Supporting Information · 1 Supporting Information PhI(OAc)2/NaX-mediated Halogenation Providing...
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Supporting Information
PhI(OAc)2/NaX-mediated Halogenation Providing Access to Valuable Synthons 3-Haloindole derivatives
Vittam Himabindua,b, Sai Prathima Parvathaneni*a, and Vaidya Jayathirth Rao*a,b
aFluoro Agro Chemicals(Org.Chem. II) Division and bAcSIR, Indian Institute of Chemical Technology, Uppal Road Tarnaka, Hyderabad-500007, India, Tel: (+) 91 40 27193933
[email protected]; [email protected]
Contents
1. General Information 2
2. Halogenation of Indoles 3
3. Characterization Data for the Products 3-13
4. 1H NMR and 13C NMR Spectra of the Products 14-50
5. References 51
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018
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1. General Information
The starting materials and reagents were purchased from various commercial sources and used without
further purification. The reactions were performed at room temperature. ACME silica gel (60-120 mesh) was
used for column chromatography. Analytical thin-layer chromatography (TLC) was performed on pre-coated
TLC plates with silica gel 60-F254 plates and visualized by UV-light. 1H NMR and 13C NMR spectra were
recorded, using tetramethylsilane (TMS) in the solvent of CDCl3+DMSO as the internal standard on a 300,
500 MHz spectrometer (1H NMR: TMS at 0.00 ppm, CDCl3 at 7.26 ppm; 13C NMR: CDCl3 at 77.0 ppm,
DMSO at 39.43). Chemical shifts (δ) were recorded in ppm with respect to TMS as an internal standard and
coupling constants are quoted in Hertz (Hz). Mass spectra were recorded on a mass spectrometer by the
electron spray ionization (ESI) and the data acquired in positive ionization mode. HRMS spectra were
determined on TOF type mass analyzer.
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2. Halogenation of Indoles
General Procedure for Chlorination:
In a 25 mL round bottom flask, substrates 1a-1j (1.0 mmol, 1 equiv) and NaCl (58 mg, 1.0 mmol, 1.0 equiv),
PhI(OAc)2 (322 mg, 1.0 mmol, 1equiv) were dissolved in 2 mL of CH3CN:H2O (1:1). The reaction mixture
was stirred at room temperature for 1-2h as monitored by TLC. The reaction mixture was diluted with 20 mL
of ethyl acetate and then treated with 10 mL of saturated Na2S aqueous solution. The organic layer was dried
over Na2SO4 and concentrated under vacuum. The residue was purified by column chromatography on silica
gel with a gradient eluent of hexane and ethyl acetate to give the chlorinated product.
3. Characterization Data for the Products:
3-chloro-1H-indole (2a) 1
Isolated yield: 72%; mp: 58-60 oC (lit)13 ; 1H NMR (500 MHz, CDCl3): δ 8.10 (s, 1H),
7.66-7.63 (d, 1H, J = 7.7 Hz), 7.39-7.36 (d, 1H, J = 7.7 Hz), 7.28-7.18 (m, 3H); 13C
NMR (500 MHz, CDCl3): δ 133.94, 124.38, 122.10, 119.79, 119.44, 117.26, 110.44,
105.48;MS (EI-MS) =151.0 (M+ ), 153.0 (M+2).
3-chloro-5-fluoro-1H-indole (2b) 1
Isolated yield: 62%; mp: 69-72 oC; 1H NMR (500 MHz, CDCl3): δ 8.01 (s, 1H), 7.22-
7.18 (m, 2H), 7.13-7.12 (d, 1H, J = 2.5 Hz), 6.94-6.89 (m, 1H); 13C NMR (500 MHz,
CDCl3): δ 159.24 (s), 157.36 (s), 131.47 (s), 125.88 (d, J = 10.4 Hz), 122.61 (s), 112.12
(dd, J = 70.7, 18.1Hz), 106.53 (s), 103.26 (d, J= 24.8.6 Hz);MS (EI-MS) = 169 (M+).
3, 5-dichloro-1H-indole (2c) 2
Isolated yield: 67%; mp: 97-99 oC (lit)6; 1H NMR (500 MHz, CDCl3): δ 8.09 (s, 1H),
7.61 (s, 1H,), 7.28-7.25 (m, 1H), 7.21-7.18 (m, 2H); 13C NMR (500 MHz, CDCl3): δ
133.32, 126.48, 126.42, 123.64, 122.22, 117.89, 112.61, 106.21;MS (EI-MS) = 184
(M+).
NH
Cl
2a
NH
Cl
2b
F
NH
Cl
2c
Cl
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5-bromo-3-chloro-1H-indole (2d)1, 3
Isolated yield: 64%; mp: 111-113 oC; 1H NMR (500 MHz, CDCl3): δ 8.22 (s, 1H),
7.56 (s, 1H), 7.30-7.29 (d, 1H, J = 8.5 Hz), 7.26-7.25 (d, 1H, J = 2.5 Hz), 7.21-7.19
(dd, 1H, J = 8.6, 10.6 Hz); 13C NMR (500 MHz, CDCl3): δ 133.59, 127.06, 126.16,
122.09, 120.96, 113.81, 113.04, 106.01; MS (EI-MS) = 229 (M+1).
3-chloro-5-iodo-1H-indole (2e)
Isolated yield: 74%; 1H NMR (500 MHz, CDCl3): δ 8.18 (s, 1H), 7.98 (s, 1H), 7.50-
7.48 (d, 1H, J = 8.8 Hz), 7.15-7.13 (d, 2H, J = 8.0 Hz); 13C NMR (400 MHz, CDCl3):
134.07, 131.57, 127.80, 127.28, 121.63, 113.42, 83.83, 60.46;MS (EI-MS) = 277
[M+], 279 [M + 2].
3-chloro-5-nitro-1H-indole (2f) 1
Isolated yield: 65%; mp: 150-152 oC; 1H NMR (300 MHz, CDCl3+d6-DMSO): δ 8.63
(s, 1H), 8.49 (s, 1H), 8.18-8.16 (dd, 1H, J = 8.9, 11.2 Hz), 7.45-7.42 (d, 1H, J = 9.0 Hz),
7.36-7.35 (d, 1H, J = 8.9 Hz ); 13C NMR (300 MHz, CDCl3+d6-DMSO): δ 140.32,
138.49, 127.49, 126.28, 116.67, 115.84, 110.65, 103.14; MS (EI-MS) = 198 (M+2).
3-chloro-5-methyl-1H-indole (2g) 1
Isolated yield: 79%; mp: 65-67 oC; 1H NMR (500 MHz, CDCl3): δ 8.00 (s, 1H), 7. 45
(s, 1H), 7.28 (s, 1H), 7.16-7.09 (m, 2H), 1.51 (s, 3H); 13C NMR (400 MHz, CDCl3): δ
133.34, 129.95, 125.60, 124.84, 120.87, 117.78, 111.16, 106.04, 21.44; MS ( EI-MS)
=166 (M+1).
3-chloro-5-methoxy-1H-indole (2h) 1, 3
Isolated yield: 78%; mp: 75-77 oC; 1H NMR (500 MHz, CDCl3): δ 8.10 (s, 1H),
7.27-7.20 (t, 2H), 7.00-6.99 (d, 1H, J = 2.5 Hz), 6.91-6.89 (dd, 1H, J = 8.8, 11.2
NH
Cl
2d
Br
NH
Cl
2e
I
NH
Cl
2f
O2N
NH
Cl
2h
MeO
NH
Cl
2g
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Hz), 3.8 (s, 3H); 13C NMR (400 MHzCDCl3): δ 154.87, 129.99, 125.79, 121.32, 113.98, 112.43, 106.04,
99.27, 29.72; MS (EI-MS) = 182 (M+1).
3-chloro-2-methyl-5-nitro-1H-indole (2i) 3
Isolated yield: 58%; mp: 170-172 oC; 1H NMR (300 MHz, CDCl3+d6-DMSO): δ
8.50 (s, 1H), 8.28 (s, 1H), 8.11-8.08 (d, 1H, J = 8.9 Hz), 7.33-7.31 (d, 1H, J = 8.9
Hz), 2.49 (s, 3H); 13C NMR (300 MHz, CDCl3+d6-DMSO): δ 140.70, 137.62,
136.58, 126.19, 116.07, 113.82, 110.49, 89.91, 11.51; MS (EI-MS) = 210 (M+).
3-chloro-1-phenyl-1H-indole (2j)4
Isolated yield: 64%; 1H NMR (400 MHz, CDCl3): δ 7.62-7.58 (m, 1H), 7.55-7.49
(m, 5H), 7.37-7.33 (m, 1H), 7.25-7.16 (m, 3H); 13C NMR (400 MHz, CDCl3): δ
200.10, 164.56, 140.52, 138.28, 132.79, 132.15, 130.51, 129.33, 127.75, 127.01,
113.06, 93.59; MS (EI-MS)=227 (M+).
General Procedure for bromination:
In a 25 mL round bottom flask, substrates 3a-31 (1.0 mmol, 1 equiv) and NaBr (103 mg, 1.0 mmol, 1.0
equiv), PhI(OAc)2 (322 mg, 1.0 mmol, 1 equiv) were dissolved in 2 mL of CH3CN:H2O (1:1). The reaction
mixture was stirred at room temperature for 1-2 h, monitored by TLC. The reaction mixture was diluted with
20 mL of ethyl acetate and then treated with 10 mL of saturated Na2S aqueous solution. The organic layer
was dried over Na2SO4 and concentrated under vacuum. The residue was purified by column chromatography
on silica gel with a gradient eluent of hexane and ethyl acetate to give the brominated product.
NH
Cl
2i
O2N
N
Cl
2j
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3-Bromo-1H-indole (3a) 1
Isolated yield: 78%; mp: 65-67 oC; 1H NMR (500 MHz, CDCl3): δ 8.19 (s, 1H), 7.61-
7.58 (d, 1H, J = 7.7 Hz), 7.39-7.37 (d, 1H, J = 7.1 Hz), 7.28-7.18 (m, 3H); 13C NMR
(500 MHz, CDCl3): δ 133.60, 127.09, 126.18, 122.03, 121.02, 113.83, 112.98, 106.09;
MS (EI-MS) = 195 (M+).
3-bromo-5-fluoro-1H-indole (3b) 1
Isolated yield: 61%; mp: 75-78 oC; 1H NMR (500 MHz, CDCl3): δ 8.45 (s, 1H), 7.53
(s, 1H,), 7.26-7.15 (m, 3H); 13C NMR (500 MHz, CDCl3): δ 139.42 (s), 134.41 (s),
131.62 (s), 129.28 (d, J = 102.9 Hz), 126.13 (s), 123.69 (s), 114.12 (s), 112.83 (s); MS
(EI-MS) = 212 (M+).
3-bromo-5-chloro-1H-indole (3c) 5
Isolated yield: 69%; mp: 81-83 oC (lit)12; 1H NMR (500 MHz, CDCl3): δ 8.22 (s, 1H),
7.57-7.56 (d, 1H, J = 8.5 Hz), 7.30-7.28 (d, 1H,J = 2.5 Hz), 7.25-7.19 (m, 2H,); 13C
NMR (400 MHz, CDCl3): δ 134.17, 128.99, 125.62, 125.49, 122.35, 120.15, 112.07,
102.43; MS (EI-MS) = 230 (M+2).
3, 5-dibromo-1H-indole (3d) 1
Isolated yield: 65%; mp: 91-93 oC (lit)12; 1H NMR (500 MHz, CDCl3): δ 8.21 (s, 1H),
7.72 (s, 1H), 7.34-7.31 (dd, 1H, J = 8.6, 10.5 Hz), 7.25-7.21 (m, 2H); 13C NMR (400
MHz, CDCl3): δ 133.98, 128.59, 126.19, 124.55, 121.90, 113.99, 112.91, 90.99; MS
(EI-MS) = 274 (M+2).
3-bromo-5-iodo-1H-indole (3e):
NH
Br
3a
NH
Br
3b
F
NH
Br
3c
Cl
NH
Br
3d
Br
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Isolated yield: 79%; mp: 90-93 oC; 1H NMR (400 MHz, CDCl3): δ 8.25 (s, 1H), 7.93
(s, 1H), 7.51-7.49 (dd, 1H, J = 8.5, 10.2 Hz), 7.20-7.14 (m, 2H); 13C NMR (500 MHz,
CDCl3):δ 134.45, 131.62,129.30, 128.19, 124.11, 113.31, 90.69, 84.04; MS (EI-MS) =
320 (M+), 321 (M+2), HRMS (EI-HRMS) (M+H)+m/z calcd for C8H5BrIN = 320.8650,
found = 320.8620.
3-bromo-5-nitro-1H-indole (3f) 6
Isolated yield: 59%; mp: 190-192 oC; 1H NMR (300 MHz, CDCl3): δ 11.31 (s, 1H),
8.19 (s, 1H), 7.83-73.79 (d, 1H, J = 8.5 Hz),7.28-7.16 (m, 2H);13C NMR (300 MHz,
CDCl3): δ 141.20, 138.20, 126.99, 125.60, 117.04, 115.48, 111.69, 91.61; MS (EI-MS)
= 241.
3-bromo-5-methyl-1H-indole (3g) 7
Isolated yield: 82%; mp: 66-68 oC; 1H NMR (500 MHz, CDCl3): δ 8.14 (s, 1H), 7.36
(s, 1H), 7.27-7.25 (t, 1H), 7.19-7.18 (d, 1H, J = 8.6 Hz), 7.08-7.06 (dd, 1H, J = 8.3, 10.2
Hz), 2.47 (s, 3H); 13C NMR (500 MHz, CDCl3): δ 134.15, 129.03, 128.18, 124.27,
123.65, 120.38, 110.70, 102.13, 21.48; MS (EI-MS) = 208 (M+).
3-bromo-5-methoxy-1H-indole (3h) 1
Isolated yield: 81%; mp: 74-76 oC; 1H NMR (500 MHz, CDCl3): δ 8.04 (s, 1H), 7.20-
7.18 (t, 1H), 7.13-7.12 (d, 1H, J = 2.4 Hz), 6.92 (s, 1H), 6.84-6.82 (dd, 1H, J = 8.8,
11.2 Hz), 3.8 (s, 3H). 13C NMR (500 MHz, CDCl3): δ 154.24, 131.14, 131.03, 128.34,
124.95, 112.39, 111.78, 102.40, 55.54; MS (EI-MS) = 226 (M+2).
3-bromo-2-methyl-5-nitro-1H-indole (3i)
Isolated yield: 62%; mp: 161-165 oC; 1H NMR (300 MHz, CDCl3+d6-DMSO): δ
11.60 (s, 1H), 8.31 (s, 1H), 8.01-7.97 (dd, 1H, J = 9.0, 11.0 Hz), 7.39-7.36 (d, 1H, J
= 8.8 Hz), 3.14 (s, 3H); 13C NMR (300 MHz, CDCl3+d6-DMSO): δ 140.70, 137.62,
NH
Br
3e
I
NH
Br
3f
O2N
NH
Br
3g
NH
Br
3h
MeO
NH
Br
3i
O2N
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136.58, 126.19, 116.07, 114.01, 110.49, 89.91, 11.51; MS (EI-MS) = 254 (M+1), HRMS (EI-HRMS) =calcd
for C8H5BrN2O2 = 253.9690, found = 253.9690.
3-bromo-1-phenyl-1H-indole (3j) 12
Isolated yield: 74%; mp: 91-93 oC; 1H NMR (400 MHz, CDCl3): δ 7.55-7.52 (t, 2H), 7.48-
7.42 (m, 4H), 7.28-7.24 (m, 1H), 7.15-7.12 (m, 1H), 6.80-6.78 (s, 1H, J = 7.9 Hz), 5.43 (s,
1H) ; 13C NMR (400 MHz, CDCl3): δ 171.73, 143.94, 133.83, 130.33, 129.78, 128.54,
126.44, 126.36, 125.98, 123.83, 110.10; MS (EI-MS) = 272 (M+2).
1-benzyl-3-bromo-1H-indole (3k) 8
Isolated yield: 71%; mp: 55-60 oC; 1H NMR (500 MHz, CDCl3+d6-DMSO): δ 7.60-7.57
(m, 1H), 7.33-7.17 (m, 7H), 7.13-7.10 (m, 2H), 5.28 (s, 2H); 13C NMR (400 MHz, CDCl3+d6-
DMSO): δ 136.79, 135.94, 128.92, 127.94, 127.56, 127.08, 126.97, 122.88, 120.39, 119.47,
109.93, 90.36, 50.37; MS (EI-MS) = 285 (M+), HRMS (EI-HRMS) =calcd for C15H12BrN=
285.0179, found = 285.0153.
3-bromo-1-methyl-2-phenyl-1H-indole (3l) 6
Isolated yield: 94%; 1H NMR (400 MHz, CDCl3+d6-DMSO): δ 7.62-7.60 (d, 1H, J =
8.6 Hz), 7.50-7.44 (m, 5H), 7.34-7.27 (m, 2H), 7.24-7.22 (m, 1H), 3.63 (s, 3H); 13C NMR
(400 MHz, CDCl3+d6-DMSO): δ 141.81, 137.84, 131.70, 131.00, 130.46, 128.88, 128.74,
128.51, 123.00, 121.54, 120.81, 109.95, 58.98, 32.10; MS (EI-MS) = 285 (M+).
General Procedure for iodination:
N
Br
3j
N
Br
3k
N
Br
3l
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In a 25 mL round bottom flask, substrates 4a-4m (1.0 mmol, 1 equiv) and NaI (150 mg, 1.0 mmol, 1.0 equiv),
PhI(OAc)2 (322 mg, 1.0 mmol, 1 equiv) were dissolved in 2 mL of CH3CN:H2O (1:1). The reaction mixture
was stirred at room temperature for 1-2 has monitored by TLC. The reaction mixture was diluted with 20 mL
of ethyl acetate and then treated with 10 mL of saturated Na2S aqueous solution. The organic layer was dried
over Na2SO4 and concentrated under vacuum. The residue was purified by column chromatography on silica
gel with a gradient eluent of hexane and ethyl acetate to give the iodinated product.
3-Iodo-1H-indole (4a)
Isolated yield: 91%; mp: 66 oC (lit)16; 1H NMR (500 MHz, CDCl3): δ 8.28 (s, 1H),
7.47-7.45 (d, 1H, J = 7.6 Hz), 7.35-7.34 (d,1H, J = 7.9 Hz) 7.26-7.19 (m, 3H); 13C NMR
(500 MHz, CDCl3): δ 135.65, 129.83, 128.42, 123.23, 121.05, 120.85, 111.28, 57.64;
MS (EI-MS) = 242 (M+).7
3-Iodo-5-Fluoro-1H-indole (4b) 10
Isolated yield: 75%; mp: 73-75 oC; 1H NMR (500 MHz, CDCl3): δ 8.34 (s, 1H), 7.32-
7.28 (m, 2H), 7.14-7.12 (d, 1H, J = 9.3 Hz), 7.01-6.97 (m, 1H); 13C NMR (500 MHz,
CDCl3): δ 159.57 (s), 157.69 (s), 132.14 (s), 130.57 (d, J = 10.5 Hz), 130.11 (s), 111.98
(dd, J = 34.6, 18.1 Hz), 106.17 (d, J = 24.6 Hz), 57.03 (d, J = 4.5 Hz); MS (EI-MS) =
261 (M+1)
3-Iodo-5-Chloro-1H-indole (4c) 10
Isolated yield: 82%; mp: 81-84 oC; 1H NMR (500 MHz, CDCl3): δ 8.38 (s, 1H) , 7.45-
7.44 (d, 1H, J = 1.9 Hz), 7.31-7.28 (m, 2H) 7.21-7.18 (dd, 1H, J = 8.6, 10.6 Hz); 13C
NMR (500 MHz,CDCl3): δ 134.08, 131.06, 129.75, 126.75, 123.66, 120.66, 112.37,
56.75; MS (EI-MS) = 277 [M+ ], 279 [M + 2].
3-Iodo-5-Bromo-1H-indole (4d) 6
NH
I
4b
F
NH
I
4c
Cl
NH
I
4a
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Isolated yield: 85%;mp: 106-108 °C (lit) 6;1H NMR (500 MHz, CDCl3): δ 10.60
(s, 1H), 7.28-7.23 (m, 1H), 7.15-7.09 (m, 2H), 6.88-6.81 (m, 1H);13C NMR (500
MHz, CDCl3): δ 131.46, 130.97, 128.87, 125.94, 122.59, 114.09, 112.34, 103.50;
MS (EI-MS) = 323 (M+2), 321 (M+).
3, 5-diiodo-1H-indole (4e) 6, 8
Isolated yield: 89%; mp: 110-112 °C ; 1H NMR (500 MHz, CDCl3): δ 8.36 (s, 1H),
7.32-7.29 (dd, 1H, J = 8.3, 10.0 Hz), 7.14-7.12 (d, 1H, J = 2.5 Hz), 7.01-6.97 (d, 1H,
J = 8.3 Hz); 13C NMR (400 MHz, CDCl3): δ 134.84, 132.30, 131.64, 129.98, 129.20,
113.22, 84.28, 56.33; MS (EI-MS) = 368 (M+ ), HRMS (EI-HRMS) =calcd for
C8H5BrN2O2 = 368.8511, found = 368.8510.
3-Iodo-5-nitro-1H-indole (4f) 9
Isolated yield: 68%; mp: 199-201 °C; 1H NMR (300 MHz, CDCl3+d6-DMSO): δ
11.73 (s, 1H), 8.38 (s, 1H), 8.12-8.08 (dd, 1H, J = 8.8, 11.0 Hz), 7.54-7.51 (m, 2H);
13C NMR (300 MHz, CDCl3+d6-DMSO): δ 143.91, 140.79, 138.45, 131.88, 128.26,
116.51, 111.27, 56.87; MS (EI-MS) = 230.5.
3-Iodo-5-methyl-1H-indole (4g) 9
Isolated yield: 94%; mp: 70-72 °C; 1H NMR (500 MHz, CDCl3): δ 8.28 (s, 1H), 7.29-
7.26 (m, 3H), 7.11-7.08 (dd, 1H, J = 8.2, 9.6 Hz), 2.51 (s, 3H); 13C NMR (500 MHz,
CDCl3): δ 133.94, 130.33, 129.97, 128.43, 124.88, 120.58, 110.98, 57.07, 21.44; MS
(EI-MS) = 257 (M+1).
NH
I
4e
I
NH
I
4g
4d
NH
IBr
NH
I
4f
O2N
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11
3-Iodo-5-methoxy-1H-indole (4h) 9
Isolated yield: 92%; mp:106-108 °C; 1H NMR (500 MHz, CDCl3): δ 7.98 (s,
1H), 7.25-7.04 (m, 3H), 6.92-6.88 (dd, 1H, J = 8.8, 11.2 Hz), 3.88 (s, 3H). 13C
NMR (500 MHz, CDCl3): δ 154.23, 130.99, 128.32, 124.90, 112.39, 111.74,
102.41, 55.90, 30.99; MS (EI-MS) = 272 (M+).
3-Iodo-2-methyl-5-nitro-1H-indole (4i)
Isolated yield: 71%; mp: 180-182 oC; 1H NMR (300 MHz, CDCl3+d6-DMSO): δ
11.58 (s, 1H), 8.23-8.22 (d, 1H, J = 2.2 Hz), 8.02-7.98 (dd, 1H, J = 8.8, 11.2 Hz),
7.36-7.33 (d, 1H, J = 8.8 Hz), 2.49 (s, 3H); 13C NMR (300 MHz, CDCl3+d6-DMSO):
δ 140.91, 140.59, 139.14, 129.58, 116.31, 115.93, 110.45, 58.65, 13.60; MS
(EI-MS) = 301.95500.
3-iodo-1-phenyl-1H-indole (4j)
Isolated yield: 90%; mp: 99-102 oC; 1H NMR (400 MHz, CDCl3+d6-DMSO): δ 7.62-7.48
(m, 7H), 7.57 (s, 1H), 7.35-7.30 (m, 1H), 7.25-7.16 (m, 2H),; 13C NMR (400 MHz, CDCl3+d6-
DMSO): δ 168.49, 139.44132.89, 129.80, 128.81, 127.73, 126.87, 122.59, 120.45, 119.61,
117.70, 117.30, 109.74, 50.15; MS (EI-MS) = 318 (M+), HRMS (EI-HRMS) =calcd for
C14H10BrIN= 318.9850, found = 318.9857.
1-benzyl-3-iodo-1H-indole (4k) 11
Isolated yield: 82%; mp: 77-80 oC; 1H NMR (500 MHz, CDCl3+d6-DMSO): δ 7.58-7.56
(d, 1H, J = 7.8 Hz), 7.33 (s, 1H), 7.29-7.24 (m, 5H), 7.20-7.17 (m, 1H), 7.13-7.10 (m, 3H),
5.26 (s, 2H); 13C NMR (400 MHz, CDCl3+d6-DMSO): δ 168.58, 137.25, 133.39, 129.80,
NH
I
4i
O2N
4h
NH
IMeO
N
I
4j
N
I
4k
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12
128.81, 127.73, 126.87, 122.59, 120.45, 119.61, 117.70, 117.30, 109.74, 50.15, 29.73; MS (EI-MS): 333
(M+).
3-iodo-1-methyl-2-phenyl-1H-indole (4l) 6
Isolated yield: 94%; 1H NMR (500 MHz, CDCl3+d6-DMSO): δ 7.51-7.43 (m, 6H), 7.30-
7.28 (m, 2H), 7.24-7.19 (m, 1H), 3.64 (s, 3H); 13C NMR (400 MHz, CDCl3+d6-DMSO):
δ 141.81, 137.84, 131.70, 131.00, 130.65, 130.46, 128.88, 128.74, 128.51, 123.00, 121.54,
120.81, 109.95, 58.98, 32.10; MS(EI-MS) = 333(M+).
3-iodo-1-methyl-1H-indole (4m) 13
Isolated yield: 94%; 1H NMR (500 MHz, CDCl3+d6-DMSO): δ 7.43-7.41 (d, 1H, J = 7.8
Hz), 7.24-7.23 (m, 2H), 7.19-7.15 (m, 1H), 7.03 (s, 1H), 3.69 (s, 3H); 13C NMR (500 MHz,
CDCl3+d6-DMSO): δ 136.82, 132.77, 130.46, 122.68, 121.18, 120.31, 109.47, 54.81, 33.15;
MS (EI-MS) = 256 (M+).
2-chloro-1H-imidazole (5a) 14
Isolated yield: 88%; 1H NMR (400 MHz, CDCl3): δ 11.81 (s, 1H), 7.84 (s, 1H), 7.09 (s, 1H); 13C NMR (400 MHz, CDCl3): δ 177.74, 134.60, 120.99; MS (EI-MS) =102 (M+).
2-chloro-1H-imidazole (5b) 15
5a
NH
N
Cl
N
I
4l
N
I
4m
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13
Isolated yield: 90%; 1H NMR (400 MHz, CDCl3): δ 11.69 (s, 1H), 7.78 (s, 1H), 7.09 (s,
1H); 13C NMR (400 MHz, CDCl3): δ 177.82, 134.80, 121.28; MS (EI-MS) =145 (M+).
4. 1H NMR and 13C NMR Spectra of the Products
1H NMR and 13C NMR Spectra of Compound 2a
5b
NH
N
Br
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14
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
3.64
1.43
1.34
1.00
7.18
7.19
7.23
7.26
7.28
7.36
7.39
7.63
7.66
8.10
0102030405060708090100110120130f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
75.6
976
.01
76.3
2
105.
57
110.
44
117.
2611
9.44
119.
7912
2.10
124.
38
133.
94
1H NMR and 13C NMR Spectra of Compound 2b
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15
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-2E+08
0
2E+08
4E+08
6E+08
8E+08
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
2E+09
2E+09
3E+09
3E+09
1.14
1.11
2.38
1.00
6.89
6.90
6.91
6.92
6.94
6.94
7.13
7.13
7.18
7.18
7.19
7.20
7.21
7.21
7.22
8.01
6.906.957.007.057.107.157.207.25f1 (ppm)
0
5E+08
1.14
1.11
2.38
6.89
6.90
6.91
6.92
6.94
6.94
7.13
7.13
7.18
7.18
7.19
7.20
7.21
7.21
7.22
0102030405060708090100110120130140150160f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
76.8
077
.05
77.3
1
103.
2610
3.46
106.
5311
1.74
111.
9511
2.37
112.
44
122.
6112
5.84
125.
92
131.
47
157.
3615
9.24
1H NMR and 13C NMR Spectra of Compound 2c
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16
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.5f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
2.43
1.65
1.12
1.00
7.18
7.18
7.19
7.20
7.21
7.25
7.26
7.28
7.61
7.61
8.09
0102030405060708090100110120130140150f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
76.7
477
.06
77.3
8
106.
21
112.
61
117.
89
122.
2212
3.64
126.
4212
6.48
133.
32
1H NMR and 13C NMR Spectra of Compound 2d
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17
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
1.19
1.09
1.27
1.21
1.00
7.19
7.19
7.21
7.21
7.25
7.25
7.26
7.29
7.30
7.56
7.57
8.22
0102030405060708090100110120130140150f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+0876.7
777
.09
77.4
1
106.
01
113.
0411
3.81
120.
9612
2.09
126.
1612
7.06
133.
59
1H NMR and 13C NMR Spectra of Compound 2e
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18
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
2.30
1.50
0.96
1.00
7.13
7.15
7.26
7.48
7.50
7.98
8.18
0102030405060708090100110120130140150f1 (ppm)
-2E+07
0
2E+07
4E+07
6E+07
8E+07
1E+08
1E+08
1E+08
2E+08
2E+08
2E+08
2E+08
2E+08
3E+08
3E+08
3E+0860.4
6
76.7
377
.05
77.2
577
.36
83.8
3
113.
42
121.
63
127.
2812
7.80
131.
5713
4.07
1H NMR and 13C NMR Spectra of Compound 2f
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19
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-2E+07
0
2E+07
4E+07
6E+07
8E+07
1E+08
1E+08
1E+08
2E+08
2E+08
2E+08
2E+08
2E+08
3E+08
3E+08
3E+08
3E+08
3E+08
4E+08
4E+08
1.08
1.18
1.09
0.83
1.00
7.26
7.35
7.36
7.42
7.45
8.16
8.16
8.18
8.18
8.49
8.63
8.63
0102030405060708090100110120130140150f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+0838
.27
38.5
538
.83
39.1
039
.38
39.6
639
.94
76.5
777
.00
77.2
077
.43
103.
14
110.
65
115.
8411
6.67
126.
2812
7.49
138.
4914
0.32
1H NMR and 13C NMR Spectra of Compound 2g
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20
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
3.00
1.44
1.35
1.57
1.39
1.11
7.09
7.09
7.11
7.11
7.15
7.16
7.26
7.28
7.45
8.00
0102030405060708090100110120130140150f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
21.4
4
76.7
377
.04
77.3
6
106.
04
111.
16
117.
7812
0.87
124.
8412
5.60
129.
95
133.
34
1H NMR and 13C NMR Spectra of Compound 2h
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21
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
8E+08
8E+08
3.00
0.91
0.91
1.58
0.85
3.89
6.89
6.89
6.91
6.91
6.99
7.00
7.20
7.20
7.25
7.26
7.27
8.10
0102030405060708090100110120130140150160f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+0829
.72
76.7
877
.04
77.2
9
99.2
7
106.
14
112.
4311
3.98
121.
32
125.
79
129.
99
154.
87
1H NMR and 13C NMR Spectra of Compound 2i
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22
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
3.00
0.96
0.90
0.74
0.75
2.49
7.26
7.31
7.33
8.08
8.11
8.28
8.50
0102030405060708090100110120130140150f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+0911.5
1
38.3
638
.64
38.9
239
.20
39.4
839
.75
40.0
3
76.5
677
.00
77.4
0
89.9
1
110.
4911
3.82
116.
07
126.
19
136.
5813
7.62
140.
70
1H NMR and 13C NMR Spectra of Compound 2j
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23
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
0.89
2.91
1.00
5.01
1.59
7.16
7.17
7.18
7.20
7.20
7.22
7.23
7.24
7.25
7.26
7.33
7.34
7.35
7.35
7.36
7.36
7.37
7.49
7.50
7.51
7.51
7.53
7.55
7.58
7.60
7.62
7.507.557.60f1 (ppm)
0
1E+08
2E+08
3E+08
5.01
1.59
7.49
7.50
7.51
7.51
7.53
7.55
7.58
7.60
7.62
0102030405060708090100110120130140150160170180190200f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
93.5
9
113.
06
127.
0112
7.75
129.
3313
0.51
132.
1513
2.79
138.
2814
0.52
164.
56
200.
10
1H NMR and 13C NMR Spectra of Compound 3a
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24
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
3.00
1.26
1.23
0.93
7.18
7.21
7.23
7.24
7.26
7.28
7.37
7.39
7.58
7.61
8.19
0102030405060708090100110120130140150f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2E+0976.7
977
.05
77.3
0
106.
09
112.
9811
3.83
121.
0212
2.03
126.
1812
7.09
133.
60
1H NMR and 13C NMR Spectra of Compound 3b
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25
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
3.77
1.10
1.00
7.15
7.17
7.19
7.21
7.21
7.23
7.24
7.26
7.26
7.53
7.53
8.45
7.157.257.357.457.55f1 (ppm)
0
1E+07
2E+07
3E+07
4E+07
5E+07
6E+07
3.77
1.10
7.15
7.17
7.19
7.21
7.21
7.23
7.24
7.26
7.26
7.53
7.53
0102030405060708090100110120130140150f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+0876.8
277
.08
77.3
3
112.
8311
4.12
123.
6912
6.13
128.
8712
9.69
131.
6213
4.41
139.
42
1H NMR and 13C NMR Spectra of Compound 3c
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26
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
2.26
1.27
1.13
1.00
7.19
7.19
7.21
7.21
7.25
7.25
7.26
7.29
7.30
7.56
7.57
8.22
7.207.257.307.357.407.457.507.557.60f1 (ppm)
0
1E+08
2E+08
3E+08
2.26
1.27
1.13
7.19
7.19
7.21
7.21
7.25
7.25
7.26
7.29
7.30
7.56
7.57
0102030405060708090110130150f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
Inte
nsi
ty
76
.79
77
.11
77
.42
10
2.4
3
11
2.0
7
12
0.1
51
22
.35
12
5.4
91
25
.62
12
8.9
91
34
.17
1H NMR and 13C NMR Spectra of Compound 3d
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27
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2.24
1.00
0.95
0.81
7.21
7.22
7.22
7.24
7.25
7.31
7.31
7.33
7.34
7.72
7.72
8.21
7.207.247.287.327.36f1 (ppm)
0
2E+08
4E+08
6E+08
2.24
1.00
7.21
7.22
7.22
7.24
7.25
7.31
7.31
7.33
7.34
0102030405060708090100110120130140150f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+0976.7
577
.07
77.3
8
90.9
9
112.
9111
3.99
121.
9012
4.55
126.
1912
8.59
133.
98
1H NMR and 13C NMR Spectra of Compound 3e
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28
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2.35
1.19
1.06
1.00
7.14
7.17
7.19
7.20
7.26
7.49
7.49
7.51
7.51
7.93
7.93
7.93
8.25
7.207.307.407.50f1 (ppm)
0
1E+08
2E+08
2.35
1.19
7.14
7.17
7.19
7.20
7.26
7.49
7.49
7.51
7.51
0102030405060708090110130150f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
Inte
nsi
ty
76
.73
77
.05
77
.36
84
.04
90
.69
11
3.3
1
12
4.1
11
28
.19
12
9.3
01
31
.62
13
4.4
5
1H NMR and 13C NMR Spectra of Compound 3f
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29
0.01.02.03.04.05.06.07.08.09.010.011.012.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
2.46
1.08
0.96
1.00
7.16
7.17
7.21
7.24
7.28
7.79
7.83
8.19
11.3
1
6.97.07.17.27.37.4f1 (ppm)
0
1E+08
2E+08
3E+08
2.46
7.16
7.17
7.21
7.24
7.28
0102030405060708090100110120130140150f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
38.6
138
.88
39.1
639
.44
39.7
239
.99
40.2
7
76.5
776
.67
77.0
077
.10
77.4
277
.53
91.6
1
111.
6911
5.48
117.
04
125.
6012
6.99
138.
20
141.
20
1H NMR and 13C NMR Spectra of Compound 3g
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30
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
3.00
0.95
0.88
1.04
0.93
0.85
7.06
7.06
7.08
7.08
7.18
7.19
7.25
7.26
7.27
7.36
8.14
7.107.207.30f1 (ppm)
0
5E+07
1E+08
2E+08
0.95
0.88
1.04
0.93
7.06
7.06
7.08
7.08
7.18
7.19
7.25
7.26
7.27
7.36
0102030405060708090100110120130140150f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
21.4
8
76.8
377
.08
77.3
4
102.
13
110.
70
120.
3812
3.65
124.
2712
8.18
129.
03
134.
15
1H NMR and 13C NMR Spectra of Compound 3h
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31
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
3.00
1.87
0.87
0.85
3.92
6.92
6.92
6.93
6.94
7.02
7.02
7.23
7.23
7.28
7.29
7.30
6.957.057.157.257.35f1 (ppm)
0
1E+08
2E+08
1.87
0.87
6.92
6.92
6.93
6.94
7.02
7.02
7.23
7.23
7.28
7.29
7.30
0102030405060708090100110120130140150160f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
8E+08
55.5
4
76.8
577
.10
77.3
6
102.
40
111.
7811
2.39
124.
9512
8.34
131.
0313
1.14
154.
24
1H NMR and 13C NMR Spectra of Compound 3i
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32
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.5f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
3.23
1.15
1.13
1.08
1.00
3.14
7.36
7.39
7.97
8.01
8.31
11.6
0
0102030405060708090100110120130140150f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
11.5
1
38.3
638
.64
38.9
239
.20
39.4
839
.75
40.0
3
76.5
677
.00
77.4
0
89.9
1
110.
4911
4.01
116.
07
126.
19
136.
5813
7.62
140.
70
1H NMR and 13C NMR Spectra of Compound 3j
![Page 33: Supporting Information · 1 Supporting Information PhI(OAc)2/NaX-mediated Halogenation Providing Access to Valuable Synthons 3- Haloindole derivatives Vittam Himabindua,b, Sai Prathima](https://reader036.fdocuments.us/reader036/viewer/2022063008/5fbc70a78b3ede675918cf37/html5/thumbnails/33.jpg)
33
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
8E+08
8E+08
1.09
1.15
1.58
7.00
6.79
6.80
7.12
7.14
7.16
7.25
7.26
7.27
7.28
7.42
7.44
7.45
7.47
7.48
7.53
7.54
7.56
0102030405060708090100110120130140150160170180f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
76.7
377
.05
77.3
7
110.
10
123.
8312
5.98
126.
3612
6.44
128.
5412
9.78
130.
3313
3.83
143.
94
171.
73
1H NMR and 13C NMR Spectra of Compound 3k
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34
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2.28
2.96
6.79
1.00
5.28
7.11
7.13
7.17
7.17
7.19
7.19
7.20
7.21
7.22
7.22
7.24
7.27
7.29
7.30
7.32
7.33
7.57
7.57
7.58
7.59
7.59
7.59
7.60
0102030405060708090100110120130140150f1 (ppm)
-2E+07
0
2E+07
4E+07
6E+07
8E+07
1E+08
1E+08
1E+08
2E+08
2E+08
2E+08
2E+08
2E+08
3E+08
3E+08
3E+08
3E+08
3E+0850.3
7
76.7
577
.07
77.3
8
90.3
6
109.
93
119.
4712
0.39
122.
8812
6.97
127.
0812
7.56
127.
9412
8.92
135.
9413
6.79
1H NMR and 13C NMR Spectra of Compound 3l
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35
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
3.20
1.17
2.16
5.10
1.00
3.63
7.22
7.23
7.24
7.27
7.29
7.31
7.32
7.34
7.44
7.49
7.49
7.50
7.60
7.62
7.257.357.457.557.65f1 (ppm)
0
5E+07
1E+08
2E+08
1.17
2.16
5.10
1.00
7.22
7.23
7.24
7.27
7.29
7.31
7.32
7.34
7.44
7.49
7.49
7.50
7.60
7.62
0102030405060708090100110120130140150f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
32.1
0
58.9
8
76.8
377
.15
77.3
677
.47
109.
95
120.
8112
1.54
123.
0012
8.51
128.
7412
8.88
130.
4613
1.00
131.
7013
7.84
141.
81
1H NMR and 13C NMR Spectra of Compound 4a
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36
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
3.00
0.93
0.94
0.82
7.19
7.19
7.21
7.22
7.22
7.23
7.23
7.24
7.24
7.25
7.26
7.26
7.34
7.35
7.45
7.47
8.28
7.157.207.257.307.357.407.457.50f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
3.00
0.93
0.94
7.19
7.19
7.21
7.22
7.22
7.23
7.23
7.24
7.24
7.25
7.26
7.26
7.34
7.35
7.45
7.47
1H NMR and 13C NMR Spectra of Compound 4b
0102030405060708090100110120130140150f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
57.6
4
76.7
577
.07
77.3
9
111.
28
120.
8512
1.05
123.
23
128.
4212
9.83
135.
65
![Page 37: Supporting Information · 1 Supporting Information PhI(OAc)2/NaX-mediated Halogenation Providing Access to Valuable Synthons 3- Haloindole derivatives Vittam Himabindua,b, Sai Prathima](https://reader036.fdocuments.us/reader036/viewer/2022063008/5fbc70a78b3ede675918cf37/html5/thumbnails/37.jpg)
37
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-2E+08
0
2E+08
4E+08
6E+08
8E+08
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
2E+09
2E+09
3E+09
3E+09
3E+09
1.13
1.13
2.16
1.00
6.97
6.98
6.99
7.00
7.01
7.01
7.12
7.12
7.14
7.14
7.26
7.29
7.30
7.31
7.31
7.32
8.35
0102030405060708090100110120130140150160170f1 (ppm)
-2E+07
0
2E+07
4E+07
6E+07
8E+07
1E+08
1E+08
1E+08
2E+08
2E+08
2E+08
2E+08
2E+08
3E+08
3E+08
3E+08
3E+08
3E+0857.0
157
.05
76.7
977
.04
77.3
0
106.
0710
6.27
111.
7411
1.95
112.
0811
2.16
130.
1113
0.53
130.
6113
2.14
157.
6915
9.57
1H NMR and 13C NMR Spectra of Compound 4c
![Page 38: Supporting Information · 1 Supporting Information PhI(OAc)2/NaX-mediated Halogenation Providing Access to Valuable Synthons 3- Haloindole derivatives Vittam Himabindua,b, Sai Prathima](https://reader036.fdocuments.us/reader036/viewer/2022063008/5fbc70a78b3ede675918cf37/html5/thumbnails/38.jpg)
38
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.5f1 (ppm)
-2E+08
0
2E+08
4E+08
6E+08
8E+08
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
2E+09
2E+09
1.10
2.51
1.09
1.00
7.18
7.19
7.20
7.21
7.26
7.28
7.30
7.30
7.31
7.45
7.45
8.38
7.207.257.307.357.407.45f1 (ppm)
0
2E+08
4E+08
6E+08
8E+08
1.10
2.51
1.09
7.18
7.19
7.20
7.21
7.26
7.28
7.30
7.30
7.31
7.45
7.45
0102030405060708090100110120130140f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
56.7
5
76.7
377
.05
77.3
6
112.
37
120.
6612
3.66
126.
7512
9.75
131.
0513
4.08
1H NMR and 13C NMR Spectra of Compound 4d
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39
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.5f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
1.11
1.82
1.12
1.00
6.81
6.82
6.84
6.85
6.87
6.88
7.09
7.10
7.12
7.13
7.14
7.15
7.23
7.25
7.26
7.28
10.6
0
6.86.97.07.17.27.3f1 (ppm)
0
2E+08
4E+08
6E+08
8E+08
1.11
1.82
1.12
6.81
6.82
6.84
6.85
6.87
6.88
7.09
7.10
7.12
7.13
7.14
7.15
7.23
7.25
7.26
7.28
0102030405060708090100110120130140f1 (ppm)
-2E+07
0
2E+07
4E+07
6E+07
8E+07
1E+08
1E+08
1E+08
2E+08
2E+08
2E+08
2E+08
2E+08
3E+08
3E+08
3E+08
3E+08
3E+0876.7
277
.04
77.3
6
103.
50
112.
3411
4.09
122.
5912
5.94
128.
8713
0.97
131.
46
1H NMR and 13C NMR Spectra of Compound 4e
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40
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
1.07
1.09
2.01
1.00
0.00
6.97
6.98
6.99
7.00
7.01
7.01
7.12
7.12
7.14
7.14
7.26
7.29
7.30
7.31
7.31
7.32
8.35
0102030405060708090100110120130140150f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
56.3
3
76.7
777
.08
77.4
0
84.2
8
113.
22
129.
2012
9.98
131.
6413
2.30
134.
84
1H NMR and 13C NMR Spectra of Compound 4f
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41
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.5f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
2.19
1.04
0.92
1.00
7.51
7.52
7.52
7.54
8.08
8.09
8.11
8.12
8.38
11.7
3
0102030405060708090100110120130140150f1 (ppm)
-1E+07
0
1E+07
2E+07
3E+07
4E+07
5E+07
6E+07
7E+07
8E+07
9E+07
1E+08
1E+08
1E+08
1E+08
1E+08
2E+08
38.0
638
.34
38.6
238
.90
39.1
839
.46
39.7
3
56.8
7
76.5
777
.00
77.4
4
111.
27
116.
51
128.
26
131.
88
138.
4514
0.79
143.
91
1H NMR and 13C NMR Spectra of Compound 4g
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42
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
3.38
1.00
3.56
0.76
2.51
7.08
7.08
7.11
7.11
7.26
7.27
7.28
7.29
8.28
0102030405060708090100110120130140150160f1 (ppm)
-2E+07
0
2E+07
4E+07
6E+07
8E+07
1E+08
1E+08
1E+08
2E+08
2E+08
2E+08
2E+08
2E+08
3E+08
3E+0821.4
4
57.0
7
76.8
077
.06
77.3
1
110.
98
120.
58
124.
8812
8.43
129.
9713
0.33
133.
94
1H NMR and 13C NMR Spectra of Compound 4h
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43
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
3.00
0.95
3.23
0.87
3.88
6.88
6.89
6.91
6.92
7.04
7.05
7.13
7.14
7.22
7.25
7.98
0102030405060708090100110120130140150160f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+0830
.99
55.9
0
76.7
677
.08
77.3
9
102.
41
111.
7411
2.39
124.
9012
8.32
130.
99
154.
23
1H NMR and 13C NMR Spectra of Compound 4i
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44
0.01.02.03.04.05.06.07.08.09.010.011.012.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
8E+08
3.34
1.07
1.05
0.94
1.00
2.49
7.33
7.36
7.98
8.02
8.23
8.23
11.5
8
0102030405060708090100110120130140150f1 (ppm)
-2E+07
0
2E+07
4E+07
6E+07
8E+07
1E+08
1E+08
1E+08
2E+08
2E+08
2E+08
2E+08
2E+08
3E+08
3E+08
3E+08
13.6
0
38.4
638
.74
39.0
139
.29
39.5
739
.85
40.1
3
58.6
5
76.5
777
.00
77.4
3
110.
45
115.
9311
6.31
129.
58
139.
1414
0.59
140.
91
1H NMR and 13C NMR Spectra of Compound 4j
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45
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
2.26
1.01
7.00
7.16
7.18
7.20
7.21
7.22
7.23
7.25
7.30
7.31
7.33
7.34
7.35
7.48
7.49
7.52
7.54
7.57
7.60
7.62
7.157.207.257.307.357.407.457.507.557.607.65f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
2.26
1.01
7.00
7.16
7.18
7.20
7.21
7.22
7.23
7.25
7.30
7.31
7.33
7.34
7.35
7.48
7.49
7.52
7.54
7.57
7.60
7.62
0102030405060708090110130150170f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
Inte
nsit
y
76.7
477
.05
77.3
7
110.
6111
7.05
117.
8512
0.44
123.
2712
4.45
126.
5112
9.65
131.
5413
2.89
139.
44
168.
41
1H NMR and 13C NMR Spectra of Compound 4k
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46
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
2.21
3.16
1.15
4.53
0.95
1.00
5.26
7.10
7.12
7.13
7.13
7.17
7.19
7.20
7.24
7.26
7.27
7.29
7.30
7.33
7.56
7.58
7.107.157.207.257.307.35f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3.16
1.15
4.53
0.95
7.10
7.12
7.13
7.13
7.17
7.19
7.20
7.24
7.26
7.27
7.29
7.30
7.33
0102030405060708090100110120130140150160170f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+0829.7
3
50.1
5
76.7
377
.05
77.3
7
109.
74
117.
3011
7.70
119.
6112
0.45
122.
5912
6.87
127.
7312
8.81
129.
8013
3.39
137.
25
168.
58
1H NMR and 13C NMR Spectra of Compound 4l
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47
0102030405060708090100110120130140150f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
32.1
0
58.9
8
76.8
377
.15
77.3
677
.47
109.
95
120.
8112
1.54
123.
0012
8.51
128.
7412
8.88
130.
4613
1.00
131.
7013
7.84
141.
81
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.5f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
8E+08
8E+08
8E+08
3.00
1.36
1.95
6.05
3.64
7.19
7.20
7.21
7.21
7.22
7.23
7.23
7.24
7.28
7.28
7.29
7.30
7.43
7.44
7.45
7.46
7.47
7.49
7.51
7.207.257.307.357.407.457.50f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
1.36
1.95
6.05
7.19
7.20
7.21
7.21
7.22
7.23
7.23
7.24
7.28
7.28
7.29
7.30
7.43
7.44
7.45
7.46
7.47
7.49
7.51
1H NMR and 13C NMR Spectra of Compound 4m
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48
0102030405060708090100110120130140150f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
8E+08
8E+08
8E+08
33.1
5
54.8
1
76.8
477
.09
77.3
5
109.
47
120.
3112
1.18
122.
68
130.
4613
2.77
136.
82
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
3.00
0.99
1.05
1.91
1.02
3.69
7.15
7.16
7.17
7.17
7.18
7.19
7.19
7.23
7.23
7.24
7.24
7.24
7.24
7.41
7.43
7.057.157.257.357.45f1 (ppm)
0
5E+07
1E+08
0.99
1.05
1.91
1.02
7.15
7.16
7.17
7.17
7.18
7.19
7.19
7.23
7.23
7.24
7.24
7.24
7.24
7.41
7.43
1H NMR and 13C NMR Spectra of Compound 5a
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49
0.01.02.03.04.05.06.07.07.58.59.510.511.5f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
7.09
7.84
11.8
1
0102030405060708090100110120130140150160170180f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
8E+08
8E+08
8E+0876.8
477
.10
77.3
5
120.
99
134.
60
177.
74
1H NMR and 13C NMR Spectra of Compound 5b
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50
0.01.02.03.04.05.06.07.08.09.010.011.012.013.0f1 (ppm)
-2E+08
0
2E+08
4E+08
6E+08
8E+08
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
2E+09
2E+09
3E+09
3E+09
3E+09
3E+09
Inte
nsity
1.12
0.57
1.00
7.09
7.78
11.6
9
0102030405060708090100110120130140150160170180190f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2E+09
76.7
977
.10
77.4
2
121.
28
134.
80
177.
82
5. References:
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1) J. Yan, T. Ni, F. Yan, Tetrahedron Lett., 2015, 56, 1096-1098.2) M. Largeron, B. Farrell, J. F. Rousseau, M. B. Fleury, P. Potier, R. H. Dodd, Tetrahedron Lett.,2000,
41, 9403-9406.3) T. Guney, J. J. Lee, G.A. Kraus, Org. Lett,. 2014, 16,1124-1127.4) Jing Zhao, Xiuzhi Cheng, Jun Le, Wei Yang, FengtianXue, Xuan Zhang and Chao Jiang., Org. Biomol.
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