Supporting Information

Supporting Information Synthesis of N-Heteropolycyclic Compounds Including Quinazolinone Skeletons by Using Friedel-Crafts Alkylation Bu Keun Oh, Eun Bi Ko, Jin Wook Han* and Chang Ho Oh* Department of Chemistry, Hanyang University, Sungdong-Gu, Seoul 133-791, Korea jwhan@hanyang.ac.kr; changho@hanyang.ac.kr Table of Contents 1. Typical experimental procedures from 5a to 1a -------------------------------------------------------------------2 2. Spectroscopic data of compounds 3c-e, 2a-e, 1a-e, 8a-b ------------------------------------------------------4 3. References ------------------------------------------------------------------------------------------------------------------7 4. 1 H and 13 C NMR spectra of compounds 3c-e, 2a-e, 1a-e, 8a-b -----------------------------------------------9 1

2

1. Typical experimental procedures from 5a to 1a Synthesis of 2-amino-N-phenylbenzamide (6a). To a DCE solution (4 ml) of compound 2-aminobenzoic acid (4.8 g,.29 mol) was added a catalytic amount of DMF (.2 ml, 2.9 mmol) and oxalyl chloride (5. ml,.58 mol) at under Ar atmosphere. After the mixture was stirred for 2h at room temperature, the crude solution was evaporated under reduced pressure. The reaction mixture was redissolved in DCE (3 ml), pyridine (5.9 ml,.73 mol) and aniline (3. g,.32 mol) in DCE (1 ml) were added at. The mixture was stirred for 8h at RT under Ar atmosphere. After TCL analysis, the crude mixture was diluted with ethyl acetate, washed with 1N HCl, NaHCO 3, NaCl solution, and dried over anhydrous MgSO 4. The residue was recrystallized from ethyl acetate and hexane to give 2-nitro-N-phenylbenzamide (6.2 g, 88%) as a brown solid. Then, the solid (6.2 g, and.26 mol) and 1% Pd on charcoal (1 wt%) in methanol (5 ml) were stirred under H 2 (1 atm) atmosphere for 4h. After completion of reduction, Pd on charcoal was filtered off on celite, washed over and over with dichloromethane. The filtrate was concentrated under reduced pressure to afford 2-amino-N-phenylbenzamide (5.5 g, quantitative yield) as a white solid. Other substrate (6b) was synthesized to similar reaction conditions. Spectral data matches that previously reported. [1] 3

Synthesis of 2-acetamido-N-phenylbenzamide (7a). To a MC solution (5 ml) of 6 (5.5 g,.26 mol) was added triethylamine (7.3 ml,.52 mol) and acetic anhydride (4.9 ml,.52 mol) at under Ar atmosphere. The reaction mixture was stirred for 2h at 4. After TLC analysis, the crude was diluted with NH 4 Cl, extracted with dichloromethane, washed with NaHCO 3, NaCl solution, and dried over anhydrous MgSO 4. The organic phase was concentrated under reduced pressure, and the residue was recrystallized from ethyl acetate and hexane to give 2-acetamido-N-phenylbenzamide (6. g, 9%) as a white solid. Other substrate (7b) was synthesized to similar reaction conditions. Spectral data matches that previously reported. [2] Synthesis of 2-methyl-3-phenylquinazolin-4(3H)-one (4a). To a DCE solution (5 ml) of 7 (6.g,.24 mol) was added triethylamine (16.7 ml,.12 mol) and chlorotrimethylsilane (15.2 ml,.12 mol) at under Ar atmosphere. The reaction mixture was heated for 3h at 1. After TLC analysis, the crude was diluted with NH 4 Cl, extracted with ethyl acetate, washed with NaCl, and dried over MgSO 4. The organic phase was concentrated under reduced pressure, and the residue was recrystallized from ethyl acetate and hexane to give 2-methyl- 3-phenylquinazolin-4(3H)-one (5. g, 88%) as a white solid. Other substrate (4b) was synthesized to similar reaction conditions. Spectral data matches that previously reported. [3] 4

Synthesis of (E)-3-phenyl-2-strylquinazolin-4(3H)-one (3a). A General procedure To a glacial acetic acid (8 ml) of 4a (5 mg, 2.1 mmol) was added benzaldehyde (.3 ml, 3.2 mmol) and sodium acetate (34 mg, 4.2 mmol) at under Ar atmosphere. The reaction mixture was refluxed for 8h at 15. After completion of reaction, the mixture was cooled to, poured into crushed ice, and the separated precipitate was filtered off. The solid state was washed with water, and recrystallized from ethyl acetate and hexane to give (E)-3-phenyl-2-strylquinazolin-4(3H)-one (51 mg, 75%) as a white solid. Other substrates (3b-e) were synthesized to similar reaction conditions. Spectral data of 3a-b matches that previously reported. [4] Synthesis of 5-phenyl-5,6-dihydro-12H-quinolino[2,1-b]quinazolin-12-one (2a). A General procedure To a DCE solution (4 ml) of 3a (32 mg, 1. mmol) was added trifluoromethanesulfonic acid (.4 ml, 5. mmol) at under Ar atmosphere. The reaction mixture was heated for 8h at 1. After TLC analysis, the crude mixture was diluted with H 2 O, extracted with ethyl acetate, washed with NaHCO 3, NaCl solution, dried over anhydrous MgSO 4, and concentrated under reduced pressure. The concentrated residue was purified by flash silica gel chromatography by using a 1:2 mixture of ethyl acetate and hexane to give 5-phenyl-5H-quinolino[2,1-b]quinazolin-12(6H)-one (23 mg, 71%) as a white solid. Other substrates (2b-e) were synthesized to similar reaction conditions. Synthesis of 5-phenyl-12H-quinolino[2,1-b]quinazolin-12-one (1a). A General procedure To a benzene solution (2 ml) of 2a (15 mg,.46 mmol) was added 2,3-dichloro-5,6-dicyano-1,4- benzoquinone (16 mg,.69 mmol) at under Ar atmosphere. The reaction mixture was heated for 1h at 1. After TLC analysis, the crude mixture was diluted with H 2 O, extracted with ethyl acetate, washed with NaHCO 3, NaCl solution, dried over MgSO 4, and concentrated under reduced 5

pressure. The concentrated residue was purified by flash silica gel chromatography by using a 1:4 mixture of ethyl acetate and hexane to give 5-phenyl-12H-quinolino[2,1-b]quinazolin-12-one (12 mg, 78%) as a white solid. Other substrates (1b-e) were synthesized to similar reaction conditions. 2. Spectroscopic data of compounds 3c: Yellow solid; M.P 212 213 ; 1 H NMR (4 MHz, CDCl 3 ) δ 8.31 (d, J 6

= 8. Hz, 1H), 7.9 (d, J = 16. Hz, 1H), 7.82 7.79 (m, 2H), 7.62 7.52 (m, 3H), 7.51 7.47 (m, 1H), 7.43 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 7.2 Hz, 2H), 7.17 (d, J = 8.4 Hz, 2H), 6.37 (d, J = 15.6 Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ 162.34, 151.51, 147.79, 138.6, 136.97, 134.79, 134.29, 132.11, 13.8, 129.55, 129.23, 128.78, 127.4, 127.3, 126.89, 123.89, 121.6, 12.63, 12.61; IR (NaCl, Cm -1 ) 359, 1681, 1632, 1548; HRMS (ESI) Calcd for (C 22 H 14 N 2 O + Na) + requires m/z 425.26, found m/z 425.26. 3d: Yellow solid; M.P 29 211 ; 1 H NMR (4 MHz, CDCl 3 ) δ 7.9 (d, J = 15.6 Hz, 1H), 7.74 (d, J = 8.8 Hz, 1H), 7.67 (d, J = 2.8 Hz, 1H), 7.62 7.56 (m, 3H), 7.4 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 7.35 7.3 (m, 7H), 6.37 (d, J = 15.6 Hz, 1H), 3.93 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 162.25, 158.5, 149.77, 142.54, 138.97, 137.28, 135.55, 13.1, 13.8, 13.2, 129.62, 129.55, 129.42, 129.22, 129.14, 128.87, 128.8, 127.76, 125.5, 121.78, 12.1, 16.63, 55.96; IR (NaCl, Cm -1 ) 363, 285, 1673, 1616, 1487; HRMS (ESI) Calcd for (C 23 H 18 N 2 O 2 + Na) + requires m/z 377.126, found m/z 377.1261. 3e: Yellow solid; M.P 263 265 ; 1 H NMR (4 MHz, CDCl 3 ) δ 7.82 (d, J = 15.6 Hz, 1H), 7.72 (d, J = 9.2 Hz, 1H), 7.66 (d, J = 2.4 Hz, 1H), 7.61 7.56 (m, 3H), 7.42 7.38 (m, 3H), 7.32 (d, J = 7.2 Hz, 2H), 7.15 (d, J = 8.8 Hz, 2H), 6.34 (d, J = 16. Hz, 1H), 3.92 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 162.15, 158.63, 149.46, 142.44, 137.58, 137.18, 134.47, 132.9, 13.5, 129.5, 129.16, 129.12, 128.79, 125.9, 123.63, 121.86, 12.73, 16.69, 55.98; IR (NaCl, Cm -1 ) 377, 2842, 1671, 1616, 1488; HRMS (ESI) Calcd for (C 23 H 17 BrN 2 O 2 + Na) + requires m/z 455.366, found m/z 7

455.364. 2a: White solid; M.P 27 29 ; 1 H NMR (4 MHz, CDCl 3 ) δ 8.34 (d, J = 7.2 Hz, 1H), 8.28 (d, J = 8.4 Hz, 1H), 7.74 7. 7 (m, 1H), 7.59 (d, J = 8. Hz, 1H), 7.46 (t, J = 8. Hz, 1H), 7.42 7.38 (m, 1H), 7.32 7.21 (m, 4H), 7.17 (d, J = 7.6 Hz, 2H), 7.6 (d, J = 7.6 Hz, 1H), 4.36 4.33 (m, 1H), 3.5 3.36 (m, 2H); 13 C NMR (1 MHz, CDCl 3 ) δ 16.8, 153.4, 146.37, 139.32, 134.57, 134.35, 129.2, 127.89, 127.59, 127.38, 127.26, 127.17, 126.8, 12.73, 124.32, 122.9, 41.48, 4.52; IR (NaCl, Cm -1 ) 36, 1683, 1594; HRMS (ESI) Calcd for (C 22 H 16 N 2 O + Na) + requires m/z 347.1155, found m/z 347.1154. 2b: Yellow solid; M.P 21 22 ; 1 H NMR (4 MHz, CDCl 3 ) δ 8.34 (d, J = 8. Hz, 1H), 8.27 (d, J = 8.4 Hz, 1H), 7.74 7.71 (m, 1H), 7.59 (d, J = 8. Hz, 1H), 7.46 (t, J = 7.6 Hz, 1H), 7.4 (t, J = 7.2 Hz, 1H), 7.24 (d, J = 7.6 Hz, 1H), 7.8 (d, J = 8.4 Hz, 3H), 6.82 (d, J = 8.4 Hz, 2H), 4.31 4.28 (m, 1H), 3.75 (s, 3H), 3.46 3.33 (m, 2H); 13 C NMR (1 MHz, CDCl 3 ) δ 16.82, 158.75, 153.57, 146.36, 134.74, 134.7, 134.59, 134.28, 131.22, 129.2, 128.97, 128.88, 127.96, 127.87, 127.59, 127.3, 127.19, 126.8, 126.71, 124.32, 122.7, 114.39, 55.3, 4.69; IR (NaCl, Cm -1 ) 363, 2836, 1683, 1594; HRMS (ESI) Calcd for (C 23 H 18 N 2 O 2 + Na) + requires m/z 377.126, found m/z 377.126. 2c: White solid; M.P 182 184 ; 1 H NMR (4 MHz, CDCl 3 ) δ 8.33 (d, J = 8. Hz, 1H), 8.28 (d, J = 8. Hz, 1H), 7.73 (t, J = 7.2 Hz, 1H), 7.58 (d, J = 8. Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H), 7.45 7.4 (m, 3H), 7.27 (t, J = 8. 8

Hz, 1H), 7.9 7.3 (m, 3H), 4.3 (t, 6. Hz, 1H), 3.46 3.35 (m, 2H); 13 C NMR (1 MHz, CDCl 3 ) δ 16.72, 152.92, 146.21, 138.36, 134.72, 134.29, 133.56, 132.15, 129.57, 127.87, 127.63, 127.57, 127.33, 126.98, 126.73, 124.48, 122.1, 121.38, 4.98, 4.37; IR (NaCl, Cm -1 ) 364, 1686, 1595; HRMS (ESI) Calcd for (C 22 H 15 BrN 2 O + Na) + requires m/z 425.26, found m/z 425.26. 2d: White solid; M.P 176 177 ; 1 H NMR (4 MHz, CDCl 3 ) δ 8.3 (d, J = 8. Hz, 1H), 7.71 (d, J = 2.8 Hz, 1H), 7.52 (d, J = 9.2 Hz, 1H), 7.41 (t, J = 7.2 Hz, 1H), 7.33 7.28 (m, 2H), 7.25 7.21 (m, 3H), 7.17 (d, J = 7.2 Hz, 2H), 7.6 (d, J = 7.2 Hz, 1H), 4.35 4.32 (m, 1H), 3.93 (s, 3H), 3.48 3.34 (m, 2H); 13 C NMR (1 MHz, CDCl 3 ) δ 16.74, 158.45, 151.13, 14.94, 139.41, 134.53, 134.5, 129.3, 128.32, 127.92, 127.38, 127.24, 127.17, 124.72, 124.4, 122.81, 17.13, 55.93, 41.63, 4.34; IR (NaCl, Cm -1 ) 363, 2851, 168, 149; HRMS (ESI) Calcd for (C 23 H 18 N 2 O 2 + Na) + requires m/z 377.126, found m/z 377.1261. 2e: White solid; M.P 221 223 ; 1 H NMR (4 MHz, CDCl 3 ) δ 8.3 (d, J = 8. Hz, 1H), 7.7 (d, J = 2.4 Hz, 1H), 7.52 (d, J = 9.2 Hz, 1H), 7.44 7.4 (m, 3H), 7.32 (dd, J = 8. Hz, 2. Hz, 1H), 7.27 (d, J = 15.2 Hz, 1H), 7.8 (d, J = 7.6 Hz, 1H), 7.4 (d, J = 7.6 Hz, 2H), 4.31 4.28 (m, 1H), 3.93 (s, 3H), 3.44-3.33 (m, 2H); 13 C NMR (1 MHz, CDCl 3 ) δ 16.66, 158.54, 15.55, 14.86, 138.48, 134.48, 133.76, 132.15, 129.6, 128.37, 127.89, 127.54, 127.29, 124.8, 124.57, 122.78, 121.35, 17.16, 5.95, 41.17, 4.24; IR (NaCl, Cm -1 ) 362, 2837, 168, 149; HRMS (ESI) Calcd for (C 23 H 17 BrN 2 O 2 + Na) + requires m/z 455.366, found m/z 455.365. 9

1a: Whit solid; M.P 168 17 ; 1 H NMR (4 MHz, CDCl 3 ) δ 9.55 (d, J = 8.8 Hz, 1H), 8.47 (d, J = 7.6 Hz, 1H), 7.84 7.8 (m, 1H), 7.75 (d, J = 8. Hz, 1H), 7.66 7.6 (m, 2H), 7.53 7.5 (m, 6H), 7.41 (t, J = 7.6 Hz, 1H), 7.22 (s, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ 162.95, 147.8, 146.98, 146.95, 136.9, 135.8, 134.76, 129.29, 129.1, 129.5, 128.89, 127.65, 126.99, 126.52, 126.25, 126.8, 124.61, 121.95, 12.15; IR (NaCl, Cm -1 ) 36, 1683, 1544; HRMS (ESI) Calcd for (C 22 H 14 N 2 O + H) + requires m/z 323.1297, found m/z 323.1297. 1b: Yellow solid; M.P 24 25 ; 1 H NMR (4 MHz, CDCl 3 ) δ 9.53 (d, J = 8.8 Hz, 1H), 8.47 (d, J = 7.6 Hz, 1H), 7.82 (t, J = 6.8 Hz, 1H), 7.76 7.7 (m, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.53 7.47 (m, 3H), 7.41 (t, J = 8. Hz, 1H), 7.2 (s, 1H), 7.7 (d, J = 8.4 Hz, 2H), 3.91 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 162.98, 16.36, 147.98, 147.6, 146.72, 135.85, 134.77, 13.44, 129.21, 129.11, 127.67, 127.4, 126.46, 126.24, 125.98, 124.81, 124.16, 121.96, 12.7, 114.37, 55.55; IR (NaCl, Cm -1 ) 367, 2853, 1685, 1546; HRMS (ESI) Calcd for (C 23 H 17 N 2 O 2 + H) + requires m/z 353.1285, found m/z 353.1284. 1c: Yellow solid; M.P 252 254 ; 1 H NMR (4 MHz, CDCl 3 ) δ 9.55 (d, J = 8.4 Hz, 1H), 8.47 (d, J = 7.6 Hz, 1H), 7.83 (t, J = 7.6 Hz, 1H), 7.75 (d, J = 8. Hz, 1H), 7.68 (d, J = 8.4 Hz, 2H), 7.65 7.58 (m, 2H), 7.53 (d, J = 7.6 1

Hz, 1H), 7.43 7.39 (m, 3H), 7.19 (s, 1H); 13 C NMR (1MHz, CDCl 3 ) δ 162.89, 147.59, 146.84, 145.79, 135.81, 135.77, 134.9, 132.21, 13.71, 129.56, 127.71, 126.71, 126.54, 126.41, 126.32, 124.71, 124.21, 123.47, 122.7, 12.19; IR (NaCl, Cm -1 ) 366, 1682, 1549; HRMS (ESI) Calcd for (C 22 H 14 BrN 2 O + H) + requires m/z 41.284, found m/z 41.284. 1d: Yellow solid; M.P 183 184 ; 1 H NMR (4 MHz, CDCl 3 ) δ 9.6 (d, J = 8.8 Hz, 1H), 7.84 (d, J = 2.4 Hz, 1H), 7.7 (d, J = 8.4 Hz, 1H), 7.65 7.59 (m, 2H), 7.53 (s, 5H), 7.45 (dd, J = 8.8 Hz, 2.8 Hz, 1H), 7.41 (t, J = 7.6 Hz, 1H), 7.2 (s, 1H), 3.99 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 162.74, 158.13, 146.5, 145.79, 141.79, 137.2, 135.78, 129.12, 129.5, 128.95, 128.89, 128.29, 126.89, 126.26, 125.74, 124.83, 124.68, 122.2, 12.8, 16.4, 55.99; IR (NaCl, Cm -1 ) 371, 285, 168, 1487; HRMS (ESI) Calcd for (C 23 H 17 N 2 O 2 + H) + requires m/z 353.1285, found m/z 353.1285. 1e: Yellow solid; M.P 196 198 ; 1 H NMR (4 MHz, CDCl 3 ) δ 9.6 (d, J = 8.4 Hz, 1H), 7.83 (d, J = 2.8 Hz, 1H), 7.71 7.64 (m, 3H), 7.62-7.56 (m, 2H), 7.46 7.36 (m, 4H), 7.17 (s, 1H), 3.99 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 162.62, 158.25, 145.76, 144.48, 141.66, 135.91, 135.81, 132.16, 13.72, 129.25, 128.32, 126.53, 126.33, 125.74, 124.86, 124.38, 123.3, 122.12, 12.87, 16.45, 55.98; IR (NaCl, Cm -1 ) 372, 285, 1671, 1485; HRMS (ESI) Calcd for (C 23 H 16 BrN 2 O 2 + H) + requires m/z 431.39, found m/z 431.389. 11

8a: Yellow solid; M.P 253 255 ; 1 H NMR (4 MHz, CDCl 3 ) δ 9.55 (d, J O N N 8a = 8.4 Hz, 1H), 8.48 (d, J = 8. Hz, 1H), 7.83 (t, J = 7.6 Hz, 1H), 7.76 (s, 2H), 7.74 (s, 2H), 7.65 7.59 (m, 5H), 7.52 (t, J = 7.6 Hz, 1H), 7.44 (t, J = 7.2 Hz, 1H), 7.31 (d, J = 8. Hz, 2H), 7.28 (s, 1H), 2.44 (s, 3H); 13 C NMR (1 MHz, CDCl 3 ) δ 162.92, 147.86, 146.88, 146.84, 141.94, 137.79, 137.45, 135.4, 134.82, 129.79, 129.56, 129.36, 127.68, 127.35, 127.8, 126.43, 126.33, 126.12, 124.58, 124.36, 121.98, 12.11, 21.29; IR (NaCl, Cm -1 ) 366, 2858, 168, 1487; HRMS (ESI) Calcd for (C 29 H 21 N 2 O + H) + requires m/z 413.1648, found m/z 413.1647. 8b: White solid; M.P 217 219 ; 1 H NMR (4 MHz, CDCl 3 ) δ 9.56 (d, O N N 8b J = 8.8 Hz, 1H), 8.49 (d, J = 8.4 Hz, 1H), 7.84 (t, J = 8. Hz, 1H), 7.78 7.74 (m, 2H), 7.71 7.69 (m, 2H), 7.65 (t, J = 7.6 Hz, 1H), 7.59 7.51 (m, 6H), 7.46 7.4 (m, 3H), 7.32 (t, J = 6.8 Hz, 1H), 7.27 (s, 1H), 7.23 (d, J = 6. Hz, 1H); 13 C NMR (1 MHz, CDCl 3 ) δ 162.9, 147.85, 147.1, 146.65, 138.27, 137.15, 135.93, 135.85, 134.81, 13.1, 129.53, 129.35, 128.9, 128.12, 127.86, 127.68, 126.98, 126.95, 126.8, 126.52, 126.32, 126.12, 124.52, 124.42, 122.1, 12.16; IR (NaCl, Cm -1 ) 327, 1682, 1544, 1468; HRMS (ESI) Calcd for (C 3 H 2 N 2 O + H) + requires m/z 425.1648, found m/z 425.1648. 3. References [1] (a) Shaterian, H. R.; Oveisi, A. R.; Honarmand, M. Synthetic Comm. 21, 4, 1231-1242. (b) J. Med. Chem. 213, 56, 344-3413. 12

[2] Hesp, K. D.; Bergman, R. G.; Ellman, J. A. J. Am. Chem. Soc. 211, 133, 1143-11433. [3] (a) Xu, L.; Jiang, Y.; Ma, D. Org. Lett. 212, 14, 115-1153. (b) J. Med. Chem. 1972, 15, 518-523. [4] Trashakhova, T. V.; Nosova, E. V.; Valova, M. S.; Slepukhin, P. A.; Lipunova, G. N.; Charushin, V. N. Russ. J. Org. Chem. 211, 47, 753-761. 13

4. 1 H and 13 C NMR Spectra of compounds 14

1 5 3. 1.3 1.98 1.97.95 2.1 1.97.97 1.4 1. 5.. 2 12.68 12.633 121.62 123.888 126.893 127.299 127.477 128.777 129.232 129.552 13.8 132.19 134.291 134.794 136.974 138.596 147.79 151.511 162.335 15 1 5 2 15 1 5 15

16. 5. 1. 5 1 15 2 25 3. 1.1.97.94 2.93 1.5 6.94.94 5 1 15 2 5 1 15 2 25 162.247 158.497 149.77 142.543 138.974 137.276 135.55 13.99 13.84 13.21 129.624 129.546 129.424 129.221 129.137 128.866 128.797 127.761 125.53 121.784 12.1 16.634 55.963

2 15 1 5.95 1.98 2.6 3.4.97.98 3. 1.8 3. 1. 5.. 17

162.154 132.85 134.474 137.179 137.58 142.441 149.459 158.628 128.79 129.117 129.155 129.52 13.52 125.92 123.634 121.855 12.73 16.692 55.977 2 15 1 5 2 15 1 5 18

19. 5. 1. 5 1 15 2 2..96 1.2.96.98.99 1.4.99 3.95 1.97.98 5 1 15 2 5 1 15 2 25 3 35 16.797 153.42 146.371 139.325 134.571 134.352 129.23 127.889 127.593 127.381 127.261 127.169 126.82 126.735 124.321 122.85 41.479 4.521

3 25 2 15 1 5 3. 2.5.97 1.98 2.95.94.97 1.3.97.97 1.1 1. 5.. 2

35 4.687 55.296 114.389 122.69 124.317 126.76 126.799 127.188 127.32 127.59 127.872 128.881 128.972 131.221 134.278 134.588 134.699 146.361 153.573 158.749 16.817 3 25 2 15 1 5 2 15 1 5 21

22. 5. 1. 5 1 2..99.94.97 1..96 1.6 2.95 1.6 3.6 5 1 15 2 5 1 15 2 25 3 16.717 152.919 146.213 138.358 134.716 134.288 133.559 132.151 129.575 127.871 127.63 127.575 127.326 126.98 126.726 124.485 122.9 121.376 4.977 4.369

3 25 2 15 1 5 3. 2.3 1.4.94 2.4 2.97 2.8 1.5 1.1.96.93 1. 5.. 23

25 4.341 41.633 55.926 17.126 122.86 124.399 124.716 127.171 127.244 127.375 127.917 128.323 129.29 134.499 134.528 139.414 14.936 151.127 158.446 16.739 2 15 1 5 2 15 1 5 24

25. 5. 1. 5 1 15 3. 2..95.99 1.5 1.4 2.95.97 1.5 1. 1.95 5 1 15 2 5 1 15 2 16.662 158.537 15.554 14.858 138.483 134.484 133.757 132.148 129.596 128.368 127.889 127.543 127.29 124.795 124.571 122.777 121.354 17.161 55.952 41.174 4.243

7 6 5 4 3 2 1 1.7.97 2. 1.4 1.8 6..92.98-1 1. 5.. 26

35 162.953 147.82 146.949 146.984 136.899 135.798 134.757 128.892 129.54 129.95 129.288 126.84 126.25 126.524 126.993 127.651 121.947 124.61 12.146 3 25 2 15 1 5 2 15 1 5 27

28. 5. 1. 5 1 3..94 1.4 1.7 1.95 1.3 3.6 1.1.95 2.7 5 1 15 2 5 1 15 2 162.979 16.361 147.976 147.6 146.72 135.848 134.766 13.442 129.212 129.111 127.668 127.35 126.462 126.243 125.982 124.86 124.16 121.96 12.67 114.368 55.545

1 5 3..99.92.92 1.94 2.2.94 1.3.94 1. 5.. 29

3 5 1 15 2 1 2 3 4 5 6 7 162.892 147.593 146.84 145.794 135.87 135.766 134.94 132.21 13.711 129.564 127.75 126.78 126.537 126.49 126.32 124.714 124.26 123.471 122.68 12.185. 5. 1. 5 3. 1.3.94 1.5 1.92 5.2 1.1 1.8.98

158.129 162.739 145.788 146.49 137.24 141.793 128.288 128.886 128.954 129.45 129.118 135.781 125.738 126.257 126.894 122.17 124.679 124.827 12.82 16.41 55.99 25 2 15 1 5 2 15 1 5 31

32. 5. 1. 5 1 15 2 25.95 1.6 3.5 2.6 3.94.94 3. 5 1 15 2 1 2 3 4 162.622 158.25 145.761 144.479 141.664 135.91 135.87 132.159 13.72 129.246 128.318 126.53 126.325 125.739 124.861 124.384 123.295 122.115 12.865 16.445 55.98

15 1 5 1.92.96 5.4 1.4 1. 1.1 2..99.97 3. 1. 5.. 33

5 21.291 12.112 121.981 124.355 124.579 126.119 126.328 126.428 127.81 127.353 127.678 129.357 129.556 129.794 134.82 135.397 135.81 137.449 137.785 141.939 146.837 146.88 147.858 162.923 4 3 2 1 2 15 1 5 34

35. 5. 1. 5 1 1..94 1.6 6. 2.97 1.8.99 2.4 1.94.97 1.5 5 1 15 2 1 2 3 4 5 162.958 147.846 147.12 146.65 138.273 137.146 135.933 135.846 134.811 13.1 129.529 129.347 128.899 128.12 127.859 127.684 126.982 126.946 126.797 126.522 126.315 126.123 124.521 124.415 122.8 12.157