Supporting Information

Supporting Information A Regioselective Ring-Expansion of Isatins with In-situ Generated α-aryldiazomethanes; Direct Access to Viridicatin Alkaloids Yellaiah Tangella,, Kesari Lakshmi Manasa,, Namballa Hari Krishna,, B. Sridhar, Ahmed Kamal*,, and Bathini Nagendra Babu*,,, Fluoro-Agrochemicals, Centre for X-ray Crystallography, CSIR-Indian Institute of Chemical Technology, Hyderabad- 500 007, India Academy of Scientific and Innovative Research (AcSIR), New Delhi 110025, India Department of Medicinal Chemistry, National Institute of Pharmaceutical Education and Research (NIPER), Hyderabad-500 037, India. School of Pharmaceutical Education and Research (SPER), Jamia Hamdard University, New Delhi-110062, India Email: bathini@iict.res.in Contents General information..s2 X-ray crystal structure and crystal data of 4j S2 References..S3 General procedure for the synthesis of 4 and 5.S4 Characterization data for compounds 4 and 5..S4 Procedure and characterization data for the synthesis of 6, 7 and 8 S19 Copies of 1 H NMR and 13 C NMR spectra of 4, 5, 6, 7 and 8..S21 1

General Information All solvents and reagents were purchased from commercial suppliers and used without any further purification. The methyl- and benzyl- protected isatins were prepared according to the literature. All the reagents were handled and weighed in the air at room temperature. Thin layer chromatography (TLC) was performed using pre-coated silica gel 60 F254 MERCK. TLC plates were visualized by exposure to UV light. Silica gel (60 120) column chromatography was performed by using indicated solvent system. 1 H and 13 C NMR spectra were recorded relative to tertramethylsilane (TMS) and chemical shifts were reported in parts per million (δ). Melting points were recorded on an Electrothermal melting apparatus and are uncorrected. HRMS were performed on an ESI-QTOF mass spectrometer. X-ray Crystallography: 3-Hydroxy-4-(4-methoxyphenyl)-1-methylquinolin-2(1H)-one (4j) (CCDC: 1832714) O OH N O Figure S1. X-Ray crystal structure of 4j, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented by circles of arbitrary radii. 2

X-ray data for the compound 4j was collected at room temperature on a Bruker D8 QUEST instrument with an IµS Mo microsource (λ = 0.7107 A) and a PHOTON-100 detector. The raw data frames were reduced and corrected for absorption effects using the Bruker Apex 3 software suite programs. 1 The structure was solved using intrinsic phasing method 2 and further refined with the SHELXL 2 program and expanded using Fourier techniques. Anisotropic displacement parameters were included for all non-hydrogen atoms. O bound H atom was located in difference Fourier maps and their positions and isotropic displacement parameters were refined. All other C bound H atoms were positioned geometrically and treated as riding on their parent C atoms [C-H = 0.93-0.97 Å, and U iso (H) = 1.5U eq (C) for methyl H or 1.2U eq (C) for other H atoms]. Crystal Data for KA244: C 17 H 15 NO 3 (M =281.31 g/mol): monoclinic, space group P2 1 /n (no. 14), a = 6.0088(1) Å, b = 21.3777(5) Å, c = 10.8832(2) Å, β = 93.6225(7), V = 1395.20(5) Å 3, Z = 4, T = 294.15 K, µ(mo Kα) = 0.092 mm -1, Dcalc = 1.3391 g/cm 3, 50265 reflections measured (5.34 2Θ 61.42 ), 4330 unique (R int = 0.0856, R sigma = 0.0516) which were used in all calculations. The final R 1 was 0.0686 (I>2σ(I)) and wr 2 was 0.1577 (all data). CCDC 1832714 contains supplementary Crystallographic data for the structure. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0) 1223 336 033; email: deposit@ccdc.cam.ac.uk]. References: 1. Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA. 2. Sheldrick, G. M. Acta Cryst. 2015, C71, 3-8. 3

General procedure for the synthesis of 4 and 5: A mixture of aldehydes (2, 1 mmol) and p- toluenesulfonyl hydrazide (3, 1 mmol) in ethanol was stirred at room temperature until complete consumption of starting materials (monitored by TLC). Then, isatins (1, 1 mmol) and K 2 CO 3 (2 mmol) was added to the reaction mixture and stirred at 80 o C for 8 h. After the reaction was finished, the solvent was removed under reduced pressure and the residue was purified by silica gel column chromatography (Petroleum ether/ethyl acetate) to afford the desired products 4 and 5. 3-Hydroxy-4-phenylquinolin-2(1H)-one (4a or II): By following the general procedure, 4a was purified by silica gel chromatography (EA/PE = 20/80). White solid; Yield: 203 mg (86%); mp: 267 269 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.17 (s, 1H), 9.16 (s, 1H), 7.45 (t, J = 7.2 Hz, 2H), 7.37 (t, J = 7.3 Hz, 1H), 7.28 (t, m, 4H), 7.05 6.96 (m, 2H); 13 C NMR (101 MHz, DMSO d 6 ) δ 158.7, 142.9, 134.2, 133.6, 130.3, 128.8, 128.1, 126.9, 124.7, 124.4, 122.6, 121.4, 115.7; MS (ESI): m/z 238 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 12 O 2 N: 238.0863; found: 238.0857 [M + H] +. 3-Hydroxy-4-(4-methoxyphenyl)quinolin-2(1H)-one (4b): By following the general procedure, 4b was purified by silica gel chromatography (EA/PE = 30/70). White solid; Yield: 248 mg (93%); mp: 242 244 o C; 1 H NMR (400 MHz, DMSO d 6 ) δ 12.19 (s, 1H), 9.11 (s, 1H), 7.31 (dt, J = 16.3, 7.4 Hz, 4H), 7.10 (dt, J = 13.3, 8.2 Hz, 4H), 3.83 (s, 3H); 13 C NMR (101 MHz, DMSO d 6 ) δ 159.1, 158.7, 142.9, 133.6, 131.6, 126.8, 126.0, 124.9, 124.2, 122.5, 121.6, 115.7, 114.2, 55.6; MS (ESI): m/z 268 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 14 O 3 N: 268.0968; found: 268.0963 [M + H] +. 4

3-Hydroxy-4-(3-methoxyphenyl)quinolin-2(1H)-one (4c): By following the general procedure, 4c was purified by silica gel chromatography (EA/PE = 30/70). Off white solid; Yield: 245 mg (92%); mp: 260 262 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.22 (s, 1H), 9.21 (s, 1H), 7.43 (t, J = 7.9 Hz, 1H), 7.33 (bs, 2H), 7.07 (s, 2H), 7.01 (d, J = 7.4 Hz, 1H), 6.88 (d, J = 7.2 Hz, 2H), 3.78 (s, 3H); 13 C NMR (101 MHz, DMSO d 6 ) δ 159.7, 158.7, 142.8, 135.6, 133.6, 129.9, 126.9, 124.8, 124.3, 122.6, 122.5, 121.3, 115.9, 115.7, 113.6, 55.5; MS (ESI): m/z 268 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 14 O 3 N: 268.0968; found: 268.0975 [M + H] +. 3-Hydroxy-4-(2-methoxyphenyl)quinolin-2(1H)-one (4d): By following the general procedure, 4d was purified by silica gel chromatography (EA/PE = 35/65). White solid; Yield: 235 mg (88%); mp: 254 256 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.17 (s, 1H), 9.09 (s, 1H), 7.47 7.40 (m, 1H), 7.29 (q, J = 7.9 Hz, 2H), 7.19 7.12 (m, 2H), 7.09 7.00 (m, 2H), 6.83 (d, J = 7.9 Hz, 1H), 3.65 (s, 3H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.3, 156.6, 142.8, 132.9, 131.0, 129.4, 126.1, 124.3, 122.3, 121.97, 121.4, 121.0, 120.4, 115.0, 111.4, 55.2; MS (ESI): m/z 268 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 14 O 3 N: 268.0968; found: 268.0974 [M + H] +. 4-(4-Chlorophenyl)-3-hydroxyquinolin-2(1H)-one (4e): 5

By following the general procedure, 4e was purified by silica gel chromatography (EA/PE = 25/75). Off white solid; Yield: 227 mg (84%); mp: 266 268 o C; 1 H NMR (400 MHz, DMSO d 6 ) δ 12.23 (s, 1H), 9.20 (s, 1H), 7.52 (dd, J = 10.1, 4.5 Hz, 2H), 7.47 7.42 (m, 1H), 7.37 7.29 (m, 3H), 7.12 7.04 (m, 2H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.1, 142.6, 133.1, 132.5, 132.4, 131.8, 128.4, 126.5, 124.0, 122.6, 122.2, 120.5, 115.3; MS (ESI): m/z 272 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 11 O 2 NCl: 272.0473; found: 272.0467 [M + H] +. 3-Hydroxy-4-(4-nitrophenyl)quinolin-2(1H)-one (4f): By following the general procedure, 4f was purified by silica gel chromatography (EA/PE = 35/65). Pale yellow solid; Yield: 223 mg (79%); mp: 285 287 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.32 (s, 1H), 9.67 (s, 1H), 8.37 (d, J = 8.7 Hz, 2H), 7.66 (d, J = 8.7 Hz, 2H), 7.42 7.27 (m, 2H), 7.10 (ddd, J = 8.1, 5.3, 2.9 Hz, 1H), 7.01 (d, J = 8.0 Hz, 1H); 13 C NMR (101 MHz, DMSO d 6 ) δ 158.4, 147.4, 143.3, 141.5, 133.6, 132.0, 127.2, 124.3, 124.0, 122.8, 122.4, 120.4, 115.9; MS (ESI): m/z 283 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 11 O 4 N 2 : 283.0713; found: 283.0707 [M + H] +. 4-(2-Ethoxyphenyl)-3-hydroxyquinolin-2(1H)-one (4g): By following the general procedure, 4gwas purified by silica gel chromatography (EA/PE = 30/70). Off white solid; Yield: 239 mg (85%); mp: 193 195 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.17 (s, 1H), 9.06 (s, 1H), 7.45 7.37 (m, 1H), 7.30 (d, J = 6.3 Hz, 2H), 7.19 7.12 (m, 2H), 7.04 (td, J = 7.8, 4.0 Hz, 2H), 6.88 (d, J = 8.0 Hz, 1H), 3.98 (qd, J = 6.9, 2.4 Hz, 2H), 1.04 (t, J = 6.9 Hz, 3H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.3, 155.9, 142.7, 132.8, 131.3, 129.3, 126.1, 124.4, 122.7, 121.8, 121.6, 121.0, 120.3, 115.0, 112.7, 63.3, 14.4; MS (ESI): m/z 282 [M + H] + ; HRMS (ESI): m/z calcd for C 17 H 16 O 3 N: 282.1130; found: 282.1131 [M + H] +. 6

4-(2-Bromophenyl)-3-hydroxyquinolin-2(1H)-one (4h): By following the general procedure, 4h was purified by silica gel chromatography (EA/PE = 25/75). Off white solid; Yield: 245 mg (78%); mp: 302 304 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.28 (s, 1H), 9.48 (s, 1H), 7.80 (dd, J = 8.0, 0.9 Hz, 1H), 7.52 (td, J = 7.4, 1.1 Hz, 1H), 7.41 (td, J = 7.7, 1.7 Hz, 1H), 7.37 7.29 (m, 3H), 7.07 (ddd, J = 8.2, 6.3, 2.1 Hz, 1H), 6.74 (d, J = 7.9 Hz, 1H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.2, 142.8, 135.0, 133.0, 132.5, 131.7, 129.9, 127.9, 126.4, 123.8, 123.4, 123.2, 122.2, 120.3, 115.2; MS (ESI): m/z 315 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 11 O 2 NBr: 315.9968; found: 315.9978 [M + H] +. 3-Hydroxy-1-methyl-4-phenylquinolin-2(1H)-one (4i): By following the general procedure, 4iwas purified by silica gel chromatography (EA/PE = 10/90). White solid; Yield: 226 mg (90%); mp: 212 214 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 9.23 (s, 1H), 7.57 (d, J = 8.5 Hz, 1H), 7.55 7.49 (m, 2H), 7.49 7.42 (m, 2H), 7.35 7.30 (m, 2H), 7.21 7.09 (m, 2H), 3.79 (s, 3H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.0, 141.6, 134.2, 133.6, 129.8, 128.3, 127.7, 126.8, 124.9, 122.9, 122.4, 121.3, 114.7, 29.9; MS (ESI): m/z 252 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 14 O 2 N: 252.1019; found: 252.1013 [M + H] +. 3-Hydroxy-4-(4-methoxyphenyl)-1-methylquinolin-2(1H)-one (4j): By following the general procedure, 4j was purified by silica gel chromatography (EA/PE = 15/85). White solid; Yield: 270 mg (96%); mp: 223 225 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.49 7

7.40 (m, 3H), 7.38 7.34 (m, 2H), 7.20 (ddd, J = 8.2, 6.8, 1.5 Hz, 1H), 7.13 (s, 1H), 7.09 7.04 (m, 2H), 3.89 (s, 6H); 13 C NMR (101 MHz, CDCl 3 ) δ 159.4, 159.0, 140.9, 134.4, 131.1, 127.2, 126.2, 124.9, 123.0, 122.9, 122.3, 114.1, 114.0, 55.3, 30.4;MS (ESI): m/z 282 [M + H] + ; HRMS (ESI): m/z calcd for C 17 H 16 O 3 N: 282.1125; found: 282.1116 [M + H] +. 4-(4-Chlorophenyl)-3-hydroxy-1-methylquinolin-2(1H)-one (4k): By following the general procedure, 4k was purified by silica gel chromatography (EA/PE = 15/85). Off white solid; Yield: 248 mg (87%) mp: 244 246 o C; 1 H NMR (400 MHz, DMSO d 6 ) δ 9.37 (s, 1H), 7.59 (dt, J = 4.3, 2.4 Hz, 3H), 7.47 (ddd, J = 8.5, 7.1, 1.5 Hz, 1H), 7.40 7.35 (m, 2H), 7.22 7.15 (m, 1H), 7.12 (dd, J = 8.0, 1.4 Hz, 1H), 3.79 (s, 3H); 13 C NMR (101 MHz, DMSO d 6 ) δ 158.4, 142.3, 134.8, 133.0, 132.9, 132.3, 128.9, 127.4, 125.2, 123.1, 122.2, 121.5, 115.3, 30.5; MS (ESI): m/z 286 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 13 O 2 NCl: 286.0629; found: 286.0622 [M + H] +. NO 2 OH N O 3-Hydroxy-1-methyl-4-(4-nitrophenyl)quinolin-2(1H)-one (4l): By following the general procedure, 4l was purified by silica gel chromatography (EA/PE = 25/75). Pale yellow solid; Yield: 245 mg (83%); mp: 276 278 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 9.71 (s, 1H), 8.43 (d, J = 8.6 Hz, 2H), 7.69 (d, J = 8.6 Hz, 2H), 7.65 (d, J = 8.7 Hz, 1H), 7.54 (t, J = 7.5 Hz, 1H), 7.25 (t, J = 7.5 Hz, 1H), 7.12 (d, J = 7.8 Hz, 1H), 3.84 (s, 3H); 13 C NMR (75 MHz, DMSO d 6 ) δ 157.7, 146.9, 141.8, 140.9, 134.2, 131.5, 127.2, 124.4, 123.5, 122.8, 121.0, 120.4, 114.9, 30.0; MS (ESI): m/z 297 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 13 O 4 N 2 : 297.0870 found: 297.0862 [M + H] +. 8

4-(2-Bromophenyl)-3-hydroxy-1-methylquinolin-2(1H)-one (4m) By following the general procedure, 4m was purified by silica gel chromatography (EA/PE = 20/80). Off white solid; Yield: 260 mg (79%); mp: 238 240 o C; 1 H NMR (500 MHz, CDCl 3 ) δ 7.77 (dd, J = 8.0, 1.0 Hz, 1H), 7.50 7.42 (m, 3H), 7.37 7.29 (m, 2H), 7.19 (ddd, J = 8.1, 6.9, 1.4 Hz, 1H), 7.15 (s, 1H), 7.08 (dd, J = 8.0, 1.2 Hz, 1H), 3.91 (s, 3H); 13 C NMR (101 MHz, DMSO d 6 ) δ 158.5, 142.5, 135.4, 134.6, 133.0, 132.2, 130.5, 128.5, 127.4, 124.9, 124.0, 123.2, 122.8, 121.2, 115.3, 30.5; MS (ESI): m/z 330 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 13 O 2 NBr: 330.0124; found: 330.0135 [M + H] +. 1-Benzyl-3-hydroxy-4-phenylquinolin-2(1H)-one (4n): By following the general procedure, 4n was purified by silica gel chromatography (EA/PE = 15/85). White solid; Yield: 291 mg (89%); mp: 243 245 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 9.41 (s, 1H), 7.54 (t, J = 7.2 Hz, 2H), 7.45 (dd, J = 11.1, 7.9 Hz, 2H), 7.40 7.31 (m, 5H), 7.28 (d, J = 7.3 Hz, 3H), 7.13 (d, J = 3.5 Hz, 2H), 5.68 (s, 2H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.4, 141.5, 136.54, 133.6, 133.5, 129.9, 128.6, 128.4, 127.7, 127.1, 126.8, 126.5, 125.1, 123.7, 122.5, 121.7, 115.1, 45.6; MS (ESI): m/z 328 [M + H] + ; HRMS (ESI): m/z calcd for C 22 H 18 O 2 N: 328.1332; found: 328.1323 [M + H] +. 9

1-Benzyl-3-hydroxy-4-(4-methoxyphenyl)quinolin-2(1H)-one (4o): By following the general procedure, 4o was purified by silica gel chromatography (EA/PE = 20/80). Off white solid; Yield: 335 mg (94%); mp: 266 268 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.47 7.43 (m, 1H), 7.42 7.38 (m, 2H), 7.37 7.31 (m, 4H), 7.28 (dt, J = 4.6, 2.8 Hz, 3H), 7.14 (td, J = 6.7, 1.9 Hz, 2H), 7.11 7.06 (m, 2H), 5.69 (s, 2H), 3.89 (s, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 159.5, 159.4, 140.8, 135.8, 133.9, 131.2, 128.9, 127.5, 127.3, 126.6, 126.4, 124.9, 123.7, 123.0, 122.5, 115.1, 114.1, 55.3, 47.1; MS (ESI): m/z 357 [M + H] + ; HRMS (ESI): m/z calcd for C 23 H 20 O 3 N: 358.1438; found: 358.1432 [M + H] +. 1-Benzyl-4-(4-chlorophenyl)-3-hydroxyquinolin-2(1H)-one (4p): By following the general procedure, 4p was purified by silica gel chromatography (EA/PE = 20/80). White solid; Yield: 310 mg (86%); mp: 215 217 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 9.50 (s, 1H), 7.54 (d, J = 7.5 Hz, 2H), 7.42 7.15 (m, 9H), 7.06 (s, 2H), 5.61 (s, 2H); 13 C NMR (101 MHz, DMSO d 6 ) δ 158.8, 142.3, 136.9, 134.0, 133.0, 133.0, 132.4, 129.2, 129.0, 127.6, 127.4, 127.0, 125.5, 123.2, 123.0, 121.9, 115.7, 46.1; MS (ESI): m/z 362 [M + H] + ; HRMS (ESI): m/z calcd for C 22 H 17 O 2 NCl: 362.0942; found: 362.0937 [M + H] +. 1-Benzyl-3-hydroxy-4-(4-nitrophenyl)quinolin-2(1H)-one (4q): By following the general procedure, 4q was purified by silica gel chromatography (EA/PE = 30/70). Off white solid, Yield: 297 mg (80%); mp: 258 260 o C; 1 H NMR (400 MHz, DMSO d 6 ) δ 9.69 (s, 1H), 8.39 (d, J = 7.9 Hz, 2H), 7.69 (d, J = 7.8 Hz, 2H), 7.43 (d, J = 8.1 Hz, 1H), 7.38 10

7.22 (m, 6H), 7.12 (d, J = 3.6 Hz, 2H), 5.69 (s, 2H); 13 C NMR (75 MHz, DMSO d 6 + CDCl 3 ) δ 158.2, 146.9, 141.9, 140.9, 136.3, 133.5, 131.5, 128.6, 127.1, 126.9, 126.53, 124.7, 123.4, 122.7, 121.6, 120.8, 115.3, 45.7; MS (ESI): m/z 373 [M + H] + ; HRMS (ESI): m/z calcd for C 22 H 17 O 4 N 2 : 373.1183; found: 373.1180 [M + H] +. OH 3-Hydroxy-4-(3-hydroxyphenyl)quinolin-2(1H)-one or Viridicatol (4r or III): N H By following the general procedure, IV was purified by silica gel chromatography (EA/PE = 35/65). White solid; Yield: 184 mg (73%); mp: 238 240 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.22 (s, 1H), 9.54 (s, 1H), 9.18 (s, 1H), 7.41 7.22 (m, 3H), 7.09 (s, 2H), 6.82 (d, J = 7.4 Hz, 1H), 6.72 (d, J = 6.5 Hz, 2H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.2, 157.2, 142.1, 134.8, 133.0, 129.3, 126.3, 124.4, 124.0, 122.0, 120.8, 120.3, 116.6, 115.18, 114.5; MS (ESI): m/z 284 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 14 O 4 N: 254.0812; found: 254.0820 [M + H] +. N OH O OH 3-Hydroxy-4-(pyridin-4-yl)quinolin-2(1H)-one (4s): N H By following the general procedure, 4s was purified by silica gel chromatography (MeOH/EA = 5/95). Off white solid, Yield: 190 mg (80%); mp: 390 392 o C; 1 H NMR (400 MHz, DMSO d 6 ) δ 12.30 (s, 1H), 9.59 (s, 1H), 8.72 (d, J = 5.8 Hz, 2H), 7.39 (d, J = 5.9 Hz, 2H), 7.37 (d, J = 2.7 Hz, 2H), 7.11 (ddd, J = 8.2, 5.4, 2.9 Hz, 1H), 7.02 (d, J = 8.0 Hz, 1H); 13 C NMR (75 MHz, DMSO d 6 ) δ 157.9, 149.7, 142.6, 141.9, 133.1, 126.7, 125.0, 123.7, 122.4, 121.3, 119.7, 115.4; MS (ESI): m/z 239 [M + H] + ; HRMS (ESI): m/z calcd for C 14 H 11 O 2 N 2 : 239.0815; found: 239.0813 [M + H] +. O 11

3-Hydroxy-4-(thiophen-2-yl)quinolin-2(1H)-one (4t): By following the general procedure, 4t was purified by silica gel chromatography (EA/PE = 30/70). Off white solid, Yield: 211 mg (87%); mp: 256 258 o C; 1 H NMR (400 MHz, DMSO d 6 ) δ 12.27 (s, 1H), 9.67 (s, 1H), 7.76 (dd, J = 5.1, 1.1 Hz, 1H), 7.40 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 3.7 Hz, 2H), 7.24 (dd, J = 5.1, 3.5 Hz, 1H), 7.20 (dd, J = 3.5, 1.1 Hz, 1H), 7.17 7.12 (m, 1H); 13 C NMR (101 MHz, DMSO d 6 ) δ 158.2, 144.3, 133.7, 133.4, 129.3, 127.6, 127.5, 127.1, 124.7, 122.8, 121.2, 117.1, 115.8; MS (ESI): m/z 244 [M + H] + ; HRMS (ESI): m/z calcd for C 13 H 10 O 2 NS: 244.0427; found: 244.0435 [M + H] +. 3-Hydroxy-6-methoxy-4-phenylquinolin-2(1H)-one (5a): By following the general procedure, 5a was purified by silica gel chromatography (EA/PE = 30/70). White solid; Yield: 235 mg (88%); mp: 222 224 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.13 (s, 1H), 9.20 (s, 1H), 7.52 (t, J = 7.2 Hz, 2H), 7.44 (t, J = 7.3 Hz, 1H), 7.38 7.32 (m, 2H), 7.29 (d, J = 8.9 Hz, 1H), 7.01 (dd, J = 8.9, 2.7 Hz, 1H), 6.51 (d, J = 2.7 Hz, 1H), 3.59 (s, 3H). 13 C NMR (75 MHz, DMSO d 6 ) δ 157.7, 154.4, 142.9, 133.7, 129.7, 128.3, 127.6, 127.5, 123.4, 121.7, 116.4, 114.3, 107.2, 55.1; MS (ESI): m/z 268 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 14 O 3 N: 268.0968; found: 268.0963 [M + H] +. 3-Hydroxy-6-methoxy-4-(4-methoxyphenyl)quinolin-2(1H)-one (5b): By following the general procedure, 58 was purified by silica gel chromatography (EA/PE = 35/65). Off white solid, Yield: 282 mg (95%) mp: 243 245 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.09 (s, 1H), 9.10 (s, 1H), 7.28 (d, J = 8.0 Hz, 3H), 7.07 (d, J = 8.5 Hz, 2H), 7.00 (d, J = 8.8 Hz, 2H), 6.59 (s, 1H), 3.82 (s, 3H), 3.61 (s, 3H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.6, 157.7, 154.4, 142.9, 131.0, 127.5, 125.5, 123.1, 121.9, 116.4, 114.3, 113.7, 107.3, 55.1, 55.0; MS (ESI): 12

m/z 298 [M + H] + ; HRMS (ESI): m/z calcd for C 17 H 16 O 4 N: 298.1074; found: 298.1067 [M + H] +. 4-(4-Chlorophenyl)-3-hydroxy-6-methoxyquinolin-2(1H)-one (5c): By following the general procedure, 5c was purified by silica gel chromatography (EA/PE = 30/70). White solid; Yield: 262 mg (87%); mp: 258 260 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.16 (s, 1H), 9.39 (s, 1H), 7.58 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.9 Hz, 1H), 7.01 (dd, J = 8.9, 2.7 Hz, 1H), 6.49 (d, J = 2.6 Hz, 1H), 3.61 (s, 3H); 13 C NMR (75 MHz, DMSO d 6 ) δ 157.5, 154.5, 143.1, 132.5, 132.4, 131.7, 128.4, 127.5, 122.2, 121.3, 116.5, 114.5, 106.8, 55.1; MS (ESI): m/z 302 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 13 O 3 NCl: 302.0576; found: 302.0571 [M + H] +. NO 2 O OH 3-Hydroxy-6-methoxy-4-(4-nitrophenyl)quinolin-2(1H)-one (5d): By following the general procedure, 5d was purified by silica gel chromatography (EA/PE = 40/60). Yellow solid; Yield: 249 mg (80%); mp: 319 321 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.16 (s, 1H), 9.61 (s, 1H), 8.31 (d, J = 8.2 Hz, 2H), 7.61 (d, J = 8.1 Hz, 2H), 7.25 (d, J = 8.6 Hz, 1H), 6.97 (d, J = 7.7 Hz, 1H), 6.39 (s, 1H), 3.54 (s, 3H); 13 C NMR (75 MHz, DMSO d 6 ) δ 157.3, 154.6, 146.9, 143.3, 141.0, 131.4, 127.5, 123.5, 121.4, 120.72, 116.6, 114.7, 106.6, 55.2; MS (ESI): m/z 313 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 13 O 5 N 2 : 313.0819; found: 313.0812 [M + H] +. N H O 13

6-Chloro-3-hydroxy-4-phenylquinolin-2(1H)-one (5e): By following the general procedure, 5e was purified by silica gel chromatography (EA/PE = 30/70). White solid; Yield: 230 mg (85%); mp: 257 259; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.38 (s, 1H), 9.55 (s, 1H), 7.54 (t, J = 7.2 Hz, 2H), 7.47 (d, J = 7.1 Hz, 1H), 7.35 (dd, J = 6.3, 4.8 Hz, 4H), 6.94 (s, 1H); 13 C NMR (101 MHz, DMSO d 6 ) δ 158.0, 143.5, 133.0, 131.8, 129.7, 128.5, 127.9, 126.2, 126.1, 122.9, 122.8, 122.4, 117.1; MS (ESI): m/z 272 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 11 O 2 NCl: 272.0478; found: 272.0467 [M + H] +. 6-Chloro-3-hydroxy-4-(4-methoxyphenyl)quinolin-2(1H)-one (5f): By following the general procedure, 5f was purified by silica gel chromatography (EA/PE = 35/65). White solid; Yield: 271 mg (90%) mp: 296 298 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.28 (s, 1H), 9.39 (s, 1H), 7.34 7.25 (m, 2H), 7.21 (d, J = 8.6 Hz, 2H), 7.02 (d, J = 8.6 Hz, 2H), 6.96 (s, 1H), 3.77 (s, 3H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.8, 158.0, 143.5, 131.8, 131.0, 126.1, 124.9, 123.1, 122.7, 122.7, 117.1, 113.9, 55.0; MS (ESI): m/z 302 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 13 O 3 NCl: 302.0579; found: 302.0573 [M + H] +. 6-Chloro-4-(4-chlorophenyl)-3-hydroxyquinolin-2(1H)-one (5g) By following the general procedure, 5g was purified by silica gel chromatography (EA/PE = 35/65). Off white solid; Yield: 244 mg (80%); mp: 322 324 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.34 (s, 1H), 9.65 (s, 1H), 7.53 (d, J = 8.4 Hz, 2H), 7.31 (dd, J = 10.3, 6.1 Hz, 4H), 6.87 (d, J = 1.6 Hz, 1H); 13 C NMR (75 MHz, DMSO d 6 ) δ 157.9, 143.7, 132.7, 131.9, 131.8, 131.7, 128.6, 126.3, 122.7, 122.1, 121.6, 117.1; MS (ESI): m/z 306 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 10 O 2 NCl 2 : 306.0083; found: 306.0077 [M + H] +. 14

6-Chloro-3-hydroxy-4-(4-nitrophenyl)quinolin-2(1H)-one (5h): By following the general procedure, 5h was purified by silica gel chromatography (EA/PE = 45/55). Pale yellow solid; Yield: 246 mg (78%); mp: 323 324 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.46 (s, 1H), 9.97 (s, 1H), 8.38 (d, J = 8.7 Hz, 2H), 7.66 (d, J = 8.6 Hz, 2H), 7.44 7.35 (m, 2H), 6.92 (s, 1H); 13 C NMR (101 MHz, DMSO d 6 ) δ 158.2, 147.6, 144.4, 140.8, 132.4, 131.9, 127.0, 126.9, 124.2, 123.1, 122.0, 121.4, 117.7; MS (ESI): m/z 317 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 9 O 4 N 2 Cl: 317.0329; found: 317.2420 [M + H] +. 3-Hydroxy-6-nitro-4-phenylquinolin-2(1H)-one (5i): By following the general procedure, 5i was purified by silica gel chromatography (EA/PE = 35/65). Yellow solid; Yield: 216 mg (77%); mp: 333 335 o C; 1 H NMR (400 MHz, DMSO d 6 ) δ 12.80 (s, 1H), 9.88 (s, 1H), 8.19 (dd, J = 9.0, 2.5 Hz, 1H), 7.90 (d, J = 2.5 Hz, 1H), 7.58 (t, J = 7.3 Hz, 2H), 7.51 (dt, J = 7.3, 2.7 Hz, 2H), 7.43 7.38 (m, 2H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.5, 144.0, 141.9, 137.7, 132.6, 129.8, 128.6, 128.2, 123.4, 121.2, 121.0, 120.0, 116.2; MS (ESI): m/z 283 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 11 O 4 N 2 : 283.0713; found: 283.0706 [M + H] +. 3-Hydroxy-4-(4-methoxyphenyl)-6-nitroquinolin-2(1H)-one (5j): By following the general procedure, 5j was purified by silica gel chromatography (EA/PE = 40/60). Yellow solid; Yield: 259 mg (83%); mp: 250 252 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 15

12.78 (s, 1H), 9.81 (s, 1H), 8.18 (d, J = 9.0 Hz, 1H), 7.97 (s, 1H), 7.49 (d, J = 8.9 Hz, 1H), 7.33 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.4 Hz, 2H), 3.85 (s, 3H); 13 C NMR (101 MHz, DMSO d 6 ) δ 159.5, 159.0, 144.6, 142.4, 138.2, 131.6, 124.9, 123.8, 121.8, 120.7, 116.7, 114.5, 55.6; MS (ESI): m/z 313 [M + H] + ; HRMS (ESI): m/z calcd for C 16 H 13 O 5 N 2 : 313.0819; found: 313.0812 [M + H] +. 4-(4-Chlorophenyl)-3-hydroxy-6-nitroquinolin-2(1H)-one (5k) By following the general procedure, 5k was purified by silica gel chromatography (EA/PE = 45/55). Yellow solid; Yield: 253 mg (80%); mp: 374 376 o C; 1 H NMR (300 MHz, DMSO d 6 ) δ 12.82 (s, 1H), 10.05 (s, 1H), 8.19 (dd, J = 9.0, 2.4 Hz, 1H), 7.86 (d, J = 2.3 Hz, 1H), 7.64 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 9.0 Hz, 1H), 7.44 (d, J = 8.4 Hz, 2H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.3, 144.3, 141.9, 137.7, 133.0, 131.8, 131.4, 128.7, 122.2, 121.3, 120.6, 119.7, 116.2; MS (ESI): m/z 317 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 10 O 4 N 2 Cl: 317.0324; found: 317.0315[M + H] +. 3-Hydroxy-6-nitro-4-(4-nitrophenyl)quinolin-2(1H)-one (5l): By following the general procedure, 5l was purified by silica gel chromatography (EA/PE = 55/45). Yellow solid; Yield: 235 mg (72%); mp: 380 382 o C; 1 H NMR (400 MHz, DMSO d 6 ) δ 12.88 (s, 1H), 10.31 (s, 1H), 8.42 (d, J = 7.6 Hz, 2H), 8.22 (d, J = 8.9 Hz, 1H), 7.83 (s, 1H), 7.73 (d, J = 7.5 Hz, 2H), 7.53 (d, J = 8.9 Hz, 1H); 13 C NMR (75 MHz, DMSO d 6 ) δ 158.2, 147.2, 144.5, 142.0, 139.7, 137.7, 131.5, 123.8, 121.5, 121.4, 120.1, 119.5, 116.3; MS (ESI): m/z 328 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 10 O 6 N 3 : 328.0570; found: 328.0554 [M + H] +. 16

4-(4-Chlorophenyl)-8-fluoro-3-hydroxyquinolin-2(1H)-one (5m): The compound 5m was prepared by following the general procedure by taking 4- chlorobenzaldehyde (30 mg, 0.21 mmol), p-toluenesulfonyl hydrazide (39 mg, 0.21 mmol), 7- fluoroisatin (35 mg, 0.21 mmol) and K 2 CO 3 (59 mg, 0.42 mmol) and purified by silica gel chromatography (EA/PE = 25/75). White solid; Yield: 50 mg (81%); mp: 282 284 o C; 1 H NMR (500 MHz, DMSO d 6 ) δ 12.28 (s, 1H), 9.65 (s, 1H), 7.58 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.25 (dd, J = 10.2, 8.3 Hz, 1H), 7.07 (td, J = 8.1, 5.3 Hz, 1H), 6.86 (d, J = 8.1 Hz, 1H); 13 C NMR (126 MHz, DMSO d 6 ) δ 158.5, 149.7 (d, J = 245.0 Hz), 133.0, 132.8, 132.2, 128.9, 123.4 (d, J = 3.0 Hz), 122.8 (d, J = 2.6 Hz), 122.5 (d, J = 7.4 Hz), 122.1 (d, J = 13.9 Hz), 120.3 (d, J = 3.1 Hz); MS (ESI): m/z 290 [M + H] + ; HRMS (ESI): m/z calcd for C 14 H 10 O 2 N 2 FCl: 290.0384; found: 290.0375 [M + H] +. 3-Hydroxy-6,8-dimethyl-4-phenylquinolin-2(1H)-one (5n): The compound 5n was prepared by following the general procedure by taking benzaldehyde (30 mg, 0.28 mmol), p-toluenesulfonyl hydrazide (52 mg, 0.28 mmol), 5,7-dimethylisatin (49 mg, 0.28 mmol) and K 2 CO 3 (78 mg, 0.56 mmol) and purified by silica gel chromatography (EA/PE = 20/80). White solid; Yield: 62 mg (83%); mp: 242 244 o C; 1 H NMR (500 MHz, DMSO d 6 ) δ 11.30 (s, 1H), 9.11 (s, 1H), 7.48 (dd, J = 31.0, 6.6 Hz, 3H), 7.31 (d, J = 6.3 Hz, 2H), 7.02 (s, 1H), 6.68 (s, 1H), 2.45 (s, 3H), 2.17 (s, 3H); 13 C NMR (126 MHz, DMSO d 6 ) δ 159.0, 142.6, 134.6, 131.0, 130.2, 130.0, 129.8, 128.7, 128.0, 124.7, 123.8, 122.6, 121.5, 21.0, 17.9; MS (ESI): m/z 266 [M + H] + ; HRMS (ESI): m/z calcd for C 17 H 16 O 2 N: 266.1181; found: 266.1184 [M + H] +. 17

4-(4-Chlorophenyl)-3-hydroxy-6,8-dimethylquinolin-2(1H)-one (5o): The compound 5o was prepared by following the general procedure by taking 4- chlorobenzaldehyde (30 mg, 0.21 mmol), p-toluenesulfonyl hydrazide (39 mg, 0.21 mmol), 5,7- dimethylisatin (37 mg, 0.21 mmol) and K 2 CO 3 (59 mg, 0.42 mmol) purified by silica gel chromatography (EA/PE = 25/75). White solid; Yield: 50 mg (79%); mp: 267 269 o C; 1 H NMR (500 MHz, DMSO d 6 ) δ 11.32 (s, 1H), 9.28 (s, 1H), 7.57 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.3 Hz, 2H), 7.03 (s, 1H), 6.67 (s, 1H), 2.44 (s, 3H), 2.18 (s, 3H); 13 C NMR (126 MHz, DMSO d 6 ) δ 158.8, 142.8, 133.5, 132.8, 132.2, 131.2, 130.0, 129.9, 128.9, 123.9, 123.5, 122.4, 121.1, 21.0, 17.8; MS (ESI): m/z 300 [M + H] + ; HRMS (ESI): m/z calcd for C 17 H 15 O 2 NCl: 300.0791; found: 300.0782 [M + H] +. 5,6-Dichloro-3-hydroxy-4-phenylquinolin-2(1H)-one (5p): The compound 5p was prepared by following the general procedure by taking benzaldehyde (30 mg, 0.28 mmol), p-toluenesulfonyl hydrazide (52 mg, 0.28 mmol), 4,5-dichlorolisatin (61 mg, 0.28 mmol) and K 2 CO 3 (78 mg, 0.56 mmol) and purified by silica gel chromatography (EA/PE = 35/65). Off white solid; Yield: 60 mg (70%); mp: 278 280 o C; 1 H NMR (500 MHz, DMSO d 6 ) δ 12.56 (s, 1H), 9.63 (s, 1H), 7.57 (d, J = 8.7 Hz, 1H), 7.45 7.33 (m, 4H), 7.22 (d, J = 6.8 Hz, 2H); 13 C NMR (126 MHz, DMSO d 6 ) δ 157.5, 146.3, 136.5, 134.0, 130.0, 128.1, 127.8, 127.7, 127.6, 127.1, 123.6, 119.8, 116.4; MS (ESI): m/z 306 [M + H] + ; HRMS (ESI): m/z calcd for C 15 H 10 O 2 NCl 2 : 306.0089; found: 306.0093 [M + H] +. 18

3-Methoxy-1-methyl-4-phenylquinolin-2(1H)-one (6): To a stirred solution of viridicatin (4a, 110 mg, 0.42 mmol) in THF:H 2 O (1:1) was added NaOH (34 mg, 0.84 mmol) and dimethyl sulfate (106 mg, 0.84 mmol), the resulting mixture was stirred at room temperature for 12 h. After completion of the reaction monitored by TLC, the reaction mixture was concentrated under reduced pressure and diluted with water, extracted with DCM. The organic layer was washed with brine, dried over anhydrous Na 2 SO 4, and evaporated to afford crude product. The residue was purified by silica gel chromatography (EA/PE = 30/70). White solid; Yield: 107 mg (96%); mp: 197 199 o C; Mp: 200 203 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.54 7.43 (m, 1H), 7.42 7.37 (m, 1H), 7.35 7.30 (m, 1H), 7.24 (dd, J = 8.1, 1.4 Hz, 1H), 7.13 (ddd, J = 8.1, 7.1, 1.1 Hz, 1H), 3.83 (s, 1H), 3.76 (s, 1H); 13 C NMR (101 MHz, CDCl 3 ) δ 159.3, 145.1, 137.3, 137.1, 133.5, 129.5, 128.9, 128.4, 128.1, 127.4, 122.3, 121.3, 114.0, 60.2, 29.9; MS (ESI): m/z 266 [M + H] + ; HRMS (ESI): m/z calcd for C 17 H 16 O 2 N: 266.1176; found: 266.1180 [M + H] +. 2-Oxo-4-phenyl-1,2-dihydroquinolin-3-yl acetate (7): To mixture of viridicatin (4a, 100 mg 0.42 mmol) and Et 3 N (87 µl, 0.63 mmol) in DCM, acetyl chloride (30 µl, 0.42 mmol) was added at 0 o C. Then the reaction mixture was allowed to stir at room temperature for 4 h. After completion of the reaction monitored by TLC, the reaction mixture was diluted with water and extracted with DCM. The organic layer was washed with brine, dried over anhydrous Na 2 SO 4, and evaporated to afford the crude product, which was purified by silica gel chromatography (EA/PE = 25/75). White solid; Yield: 109 mg (93%); mp: 188 190 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 11.99 (s, 1H), 7.54 7.47 (m, 4H), 7.44 (d, J = 8.0 Hz, 1H), 7.36 7.32 (m, 2H), 7.29 7.25 (m, 1H), 7.15 (t, J = 7.5 Hz, 1H), 2.17 (s, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 168.9, 159.0, 141.9, 137.3, 136.5, 132.3, 130.1, 128.9, 128.7, 128.5, 126.8, 122.9, 120.0, 116.4, 20.4; 19

MS (ESI): m/z 280 [M + H] + ; HRMS (ESI): m/z calcd for C 17 H 14 O 3 N: 280.0968; found: 280.0974 [M + H] +. (E)-N'-Benzylidene-4-methylbenzenesulfonohydrazide (8): A mixture of benzaldehyde (106 mg, 1 mmol) and p-toluenesulfonyl hydrazide (186 mg, 1 mmol) in ethanol was stirred at room temperature for 1 h. After the reaction was finished monitored by TLC, the solvent was evaporated under reduced pressure and dried in vacuum to afford the desired product as White solid; Yield: 264 mg (96%); mp: 72-74 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.98 (s, 1H), 7.93 7.86 (m, 2H), 7.76 (s, 1H), 7.61 7.56 (m, 2H), 7.36 (ddd, J = 5.5, 3.5, 1.7 Hz, 3H), 7.31 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 148.1, 144.3, 135.2, 133.2, 130.3, 129.7, 128.6, 127.9, 127.4, 21.6; MS (ESI): m/z 275 [M + H] + ; HRMS (ESI): m/z calcd for C 14 H 15 O 2 N 2 S: 275.0849; found: 275.0853 [M + H] +. 20

3-Hydroxy-4-phenylquinolin-2(1H)-one or Viridicatin (4a or II): OH N O H 4a 1 H NMR, 300 MHz 21

3-Hydroxy-4-(4-methoxyphenyl)quinolin-2(1H)-one (4b) 159.17 158.77 142.94 133.64 131.60 126.89 126.07 124.90 124.21 122.59 121.62 115.74 114.29 55.62 0.92 0.96 4.00 4.05 3.00 12.19 12.09 9.11 7.36 7.34 7.33 7.30 7.28 7.26 7.14 7.12 7.10 7.10 7.09 7.06 3.83 22

23 3-Hydroxy-4-(3-methoxyphenyl)quinolin-2(1H)-one (4c): 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.5 12.0 13.5 f1 (ppm) 3.00 1.98 0.99 2.07 1.92 1.09 0.92 0.90 3.78 6.87 6.89 6.99 7.02 7.07 7.33 7.40 7.43 7.45 9.21 12.22 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 f1 (ppm) 55.59 113.60 115.72 115.95 121.39 122.51 122.63 124.35 124.87 126.91 129.96 133.60 135.63 142.88 158.77 159.72

3-Hydroxy-4-(2-methoxyphenyl)quinolin-2(1H)-one (4d): 24

4-(4-Chlorophenyl)-3-hydroxyquinolin-2(1H)-one (4e): 25

3-Hydroxy-4-(4-nitrophenyl)quinolin-2(1H)-one (4f): 26

27 4-(2-Ethoxyphenyl)-3-hydroxyquinolin-2(1H)-one (4g): 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.5 12.0 13.5 f1 (ppm) 3.00 2.08 0.98 1.99 1.98 2.04 1.08 0.93 0.94 1.01 1.04 1.06 3.94 3.95 3.97 3.98 3.99 4.00 4.01 4.02 6.87 6.89 7.01 7.02 7.04 7.05 7.06 7.07 7.14 7.14 7.16 7.29 7.31 7.38 7.39 7.41 7.43 7.44 9.06 12.17 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 f1 (ppm) 14.44 63.35 112.70 115.00 120.39 121.00 121.60 121.81 122.76 124.49 126.10 129.39 131.23 132.86 142.75 155.95 158.36

4-(2-Bromophenyl)-3-hydroxyquinolin-2(1H)-one (4h): 28

3-Hydroxy-1-methyl-4-phenylquinolin-2(1H)-one (4i): 29

3-Hydroxy-4-(4-methoxyphenyl)-1-methylquinolin-2(1H)-one (4j): 30

4-(4-Chlorophenyl)-3-hydroxy-1-methylquinolin-2(1H)-one (4k): 31

32 3-Hydroxy-1-methyl-4-(4-nitrophenyl)quinolin-2(1H)-one (4l): 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 f1 (ppm) 3.75 1.00 1.04 0.96 0.96 1.94 2.02 0.92 3.84 7.11 7.13 7.23 7.25 7.28 7.52 7.54 7.57 7.63 7.66 7.68 7.71 8.42 8.45 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 f1 (ppm) 30.08 114.95 120.40 121.08 122.81 123.58 124.47 127.24 131.55 134.29 140.94 141.86 146.97 157.79

4-(2-Bromophenyl)-3-hydroxy-1-methylquinolin-2(1H)-one (4m): 158.54 142.52 134.68 133.07 132.26 130.54 128.50 127.44 124.92 123.22 115.33 30.50 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 33

1-Benzyl-3-hydroxy-4-phenylquinolin-2(1H)-one (4n): 0.94 2.21 2.35 5.23 3.11 2.00 1.92 9.41 7.56 7.54 7.51 7.48 7.46 7.45 7.42 7.39 7.36 7.36 7.35 7.33 7.29 7.26 7.13 7.12 5.68 34

35 1-Benzyl-3-hydroxy-4-(4-methoxyphenyl)quinolin-2(1H)-one (4o): 3.00 1.95 2.09 2.09 3.15 4.13 2.06 1.04 3.89 5.69 7.07 7.07 7.09 7.09 7.14 7.15 7.26 7.27 7.29 7.31 7.32 7.32 7.33 7.34 7.34 7.39 7.40 7.41 7.41 7.44 7.44 7.46 47.13 55.37 114.16 115.11 122.59 123.08 123.75 124.98 126.40 126.67 127.34 127.59 128.96 131.25 133.91 135.80 140.83 159.40 159.56

1-Benzyl-4-(4-chlorophenyl)-3-hydroxyquinolin-2(1H)-one (4p): 36

1-Benzyl-3-hydroxy-4-(4-nitrophenyl)quinolin-2(1H)-one (4q): 37

3-Hydroxy-4-(3-hydroxyphenyl)quinolin-2(1H)-one or Viridicatol ( 4r or III): 38

39 3-Hydroxy-4-(pyridin-4-yl)quinolin-2(1H)-one (4s): -3-2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 f1 (ppm) 1.07 1.10 2.00 2.16 2.15 0.91 1.00 7.01 7.03 7.09 7.10 7.10 7.11 7.12 7.12 7.13 7.36 7.37 7.39 7.40 8.71 8.73 9.59 12.30 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 f1 (ppm) 115.40 119.72 121.36 122.42 123.78 125.05 126.71 133.16 141.98 142.65 149.75 157.99

40 3-Hydroxy-4-(thiophen-2-yl)quinolin-2(1H)-one (4t): 0.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 11.0 12.5 f1 (ppm) 1.16 1.10 1.04 2.10 1.19 0.95 1.00 0.91 7.12 7.13 7.14 7.15 7.15 7.16 7.20 7.20 7.21 7.21 7.23 7.24 7.25 7.26 7.35 7.36 7.39 7.41 7.75 7.76 7.77 7.77 9.67 12.27 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 f1 (ppm) 115.81 117.14 121.28 122.82 124.71 127.16 127.58 127.66 129.39 133.45 133.71 144.34 158.29

3-Hydroxy-6-methoxy-4-phenylquinolin-2(1H)-one (5a): 41

42 3-Hydroxy-6-methoxy-4-(4-methoxyphenyl)quinolin-2(1H)-one (5b): 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.5 12.0 13.5 f1 (ppm) 3.00 3.13 0.80 1.24 1.98 2.93 0.89 0.87 3.34 3.61 3.82 6.59 6.99 7.02 7.05 7.08 7.27 7.30 9.10 12.09 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 f1 (ppm) 55.08 55.15 107.31 113.79 114.37 116.45 121.98 123.19 125.56 127.53 131.05 142.93 154.42 157.70 158.65

4-(4-Chlorophenyl)-3-hydroxy-6-methoxyquinolin-2(1H)-one (5c): 157.53 154.50 143.14 132.55 132.42 131.76 128.47 127.50 122.21 121.35 116.57 114.59 106.86 55.16 43

3-Hydroxy-6-methoxy-4-(4-nitrophenyl)quinolin-2(1H)-one (5d): 44

45 6-Chloro-3-hydroxy-4-phenylquinolin-2(1H)-one (5e): 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 f1 (ppm) 0.75 3.29 2.23 1.11 2.38 1.00 7.05 7.30 7.32 7.35 7.37 7.42 7.43 7.49 7.50 7.52 7.55 7.57 7.58 11.76 0 10 20 30 40 50 60 70 80 90 110 130 150 170 190 210 f1 (ppm) 117.42 123.06 124.90 125.01 127.65 128.75 128.87 129.09 129.74 130.91 132.10 141.87 159.43

46 6-Chloro-3-hydroxy-4-(4-methoxyphenyl)quinolin-2(1H)-one (5f): 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.5 12.0 13.5 f1 (ppm) 3.00 1.01 2.08 1.83 2.04 0.93 0.86 3.77 6.96 7.01 7.04 7.20 7.22 7.26 7.29 7.33 9.39 12.28 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 f1 (ppm)

6-Chloro-4-(4-chlorophenyl)-3-hydroxyquinolin-2(1H)-one (5g): 47

48 6-Chloro-3-hydroxy-4-(4-nitrophenyl)quinolin-2(1H)-one (5h) 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.5 12.0 13.5 f1 (ppm) 0.97 2.22 2.13 2.08 0.97 1.00 6.92 7.39 7.39 7.40 7.42 7.65 7.68 8.36 8.39 9.97 12.46 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 f1 (ppm) 117.79 121.48 122.09 123.11 124.22 126.96 127.02 131.95 132.41 140.85 144.45 147.61 158.28

49 3-Hydroxy-6-nitro-4-phenylquinolin-2(1H)-one (5i): 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.5 12.0 13.5 f1 (ppm) 2.04 2.06 2.09 0.96 1.00 0.94 1.05 7.39 7.41 7.41 7.49 7.50 7.51 7.52 7.52 7.53 7.56 7.58 7.60 7.90 7.90 8.18 8.19 8.20 8.21 9.88 12.80 0 10 20 30 40 50 60 70 80 90 110 130 150 170 190 210 f1 (ppm) 116.20 120.02 121.02 121.29 123.47 128.23 128.63 129.85 132.63 137.71 141.90 144.09 158.53

3-Hydroxy-4-(4-methoxyphenyl)-6-nitroquinolin-2(1H)-one (5j): 50

4-(4-Chlorophenyl)-3-hydroxy-6-nitroquinolin-2(1H)-one (5k): 51

3-Hydroxy-6-nitro-4-(4-nitrophenyl)quinolin-2(1H)-one (5l): 52

4-(4-Chlorophenyl)-8-fluoro-3-hydroxyquinolin-2(1H)-one (5m): Cl OH N O H F 5m 1 H NMR, 500 MHz 53

3-Hydroxy-6,8-dimethyl-4-phenylquinolin-2(1H)-one (5n): OH N H O 5n 1 H NMR, 500 MHz OH N H O 5n 13 C NMR, 126 MHz 180 170 160 150 140 130 120 110 100 90 f1 (ppm) 80 70 60 50 40 30 20 10 0 54

4-(4-Chlorophenyl)-3-hydroxy-6,8-dimethylquinolin-2(1H)-one (5o): 55

5,6-Dichloro-3-hydroxy-4-phenylquinolin-2(1H)-one (5p): Cl Cl OH N H O 5p 1 H NMR, 500 MHz 180 170 160 150 140 130 120 110 100 90 f1 (ppm) 80 70 60 50 40 30 20 10 0 56

57 3-Methoxy-1-methyl-4-phenylquinolin-2(1H)-one (6): 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 f1 (ppm) 2.93 3.00 1.00 0.95 1.87 1.00 4.02 3.76 3.83 7.11 7.11 7.12 7.13 7.13 7.14 7.15 7.23 7.23 7.25 7.25 7.31 7.32 7.32 7.32 7.33 7.34 7.34 7.39 7.41 7.41 7.44 7.44 7.44 7.45 7.46 7.47 7.47 7.48 7.48 7.49 7.49 7.49 7.50 7.51 7.51 7.51 7.52 7.52 7.53 7.53 7.0 7.1 7.2 7.3 7.4 7.5 7.6 f1 (ppm) 1.00 0.95 1.89 1.00 4.02 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 f1 (ppm) 29.93 60.24 114.04 121.32 122.32 127.41 128.17 128.45 128.91 129.50 133.58 137.19 137.32 145.16 159.33

4-(2-Bromophenyl)-3-hydroxy-1-methylquinolin-2(1H)-one (7): 58

(E)-N'-Benzylidene-4-methylbenzenesulfonohydrazide (8): 59