IR (KBr) ν cm -1 = 702, 748, 825, 1033, 1218, 1381, 1512, 1651, 2831, 2893. 1 H NMR (300 MHz, CDCl3): δ 2.80-2.59 (m, 2H), 3.05-2.84 (m, 2H), 3.55-3.33 (m, 1H), 3.73-3.71 (d, J= 2.27, 3H), 5.75-5.73 (d, J= 5.40, 1H), 6.77-6.70 (dd, J= 12.02, 8.65, 2H), 7.18-7.16 (d, J= 7.04, 1H), 7.45-7.24 (m, 9H), 7.80-7.75 (m, 2H), 8.00-7.98 (d, J= 8.28, 1H). 13 C NMR (75 MHz, CDCl3) δ: 33.86, 33.99, 35.12, 35.26, 38.20, 39.22, 43.96, 44.12, 55.09, 113.55, 113.71, 115.49, 116.98, 117.50, 123.74, 124.91, 126.72, 126.77, 127.00, 127.13, 128.40, 128.84, 129.45, 129.54, 131.31, 131.52, 136.88, 142.43, 142.56, 147.66, 157.84, 157.90, 163.85, 164.76, 196.21, 196.35. Anal. Calc. for C30H24O3 C, 83.31; H, 5.59; Found: C, 83.46; H, 5.64. Fig. 46. 1 H NMR of 9f. 52

Fig. 47. 13 C NMR of 9f. 53

3,3-dimethyl-12-phenyl-3,4,5,12-tetrahydrobenzo[4,5]imidazo[2,1-b]quinazolin-1(2H)-one (11a) M. P.: 318-319 C. FT-IR (KBr) ν cm -1 = 1569, 1647, 2956, 3367. 1 H NMR (300 MHz, DMSOd 6 ): δ 1.06 (s, 3H, CH3), 1.17 (s, 3H, CH3), 2.23-2.37 (dd, J= 16.43, 30.48 Hz, 2H, CH2), 2.67 (s, 2H, CH2), 6.49 (s, 1H, CH), 7.09-7.65 (m, 9H, Ar-H), 10.87 (s, 1H, NH). 13 C NMR (75 MHz, DMSO-d 6 ) δ: 26.73, 26.43, 31.79, 35.92, 49.99, 58.15, 112.56, 119.77, 125.57, 125.67, 126.19, 127.44, 127.66, 128.13, 132.02, 132.87, 142.05, 158.48, 158.53, 162.57, 195.73. Anal. Calc. for C22H21N3O: C, 76.94; H, 6.16; N, 12.24; O, 4.66, Found: C, 76.81; H, 6.18, N, 12.19; O, 4.80. Fig. 48. 1 H NMR of 11a. 54

Fig. 49. 13 C NMR of 11a. 55

12-(4-fluorophenyl)-3,3-dimethyl-3,4,5,12-tetrahydrobenzo[4,5]imidazo[2,1-b]quinazolin- 1(2H)-one (11e) M. P.: 324-326 C. FT-IR (KBr) ν cm -1 = 1565, 1652, 2958, 3361. 1 H NMR (300 MHz, DMSOd 6 ): δ 1.07 (s, 3H, CH3), 1.18 (s, 3H, CH3), 2.25-2.36 (dd, J= 11.23, 22.56 Hz, 2H, CH2), 2.77 (s, 2H, CH2), 6.48 (s, 1H, CH), 7.10-7.76 (m, 8H, Ar-H), 10.91 (s, 1H, NH). 13 C NMR (75 MHz, DMSO-d 6 ) δ: 26.83, 28.53, 31.87, 35.94, 50.20, 58.18, 112.36, 119.56, 125.47, 125.67, 126.28, 127.44, 127.66, 128.23, 132.42, 132.94, 142.15, 158.59, 158.73, 162.67, 196.01. Anal. Calc. for C22H20FN3O: C, 73.11; H, 5.58; N, 11.63; O, 4.43, Found: C, 73.17; H, 5.63, N, 11.65; O, 4.47. Fig 50. 1 H NMR of 11e. 56

Fig 51. 13 C NMR of 11e. 57

12-phenyl-3,4,5,12-tetrahydrobenzo[4,5]imidazo[2,1-b]quinazolin-1(2H)-one (12) M. P.: 312-313 C. FT-IR (KBr) ν cm -1 = 1560, 1666, 2968, 3370. 1 H NMR (300 MHz, DMSOd 6 ): δ 1.86-1.93 (m, 2H, CH3), 2.23-2.29 (m, 2H, CH3), 2.59-2.61 (d, J= 5.05 Hz, 2H, CH2), 6.49 (s, 1H, CH), 7.09-7.90 (m, 9H, Ar-H), 11.11 (s, 1H, NH). 13 C NMR (75 MHz, DMSO-d 6 ) δ: 18.55, 19.73, 26.39, 30.14, 35.97, 49.99, 58.15, 112.64, 119.67, 125.56, 125.67, 126.28, 127.34, 127.54, 128.22, 132.13, 132.89, 142.08, 159.05, 159.09, 162.74, 196.04. Anal. Calc. for C26H21N3O: C, 79.77; H, 5.41; N, 10.73; O, 4.09, Found: C, 79.82; H, 5.47, N, 10.79; O, 4.15. Fig 52. 1 H NMR of 12. 58

Fig 53. 13 C NMR of 12. 59

3,12-diphenyl-3,4,5,12-tetrahydrobenzo[4,5]imidazo[2,1-b]quinazolin-1(2H)-one (13) M. P: 335-336 C. FT-IR (KBr) ν cm -1 = 1558, 1662, 2960, 3364. 1 H NMR (300 MHz, DMSOd 6 ): δ 2.87-3.06 (m, 2H, CH2), 3.23-3.48 (t, J= 5.01, 2H, CH2), 3.51 (s, 1H, -CH), 6.41 (s, 1H, - CH), 6.42-7.35 (m, 14H, Ar-H), 10.93 (s, 1H, NH). 13 C NMR (75 MHz, DMSO-d 6 ) δ: 22.90, 23.43, 25.92, 33.52, 54.33, 107.01, 109.57, 116.78, 120.25, 121.54, 126.63, 126.89, 127.24, 127.86, 128.20, 140.95, 142.72, 159.07, 159.09, 162.81, 191.72. Anal. Calc. for C20H17N3O: C, 76.17; H, 5.43; N, 13.32; O, 5.07, Found: C, 76.24; H, 5.50, N, 13.39; O, 5.14. Fig 54. 1 H NMR of 13. 60

Fig 55. 13 C NMR of 13. 61

[1] N. Asim, S. Radiman, M.A. Yarmo, Am. J. Applied. Sci., 6 (2009) 1424-1428. 62