Electronic Supplementary Information · 2014-01-23 · Electronic Supplementary Information Ni...

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Electronic Supplementary Information Ni II -salt catalyzed activation of primary amine-sp 3 C α -H and cyclization with 1,2-diketone to tetrasubstituted imidazoles Srikanta Samanta, Dipanwita Roy, Saikat Khamarui and Dilip K. Maiti* Department of Chemistry, University of Calcutta, University College of Science, 92, A. P. C. Road, Kolkata-700009, India *Corresponding author. Fax: 91-33-2351 9755, Tel: 91-33-2350 1014 [email protected] Serial No. Content Page 1. Materials and methods S1 2. General procedure for synthesis of 1,2,4,5-tetrasubstituted imidazoles (5a-h, k and 7a-e) and polycyclic imidazoles (6a-c) using benzyl amines S1 3. Characterization data of the compounds (5a-h, k), 6a-c and 7a-e S2 4. General procedure for synthesis of 1,2,4,5-tetrasubstituted imidazoles (8a-f) and polycyclic imidazoles (9a-d) using primary aliphatic amines S12 5. Characterization data of the compounds 8a-f and 9a-d S12 6. Trapping of 10-phenyl-9-oxa-11-aza-cyclopenta[e]pyrene (10) S18 7. NMR spectra of the compounds (5a-h, k), 6a-c, 7a-e, 8a-f, 9a-d and 10 S19 8. Single crystal XRD data of compound 5a S47 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013

Transcript of Electronic Supplementary Information · 2014-01-23 · Electronic Supplementary Information Ni...

Page 1: Electronic Supplementary Information · 2014-01-23 · Electronic Supplementary Information Ni II-salt catalyzed activation of primary amine-sp 3C ααα-H and cyclization with 1,2-diketone

Electronic Supplementary Information

NiII

-salt catalyzed activation of primary amine-sp3Cαααα-H and

cyclization with 1,2-diketone to tetrasubstituted imidazoles

Srikanta Samanta, Dipanwita Roy, Saikat Khamarui and Dilip K. Maiti*

Department of Chemistry, University of Calcutta, University College of Science,

92, A. P. C. Road, Kolkata-700009, India

*Corresponding author. Fax: 91-33-2351 9755, Tel: 91-33-2350 1014

[email protected]

Serial No. Content Page

1. Materials and methods S1

2. General procedure for synthesis of 1,2,4,5-tetrasubstituted imidazoles

(5a-h, k and 7a-e) and polycyclic imidazoles (6a-c) using benzyl amines S1

3. Characterization data of the compounds (5a-h, k), 6a-c and 7a-e S2

4. General procedure for synthesis of 1,2,4,5-tetrasubstituted imidazoles

(8a-f) and polycyclic imidazoles (9a-d) using primary aliphatic amines S12

5. Characterization data of the compounds 8a-f and 9a-d S12

6. Trapping of 10-phenyl-9-oxa-11-aza-cyclopenta[e]pyrene (10) S18

7. NMR spectra of the compounds (5a-h, k), 6a-c, 7a-e, 8a-f, 9a-d

and 10 S19

8. Single crystal XRD data of compound 5a S47

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1. Materials and methods

All reagents were purchased from commercial suppliers and used without further purification,

unless otherwise specified. Commercially supplied ethyl acetate and hexane were distilled before

use. CH2Cl2 was dried by distillation over P2O5. THF was dried over sodium in presence of

benzophenone and distilled out prior to use. Column chromatography was performed on basic

alumina (100-200 mesh) and silica gel (100-200 and 230-400 mesh). Analytical thin layer

chromatography was performed on 0.25 mm extra hard silica gel plates with UV254 fluorescent

indicator. Melting range of all the compounds is reported uncorrected. 1H NMR and

13C NMR

spectra were recorded using 300 MHz spectrometer (300 MHz for 1H and 75 MHz for

13C).

Chemical shift is reported in ppm from internal reference tetramethylsilane and coupling

constant in Hz. Proton multiplicities are represented as s (singlet), brs (broad singlet), d

(doublet), dd (double doublet), dt (double triplet ), t (triplet), q (quartet), and m (multiplet).

Infrared spectra were recorded on FT-IR spectrometer as KBr pellets (solid sample) and in thin

film on NaCl window (liquid sample). HR-MS data were acquired by electron spray ionization

technique on a Q-tof-micro quadriple mass spectrophotometer. Single crystal X-ray diffraction

studies of the crystalline heterocyclic compound were done in X-ray diffractometer.

2. General procedure for synthesis of 1,2,4,5-tetrasubstituted imidazoles (5a-h, k and 7a-e)

and polycyclic imidazoles (6a-c) using benzylamines

A mixture of benzyl amine (1a) (241 mg, 2.25 mmol) and benzil (3a) (210 mg, 1 mmol) were

taken in 20 mL dry toluene in a 50 mL RB and 8 mol% NiCl2.6H2O (19 mg, 8 mol%) was added.

The set up was fitted with a Dean-Stark apparatus and refluxed for a 12 h. Progress of the

reaction was monitored by TLC. After completion of the reaction, toluene was removed to have

a crude mass. The reaction mixture was chromatographed over silica gel using hexane-ethyl

acetate (9:1) as eluent. The desired product 5a was obtained as a white solid. Similarly, other

compounds (5b-h, k), 6a-c and 7a-e were synthesized.

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3. Characterization data of the compounds (5a-h, k), 6a-c and 7a-e

3.1. 1-Benzyl-2,4,5-triphenyl-1H-imidazole (5a):

N

N

Yield: 90 % (348 mg, 0.90 mmol).

Characteristic: White solid.

Melting point: 160-164 οC.

1H NMR (300 MHz, CDCl3): δΗ 5.11 (2H, s), 6.79 (2H, dd, J = 3.6, 7.2 Hz), 7.13-7.21 (8H, m),

7.28-7.36 (4H, m), 7.39 (2H, t, J = 5.7 Hz), 7.56-7.58 (2H, m), 7.65 (2H, dd, J = 3.9, 7.5 Hz).

13C NMR (75 MHz, CDCl3): δ 48.3, 126.0, 126.3, 126.8, 127.3, 128.0, 128.5, 128.7, 128.9,

129.1, 130.0, 131.1, 137.5, 148.1.

FT-IR (KBr, cm-1

): 694, 762, 1028, 1449, 1497, 1601, 3052.

HR-MS (m/z) for C28H23NO2 (M+H)+: Calculated 387.1861, found 387.1797.

3.2. 1-(4-Methylbenzyl)-4,5-diphenyl-2-p-tolyl-1H-imidazole (5b)

N

N

Me

Me

Yield: 92 % (381 mg, 0.92 mmol).

Characteristic: Off white solid.

Melting point: 132-135 oC.

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1H NMR (300 MHz, CDCl3): δΗ 2.31 (3H, s), 2.40 (3H, s), 5.08 (2H, s), 6.70 (2H, d, J = 8.1Hz),

7.03 (2H, d, J = 7.8 Hz), 7.18-7.25 (8H, m), 7.33-7.36 (2H, m), 7.54-7.59 (4H, m).

13C NMR (75 MHz, CDCl3): δ 20.6, 20.9, 47.7, 125.5, 126.0, 126.5, 127.4, 127.7, 128.2, 128.3,

128.6, 128.8, 128.9, 129.0, 129.6, 130.6, 130.7, 133.9, 134.1, 136.6, 137.3, 138.5, 147.7.

FT-IR (KBr, cm-1

): 726, 1120, 1470, 1580, 2353, 2525, 2756, 2801, 3024.

HR-MS (m/z) for C30H26N2 (M)+: Calculated 414.2096, found 414.2097.

3.3. 1-(4-Methoxybenzyl)-2-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazole (5c) :

N

N

OMe

MeO

Yield: 94 % (420 mg, 0.94 mmol).

Characteristic: Off white solid.

Melting point: 152-154 °C.

1H NMR (300 MHz, CDCl3): δΗ 3.75 (3H, s), 3.83 (3H, s), 5.02 (2H, s), 6.68-6.75 (4H, m), 6.93

(2H, d, J = 8.7 Hz), 7.13-7.24 (4H, m), 7.29-7.36 (4H, m), 7.57 (4H, t, J = 8.7 Hz).

13C NMR (75 MHz, CDCl3): δ 47.7, 55.2, 55.3, 113.9, 114.0, 123.5, 126.2, 126.8, 127.3, 128.0,

128.5, 128.7, 129.7, 130.4, 131.1, 131.3, 134.6, 147.9, 158.8, 160.1.

FT-IR (KBr, cm-1

): 724, 806, 1029, 1243, 1442, 1537, 2834, 3052.

HR-MS (m/z) for C30H26N2O2 (M)+: Calculated 446.1994, found 446.1990.

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3.4. 1-Benzyl-4,5-bis(4-bromophenyl)-2-phenyl-1H-imidazole (5d)

N

N

Br

Br

Yield: 89 % (484 mg, 0.89 mmol).

Characteristic: White solid.

Melting point: 128-131 °C.

1H NMR (300 MHz, CDCl3): δΗ 5.11 (2H, s), 6.81-6.84 (2H, m), 7.06 (1H, d, J = 8.1 Hz), 7.13

(1H, d, J = 8.4 Hz), 7.20-7.27 (4H, m), 7.30-7.38 (2H, m), 7.41-7.52 (6H, m), 7.67 (2H, dd, J =

3.3, 6.9 Hz).

13C NMR (75 MHz, CDCl3): δ 48.4, 120.5, 123.3, 125.9, 127.6, 128.1, 128.3, 128.4, 128.7,

128.7, 128.9, 128.9, 129.0, 129.2, 129.2, 129.7, 130.6, 131.3, 132.2, 132.3, 132.5, 133.2, 135.0,

137.2, 137.5, 148.7.

FT-IR (KBr, cm-1

): 699, 835, 1070, 1120, 1494, 1603, 3060.

HR-MS (m/z) for C28H20Br2N2 (M+2)+: Calculated: 543.9973, found: 543.9968 (One of the

peaks).

3.5. 1-(4-Fluorobenzyl)-2-(4-fluorophenyl)-4,5-diphenyl-1H-imidazole (5e)

N

N

F

F

Yield: 87 % (367 mg, 0.87 mmol).

Characteristic: White solid.

Melting point: 158-162 °C.

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1H NMR (300 MHz, CDCl3): δΗ 5.05 (2H, s), 6.72 (2H, dd, J = 5.4, 8.7 Hz), 6.89 (2H, t, J = 8.7

Hz), 7.08-7.16 (2H, m), 7.17-7.24 (4H, m), 7.32-7.42 (4H, m), 7.54-7.64 (4H, m).

13C NMR (75 MHz, CDCl3): δ 47.7, 115.4, 115.6, 115.7, 115.9, 126.6, 126.8, 127.6, 127.7,

128.1, 128.8, 128.9, 129.9, 131.0, 131.1.

FT-IR (KBr, cm-1

): 698, 776, 844, 1159, 1218, 1606, 2353, 2938, 3067.

HR-MS (m/z) for C28H20F2N2 (M)+: Calculated 422.1595, found 422.1597(One of the peaks).

3.6. 4-(4,5-Diphenyl-1-(pyridin-4-ylmethyl)-1H-imidazol-2-yl)pyridine (5f)

N

N

N

N

Yield: 85 % (330 mg, 0.85 mmol).

Characteristic: Light yellow solid.

Melting point: 124-126 °C.

1H NMR (300 MHz, CDCl3): δΗ 5.11 (2H, s), 6.77 (2H, d, J = 5.4 Hz), 7.17-7.25 (2H, m), 7.33-

7.49 (6H, m), 7.53-7.64 (4H, m), 7.82-7.84 (2H, m), 8.46 (2H, d, J = 5.4 Hz).

13C NMR (75 MHz, CDCl3): δ 47.4, 121.0, 126.6, 126.8, 127.3, 128.1, 128.3, 128.6, 128.8,

129.0, 129.0, 129.2, 129.8, 130.6, 130.9, 132.0, 134.0, 146.6, 150.0.

FT-IR (KBr, cm-1

): 637, 698, 1025, 1416, 1623, 1960, 2341, 2934, 2934, 3186, 3370.

HR-MS (m/z) for C26H20N4 (M)+: Calculated 388.1688, found 388.1684.

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3.7. 1-(4-Methoxybenzyl)-2,4,5-triphenyl-1H-imidazole (5g)

N

N

OMe

Yield: 11 % (46 mg, 0.11mmol).

Characteristic: White solid.

Melting point: 150-154 oC.

1H NMR (300 MHz, CDCl3): δΗ 3.77 (3H, s), 5.07 (2H, s), 6.67-6.75 (4H, m), 7.15-7.26 (5H,

m), 7.33-7.39 (4H, m), 7.41-7.44 (2H, m), 7.56-7.59 (2H, m), 7.66-7.69 (2H, m).

13C NMR (75 MHz, CDCl3): δ 47.8, 55.2, 114.0, 126.4, 126.8, 127.3, 128.0, 128.6, 128.8, 128.9,

129.1, 129.5, 130.0, 130.9, 131.1, 134.3, 138.0, 147.9, 158.9, 164.5.

FT-IR (KBr, cm-1

): 713, 906, 1229, 1343, 1512, 1737, 2534, 2990, 3059.

HR-MS (m/z) for C29H24N2O (M)+: Calculated 416.1889, found 416.1887.

3.8. 1-Benzyl-2-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazole (5h)

N

N

OMe

Yield: 24 % (100 mg, 0.24 mmol).

Characteristic: White solid.

Melting point: 146-149 oC.

1H NMR (300 MHz, CDCl3): δΗ 3.84 (3H, s), 5.10 (2H, s), 6.82-6.85 (2H, m), 6.93 (2H, d, J =

8.7 Hz), 7.17-7.24 (7H, m), 7.32-7.35 (4H, m), 7.57-7.61 (4H, m).

13C NMR (75 MHz, CDCl3): δ 48.2, 55.3, 114.0, 123.3, 126.0, 126.3, 126.8, 127.3, 128.0, 128.5,

128.7, 129.7, 130.4, 131.1, 134.5, 137.6, 137.8, 148.0, 160.2.

FT-IR (KBr, cm-1

): 789, 909, 1329, 1543, 1712, 1937, 2434, 2890, 3159.

HR-MS (m/z) for C29H24N2O (M)+: Calculated 416.1889, found 416.1889.

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3.9. 1-(2-Nitrobenzyl)-2,4,5-triphenyl-1H-imidazole (5k)

N

N

O2N

Yield: 38 % (164 mg, 0.38 mmol).

Characteristic: Yellow solid.

Melting point: 138-142 °C.

1H NMR (300 MHz, CDCl3): δΗ 4.90 (2H, s), 6.73-6.76 (2H, m), 7.12-7.24 (6H, m), 7.33-7.42

(5H, m), 7.45-7.48 (1H, m), 7.53-7.59 (4H, m), 8.11-8.14 (1H, m).

13C NMR (75 MHz, CDCl3): δ 48.3, 124.6, 126.4, 126.5, 126.7, 127.5, 128.0, 128.4, 128.8,

128.9, 130.1, 130.3, 130.8, 131.2, 132.9, 133.3, 134.2, 136.7, 138.2, 143.0, 149.1.

FT-IR (KBr, cm-1

): 617, 1096, 1129, 1233, 1452, 1567, 2574, 2790, 2949.

HR-MS (m/z) for C28H21N3O2 (M)+: Calculated 431.1634, found 431.1633.

3.10. 1-Benzyl-2-phenyl-1H-phenanthro[9,10-d]imidazole (6a)

N

N

Yield: 89 % (342 mg, 0.89 mmol).

Characteristic: White solid.

Melting point: 238-242 °C.

1H NMR (300 MHz, CDCl3): δΗ 5.86 (2H, s), 7.21 (2H, d, J = 6.9 Hz), 7.29-7.40 (4H, m), 7.43-

7.48 (3H, m), 7.54 (1H, t, J = 7.8 Hz), 7.62-7.76 (4H, m), 7.97 (1H, d, J = 8.4 Hz), 8.72 (1H, d, J

= 8.1 Hz), 8.81 (1H, d, J = 8.4 Hz), 8.87 (1H, dd, J = 1.2, 8.1 Hz).

13C NMR (75 MHz, CDCl3): δ 50.7, 121.0, 122.7, 123.0, 123.0, 124.2, 124.8, 125.6, 125.7,

126.6, 127.3, 127.4, 127.8, 128.3, 128.7, 129.2, 129.3, 129.6, 130.5, 137.0, 153.0.

FT-IR (KBr, cm-1

): 701, 1357, 1456, 2851, 2921, 1601, 3452.

HR-MS (m/z) for C28H20N2 (M)+: Calculated 384.1626, found 384.1622.

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3.11. 1-(4-Fluorobenzyl)-2-(4-fluorophenyl)-1H-phenanthro[9,10-d]imidazole (6b)

N

N

F

F

Yield: 87 % (366 mg, 0.87 mmol).

Characteristic: White solid.

Melting point: above 250 °C

1H NMR (300 MHz, CDCl3): δΗ 5.81 (2H, s), 7.09 (2H, t, J = 8.4 Hz), 7.15-7.21 (4H, m), 7.45

(1H, t, J = 8.1 Hz), 7.59 (1H, t, J = 8.1 Hz), 7.66-7.79 (4H, m), 7.94 (1H, d, J = 8.4 Hz), 8.73

(1H, d, J = 8.1 Hz), 8.83 (1H, d, J = 8.1 Hz), 8.91 (1H, d, J = 7.8 Hz).

13C NMR (75 MHz, CDCl3): δ 50.2, 115.9, 116.1, 116.4, 116.6, 120.8, 122.6, 122.8, 123.1,

124.3, 125.1, 125.9, 126.8, 127.2, 127.3, 127.5, 128.4, 129.4, 131.6, 131.7, 132.3, 151.7, 160.7,

165.5.

FT-IR (KBr, cm-1

): 721, 843, 1092, 1155, 1508, 2344, 2853, 2923.

HR-MS (m/z) for C28H18F2N2 (M)+: Calculated 420.1438, found 420.1445 (One of the peaks).

3.12. 1-(4-Methylbenzyl)-2-p-tolyl-1H-phenanthro[9,10-d]imidazole (6c)

N

N

CH3

H3C

Yield: 90 % (371 mg, 0.90 mmol).

Characteristic: Yellow solid.

Melting point: 226-230 oC.

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1H NMR (300 MHz, CDCl3): δΗ 2.36 (3H, s), 2.43 (3H, s), 5.81 (2H, s), 7.10-7.19 (4H, m), 7.25-

7.30 (3H, m), 7.40-7.45 (1H, m), 7.52-7.68 (3H, m), 7.72-7.77 (1H, m), 8.00 (1H, d, J = 8.1 Hz),

8.72 (1H, d, J = 8.4 Hz), 8.82 (1H, d, J = 8.4 Hz), 8.88 (1H, d, J = 7.8 Hz).

13C NMR (75 MHz, CDCl3): δ 21.0, 21.3, 50.5, 121.1, 122.7, 123.0, 124.1, 124.6, 125.4, 125.5,

126.6, 127.0, 127.2, 127.4, 127.6, 128.2, 129.1, 129.4, 129.5, 130.0, 134.0, 137.4, 137.9, 139.6,

153.2.

FT-IR (KBr, cm-1

): 659, 986, 1080, 1240, 1543, 1792, 1937, 2174, 2390, 2689, 2978, 3049.

HR-MS (m/z) for C30H24N2 (M)+: Calculated 412.1939, found 412.1939.

3.13. 1-Benzyl-4,5-dimethyl-2-phenyl-1H-imidazole (7a)

N

NH3C

H3C

Yield: 75 % (197 mg, 0.75 mmol).

Characteristic: Yellow liquid.

1H NMR (300 MHz, CDCl3): δΗ 2.03 (3H, s), 2.27 (3H, s), 5.15 (2H, s), 7.01 (2H, d, J = 6.9 Hz),

7.29-7.37 (6H, m), 7.49 (2H, dd, J = 3.3, 7.2 Hz).

13C NMR (75 MHz, CDCl3): δ 9.0, 12.6, 48.0, 123.9, 125.6, 127.5, 128.5, 128.6, 129.0, 130.9,

133.6, 137.2, 146.4.

FT-IR (KBr, cm-1

): 690, 862, 1128, 1342, 1467, 1501, 2440, 2879, 2990, 3052.

HR-MS (m/z) for C18H18N2 (M)+: Calculated 262.1470, found 262.1465.

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3.14. 4,5-Diethyl-1-(4-methylbenzyl)-2-p-tolyl-1H-imidazole (7b)

Et N

NEt

Me

Me

Yield: 78 % (248 mg, 0.78 mmol).

Characteristic: Light yellow liquid.

1H NMR (300 MHz, CDCl3): δΗ 1.03 (3H, t, J = 7.5 Hz), 1.28 (3H, t, J = 7.5 Hz), 2.34 (6H, s),

2.47 (2H, q, J = 7.5 Hz), 2.64 (2H, q, J = 7.5 Hz), 5.15 (2H, s), 6.85 (2H, d, J = 7.8 Hz), 7.15

(4H, d, J = 8.4 Hz), 7.34 (2H, d, J = 7.8 Hz).

13C NMR (75 MHz, CDCl3): δ 14.6, 14.9, 16.8, 19.7, 21.0, 21.4, 47.9, 125.5, 127.6, 128.8,

129.4, 129.6, 129.7, 133.6, 137.5, 137.7, 139.7, 145.7.

FT-IR (KBr, cm-1

): 468, 803, 1064, 1457, 1650, 2349, 2853, 2930, 3415.

HR-MS (m/z) for C22H26N2 (M)+: Calculated 318.2096, found 318.2099.

3.15. 1-Benzyl-2-phenyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazole (7c)

N

N

Yield: 81 % (233 mg, 0.81 mmol).

Characteristic: Brown solid.

Melting point: 134-137°C.

1H NMR (300 MHz, CDCl3): δΗ 1.77-1.83 (4H, m), 2.36 (2H, t, J = 4.8 Hz), 2.70 (2H, t, J = 4.2

Hz), 5.14 (2H, s), 7.03 (2H, d, J = 7.2 Hz), 7.28-7.37 (6H, m), 7.49-7.53 (2H, m).

13C NMR (75 MHz, CDCl3): δ 21.1, 23.0, 23.4, 24.3, 47.8, 125.8, 127.5, 128.3, 128.4, 128.5,

128.9, 131.1, 136.7, 137.3, 146.6.

FT-IR (KBr, cm-1

): 459, 703, 1364, 1448, 1597, 2853, 2924.

HR-MS (m/z) for C20H20N2 (M)+: Calculated 288.1626, found 288.1627.

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3.16. 1-(4-Methylbenzyl)-2-p-tolyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazole (7d)

N

N

Me

Me

Yield: 83 % (262 mg, 0.83 mmol).

Characteristic: Yellow liquid.

1H NMR (300 MHz, CDCl3): δΗ 1.80 (4H, t, J = 2.7 Hz), 2.33 (8H, brs), 2.68 (2H, d, J = 5.1 Hz),

5.08 (2H, s), 6.91 (2H, d, J = 8.1 Hz), 7.14 (4H, d, J = 8.1 Hz), 7.40 (2H, d, J = 8.1 Hz).

13C NMR (75 MHz, CDCl3): δ 21.1, 21.3, 23.0, 23.4, 24.2, 47.6, 125.7, 127.3, 127.9, 128.4,

129.2, 129.6, 134.3, 136.2, 137.1, 138.3, 146.6.

FT-IR (KBr, cm-1

): 730, 1020, 1445, 1515, 2853, 2925, 3024.

HR-MS (m/z) for C22H24N2 (M)+: Calculated 316.1939, found 316.1945.

3.17. 1-(4-Methoxybenzyl)-2-(4-methoxyphenyl)-4,5,6,7-tetrahydro-1H-benzo[d]imidazole (7e)

N

N

OMe

MeO

Yield: 83 % (289 mg, 0.83 mmol).

Characteristic: Yellow liquid.

1H NMR (300 MHz, CDCl3): δΗ 1.78 (4H, brs), 2.34 (2H, brs), 2.66 (2H, brs), 3.76 (6H, s), 5.02

(2H, s), 6.82-6.86 (4H, m), 6.92 (2H, d, J = 8.7 Hz), 7.42 (2H, dd, J = 2.1, 6.9 Hz).

13C NMR (75 MHz, CDCl3): δ 21.1, 23.0, 23.4, 24.3, 47.2, 55.2, 55.2, 113.9, 114.3, 123.7,

127.0, 129.4, 129.8, 136.3, 146.4, 158.9, 159.7.

FT-IR (KBr, cm-1

): 735, 837, 1030, 1250, 15413, 1612, 1668, 2838, 2933, 3367.

HR-MS (m/z) for C22H24N2O2 (M)+: Calculated 348.1838, found 348.1833.

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4. General procedure for synthesis of 1,2,4,5-tetrasubstituted imidazoles

(8a-f) and polycyclic imidazoles (9a-d) using primary aliphatic amines

A mixture of β-phenylethyl amine (2a, 273 mg, 2.25 mmol) and benzil (3a, 210 mg, 1 mmol)

were taken in 20 mL dry toluene in a 50 mL round bottomed flask and 8 mol% Ni(OAc)2.4H2O

(20 mg, 8 mol%) was added. The set up was fitted with a Dean-Stark apparatus and refluxed for

a 12 h. Progress of the reaction was monitored by TLC. After completion of the reaction, toluene

was removed to have a crude mass. The residue was chromatographed over silica gel using

hexane-ethyl acetate (19:1) as eluent. The desired product 8a was obtained as a white solid.

Similarly, other compounds 8b-f and 9a-d were synthesized.

5. Characterization data of the compounds 8a-f and 9a-d

5.1. 2-Benzyl-1-phenethyl-4,5-diphenyl-1H-imidazole (8a)

N

N

Yield: 86 % (356 mg, 0.86 mmol).

Characteristic: White solid.

Melting point: 124-127 °C.

1H NMR (300 MHz, CDCl3): δΗ 2.33 (2H, t, J = 8.1 Hz), 3.78 (2H, t, J = 8.1 Hz), 4.09 (2H, s),

6.61 (2H, dd, J = 3.6, 7.2 Hz), 7.09-7.22 (8H, m), 7.23-7.35 (5H, m), 7.42-7.51 (5H, m).

13C NMR (75 MHz, CDCl3): δ 34.1, 36.6, 45.8, 126.2, 126.7, 126.7, 126.8, 128.1, 128.5, 128.6,

128.7, 128.7, 128.8, 129.1, 131.1, 131.4, 134.4, 136.6, 137.4, 137.4, 146.1.

FT-IR (KBr, cm-1

): 695, 723, 1072, 1462, 1497, 1600, 2923, 3024.

HR-MS (m/z) for C30H26N2 (M)+: Calculated 414.2096, found 414.2096.

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5.2. 1-Butyl-4,5-diphenyl-2-propyl-1H-imidazole (8b)

N

N

Yield: 71 % (226 mg, 0.71 mmol).

Characteristic: Yellowish gummy liquid.

1H NMR (300 MHz, CDCl3): δΗ 0.75 (3H, t, J = 7.2 Hz), 1.07 (3H, t, J = 7.2 Hz), 1.15 (2H, q, J

= 7.5 Hz), 1.40-1.48 (2H, m), 1.84-1.91 (2H, m), 2.70-2.76 (2H, m), 3.71 (2H, t, J = 7.8 Hz),

7.08-7.18 (4H, m), 7.30-7.34 (2H, m), 7.40-7.45 (4H, m).

13C NMR (75 MHz, CDCl3): δ 13.4, 14.1, 19.7, 22.0, 29.6, 29.6, 32.8, 43.5, 125.9, 126.7, 127.9,

128.1, 128.4, 128.8, 131.1, 131.7, 134.7, 136.3, 147.8.

FT-IR (KBr, cm-1

): 691, 766, 1073, 1465, 1604, 2846, 2915.

HR-MS (m/z) for C22H27N2 (M+H)+: Calculated 319.2174; found 319.2166.

5.3. 1-Dodecyl-4,5-diphenyl-2-undecyl-1H-imidazole (8c)

N

N

Yield: 85 % (461 mg, 0.85 mmol).

Characteristic: Yellowish gummy liquid.

1H NMR (300 MHz, CDCl3): δΗ 0.85-0.90 (6H, m), 1.11-1.46 (36H, m), 1.82-1.87 (2H, m), 2.75

(2H, t, J = 7.8 Hz), 3.70 (2H, t, J = 7.8 Hz), 7.08-7.18 (4H, m), 7.31-7.34 (2H, m), 7.42 (4H, dd,

J = 1.2, 5.7 Hz).

13C NMR (75 MHz, CDCl3): δ 14.0, 22.6, 26.5, 27.5, 28.6, 28.8, 29.2, 29.3, 29.4, 29.5, 29.6,

29.7, 30.7, 31.9, 43.7, 125.9, 126.7, 127.9, 128.0, 128.4, 128.8, 131.1, 131.7, 134.7, 136.2, 148.0.

FT-IR (KBr, cm-1

): 691, 765, 1070, 1465, 1602, 2846, 2919.

HR-MS (m/z) for C38H58N2 (M)+: Calculated 542.4600, found 542.4612 (Base peak).

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5.4. 2-Heptadecyl-1-octadecyl-4,5-diphenyl-1H-imidazole (8d)

N

N

Yield: 87 % (619 mg, 0.87 mmol).

Characteristic: White solid.

Melting point: 44-50 °C.

1H NMR (300 MHz, CDCl3): δΗ 0.88 (6H, d, J = 6.6 Hz), 1.13-1.47 (60H, m), 1.87 (2H, brs),

2.75 (2H, t, J = 7.8 Hz), 3.71 (2H, t, J = 7.5 Hz), 7.08-7.19 (4H, m), 7.32-7.45 (6H, m).

13C NMR (75 MHz, CDCl3): δ 14.1, 22.7, 26.5, 27.6, 28.7, 28.9, 29.3, 29.4, 29.5, 29.6, 29.7,

30.7, 31.9, 43.7, 125.8, 126.7, 127.9, 128.0, 128.3, 128.8, 131.1, 132.0, 135.0, 136.5, 148.0.

FT-IR (KBr, cm-1

): 692, 722, 769, 1069, 1465, 1600, 2849, 2917.

HR-MS (m/z) for C50H82N2 (M)+: Calculated 710.6478, found 710.6482.

5.5. 4,5-Bis(4-bromophenyl)-1-decyl-2-nonyl-1H-imidazole (8e)

N

N

Br

Br

Yield: 83 % (535 mg, 0.83 mmol).

Characteristic: Yellowish gummy liquid.

1H NMR (300 MHz, CDCl3): δΗ 0.87-0.92 (6H, m), 1.15-1.48 (28H, m), 1.80-1.90 (2H, m),

2.71-2.77 (2H, m), 3.70 (2H, t, J = 6.9 Hz), 7.17-7.20 (1H, m), 7.27-7.34 (5H, m), 7.45-7.48 (1H,

m), 7.58-7.61 (1H, m).

13C NMR (75 MHz, CDCl3): δ 14.1, 22.7, 26.5, 27.5, 28.5, 28.8, 29.3, 29.4, 29.5, 29.7, 30.7,

31.8, 31.9, 43.7, 119.9, 122.9, 126.9, 128.2, 128.3, 129.0, 130.9, 131.0, 131.1, 132.3, 132.5,

135.9, 148.6.

FT-IR (KBr, cm-1

): 690, 769, 1067, 1465, 1605, 2839, 2922.

HR-MS (m/z) for C34H48Br2N2 (M+2)+: Calculated 644.2164, found 644.2174 (One of the peaks)

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5.6. 2-Benzyl-4,5-bis(4-bromophenyl)-1-phenethyl-1H-imidazole (8f)

N

N

Br

Br

Yield: 84 % (481 mg, 0.84 mmol).

Characteristic: White solid.

Melting point: 126-131 oC.

1H NMR (300 MHz, CDCl3): δΗ 2.42 (2H, t, J = 7.8 Hz), 3.82 (2H, t, J = 7.8 Hz), 4.08 (2H, s),

6.68 (2H, dd, J = 3.6, 7.2 Hz), 7.15 (2H, dd, J = 1.8, 6.6 Hz), 7.20-7.22 (4H, m), 7.30-7.39 (8H,

m), 7.60 (2H, dd, J = 1.8, 6.6 Hz).

13C NMR (75 MHz, CDCl3): δ 34.2, 36.6, 45.7, 120.2, 123.2, 126.9, 127.7, 128.3, 128.4, 128.5,

128.7, 128.8, 130.1, 131.3, 132.4, 133.4, 136.3, 137.1, 146.7.

FT-IR (KBr, cm-1

): 691, 750, 1067, 1455, 1600, 2837, 2929.

HR-MS (m/z) for C30H24Br2N2 (M+2)+: Calculated 572.0286, found 572.0285 (One of the

peaks).

5.7. 1-Decyl-2-nonyl-1H-phenanthro[9,10-d]imidazole (9a)

N

N

Yield: 78 % (378 mg, 0.78 mmol).

Characteristic: Yellow gummy liquid.

1H NMR (300 MHz, CDCl3): δΗ 0.84-0.90 (6H, m), 1.27-1.68 (28H, m), 1.89-1.99 (4H, m), 3.03

(2H, t, J = 8.1 Hz), 4.54 (2H, t, J = 8.1 Hz), 7.54-7.72 (4H, m), 8.22 (1H, d, J = 8.1Hz), 8.72

(2H, t, J = 8.1 Hz), 8.85 (1H, d, J = 8.1 Hz).

13C NMR (75 MHz, CDCl3): δ 14.0, 22.6, 26.7, 27.8, 28.8, 29.2, 29.2, 29.3, 29.3, 29.4, 29.4,

29.5, 29.7, 30.2, 31.4, 31.9, 46.0, 120.1, 122.5, 122.9, 123.3, 124.3, 124.4, 125.1, 125.2, 126.6,

127.1, 127.8, 128.8, 153.0.

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FT-IR (KBr, cm-1

): 750, 1039, 1469, 1533, 28451, 2916, 2953.

HR-MS (m/z) for C34H48N2 (M)+: Calculated 484.3817, found 484.3816.

5.8. 1-Tetradecyl-2-tridecyl-1H-phenanthro[9,10-d]imidazole (9b)

N

N

Yield: 80 % (477 mg, 0.80 mmol).

Characteristic: Yellow gummy liquid.

1H NMR (300 MHz, CDCl3): δΗ 0.85-0.94 (6H, m), 1.27-1.65 (42H, m), 1.92-1.99 (4H, m), 3.01

(2H, t, J = 7.8 Hz), 4.53 (2H, t, J = 7.5 Hz), 7.58-7.72 (4H, m), 8.22 (1H, d, J = 8.4Hz), 8.68-

8.73 (2H, m), 8.84 (1H, d, J = 8.4 Hz).

13C NMR (75 MHz, CDCl3): δ 14.1, 22.7, 26.8, 27.9, 28.8, 29.2, 29.3, 29.4, 29.5, 29.7, 30.4,

31.9, 45.9, 120.1, 122.4, 122.9, 123.4, 124.2, 124.4, 125.0, 125.3, 126.5, 127.0, 127.7, 153.1.

FT-IR (KBr, cm-1

): 720, 750, 1364, 1453, 1468, 1534, 1610, 2847, 2916, 2955.

HR-MS (m/z) for C42H64N2 (M)+: Calculated 596.5069, found 596.5072.

5.9. 2-Heptadecyl-1-octadecyl-1H-phenanthro[9,10-d]imidazole (9c)

N

N

Yield: 81 % (574 mg, 0.81 mmol).

Characteristic: Brownish solid.

Melting point: 74-80 °C

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1H NMR (300 MHz, CDCl3): δΗ 0.88 (6H, t, J = 6.3 Hz), 1.26-1.50 (58H, m), 1.90-1.97 (4H,

m), 3.00 (2H, t, J = 7.8 Hz), 4.51 (2H, t, J = 7.8 Hz), 7.57-7.68 (4H, m), 8.20 (2H, d, J = 7.8 Hz),

8.69 (2H, t, J = 7.8 Hz), 8.82 (2H, d, J = 7.2 Hz).

13C NMR (75 MHz, CDCl3): δ 14.1, 22.7, 26.8, 27.9, 28.8, 29.2, 29.3, 29.5, 29.5, 29.7, 30.4,

31.9, 46.0, 120.1, 122.4, 122.9, 123.4, 124.2, 124.4, 125.0, 125.3, 126.6, 127.0, 127.3, 127.7,

128.7, 137.0, 153.1.

FT-IR (KBr, cm-1

): 721, 749, 1364, 1467, 1532, 2849, 2916, 2954.

HR-MS (m/z) for C50H80N2 (M)+: Calculated 708.6321; found 708.6325.

5.10. 9-Hexadecyl-10-pentadecyl-9H-9,11-diaza-cyclopenta[e]pyrene (9d)

N

N

Yield: 74 % (501 mg, 0.74 mmol).

Characteristic: Off white solid.

Melting point: 52-55 °C.

1H NMR (300 MHz, CDCl3): δΗ 0.85-0.92 (6H, m), 1.27-1.65 (48H, m), 2.01-2.08 (4H, m), 3.10

(2H, t, J = 7.5 Hz), 4.64 (2H, t, J = 8.1 Hz), 8.04-8.16 (6H, m), 8.46 (1H, d, J = 7.5 Hz), 8.99

(1H, t, J = 6.3 Hz).

13C NMR (75 MHz, CDCl3): δ 14.0, 22.6, 26.8, 27.9, 28.8, 29.2, 29.3, 29.4, 29.5, 29.5, 29.6,

29.7, 30.2, 30.6, 31.4, 31.9, 46.1, 117.0, 119.5, 122.5, 124.1, 125.5, 126.2, 127.5, 128.0, 131.9,

132.4, 153.3.

FT-IR (KBr, cm-1

): 712, 739, 820, 1025, 1364, 1490, 1610, 2849, 2926.

HR-MS (m/z) for C48H72N2 (M)+: Calculated 676.5695; found 676.5699.

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6. Trapping of 10-phenyl-9-oxa-11-aza-cyclopenta[e]pyrene (10)

A mixture of benzyl amine (1a) (129 mg, 1.20 mmol) and pyrene-4,5-dione (3e) (232 mg, 1

mmol) were taken in 20 mL dry toluene in a 50 mL RB and 8 mol% NiCl2.6H2O (19 mg, 8

mol%) was added. The set up was fitted with a Dean-Stark apparatus and refluxed. The reaction

was quenched after 6 h. Solvent was removed in a rotary evaporator at ambient under reduced

pressure. The residue was chromatographed over silica gel using hexane-ethyl acetate (10:1) as

eluent. The oxadiazole 10 was obtained as a yellow solid.

Characterization data of 10-Phenyl-9-oxa-11-aza-cyclopenta[e]pyrene (10):

O

N

Yield: 32 % (102 mg, 0.32 mmol).

Characteristic: Yellow solid.

Melting point: 246-248 οC.

1H NMR (300 MHz, CDCl3): δΗ 7.56-7.66 (3H, m), 8.09-8.19 (5H, m), 8.24 (1H, t, J = 6.3 Hz),

8.48 (2H, dd, J = 2.1, 8.1 Hz), 8.60 (1H, dd, J = 0.6, 7.5 Hz), 8.91 (1H, dd, J = 0.9, 7.5 Hz).

13C NMR (75 MHz, CDCl3): δ 117.8, 120.3, 123.3, 123.4, 125.3, 126.2, 126.5, 127.3, 127.4,

127.7, 128.2, 128.9, 131.0, 131.8, 131.9, 136.3, 145.6, 162.5.

FT-IR (KBr, cm-1

): 684, 701, 830, 1445, 2368, 2920, 3415.

HR-MS (m/z) for C23H14NO (M+1)+: Calculated 320.1075, found 320.1077.

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7. NMR spectra of the compounds (5a-h, k), 6a-c, 7a-e, 8a-f, 9a-d and 10

7.1.1H and

13C NMR of 1-benzyl-2,4,5-triphenyl-1H-imidazole (5a)

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N

N

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7.2. 1

H and 13

C NMR of 1-(4-methylbenzyl)-4,5-diphenyl-2-p-tolyl-1H-imidazole (5b)

S20

N

N

Me

Me

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7.3. 1

H and 13

C NMR of 1-(4-methoxybenzyl)-2-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazole

(5c)

S21

N

N

OMe

MeO

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7.4. 1

H and 13

C NMR of 1-benzyl-4,5-bis(4-bromophenyl)-2-phenyl-1H-imidazole (5d)

S22

N

N

Br

Br

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7.5. 1

H and 13

C NMR of 1-(4-fluorobenzyl)-2-(4-fluorophenyl)-4,5-diphenyl-1H-imidazole (5e)

S23

N

N

F

F

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7.6. 1

H and 13

C NMR of 4-(4,5-diphenyl-1-(pyridin-4-ylmethyl)-1H-imidazol-2-yl)pyridine (5f)

S24

N

N

N

N

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7.7. 1

H and 13

C NMR of 1-(4-methoxybenzyl)-2,4,5-triphenyl-1H-imidazole (5g)

S25

N

N

OMe

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7.8. 1

H and 13

C NMR of 1-benzyl-2-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazole (5h)

S26

N

N

OMe

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7.9. 1

H and 13

C NMR of 1-(2-nitrobenzyl)-2,4,5-triphenyl-1H-imidazole (5k)

S27

N

N

O2N

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7.10. 1

H and 13

C NMR of 1-benzyl-2-phenyl-1H-phenanthro[9,10-d]imidazole (6a)

S28

N

N

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7.11. 1

H and 13

C NMR of 1-(4-fluorobenzyl)-2-(4-fluorophenyl)-1H-phenanthro[9,10-

d]imidazole (6b)

S29

N

N

F

F

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7.12. 1

H and 13

C NMR of 1-(4-methylbenzyl)-2-p-tolyl-1H-phenanthro[9,10-d]imidazole (6c)

S30

N

N

CH3

H3C

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7.13. 1

H and 13

C NMR of 1-benzyl-4,5-dimethyl-2-phenyl-1H-imidazole (7a)

S31

N

NH3C

H3C

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7.14. 1

H and 13

C NMR of 4,5-diethyl-1-(4-methylbenzyl)-2-p-tolyl-1H-imidazole (7b)

S32

Et N

NEt

Me

Me

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7.15. 1

H and 13

C NMR of 1-benzyl-2-phenyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazole (7c)

S33

N

N

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7.16. 1

H and 13

C NMR of 1-(4-methylbenzyl)-2-p-tolyl-4,5,6,7-tetrahydro-1H-benzo[d]imidazole

(7d)

S34

N

N

Me

Me

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7.17. 1

H and 13

C NMR of 1-(4-methoxybenzyl)-2-(4-methoxyphenyl)-4,5,6,7-tetrahydro-1H-

benzo[d]imidazole (7e)

S35

N

N

OMe

MeO

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7.18. 1

H and 13

C NMR of 2-benzyl-1-phenethyl-4,5-diphenyl-1H-imidazole (8a)

S36

N

N

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7.19. 1

H and 13

C NMR of 1-butyl-4,5-diphenyl-2-propyl-1H-imidazole (8b)

S37

N

N

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7.20. 1

H and 13

C NMR of 1-dodecyl-4,5-diphenyl-2-undecyl-1H-imidazole (8c)

S38

N

N

9

9

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7.21. 1

H and 13

C NMR of 2-heptadecyl-1-octadecyl-4,5-diphenyl-1H-imidazole (8d)

S39

N

N

15

15

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7.22. 1

H and 13

C NMR of 4,5-bis(4-bromophenyl)-1-decyl-2-nonyl-1H-imidazole (8e)

S40

N

N

7

7

Br

Br

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7.23. 1

H and 13

C NMR of 2-benzyl-4,5-bis(4-bromophenyl)-1-phenethyl-1H-imidazole (8f)

S41

N

N

Br

Br

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7.24. 1

H and 13

C NMR of 1-decyl-2-nonyl-1H-phenanthro[9,10-d]imidazole (9a)

S42

N

N

7

7

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7.25. 1

H and 13

C NMR of 1-tetradecyl-2-tridecyl-1H-phenanthro[9,10-d]imidazole (9b)

S43

N

N

11

11

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7.26. 1

H and 13

C NMR of 2-heptadecyl-1-octadecyl-1H-phenanthro[9,10-d]imidazole (9c)

S44

N

N

15

15

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7.27. 1

H and 13

C NMR of 9-Hexadecyl-10-pentadecyl-9H-9,11-diaza-cyclopenta[e]pyrene (9d)

S45

N

N

14

14

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8. 1

H and 13

C NMR of 10-Phenyl-9-oxa-11-aza-cyclopenta[e]pyrene (10):

S46

O

N

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9. Summary of data CCDC 964954 (compound 5a)

� Chemical formula and formula weight (M): C28 H22 N2 and 386.48

� Crystal system: Triclinic Unit-cell dimensions (angstrom or pm, degrees) and volume, with

edges: a 10.24 (2), b 10.26 (2), c 21.35 (4), 21.37 (3), 94.42 (3), 103.09 (3), 91.42 (2), 2176 (7)

� Temperature: 296 K

� Space group symbol: P-1

� No. of formula units in unit cell (Z): 4

� Number of reflections measured and/or number of independent reflections: 6493

� Final R values (and whether quoted for all or observed data): 0.0888

S-47

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