Experimental Section - Plausible mechanism for the formation of the product 13

Scheme 5.2. Plausible mechanism for the formation of the product 13

5.2 Experimental Section

Materials and Methods

All the reagents and solvents were purchased from Aldrich Chemicals (India), Merck (India) or Ranbaxy (India) and were used as received. Milli-Q water was used in all the experiments.

The solutions of metal ions from NaCl, KCl, CaCl2.2H2O, MgCl2, Zn(ClO4)2.6H2O, Mn(ClO4)2.H2O, Co(ClO4)2.6H2O, Fe(ClO4)3.H2O, Fe(ClO4)2.H2O, Cd(ClO4)2.H2O, CuCl2, HgCl2 were prepared in deionized water.

General UV-vis and fluorescence spectra measurements

CH3CN/H2O (9:1) solution of ligand (33 µM solution) was placed in the quartz cell and the UV-vis as well as fluorescence spectra were recorded for increasing portions of metal salts up to 50 µM. The experiments were performed at room temperature and changes monitored and recorded carefully.

General procedure for synthesis of compounds (13)

Hydrated ferric sulfate (0.042 g, 0.1 mmol) was added to a stirred mixture of indole (1 mmol) and aldehyde (1 mmol) in 3 mL of ethanol at room temperature. Subsequently, thiol (1.2 mmol) was added into it and stirring was further continued. After completion of the reaction as monitored by TLC, ethanol was removed in rotary evaporator and the crude residue was extracted with dichloromethane (2 × 15 mL). The organic layer was washed with water followed by brine solution. The organic extract was dried over anhydrous sodium sulfate and it was concentrated in a rotary evaporator. Finally, the crude residue was passed through a silica gel column to obtain the desired pure product. All the desired products were eluted with ethyl acetate: hexane (1:9) mixture during column chromatography except the compound 13aam and 13ahn were eluted with 1:1 mixture of the same solvent system.

For recovery of the catalyst, the reaction was carried out in 3 mmol scale in ethanol. After completion of reaction, ethanol was removed and dichloromethane (9 mL) was added into it.

Then the catalyst comes out, and it was filtered and dried for next cycle reaction.

Spectral data of Compounds:

3-((Ethylthio)(phenyl)methyl)-1H-indole (13aaa):

Nature: Dark pink semi-solid; Rf = 0.40; IR (KBr): 3396 (-NH) cm^-1.

1H NMR (400 MHz, CDCl3): δ 1.14 (t, J = 7.6 Hz, 3H), 2.35-2.38 (m, 2H), 5.35 (s, 1H), 6.95 (s, 1H), 6.98 (t, J = 6.8 Hz, 1H), 7.07 (t, J = 7.6 Hz, 1H), 7.13 (t, J = 7.6 Hz, 1H), 7.17 (d, J = 8.4 Hz, 1H), 7.21 (t, J = 7.2 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 8.0 Hz, 1H), 7.81 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 14.6, 26.3, 45.9, 111.4, 116.9, 119.7, 119.9, 122.4, 123.3, 126.5, 127.1, 128.5 (2C), 128.6 (2C), 136.7, 142.2. Anal. Calcd for C17H17NS (267.39): C, 76.36; H, 6.41; N, 5.24. Found: C, 76.23; H, 6.34; N, 5.15.

3-((p-Chlorophenyl)(ethylthio)methyl)-1H-indole (13aea):

Nature: Red oily liquid; Rf = 0.40; IR (KBr): 3412 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 1.23 (t, J = 7.6 Hz, 3H), 2.44 (q, J = 7.2 Hz, 2H), 5.40 (s, 1H), 7.05 (s, 1H), 7.07 (t, J = 8.0 Hz, 1H), 7.17 (t, J = 8.0 Hz, 1H), 7.26 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.4 Hz, 1H), 7.41 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 8.0 Hz, 1H), 7.97 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 14.6, 26.3, 45.3, 111.5, 116.4, 119.7, 119.8, 122.6, 123.3, 126.3, 128.7 (2C), 129.8 (2C), 132.7, 136.7, 140.8. Anal. Calcd for C17H16ClNS (301.83): C, 67.65; H, 5.34, N, 4.64. Found: C, 67.53; H, 5.26; N, 4.57.

3-((p-Bromophenyl)(ethylthio)methyl)-1H-indole (13afa):

Nature: Red oily liquid; Rf = 0.60; IR (KBr): 3413 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 1.20 (t, J = 7.6 Hz, 3H), 2.41 (q, J = 7.2 Hz, 2H), 5.36 (s, 1H), 6.93 (s, 1H), 7.06 (t, J = 8.0 Hz, 1H), 7.14 (t, J = 8.0 Hz, 1H), 7.20 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.58 (d, J = 7.6 Hz, 1H), 7.85 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 14.5, 26.2, 45.3, 111.5, 116.2, 119.7, 119.8, 120.8, 122.5, 123.3, 126.2, 130.2 (2C), 131.6 (2C), 136.6, 141.2. Anal. Calcd for C17H16BrNS (346.28): C, 58.96; H, 4.66; N, 4.04. Found: C, 58.81; H, 4.57; N, 3.96.

N H

S Cl

N H

S Br

3-((Ethylthio)(p-methoxyphenyl)methyl)-1H-indole (13aba):

Nature: Dark red oily liquid; Rf = 0.40; IR (KBr): 3416 (-NH) cm^-

1. ¹H NMR (400 MHz, CDCl3): δ 1.20 (t, J = 7.6 Hz, 3H), 2.38- 2.44 (m, 2H), 3.70 (s, 3H), 5.39 (s, 1H), 6.80 (d, J = 8.4 Hz, 2H), 6.94 (s, 1H), 7.04 (t, J = 7.2 Hz, 1H), 7.11 (t, J = 8.0 Hz, 1H), 7.16 (d, J = 7.6 Hz, 1H), 7.38 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 7.6 Hz, 1H), 7.90 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 14.6, 26.1, 45.2, 55.3, 111.4, 113.9 (2C), 116.9, 119.5, 119.8, 122.2, 123.3, 126.4, 129.4 (2C), 134.2, 136.6, 158.5. Anal. Calcd for C18H19NOS (297.41): C, 72.69; H, 6.44; N, 4.71. Found: C, 72.57; H, 6.36; N, 4.65.

3-((Ethylthio)(p-nitrophenyl)methyl)-1H-indole (13aha):

Nature: Yellow solid; mp 128 °C; Rf = 0.37; IR (KBr): 3395 (-NH), 1508 (-NO2), 1340 (-NO2) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 1.25 (t, J = 7.6 Hz, 3H), 2.48 (q, J = 7.6 Hz, 2H), 5.49 (s, 1H), 7.08 (t, J = 8.0 Hz, 1H), 7.14 (d, J = 2.0 Hz, 1H), 7.19 (t, J = 7.6 Hz, 1H), 7.34 (d, J = 8.0 Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.64 (d, J = 8.8 Hz, 2H), 8.14 (d, J = 8.8 Hz, 2H), 8.17 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 14.5, 26.5, 45.5, 111.6, 115.4, 119.5, 120.1, 122.8, 123.5, 123.9 (2C), 126.2, 129.3 (2C), 136.8, 147.0, 150.0. Anal. Calcd for C17H16N2O2S (312.39): C, 65.36; H, 5.16; N, 8.97.

Found: C, 65.24; H, 5.08, N, 8.90.

3-((o-Chlorophenyl)(ethylthio)methyl)-1H-indole (13aoa):

Nature: Reddish oily liquid; Rf = 0.33; IR (KBr): 3412 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 1.17 (t, J = 7.6 Hz, 3H), 2.42 (q, J = 7.2 Hz, 2H), 5.91 (s, 1H), 6.97 (s, 1H), 6.99 (d, J = 7.2 Hz, 1H), 7.03 (dd, J

= 1.2 Hz, J = 7.6 Hz, 1H), 7.07 (d, J = 7.6 Hz, 2H), 7.14 (d, J = 8.0 Hz, 1H), 7.25 (dd, J = 1.2 Hz, J = 7.6 Hz, 1H), 7.54-7.57 (m, 2H), 7.82 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 14.7, 26.4, 41.6, 111.4, 115.9, 119.5, 119.7, 122.4, 123.6, 126.4, 127.2, 128.2, 129.4, 130.3, 133.4, 136.5, 139.7. Anal. Calcd for C17H16ClNS (301.83): C, 67.65; H, 5.34, N, 4.64. Found: C, 67.52; H, 5.26, N, 4.57.

N H

S H₃CO

N H

S O₂N

N H

S Cl

3-((Ethylthio)(o-nitrophenyl)methyl)-1H-indole (13ama):

Nature: Yellowish oily liquid; Rf = 0.33; IR (KBr): 3420 (-NH), 1524 (-NO2), 1353 (-NO2) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 1.23 (t, J = 7.6 Hz, 3H), 2.51 (q, J = 7.2 Hz, 2H), 6.25 (s, 1H), 7.07 (t, J = 8.0 Hz, 1H), 7.15 (d, J = 1.6 Hz, 1H), 7.17 (t, J = 6.8 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 7.2 Hz, 1H), 7.45 (t, J = 8.0 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 8.0 Hz, 1H), 8.12 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 14.5, 26.9, 40.0, 111.5, 115.2, 119.6, 119.9, 122.6, 124.0, 124.3, 126.3, 127.9, 131.0, 132.9, 136.7, 136.8, 149.3. Anal. Calcd for C17H16N2O2S (312.39): C, 65.36;

H, 5.16; N, 8.97. Found: C, 65.25; H, 5.08; N, 8.89.

3-((Ethylthio)(m-nitrophenyl)methyl)-1H-indole (13aja):

Nature: Yellowish oily liquid; Rf = 0.46; IR (KBr): 3420 (-NH), 1526 (-NO2), 1350 (-NO2) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 1.27 (t, J = 7.2 Hz, 3H), 2.50 (q, J = 7.2 Hz, 2H), 5.53 (s, 1H), 7.11 (t, J = 8.0 Hz, 1H), 7.14 (s, 1H), 7.21 (t, J = 8.0 Hz, 1H), 7.34 (d, J = 8.0 Hz, 1H), 7.44 (t, J = 8.0 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H), 7.83 (d, J = 7.6 Hz, 1H), 8.08 (d, J = 8.0 Hz, 1H), 8.21 (s, 1H, NH), 8.39 (t, J = 2.0 Hz, 1H); ¹³C NMR (100 MHz, CDCl3): δ 14.4, 26.4, 45.3, 111.6, 115.2, 119.3, 119.8, 122.1, 122.6, 123.2, 123.5, 126.0, 129.4, 134.6, 136.7, 144.7, 148.3. Anal. Calcd for C17H16N2O2S (312.39): C, 65.36; H, 5.16; N, 8.97. Found: C, 65.22; H, 5.07, N, 8.83.

3-(Phenyl(propylthio)methyl)-1H-indole (13aab):

Nature: Light red oily liquid; Rf = 0.40; IR (KBr): 3415 (-NH) cm^-

1. ¹H NMR (400 MHz, CDCl3): δ 0.94 (t, J = 7.6 Hz, 3H), 1.55-1.62 (m, 2H), 2.38-2.44 (m, 2H), 5.40 (s, 1H), 7.04 (s, 1H), 7.07 (d, J = 7.2 Hz, 1H), 7.15 (t, J = 8.0 Hz, 1H), 7.21 (t, J = 7.6 Hz, 1H), 7.29 (t, J = 7.6 Hz, 3H), 7.49 (d, J = 7.6 Hz, 2H), 7.63 (d, J = 8.0 Hz, 1H), 7.92 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 13.8, 22.8, 34.4, 46.2, 111.4, 117.0, 119.7, 119.8, 122.4, 123.4, 126.5, 127.1, 128.5 (2C), 128.6 (2C), 136.7, 142.3. Anal. Calcd for C18H19NS (281.42): C, 76.82; H, 6.81; N, 4.98. Found: C, 76.70; H, 6.73, 4.88.

N H

S NO₂

N H

S NO₂

N H

3-((p-Chlorophenyl)(propylthio)methyl)-1H-indole (13aeb):

Nature: Dark pink semi-solid; Rf = 0.50; IR (KBr): 3433 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3/DMSO): δ 0.87 (t, J = 7.6 Hz, 3H), 1.47-1.57 (m, 2H), 2.38-2.44 (m, 2H), 5.30 (s, 1H), 6.95 (t, J = 7.6 Hz, 1H), 7.01 (s, 1H), 7.06 (t, J = 7.2 Hz, 1H), 7.17 (d, J = 7.6 Hz, 2H), 7.26 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 8.0 Hz, 1H), 9.42 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 13.7, 22.8, 34.4, 45.6, 111.5, 116.6, 119.7, 119.8, 122.6, 123.3, 126.4, 128.7 (2C), 129.9 (2C), 132.7, 136.7, 140.9. Anal. Calcd for C18H18ClNS (315.86): C, 68.45; H, 5.74, N, 4.43.

Found: C, 68.36; H, 5.65, N, 4.35.

3-((Propylthio)(p-tolyl)methyl)-1H-indole (13acb):

Nature: Dark red semi-solid; Rf = 0.33; IR (KBr): 3389 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 0.94 (t, J = 7.2 Hz, 3H), 1.55-1.63 (m, 2H), 2.30 (s, 3H), 2.37-2.43 (m, 2H), 5.38 (s, 1H), 7.03-7.08 (m, 2H), 7.10 (d, J = 8.0 Hz, 2H), 7.14 (t, J = 8.0 Hz, 1H), 7.25 (d, J = 8.4 Hz, 1H), 7.37 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 8.0 Hz, 1H), 7.90 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 13.8, 21.3, 22.8, 34.4, 45.9, 111.4, 117.2, 119.6, 119.9, 122.3, 123.3, 126.6, 128.4 (2C), 129.3 (2C), 136.7 (2C), 139.2. Anal. Calcd for C19H21NS (295.44): C, 77.24; H, 7.16, N, 4.74. Found: C, 77.18; H, 7.04; N, 4.68.

3-((Benzylthio)(phenyl)methyl)-1H-indole (13aac):

Nature: Dark red semi-solid; Rf = 0.40; IR (KBr): 3408 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 3.57 (d, J = 13.2 Hz, 1H), 3.64 (d, J = 13.2 Hz, 1H), 5.23 (s, 1H), 6.94 (d, J = 1.6 Hz, 1H), 7.06 (t, J = 7.6 Hz, 2H), 7.15 (t, J = 8.0 Hz, 2H), 7.22-7.34 (m, 7H), 7.48 (d, J = 8.8 Hz, 2H), ), 7.53 (d, J = 8.0 Hz, 1H), 7.84 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 36.7, 45.5, 111.4, 116.5, 119.7, 119.8, 122.4, 123.6, 126.4, 127.1, 127.2, 128.5 (2C), 128.6 (2C), 128.7 (2C), 129.2 (2C), 136.6, 138.5, 141.7. Anal. Calcd for C22H19NS (329.46): C, 80.20; H, 5.81; N, 4.25. Found: C, 80.08; H, 5. 74; N, 4.13.

N H

S Cl

N H

S H₃C

N H

2-(((1H-indol-3-yl)(phenyl)methyl)thio)ethanol (13aam):

Nature: Dark red oily liquid; Rf = 0.73; IR (KBr): 3410 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 2.35 (s, 1H, OH ), 2.52 (t, J

= 6.0 Hz, 2H), 3.50-3.54 (m, 2H), 5.35 (s, 1H), 6.92 (s, 1H), 6.98 (t, J = 8.0 Hz, 1H), 7.08 (t, J = 8.0 Hz, 1H), 7.11-7.21 (m, 4H), 7.38 (d, J = 7.6 Hz, 2H), 7.54 (d, J = 8.0 Hz, 1H), 8.06 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 35.2, 46.1, 60.7, 111.5, 116.0, 119.7 (2C), 122.4, 123.6, 126.2, 127.3, 128.4 (2C), 128.6 (2C), 136.7, 141.7. Anal. Calcd for C17H17NOS (283.39): C, 72.05; H, 6.05; N, 4.94. Found: C, 71.94; H, 5.98; N, 4.87.

3-(Phenyl(phenylthio)methyl)-1H-indole (13aad):

Nature: Dark red semi-solid; Rf = 0.40; IR (KBr): 3414 (-NH) cm^-1.

1H NMR (400 MHz, CDCl3): δ 5.68 (s, 1H), 6.84 (s, 1H), 6.94-7.08 (m, 6H), 7.10 (s, 1H), 7.15 (t, J = 8.4 Hz, 4H), 7.34 (d, J = 7.6 Hz, 2H), 7.51 (d, J = 8.0 Hz, 1H), 7.68 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 49.9, 111.5, 116.3, 119.8 (2C), 122.5, 124.1, 126.4, 126.5, 127.3, 128.5 (2C), 128.6 (2C), 128.9 (2C), 130.5 (2C), 136.7, 136.8, 141.4. Anal.

Calcd for C21H17NS (315.43): C, 79.96; H,5.43; N, 4.44. Found: C, 79.82; H, 5.37; N, 4.35.

3-(Phenyl(p-tolylthio)methyl)-1H-indole (13aae):

Nature: Dark red semi-solid; Rf = 0.37; IR (KBr): 3396 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 2.15 (s, 3H), 5.63 (s, 1H), 6.89 (t, J = 8.0 Hz, 2H), 6.92 (s, 1H), 6.98 (t, J = 7.6 Hz, 2H), 7.07 (t, J = 8.0 Hz, 2H), 7.12 (d, J = 7.6 Hz, 1H), 7.17 (t, J = 8.0 Hz, 3H), 7.33 (d, J = 7.6 Hz, 2H), 7.53 (d, J = 8.0 Hz, 1H), 7.80 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 21.2, 50.6, 111.5, 116.3, 119.7, 119.8, 122.4, 124.0, 126.3, 127.2, 128.4 (2C), 128.5 (2C), 129.6 (2C), 131.3 (2C), 132.9, 136.6, 136.7, 141.7. Anal. Calcd for C22H19NS (329.46): C, 80.20; H, 5.81; N, 4.25. Found: C, 80.09; H, 5.72; N, 4.18.

N H

CH₃

3-(((p-Methoxyphenyl)thio)(phenyl)methyl)-1H-indole (13aai):

Nature: Dark red oily liquid; Rf = 0.37; IR (KBr): 3415 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 3.58 (s, 3H), 5.50 (s, 1H), 6.59 (d, J = 8.8 Hz, 2H), 6.87 (d, J = 2.4 Hz, 1H), 6.98 (t, J = 7.2 Hz, 1H), 7.05 (t, J = 8.0 Hz, 2H), 7.08-7.16 (m, 5H), 7.30 (d, J = 7.2 Hz, 2H), 7.54 (d, J = 7.6 Hz, 1H), 7.83 (s, 1H, NH);

13C NMR (100 MHz, CDCl3): δ 51.9, 55.4, 111.4, 114.4 (2C), 116.4, 119.7, 120.0, 122.4, 123.8, 126.5, 126.6, 127.2, 128.4 (2C), 128.6 (2C), 134.7 (2C), 136.7, 141.9, 159.3. Anal.

Calcd for C22H19NOS (345.46): C, 76.49; H, 5.54; N, 4.05. Found: C, 76.36; H, 5.48; N, 3.97.

3-(((4-nitrophenyl)thio)(phenyl)methyl)-1H-indole (13aan):

Nature: Yellowish oily liquid; Rf = 0.33; IR (KBr): 3421 (- NH), 1511 (-NO2), 1337 (-NO2) cm^-1. ¹H NMR (300 MHz, CDCl3): δ 6.02 (s, 1H), 7.06 (s, 1H), 7.14 (t, J = 7.8 Hz, 1H), 7.21-7.40 (m, 7H), 7.54 (d, J = 6.9 Hz, 2H), 7.63 (d, J = 7.8 Hz, 1H), 8.00 (d, J = 8.7 Hz, 2H), 8.18 (s, 1H, NH); ¹³C NMR (75 MHz, CDCl3): δ 48.0, 111.5, 114.8, 119.2, 120.0, 122.7, 123.8 (2C), 124.2, 125.9, 126.9 (2C), 127.8, 128.2 (2C), 128.8 (2C), 136.6, 139.5, 144.9, 147.7.

Anal. Calcd for C21H16N2O2S (360.43): C, 69.98; H, 4.47; N, 7.77. Found: C, 69.78; H, 4.39;

N, 7.62.

3-((p-Bromophenyl)(p-tolylthio)methyl)-1H-indole (13afe):

Nature: Dark red oily liquid; Rf = 0.40; IR (KBr): 3434 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 2.19 (s, 3H), 5.58 (s, 1H), 6.92 (d, J = 7.6 Hz, 2H), 6.97 (d, J = 1.6 Hz, 1H), 7.02 (t, J = 8.0 Hz, 1H), 7.09 (d, J = 8.0 Hz, 2H), 7.13 (t, J = 7.2 Hz, 1H), 7.23 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 1H), 7.31 (d, J = 8.8 Hz, 2H), 7.51 (d, J = 8.0 Hz, 1H), 7.95 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 21.3, 50.2, 111.5, 116.1, 119.8, 119.9, 121.1, 122.7, 123.9, 126.3, 129.8 (2C), 130.3 (2C), 131.6 (2C), 131.8 (2C), 132.4, 136.8, 137.2, 140.9. Anal.

Calcd for C22H18BrNS (408.35): C, 64.71; H, 4.44; N, 3.43. Found: C, 64.60; H, 4.35; N, 3.37.

N H

OCH₃

N H

CH₃ Br

N H

NO₂

3-(p-Tolyl(p-tolylthio)methyl)-1H-indole (13ace):

Nature: Dark red oily liquid; Rf = 0.40; IR (KBr): 3445 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 2.19 (s, 3H), 2.25 (s, 3H), 5.65 (s, 1H), 6.92 (d, J = 8.0 Hz, 2H), 6.97-7.06 (m, 4H), 7.08-7.15 (m, 3H), 7.25 (d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 7.56 (d, J = 8.0 Hz, 1H), 7.92 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 21.2, 21.3, 50.2, 111.4, 116.8, 119.8, 119.9, 122.4, 124.0, 126.5, 128.4 (2C), 129.3 (2C), 129.6 (2C), 131.1 (2C), 133.3, 136.6, 136.7, 136.8, 138.7. Anal. Calcd for C23H21NS (343.48): C, 80.42; H, 6.16; N, 4.08. Found:

C, 80.40; H, 6.09; N, 4.01.

3-((p-Methoxyphenyl)(p-tolylthio)methyl)-1H-indole (13abe):

Nature: Dark red oily liquid; Rf = 0.46; IR (KBr): 3429 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 2.15 (s, 3H), 3.65 (s, 3H), 5.60 (s, 1H), 6.71 (d, J = 8.8 Hz, 2H), 6.88 (d, J = 7.6 Hz, 2H), 6.93 (s, 1H), 6.95-7.00 (m, 1H), 7.05-7.10 (m, 3H), 7.17 (d, J = 8.0 Hz, 1H), 7.26 (d, J = 8.8 Hz, 2H), 7.51 (d, J = 8.0 Hz, 1H), 7.84 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 21.2, 49.9, 55.4, 111.4, 113.9 (2C), 116.8, 119.7, 119.9, 122.4, 124.0, 126.4, 129.6 (3C), 130.0, 131.2 (2C), 133.1, 133.8, 136.6, 136.8, 158.7. Anal. Calcd for C23H21NOS (359.48):

C, 76.85; H, 5.89; N, 3.90. Found: C, 76.73; H, 5.80; N, 3.82.

3-(((4-methoxyphenyl)thio)(4-nitrophenyl)methyl)-1H-indole (13ahi):

Nature: Red oily liquid; Rf = 0.26; IR (KBr): 3419 (-NH), 1517 (-NO2), 1345 (-NO2) cm^-1. ¹H NMR (400 MHz, CDCl3):

δ 3.74 (s, 3H), 5.62 (s, 1H), 6.72 (d, J = 8.8 Hz, 2H), 7.09 (t, J

= 8.0 Hz, 1H), 7.12 (s, 1H), 7.18-7.22 (m, 3H), 7.36 (d, J = 8.0 Hz, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.0 Hz, 1H), 8.08 (d, J = 8.8 Hz, 2H), 8.13 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 51.5, 55.4, 111.6, 114.6 (2C), 114.8, 119.5, 120.0, 122.7, 123.6 (2C), 123.7, 125.0, 126.1, 129.3 (2C), 135.5 (2C), 136.7, 146.8, 149.7, 159.9. Anal. Calcd for C H N O S (390.45): C, 67.67; H, 4.65; N, 7.17. Found: C, 67.55; H, 4.58; N, 7.09.

N H

CH₃ H₃C

N H

CH₃ H₃CO

N H

OCH₃ O₂N

4-((1H-indol-3-yl)(p-tolylthio)methyl)benzonitrile (13aie):

Nature: Red oily liquid; Rf = 0.36; IR (KBr): 3406 (-NH), 2226 (-CN) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 2.25 (s, 3H), 5.68 (s, 1H), 6.98 (d, J = 8.0 Hz, 2H), 7.02 (s, 1H), 7.08 (t, J = 8.0 Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 7.2 Hz, 1H), 7.30 (d, J = 8.4 Hz, 1H), 7.46 (s, 4H), 7.54 (d, J = 8.0 Hz, 1H), 8.17 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 21.1, 50.6, 110.4, 111.7, 114.7, 119.0, 119.4, 119.8, 122.5, 123.8, 125.9, 129.1 (2C), 129.7 (2C), 131.4, 132.1 (4C), 136.6, 137.5, 147.4. Anal. Calcd for C23H18N2S (354.46): C, 77.93; H, 5.12; N, 7.90. Found: C, 77.82; H, 5.03; N, 7.81.

3-((p-Fluorophenyl)((p-methoxyphenyl)thio)methyl)-1H-indole (13avi):

Nature: Dark red oily liquid; Rf = 0.30; IR (KBr): 3431 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 3.63 (s, 3H), 5.49 (s, 1H), 6.63 (d, J = 8.4 Hz, 2H), 6.84 (t, J = 8.8 Hz, 2H), 6.94 (s, 1H), 7.00 (t, J = 7.6 Hz, 1H), 7.08 (d, J = 7.2 Hz, 1H), 7.12 (d, J = 8.4 Hz, 2H), 7.19-7.26 (m, 3H), 7.52 (d, J = 8.0 Hz, 1H), 7.90 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 51.3, 55.4, 111.5, 114.5 (3C), 115.1, 115.3, 116.4, 119.8, 119.9, 122.6, 123.7, 126.3, 126.4, 130.1, 130.2, 135.0 (3C), 136.8, 159.6. Anal. Calcd for C22H18FNOS (363.45): C, 72.70; H, 4.99; N, 3.85.

Found: C, 72.68; H, 4.87; N, 3.77.

3-((4-nitrophenyl)((4-nitrophenyl)thio)methyl)-1H-indole (13ahn):

Nature: Yellow solid; mp 183 °C; Rf = 0.15; IR (KBr): 3474 (-NH), 1518 (-NO2), 1334 (-NO2) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 6.07 (s, 1H), 6.09 (s, 1H), 7.14 (t, J = 7.6 Hz, 1H), 7.26 (t, J = 8.4 Hz, 1H), 7.30 (d, J = 8.8 Hz, 2H), 7.41 (d, J = 8.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.70 (d, J = 8.8 Hz, 2H), 7.04 (d, J = 8.8 Hz, 2H), 7.19 (d, J = 8.8 Hz, 2H), 8.24 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3/CD2Cl2): δ 47.9, 111.8, 113.6, 119.1, 120.5, 123.2, 124.1 (2C), 124.2 (2C), 124.4, 125.7, 127.9 (2C), 129.4 (2C), 136.9, 145.7, 146.1, 147.3, 147.5.

Anal. Calcd for C21H15N3O4S (405.43): C, 62.21; H, 3.73; N, 10.36. Found: C, 62.08; H, 3.65; N, 10.28.

N H

CH₃ NC

N H

OCH₃ F

N H

NO₂ O₂N

3-(Naphthalen-2-yl(p-tolylthio)methyl)-1H-indole (13ale):

Nature: Dark pink solid; mp 145 °C; Rf = 0.48; IR (KBr): 3434 (-NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 2.11 (s, 3H), 5.77 (s, 1H), 6.84 (d, J = 8.0 Hz, 2H), 6.86 (d, J = 1.6 Hz, 1H), 6.96 (t, J

= 8.0 Hz, 1H), 7.05 (t, J = 8.0 Hz, 1H), 7.10 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 8.0 Hz, 1H), 7.29-7.33 (m, 2H), 7.55 (t, J = 7.6 Hz, 2H), 7.59-7.62 (m, 1H), 7.64-7.68 (m, 2H), 7.73 (s, 1H), 7.77 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 21.2, 51.0, 111.5, 116.5, 119.8, 119.9, 122.5, 124.1, 126.0, 126.2, 126.5, 127.0, 127.1, 127.8, 128.2, 128.3, 129.7 (2C), 131.5 (2C), 132.8, 132.9, 133.5, 136.8, 136.9, 139.1. Anal. Calcd for C26H21NS (379.52): C, 82.28; H, 5.58; N, 3.69. Found: C, 82.15; H, 5.51; N, 3.61.

5-bromo-3-((4-chlorophenyl)(ethylthio)methyl)-1H-indole (13bea):

Nature: Light yellow oily liquid; Rf = 0.40; IR (KBr): 3431 (- NH) cm^-1. ¹H NMR (400 MHz, CDCl3): δ 1.27 (t, J = 7.6 Hz, 3H), 2.44-2.50 (m, 2H), 5.37 (s, 1H), 7.10 (s, 1H), 7.23 (d, J = 8.8 Hz, 2H), 7.32 (d, J = 8.8 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 7.78 (s, 1H), 8.13 (s, 1H, NH); ¹³C NMR (100 MHz, CDCl3): δ 14.6, 26.4, 45.0, 112.9, 113.2, 116.4, 122.4, 124.5, 125.6, 128.1, 128.9 (2C), 129.8 (2C), 133.0, 135.4, 140.3. Anal. Calcd for C17H15BrClNS (380.73): C, 53.63; H, 3.97, N, 3.68. Found: C, 53.48; H, 3.85; N, 3.56.

Crystallographic description:

Complete crystallographic data of 13aha for the structural analysis has been deposited with the Cambridge Crystallographic Data Centre, CCDC No. 930601. Copies of this information may be obtained free of charge from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44-1223-336033, e-mail:

[email protected] or via: www.ccdc.cam.ac.uk).

N H

CH₃

N H

S Br

Table 5.4. Crystal data and structures refinement for the compound 13aha for atomic coordinates, equivalent isotropic displacement parameters and bond angles, please check the CIF.

Parameters Compound 13aha

Empirical Formula C17 H16 N2 O2 S

Formula weight 312.39

Temperature 0 K

Wavelength 0.71070 (Å)

Crystal system Monoclinic

Space group C 1 2/c 1

Radiation type Mo K\a

Radiation source 'SuperNova (Mo) X-ray Source' Unit cell dimensions a = 16.315 (2) (Å), α = 90°

b = 10.4846 (7) (Å), β = 118.484(18)°

c = 21.538 (3) (Å), γ = 90°

Unit cell volume 3238.3 (9) Å³

Z 8

Density 1.281 g/cm³

F(0 0 0) 1313.5

Index ranges -20 ≤ h ≤ 20, -12 ≤ k ≤ 14, -28 ≤ l ≤ 24 Reflections collected 7030

Independent reflections 3686 [R(int) = 0.0274]

Theta range for data collection 2.90 to 28.78°

Completeness to theta 28.78° 97.71 % Number of parameters 199

Number of restraints 0 Goodness-of-fit (GOF)^a on F² 1.147

Refinement method Full-matrix least-squares on F²

CCDC number 930601

1H NMR (400 MHz, CDCl3): 3-((Ethylthio)(p-methoxyphenyl)methyl)-1H-indole (13aba)

13C NMR (100 MHz, CDCl3): 3-((Ethylthio)(p-methoxyphenyl)methyl)-1H-indole (13aba)

Figure 5.6 N H

S H₃CO

13aba

N H

S H₃CO

13aba

1H NMR (400 MHz, CDCl3): 3-((Ethylthio)(m-nitrophenyl)methyl)-1H-indole (13aja)

13C NMR (100 MHz, CDCl3): 3-((Ethylthio)(m-nitrophenyl)methyl)-1H-indole (13aja)

Figure 5.7 N H

S NO₂

13aja

N H

S NO₂

13aja

1H NMR (400 MHz, CDCl3): 3-(Phenyl(phenylthio)methyl)-1H-indole (13aad)

13C NMR (100 MHz, CDCl3): 3-(Phenyl(phenylthio)methyl)-1H-indole (13aad)

N H

13aad

N H

13aad

1H NMR (400 MHz, CDCl3): 4-((1H-indol-3-yl)(p-tolylthio)methyl)benzonitrile (13aie)

13C NMR (100 MHz, CDCl3): 4-((1H-indol-3-yl)(p-tolylthio)methyl)benzonitrile (13aie)

Figure 5.9 N H

CH₃ NC

13aie

N H

CH₃ NC

13aie

Dalam dokumen Synthesis of Sulfur Containing Organic Compounds Using Multicomponent Reactions (MCRs): Their Biological and Photophysical Studies (Halaman 185-200)