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Electronic Supplementary Information

Brønsted Acidic Reduced Graphene Oxide as a Sustainable Carbocatalyst: A Selective Method for the Synthesis of C-2

Substituted Benzimidazole

Murugan Karthik, Palaniswamy Suresh*

Supramolecular and Catalysis Lab, Dept. of Natural Products Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai-625021, India

*[email protected], [email protected]

Table of Contents

1. Synthesis and Characterization of G-SO3H Catalyst 2

2. Pyridine adsorption study 5

3. LC-MS Analysis 6

4. NMR and Mass data 7

5. NMR spectra of isolated compounds from 4a – 4v 12

6. Mass spectra of isolated compounds from 4a – 4v 34

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

mailto:*[email protected]

1. Synthesis of Reduced Graphene Oxide (RGO)

Graphene oxide (GO) was prepared by modified Hummers and Offmann method.2

In a typical synthesis, 2.5 g of graphite powder was added to 115 mL of concentrated

H2SO4 in an ice bath. Then, NaNO3 (2.5 g) and KMnO4 (15.0 g) were added gradually

under stirring, and the temperature of the mixture was kept below 5 ºC, and the

mixture was stirred for 4 h. After that, the mixture was stirred at room temperature for

12 h, and then diluted with 200 mL of double distilled (DD) water by keeping the

mixture in an ice bath. After adding 500 mL of DD water, the mixture was transferred

to an oil bath and maintained at 98 ºC for 1 h. Then the reaction was terminated by

adding 15 mL of 30 % H2O2 aqueous solution followed by 5 % HCl solution to

remove sulfate. Finally, the resulting graphite oxide was repeatedly washed with DD

water and then dialyzed for three days to remove residual salts and acids with

periodically changing the water. Then it was dried in a vacuum oven at 45 ºC for 24 h

to obtain graphite oxide. Before using it in reactions, it was exfoliated by sonication in

water gave graphene oxide (GO). The resulting GO suspension (400 mL, 1.0 mg/mL

in DD H2O) was reduced with Sodium borohydride (0.960 g) at 100 ºC for 24 h

followed by washing with deionized water several times. The obtained black

precipitate was dialyzed for 24 h to get a purified reduced graphene oxide.

2. Characterization of G-SO3H

Fig. S1 FT-IR Spectra a) GO, b) RGO, c) G-SO3H

Fig. S2 PXRD Pattern of a) GO, b) RGO, c) G-SO3H

Fig. S3 Raman spectra of a) GO, b) RGO, c) G-SO3H

Fig.S4 SEM Images of a) GO b) RGO c) G-SO3H

Fig.S5 SEM elemental mapping of a) G-SO3H, b) C, c) O, d) S

Fig. S6 TEM images of a) GO, b) RGO, c & d) G-SO3H

(a) (b)

(c) (d)

3. Pyridine Absorption Study

Synthesis of Graphene Sulfonic Acid-Pyridine (G-SO3H-Py)

G-SO3H (20 mg) was dispersed in 2 mL of 1,4-dioxane via sonication. Then 2 mL (0.025 mol) of pyridine was added dropwise to the dispersed solution. The resulting mixture was sonicated for 1 h and further allow to vigorous stirring for 24 h at room temperature. The resulting black precipitate was separated by centrifugation and washed with excess of dichloromethane, dried under vacuum at 60 °C for further use. The resulting pyridine chemisorbed graphene sulfonic acid was denoted as G-SO3H-Py.

General Procedure for G-SO3H-Py Catalysed Benzimidazole Synthesis

In a typical procedure 6 mg of G-SO3H-Py catalyst was dispersed in 2 mL of 1,4-dioxane under sonication. Then 0.5 mmol of the benzen-1,2-diamine was added followed by the addition of 0.5 mmol of benzaldehyde and allowed to stir at room temperature. The progress of the reaction was monitored by TLC.

4. LC-MS Analysis of Products

In the present work, benzimidazole was synthesised through the condensation between benzene-1,2-diamine (0.5 mmol, 1eq) and benzaldehyde (0.5 mmol, 1eq) using G-SO3H as a Brønsted acid catalyst in 2 mL of 1,4-dioxane at 80 °C. The course of the reaction was monitored through LC-MS analysis using UV-vis. and ESI-Mass detectors. Due to the poor stability of the diimine, analysis and its formation was confirmed using LC-MS analysis. One of the representative HPLC chromatogram and corresponding ESI- mass spectra are given below. (Table-1, Entry 11).

Fig. S7 LC-MS chromatogram of crude product

N

HN

N

N

MKK-154 #990-1043 RT: 14.26-15.02 AV: 54 SB: 2573 1.39-20.29 , 21.72-39.87 NL: 5.60E3T: ITMS + c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

194.96

91.99 312.18235.51133.03 338.99177.00 278.95 450.97 472.70410.32388.3264.10

Fig. S8 Mass of 2-Phenyl-1H-benzo[d]imidazole at RT -14.3 min

MKK-154 #1406-1470 RT: 20.25-21.17 AV: 65 SB: 2573 1.39-20.29 , 21.72-39.87 NL: 1.08E3T: ITMS + c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

285.02

99.52

312.18214.08 242.0758.95 387.90180.85113.13 362.21 443.06139.88 476.68326.17 424.61258.12

Fig. S9 Mass of (1E,1'E)-N,N'-(1,2-Phenylene)bis(1-phenylmethanimine) at RT -20.3 min

N

HN

Molecular Weight: 194.24(M+1)

N

N

Molecular Weight: 284.36(M+1)

NMR and Mass data

2-phenyl-1H-benzo[d]imidazole (4a)

1H NMR (300 MHz, CDCl3+DMSO) δ: 12.65 (s, 1H), 8.19 (d, J = 6.9 Hz, 2H), 7.69 (s, 1H), 7.49 (dd, J = 14.9, 7.3 Hz, 4H), 7.21 (dd, J = 5.8, 2.9 Hz, 2H). (Fig. S10)13C NMR (75 MHz, CDCl3+DMSO) δ: 150.51, 129.10, 128.50, 127.51, 125.44, 121.32, 120.49, 117.65. (Fig. S11)Mass (ESI): 194.06 (M+1) (Fig. S54)2-(p-tolyl)-1H-benzo[d]imidazole (4b)

1H NMR (400 MHz, DMSO) δ: 12.81 (s, 1H), 8.06 (d, J = 8.4 Hz, 2H), 7.64 (d, J = 6.8, Hz, 1H), 7.50 (d, J = 6.8, Hz, 1H), 7.35 (d, J = 8.6 Hz, 2H), 7.19 (d, J = 5.2 Hz, 2H), 2.46 (s, 3H). (Fig. S12)13C NMR (100 MHz, DMSO) δ: 151.86, 144.32, 140.00, 135.43, 129.96, 127.94, 126.86, 122.78, 122.01, 119.18, 111.64, 21.43. (Fig. S13)Mass (ESI): 207.12 (M-1) (Fig. S55)2-(4-isopropylphenyl)-1H-benzo[d]imidazole (4c)

1H NMR (300 MHz, DMSO) δ: 12.85 (s, 1H), 8.10 (d, J = 8.2 Hz, 2H), 7.64 (d, J = 7.1 Hz, 1H), 7.51 (d, J = 6.8 Hz, 1H), 7.42 (d, J = 8.2 Hz, 2H), 7.18 (dd, J = 5.6, 3.1 Hz, 2H), 2.96 (dt, J = 13.7, 6.9 Hz, 1H), 1.24 (d, J = 6.9 Hz, 6H). (Fig. S14)13C NMR (75 MHz, DMSO) δ: 151.42, 150.39, 127.87, 126.92, 126.55, 121.70, 118.77, 111.23. (Fig. S15)Mass (ESI): 237.15 (M+1) (Fig. S56)

4-(1H-benzo[d]imidazol-2-yl)phenol (4d)

1H NMR (300 MHz, DMSO) δ: 9.99 (s, 1H), 8.00 (d, J = 8.6 Hz, 2H), 7.53 (dd, J = 5.9, 3.2 Hz, 2H), 7.15 (dd, J = 6.0, 3.2 Hz, 2H), 6.91 (d, J = 8.6 Hz, 2H), 6.55 (s, 1H). (Fig. S16)13C NMR (75 MHz, DMSO) δ: 163.19, 159.28, 151.84, 139.28, 128.28, 121.77, 121.05, 115.79. (Fig. S17)Mass (ESI): 211.11 (M+1) (Fig. S57)

2-(4-methoxyphenyl)-1H-benzo[d]imidazole (4e)

1H NMR (400 MHz, DMSO) δ: 12.72 (s, 1H), 8.12-8.02 (m, J = 8.4, 2H), 7.61 (d, J = 6.8, Hz, 1H), 7.48 (d, J = 6.8, Hz, 1H), 7.19-7.08 (m, 4H), 3.83 (s, 3H). (Fig. S18)13C NMR (100 MHz, DMSO) δ: 161.07, 151.82, 146.70, 135.97, 128.47, 123.19, 122.86, 122.52, 121.89, 118.95, 114.83, 111.48, 55.79. (Fig. S19)Mass (ESI): 225.09 (M+1) (Fig. S58)2-(4-fluorophenyl)-1H-benzo[d]imidazole (4f)

1H NMR (300 MHz, DMSO+CDCl3) δ: 8.25-8.18 (m, 2H), 7.60 (s,

N

HN

N

HN

CH3

N

HN

OH

N

HN

OCH3

N

HN

2H), 7.24-7.17 (m, 4H), 7.16 (s, 1H). (Fig. S20)13C NMR (75 MHz, DMSO+CDCl3) δ: 164.27, 160.97, 150.16, 128.00, 127.95, 125.91, 121.38, 114.97, 114.68. (Fig. S21)Mass (ESI): 211.08 (M-1) (Fig. S59)2-(4-chlorophenyl)-1H-benzo[d]imidazole (4g)

1H NMR (300 MHz, DMSO) δ: 13.00 (s, 1H), 8.19 (d, J = 8.6 Hz, 2H), 7.68-7.62 (m, 3H), 7.53 (s, J = 8.0 Hz, 1H), 7.22 (s, 2H). (Fig. S22)13C NMR (100 MHz, DMSO) δ: 150.61, 144.24, 135.48, 134.93, 129.51, 128.59, 123.22, 122.28, 119.41, 111.87. (Fig. S23)Mass (ESI): 229.04 (M+1) (Fig. S60)2-(4-bromophenyl)-1H-benzo[d]imidazole (4h)

1H NMR (300 MHz, DMSO) δ: 13.02 (s, 1H), 8.11 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.3 Hz, 2H), 7.60 (s, 2H), 7.21 (s, 2H). (Fig. S24)13C NMR (75 MHz, DMSO) δ: 151.07, 132.83, 130.24, 129.21, 124.11. (Fig. S25) Mass (ESI): 275.03 (M+2) (Fig. S61)2-(4-nitrophenyl)-1H-benzo[d]imidazole (4i)

1H NMR (300 MHz, DMSO+CDCl3) δ: 8.44 (d, J = 9.0 Hz, 2H), 8.34 (d, J = 9.0 Hz, 2H), 7.65 (s, 2H), 7.30-7.23 (m, 2H), 4.09 (s, 1H). (Fig. S26)13C NMR (75 MHz, DMSO+CDCl3) δ: 148.22, 146.92, 138.48, 135.21, 126.41, 122.92, 122.06, 114.52. (Fig. S27)Mass (ESI): 238.10 (M-1) (Fig. S62)4-(1H-benzo[d]imidazol-2-yl)benzonitrile (4j)

1H NMR (400 MHz, DMSO) δ: 13.20 (s, 1H), 8.34 (d, J = 8.0 Hz, 2H), 8.03 (d, J = 8.0 Hz 2H), 7.7-7.6 (m, 2H), 7.26 (s, 2H). (Fig. S28)13C NMR (100 MHz, DMSO) δ: 149.83, 134.73, 133.43, 127.44, 123.69, 122.80, 119.77, 119.07, 112.34. (Fig. S29)Mass (ESI): 218.12 (M-1) (Fig. S63)3-(1H-benzo[d]imidazol-2-yl)benzonitrile (4k)

1H NMR (300 MHz, DMSO) δ: 13.11 (s, 1H), 8.55 (m, 1H), 8.51-8.47(m, 1H), 7.98-7.95 (m, 1H), 7.80-7.75 (m, 1H), 7.70 (d, J = 6.0 Hz, 1H), 7.57 (d, J = 9.0 Hz, 1H) 7.25 (s, 2H). (Fig. S30)

13C NMR (75 MHz, DMSO) δ: 149.65, 144.05,135.46, 133.54, 131.81, 131.36, 130.81, 130.18, 123.61, 122.54, 119.65, 118.85, 112.62, 112.04 (Fig. S31)Mass (ESI): 220.09 (M+1) (Fig. S64)

N

HN

Cl

HN

NBr

N

HN

NO2

N

HN

CN

N

HN

CN

N

HN

F

2-(1H-benzo[d]imidazol-2-yl)-4-bromophenol (4l)

1H NMR (300 MHz, DMSO) δ: 13.28 (s, 2H), 8.29 (d, J = 2.4 Hz, 1H), 7.73 (d, J = 6.0 Hz, 1H), 7.62 (d, J = 6.6 Hz, 1H), 7.54-7.50 (m, 1H), 7.31 (s, 2H).7.02 (d, J = 8.7 Hz, 1H). (Fig. S32)13C NMR (100 MHz, DMSO) δ: 157.59, 150.70, 134.46, 128.90, 124.06, 123.14, 119.93, 118.56, 115.11, 112.20, 110.61. (Fig. S33)Mass (ESI): 291.04 (M+2) (Fig. S65)4-(1H-benzo[d]imidazol-2-yl)-2-methylphenol (4m)

1H NMR (300 MHz, DMSO) δ: 9.91 (s, 1H), 8.13 (s, 1H), 7.91 (s, 1H), 7.81 (d, J = 8.4 Hz, 1H), 7.52 (dd, J = 5.9, 3.1 Hz, 2H), 7.14 (dd, J = 5.9, 3.1 Hz, 2H), 6.90 (d, J = 8.3 Hz, 1H), 2.20 (s, 3H). (Fig. S34)13C NMR (75 MHz, DMSO) δ: 158.28, 152.70, 139.90, 130.03, 126.41, 125.32, 122.59, 121.39, 115.74, 115.37, 16.93. (Fig. S35)Mass (ESI): 225.10 (M+1) (Fig. S66)2-(3,4-dimethoxyphenyl)-1H-benzo[d]imidazole (4n)

1H NMR (300 MHz, DMSO+CDCl3) δ: 7.84-7.72 (m, 2H), 7.57 (s, 2H), 7.19 (dd, J = 5.9, 3.1 Hz, 2H), 7.00 (d, J = 8.3 Hz, 1H), 3.94 (d, J = 10.1 Hz, 6H). (Fig. S36)13C NMR (75 MHz, DMSO+CDCl3) δ: 151.10, 149.42, 148.08, 138.53, 122.08, 121.02, 118.68, 113.77, 110.29, 109.02, 54.81. (Fig. S37)Mass (ESI): 255.27 (M+1) (Fig. S67)2-(2-chloropyridin-3-yl)-1H-benzo[d]imidazole (4o)

1H NMR (300 MHz, DMSO) δ: 8.88-8.85 (m, 1H), 7.90-7.88 (m, 1H), 7.82-7.79 (m, 2H), 7.45-7.42 (m, 2H), 6.67-6.62 (m, 1H), (Fig. S38)13C NMR (75 MHz, DMSO) δ: 160.55 146.70, 143.47, 141.47, 133.02, 125.81, 125.35, 114.84, 113.48, 106.69. (Fig. S39)Mass (ESI): 227.12 (M-2) (Fig. S68)2-(naphthalen-2-yl)-1H-benzo[d]imidazole (4p)

1H NMR (300 MHz, DMSO+CDCl3) δ: 8.72 (s, 1H), 8.33 (d, J = 10.1 Hz, 1H), 7.98 (dt, J = 16.9, 9.2 Hz, 3H), 7.71 (d, J = 8.6 Hz, 1H), 7.55 (dd, J = 9.2, 4.4 Hz, 3H), 7.27-7.16 (m, 2H). (Fig. S40)13C NMR (75 MHz, DMSO+CDCl3) δ: 149.90, 142.42, 133.55, 131.96, 131.82, 131.34, 126.72, 126.08, 125.27, 125.16, 124.35, 122.41. (Fig. S41)Mass (ESI): 243.15 (M-1) (Fig. S69)1H,1'H-2,5'-bibenzo[d]imidazole (4q)

1H NMR (300 MHz, DMSO) δ: 12.78 (s, 2H), 8.38 (s, 1H), 8.34 (s, 1H), 8.13-8.07 (m, 1H), 7.72 (d, J = 9.0 Hz, 1H), 7.59-7.56 (m, 2H), 7.21-7.16 (m, 2H). (Fig. S42)

N

HN

HO

Br

HN

N

CH3

OH

N

HN

OCH3

OCH3

N

HN N

Cl

N

HN

N

NH

HN

N

13C NMR (100 MHz, DMSO) δ: 152.76, 144.60, 124.56, 122.24, 121.34, 116.03. (Fig. S43)Mass (ESI): 235.10 (M+1) (Fig. S70)3-(1H-benzo[d]imidazol-2-yl)-5-(4-chlorophenyl)isoxazole (4r)

1H NMR (300 MHz, DMSO) δ: 13.27 (s, 1H), 8.01(d, J = 8.5 Hz, 2H) 7.73-7.62 (m, 5H), 7.29-7.26 (m, 2H). (Fig. S44)13C NMR (75 MHz, DMSO) δ: 169.57, 157.01, 142.25, 135.97, 129.91, 128.12, 125.68, 123.50, 100.61. (Fig. S45)Mass (ESI): 294.11 (M-1) (Fig. S71)1H-benzo[d]imidazole (4s)

1H NMR (300 MHz, DMSO+CDCl3) δ: 8.07 (s, 1H), 7.60 (s, 2H), 7.25-7.14 (m, 2H). (Fig. S46)13C NMR (75 MHz, DMSO+CDCl3) δ: 141.50, 138.39, 122.66, 115.80. (Fig. S47)Mass (ESI): 118.10 (M+1) (Fig. S72)2-ethyl-1H-benzo[d]imidazole (4t)

1H NMR (300 MHz, CDCl3) δ: 7.56 (dd, J = 5.9, 3.2 Hz, 2H), 7.25 (ddd, J = 17.6, 6.0, 3.1 Hz, 2H), 3.80 (s, 1H), 2.99 (q, J = 7.6 Hz, 2H), 1.41 (t, J = 7.6 Hz, 3H). (Fig. S48)13C NMR (75 MHz, CDCl3) δ: 156.18, 137.56, 122.61, 114.46 22.22, 12.22. (Fig. S49)Mass (ESI): 147.07 (M+1) (Fig. S73)2-cyclohexyl-1H-benzo[d]imidazole (4u)

1H NMR (400 MHz, CDCl3+DMSO) δ: 7.49-7.17 (m, 2H), 7.15-7.05 (m, 2H), 2.87-2.85 (m, 2H), 2.84-2.83 (m, 2H), 2.82-2.79 (m, 3H), 2.78-2.77 (m, 3H). (Fig. S50)13C NMR (75 MHz, CDCl3+DMSO) δ: 157.61, 136.87, 119.59, 112.85, 29.87, 24.16. (Fig. S51)Mass (ESI): 199.16 (M-1) (Fig. S74)2-(p-tolyl)-1H-imidazo[4,5-b]pyridine (4v)

1H NMR (300 MHz, CDCl3) δ: 8.49 (s, 1H), 7.96 (dd, J = 5.0, 1.6 Hz, 1H), 7.80 (d, J = 8.1 Hz, 2H), 7.36-7.16 (m, 3H), 6.67 (dd, J = 7.6, 5.0 Hz, 1H), 2.43 (s, 3H). (Fig. S52)13C NMR (75 MHz, CDCl3) δ: 159.37, 154.56, 145.90, 142.20, 133.42, 132.37, 129.52, 128.78, 123.32, 114.02, 21.63. (Fig. S53)Mass (ESI): 208.08 (M-1) (Fig. S75)

N

HN

N O

Cl

N

HN

H

NH

N

N N

HN

CH3

N

HN

NMR Spectrum of Substituted benzimidazole

0123456789101112131415f1 (ppm)

MKK-153

2.02

4.17

1.18

2.00

1.00

-0.0

0

2.57

3.34

7.19

7.20

7.21

7.22

7.45

7.48

7.50

7.52

7.69

7.82

8.18

8.21

12.6

5

Fig. S10 1H NMR Spectrum of 2-phenyl-1H-benzo[d]imidazole. (4a) (300 MHz, CDCl3+DMSO)

Fig. S11 13C NMR Spectrum of 2-phenyl-1H-benzo[d]imidazole (4a) (75 MHz, CDCl3+DMSO),

N

HN

N

HN

Fig. S12 1H NMR Spectrum of 2-(p-tolyl)-1H-benzo[d]imidazole (4b) (400 MHz, DMSO)

Fig. S13 13C NMR Spectrum of 2-(p-tolyl)-1H-benzo[d]imidazole (4b) (100 MHz, DMSO)

N

HN

CH3

N

HN

CH3

Fig. S14 1H NMR Spectrum of 2-(4-isopropylphenyl)-1H-benzo[d]imidazole (4c) (300 MHz, DMSO)

Fig. S15 13C NMR Spectrum of 2-(4-isopropylphenyl)-1H-benzo[d]imidazole (4c) (75 MHz, DMSO)

N

HN

N

HN

Fig. S16 1H NMR Spectrum of 4-(1H-benzo[d]imidazol-2-yl)phenol (4d) (300 MHz, DMSO)

Fig. S17 13C NMR Spectrum of 4-(1H-benzo[d]imidazol-2-yl)phenol (4d) (75 MHz, DMSO)

N

HN

OH

N

HN

OH

Fig. S18 1H NMR Spectrum of 2-(4-methoxyphenyl)-1H-benzo[d]imidazole (4e) (400 MHz, DMSO)

Fig. S19 13C NMR Spectrum 2-(4-methoxyphenyl)-1H-benzo[d]imidazole (4e) (100 MHz, DMSO)

N

HN

OCH3

N

HN

OCH3

Fig. S20 1H NMR Spectrum of 2-(4-fluorophenyl)-1H-benzo[d]imidazole (4f) (300 MHz, DMSO+CDCl3)

0102030405060708090100110120130140150160170180190200f1 (ppm)

MKK-223

38.2

738

.55

38.8

339

.11

39.3

939

.67

39.9

5

76.5

777

.00

77.4

3

114.

6811

4.97

121.

3812

5.91

127.

8912

8.00

150.

16

160.

97

164.

27

Fig. S21 13C NMR Spectrum of 2-(4-fluorophenyl)-1H-benzo[d]imidazole (4f) (75 MHz, DMSO+CDCl3)

N

HN

F

N

HN

F

Fig. S22 1H NMR Spectrum of 2-(4-chlorophenyl)-1H-benzo[d]imidazole (4g) (300 MHz, DMSO)

Fig. S23 13C NMR Spectrum of 2-(4-chlorophenyl)-1H-benzo[d]imidazole (4g) (100 MHz, DMSO)

N

HN

Cl

N

HN

Cl

Fig. S24 1H NMR Spectrum of 2-(4-bromophenyl)-1H-benzo[d]imidazole (4h) (300 MHz, DMSO)

Fig. S25 13C NMR Spectrum of 2-(4-bromophenyl)-1H-benzo[d]imidazole (4h) (75 MHz, DMSO)

HN

NBr

HN

NBr

Fig. S26 1H NMR Spectrum of 2-(4-nitrophenyl)-1H-benzo[d]imidazole (4i) (300 MHz, DMSO+CDCl3)

Fig. S27 13C NMR Spectrum of 2-(4-nitrophenyl)-1H-benzo[d]imidazole (4i) (75 MHz, DMSO+CDCl3)

N

HN

NO2

N

HN

NO2

Fig. S28 1H NMR Spectrum of 4-(1H-benzo[d]imidazol-2-yl)benzonitrile (4j) (400 MHz, DMSO)

Fig. S29 13C NMR Spectrum of 4-(1H-benzo[d]imidazol-2-yl)benzonitrile (4j) (100 MHz, DMSO)

N

HN

CN

N

HN

CN

Fig. S30 1H NMR Spectrum of 3-(1H-benzo[d]imidazol-2-yl)benzonitrile (4k) (300 MHz, DMSO)

Fig. S31 13C NMR Spectrum of 3-(1H-benzo[d]imidazol-2-yl)benzonitrile (4k) (75 MHz, DMSO)

N

HN

CN

N

HN

CN

Fig. S32 1H NMR Spectrum of 2-(1H-benzo[d]imidazol-2-yl)-4-bromophenol (4l) (300 MHz, DMSO)

Fig. S33 13C NMR Spectrum of 2-(1H-benzo[d]imidazol-2-yl)-4-bromophenol (4l) (100 MHz, DMSO)

N

HN

HO

Br

N

HN

HO

Br

Fig. S34 1H NMR Spectrum of 4-(1H-benzo[d]imidazol-2-yl)-2-methylphenol (4m) (300 MHz, DMSO)

Fig. S35 13C NMR Spectrum of 4-(1H-benzo[d]imidazol-2-yl)-2-methylphenol (4m) (75 MHz, DMSO)

HN

N

CH3

OH

HN

N

CH3

OH

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

MKK-3,4OME

6.09

0.91

1.92

1.91

2.11

0.00

2.57

3.93

3.96

6.98

7.01

7.17

7.18

7.19

7.20

7.57

7.73

7.74

7.76

7.79

7.81

Fig. S36 1H NMR Spectrum of 2-(3,4-dimethoxyphenyl)-1H-benzo[d]imidazole (4n) (300 MHz, DMSO+CDCl3)

0102030405060708090100110120130140150160170180190200f1 (ppm)

MKK-3,4OME

38.0

838

.36

38.6

438

.92

39.1

939

.47

39.7

5

54.8

1

76.5

777

.00

77.4

3

109.

0211

0.29

113.

77

118.

6812

1.02

122.

08

138.

53

148.

0814

9.42

151.

10

Fig. S37 13C NMR Spectrum of 2-(3,4-dimethoxyphenyl)-1H-benzo[d]imidazole (4n) (75 MHz, DMSO+CDCl3)

N

HN

OCH3

OCH3

N

HN

OCH3

OCH3

Fig. S38 1H NMR Spectrum of 2-(2-chloropyridin-3-yl)-1H-benzo[d]imidazole (4o) (300 MHz, DMSO)

Fig. S39 13C NMR Spectrum of 2-(2-chloropyridin-3-yl)-1H-benzo[d]imidazole (4o) (75 MHz, DMSO)

N

HN N

Cl

N

HN N

Cl

Fig. S40 1H NMR Spectrum of 2-(naphthalen-2-yl)-1H-benzo[d]imidazole (4p) (300 MHz, DMSO+CDCl3)

Fig. S41 13C NMR Spectrum of 2-(naphthalen-2-yl)-1H-benzo[d]imidazole (4p) (75 MHz, DMSO+CDCl3)

HN

N

HN

N

Fig. S42 1H NMR Spectrum of 1H,1'H-2,5'-bibenzo[d]imidazole (4q) (300 MHz, DMSO)

Fig. S43 13C NMR Spectrum of 1H,1'H-2,5'-bibenzo[d]imidazole (4q) (75 MHz, DMSO+CDCl3)

N

HN

N

NH

N

HN

N

NH

Fig. S44 1H NMR Spectrum of 3-(1H-benzo[d]imidazol-2-yl)-5-(4-chlorophenyl)isoxazole (4r) (300 MHz, DMSO)

Fig. S45 13C NMR Spectrum of3-(1H-benzo[d]imidazol-2-yl)-5-(4-chlorophenyl)isoxazole (4r) (75 MHz, DMSO)

N

HN

N O

Cl

N

HN

N O

Cl

Fig. S46 1H NMR Spectrum of 1H-benzo[d]imidazole (4s) (300 MHz, DMSO+CDCl3)

Fig. S47 13C NMR Spectrum of 1H-benzo[d]imidazole (4s) (75 MHz, DMSO+CDCl3)

N

HN

N

HN

Fig. S48 1H NMR Spectrum of 2-ethyl-1H-benzo[d]imidazole (4t) (300 MHz, CDCl3)

Fig. S49 13C NMR Spectrum of 2-ethyl-1H-benzo[d]imidazole (4t) (75 MHz, CDCl3)

NH

N

NH

N

Fig. S50 1H NMR Spectrum of 2-cyclohexyl-1H-benzo[d]imidazole (4u) (400 MHz, CDCl3+DMSO)

0102030405060708090100110120130140150160170180190200f1 (ppm)

MKK-195

24.1

024

.21

29.8

736

.52

37.3

937

.67

37.9

538

.23

38.5

138

.79

39.0

7

76.5

677

.00

77.4

4

112.

85

119.

59

136.

87

157.

61

Fig. S51 13C NMR Spectrum of 2-cyclohexyl-1H-benzo[d]imidazole (4u) (75 MHz, CDCl3+DMSO)

N

HN

N

HN

Fig. S52 1H NMR Spectrum of 2-(p-tolyl)-1H-imidazo[4,5-b]pyridine (4v) (300 MHz, CDCl3)

102030405060708090100110120130140150160170180190200f1 (ppm)

MKK-222S1

21.6

3

76.5

877

.00

77.4

2

114.

02

123.

32

128.

7812

9.52

132.

3713

3.42

142.

20

145.

90

154.

56

159.

37

Fig. S53 13C NMR Spectrum of 2-(p-tolyl)-1H-imidazo[4,5-b]pyridine (4v) (75 MHz, CDCl3)

N N

HN

CH3

N N

HN

CH3

Mass Spectrum

MKK-68-S1 #29 RT: 0.36 AV: 1 SB: 113 0.28-2.99 , 0.01-0.19 NL: 2.65E3F: ITMS + c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

195.05

191.91

119.01 138.14 261.32 403.15233.06 312.30 473.00443.01353.6595.07

Fig. S54 ESI Mass Spectrum of 2-phenyl-1H-benzo[d]imidazole (4a) (M+1)

MKK-179_140918225312 #79-119 RT: 0.99-1.51 AV: 41 SB: 55 1.23-1.80 , 0.99-1.11 NL: 5.87E1F: ITMS - c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

207.12

223.13

281.16

325.23 413.23395.31355.17191.16 297.22235.15 265.18 471.22443.1489.20 117.20 172.07

Fig. S55 ESI Mass Spectrum of 2-(p-tolyl)-1H-benzo[d]imidazole (4b) (M-1)

N

HN

CH3

Molecular Weight: 208.26

N

HN

MKK-224 #23 RT: 0.27 AV: 1 NL: 1.56E5T: ITMS + c ESI Full ms [50.00-1100.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

237.15

301.16259.10 472.91 495.05369.18 449.19221.21195.22 391.28333.07129.2792.07 171.10

Fig. S56 ESI Mass Spectrum of 2-(4-isopropylphenyl)-1H-benzo[d]imidazole (4c) (M+1)


100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

211.11

215.05317.06193.17 245.05 289.04131.11 489.14395.21339.17 423.1292.10 151.17 452.83

Fig. S57 ESI Mass Spectrum of 4-(1H-benzo[d]imidazol-2-yl)phenol (4d) (M+1)

N

HN

OH


N

HN



50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

225.09

182.12 345.10210.16121.10 248.09 447.15367.06 413.27327.16 495.45268.9592.24 156.17

Fig. S58 ESI Mass Spectrum of 2-(4-methoxyphenyl)-1H-benzo[d]imidazole (4e) (M+1)

MKK-223 #16 RT: 0.19 AV: 1 NL: 3.18E4T: ITMS - c ESI Full ms [50.00-1100.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

211.08

422.70227.01438.79247.02 484.95270.71 351.08113.17 191.32 406.89313.38133.06 372.1495.12

Fig. S59 ESI Mass Spectrum of 2-(4-fluorophenyl)-1H-benzo[d]imidazole (4f) (M-1)

N

HN

OCH3


N

HN

F


MKK-178SOLID_140918225312 #106-130 RT: 1.37-1.67 AV: 25 NL: 1.98E3T: ITMS + c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

229.04

320.18 353.06278.18194.14 413.2592.13 471.20455.23125.08 391.14156.17 499.26243.1678.63

Fig. S60 ESI Mass Spectrum of 2-(4-chlorophenyl)-1H-benzo[d]imidazole (4g) (M+1)

MKK-188_150123161459 #26 RT: 0.31 AV: 1 SB: 151 0.45-1.88 , 0.04-0.52 NL: 4.68E3T: ITMS + c ESI Full ms [50.00-1500.00]

100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

275.03

407.07

289.05

193.14 493.18442.95304.97242.30 393.20363.12220.10 465.20419.18479.17131.08 347.14

147.13 319.26104.1990.27

Fig. S61 ESI Mass Spectrum of 2-(4-bromophenyl)-1H-benzo[d]imidazole (4h) (M+1)

N

HN

Cl


N

HN

Br


MKK-194_150123161459 #46 RT: 0.53 AV: 1 NL: 1.43E4T: ITMS - c ESI Full ms [50.00-1500.00]

100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

238.10

273.85 476.68404.99340.05 428.99312.16268.12208.22 473.30192.18166.17 387.24 493.09143.16117.20

Fig. S62 ESI Mass Spectrum of 2-(4-nitrophenyl)-1H-benzo[d]imidazole (4i) (M-1)

MKK-185A_150123161459 #102 RT: 1.25 AV: 1 NL: 1.31E4T: ITMS - c ESI Full ms [50.00-1500.00]

100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

218.12

254.05 436.85199.36157.18 364.94 472.86129.23 292.16 408.62338.09 504.40101.20

Fig. S63 ESI Mass Spectrum of 4-(1H-benzo[d]imidazol-2-yl)benzonitrile (4j) (M-1)

N

HN

NO2


N

HN

CN


MKK-186_150123161459 #28 RT: 0.35 AV: 1 NL: 3.74E4T: ITMS + c ESI Full ms [50.00-1500.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

220.09

413.24344.0092.07 507.20236.09 312.42279.09 390.96 470.68180.86149.16130.11

Fig. S64 ESI Mass Spectrum of 3-(1H-benzo[d]imidazol-2-yl)benzonitrile (4k)

MKK-182_140918225312 #79-105 RT: 1.02-1.33 AV: 27 SB: 66 1.26-1.58 , 0.54-1.04 NL: 7.58E2T: ITMS + c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

291.04

475.05

377.08210.17 413.23182.16 481.13303.09 354.02 429.16131.12 225.16 449.29265.12145.1392.1570.57

Fig. S65 ESI Mass Spectrum of 2-(1H-benzo[d]imidazol-2-yl)-4-bromophenol (4l) (M+1)

N

HN

CN


N

HN

HO

Br


MKK-180_140918225312 #51-68 RT: 0.65-0.86 AV: 18 NL: 1.46E3T: ITMS + c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

225.10

313.16 419.16237.13345.14 387.21 483.23299.16207.15119.07 443.28281.21 493.26369.22251.15193.13151.1192.12

Fig. S66 ESI Mass Spectrum of 4-(1H-benzo[d]imidazol-2-yl)-2-methylphenol (4m) (M+1)

Mass-Benz #25 RT: 0.30 AV: 1 NL: 5.08E4T: ITMS + c ESI Full ms [50.00-1000.00]

100 200 300 400 500 600 700 800 900 1000m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

255.27

509.14

405.40 533.39 764.42240.34 667.48 815.68621.33 905.01 960.80277.33155.22 497.70338.47104.28

Fig. S67 ESI Mass Spectrum of 2-(3,4-dimethoxyphenyl)-1H-benzo[d]imidazole (4n) (M+1)

N

HN


CH3

OH

N

HN

OCH3

OCH3


MKK-178 #4-23 RT: 0.04-0.26 AV: 10 NL: 1.18E4F: ITMS - c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

227.12

262.91

453.06191.20 243.07 325.21 417.11277.14 359.07157.15 382.92 505.00117.1889.20

Fig. S68 ESI Mass Spectrum of 2-(2-chloropyridin-3-yl)-1H-benzo[d]imidazole (4o) (M-1)

MKK-189_150123161459 #91 RT: 1.13 AV: 1 SB: 65 0.09-0.49 , 0.72-1.14 NL: 2.12E3T: ITMS - c ESI Full ms [50.00-1500.00]

50 100 150 200 250 300 350 400 450m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

243.15

199.28 255.23233.18 275.36 403.05 492.91145.12 383.18129.18 459.52326.29 428.38102.43

Fig. S69 ESI Mass Spectrum of 2-(naphthalen-2-yl)-1H-benzo[d]imidazole (4p) (M-1)

N

HN


N

HN N

Cl



50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

235.10

365.08257.01 413.26229.26 309.12165.02 467.2192.03 331.14193.14131.08 489.04

Fig. S70 ESI Mass Spectrum of 1H,1'H-2,5'-bibenzo[d]imidazole (4q) (M+1)

MKK-199 #4-24 RT: 0.04-0.30 AV: 11 NL: 6.14E3F: ITMS - c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

294.11

329.92255.32178.12 325.24 339.24142.15 227.24 396.10 432.05 465.2389.16 117.17 481.16

Fig. S71 ESI Mass Spectrum of 3-(1H-benzo[d]imidazol-2-yl)-5-(4-chlorophenyl)isoxazole (4r) (M-1)

N

HN

N

NH


N

HN

N O

Cl


MKK-214_150401153139 #85 RT: 1.08 AV: 1 NL: 3.83E3T: ITMS + c ESI Full ms [100.00-1000.00]

100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

118.10

134.04275.12

267.01220.14

401.07146.04 289.10247.08194.07 349.19312.25 488.30430.31384.40 471.30

Fig. S72 ESI Mass Spectrum of 1H-benzo[d]imidazole (4s) (M+1)

MKK-210_150409132204 #139 RT: 1.92 AV: 1 NL: 2.16E3F: ITMS + c ESI Full ms [50.00-1000.00]

50 100 150 200 250 300 350 400 450 500m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

147.07

413.23

205.10 391.21 436.13132.08

229.18189.14 252.23 279.20329.03102.21 349.09174.96 449.78 478.2688.09

Fig. S73 ESI Mass Spectrum 2-ethyl-1H-benzo[d]imidazole (4t) (M+1)

N

HN


N

HN


Fig. S74 ESI Mass Spectrum of 2-cyclohexyl-1H-benzo[d]imidazole (4u) (M-1)

MKK-222-DCM #7-29 RT: 0.10-0.36 AV: 11 NL: 1.12E3F: ITMS - c ESI Full ms [50.00-1100.00]

100 150 200 250 300 350 400 450m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

208.08

243.98113.03 143.10 311.10 478.98239.02 255.17171.15135.02 452.63418.72325.17 343.98 394.9395.0274.83

Fig. S75 ESI Mass Spectrum of 2-(p-tolyl)-1H-imidazo[4,5-b]pyridine (4v) (M-1)

N N

HN


CH3

N

HN


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