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Organic & Biomolecular Chemistry
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DOI: 10.1039/C8OB00897C
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refluxed 12 hours in MeCN (1 mL). The solvent was evaporated (100 mg, 0.24 mmol) and dodecylbromide (173 μL, 0.72 mmol)
and the residue was triturated with EtOAc to remove any trace was refluxed 12 hours in MeCN (1 mL). The solvent was
of hexyliodide. Evaporation of the residual solvent afforded evaporated and the residue was triturated with EtOAc to
the salt (5b) as a white powder (124 mg, 0.216 mmol, 90 %). 1H remove any trace of dodecylbromide. Evaporation of the
NMR (CDCl3,400 MHz) δ 10.53 (s, 1H), 7.63 – 7.39 (m, 3H), 7.39 residual solvent afforded the salt (5e) as a white powder (144
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– 7.27 (m,3H), 7.24 (d, J = 6.9 Hz, 2H), 5.24 (dd, J = 6.9, 4.3 Hz, mg, 0.22 mmol, 90 %). H NMR (CDCl3, 400 MHz) δ 10.45 (s,
1H), 4.80 – 4.61 (m, 2H), 4.54 (d, J = 12.0 Hz, 1H), 4.45 (d, J = 1H), 7.51 – 7.41 (m, 3H), 7.34 – 7.28 (m, 3H), 7.25 – 7.20 (m,
11.9 Hz, 1H), 4.33 (dh, J = 20.9, 7.4, 6.9 Hz, 2H), 1.95 – 1.84 (m, 2H), 5.42 – 5.10 (m, 1H), 4.70 – 4.62 (m, 2H), 4.50 (d, J = 12.0
2H), 1.32 (s, 6H), 0.91 (t, J = 6.2 Hz, 3H); 13C NMR (126 MHz, Hz, 1H), 4.41 (d, J = 12.0 Hz, 1H), 4.30 (dh, J = 16.8, 13.7, 6.4
CDCl3) δ 138.64, 135.94, 135.02, 134.29, 133.77, 132.85, Hz, 2H), 2.03 – 1.73 (m, 2H), 1.25 (d, J = 17.6 Hz, 18H), 0.86 (t, J
132.22, 131.50, 130.15, 129.39, 129.30, 128.37, 127.72, = 6.7 Hz, 3H); 13C NMR (126 MHz, CDCl3) δ 138.52, 135.90,
122.57, 121.28, 76.18, 68.46, 53.24, 50.43, 31.18, 30.33, 26.00, 134.98, 134.23, 133.77, 132.85, 132.22, 131.44, 130.12,
22.50, 14.06; HRMS: (ESI) calcd. for [M+] C24H27Cl4N2O: 129.37, 129.28, 128.35, 127.70, 122.61, 121.35, 77.16, 68.43,
499.0876, found 499.0877; IR (neat, cm-1) 3146.9, 3051.6, 53.21, 50.42, 32.02, 30.39, 29.71, 29.63, 29.49, 29.45, 29.10,
2943.9, 2864.9, 1650.4, 1587.3, 1468.8, 1379.4; Melting point: 26.36, 22.80, 14.24. HRMS: (ESI) calcd. for [M+] C30H39Cl4N2O:
106-109 °C.
Miconazoctylium bromide, 1-(2-((2,4-dichlorobenzyl)oxy)-2- 3052.7, 2920.4, 2852.1, 1649.8, 1589.0, 1468.5, 1380.9,
(2,4-dichlorophenyl)ethyl)-3-octyl-1H-imidazol-3-ium 1342.6; Melting point: 71-74 °C.
583.1823, found 583.1816; IR (neat, cm-1) 3148.6, 3106.1,
bromide (5c). A solution of (4) (100 mg, 0.24 mmol) and 1-(2-((2,4-dichlorobenzyl)oxy)-2-(2,4-dichlorophenyl)ethyl)-3-
octylbromide (125 μL, 0.72 mmol) was refluxed 12 hours in tetradecyl-1H-imidazol-3-ium bromide (5f). A solution of (4)
MeCN (1 mL). The solvent was evaporated and the residue was (100 mg, 0.24 mmol) and tetradecylbromide (214 μL, 0.72
triturated with EtOAc to remove any trace of octylbromide. mmol) was refluxed 12 hours in MeCN (1 mL). The solvent was
Evaporation of the residual solvent afforded the salt (5c) as a evaporated and the residue was triturated with EtOAc to
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white powder (135 mg,0.22 mmol, 93 %). H NMR (CDCl3,400 remove any trace of tetradecylbromide. Evaporation of the
MHz) δ 10.51 (s, 1H), 7.49 (d, J = 8.3 Hz, 1H), 7.46 – 7.43 (m, residual solvent afforded the salt (5f) as a white powder (140
2H), 7.34 – 7.26 (m, 3H), 7.23 – 7.19 (m, 2H), 5.21 (dd, J = 7.5, mg, 0.20 mmol, 85 %). 1H NMR (CDCl3,400 MHz) δ 10.63 (s,
4.3 Hz, 1H), 4.74 – 4.60 (m, 2H), 4.51 (d, J = 11.9 Hz, 1H), 4.42 1H), 7.57 – 7.47 (m, 3H), 7.39 – 7.30 (m, 3H), 7.20 – 7.08 (m,
(d, J = 12.0 Hz, 1H), 4.29 (dh, J = 20.9, 7.3, 6.9 Hz, 2H), 1.91 – 2H), 5.24 (dd, J = 7.3, 4.3 Hz, 1H), 4.75 – 4.64 (m, 2H), 4.55 (d, J
1.80 (m, 2H), 1.26 (d, J = 20.4 Hz, 10H), 0.87 (t, J = 6.7 Hz, 3H); = 12.0 Hz, 1H), 4.46 (d, J = 11.9 Hz, 1H), 4.34 (ddt, J = 26.9,
13C NMR (101 MHz, CDCl3) d 138.64, 135.93, 135.02, 134.28, 13.9, 7.5 Hz, 2H), 1.90 (s, 2H), 1.31 (d, J = 20.1 Hz, 22H), 0.91 (t,
133.77, 132.86, 132.22, 131.49, 130.14, 129.39, 129.30, J = 6.7 Hz, 3H); 13C NMR (126 MHz, CDCl3) δ 138.89, 135.99,
128.37, 127.71, 122.57, 121.27, 76.18, 68.46, 53.25, 50.44, 135.08, 134.34, 133.77, 132.84, 132.19, 131.56, 130.19,
31.80, 30.38, 29.14, 29.05, 26.36, 22.71, 14.19; HRMS: (ESI) 129.42, 129.33, 128.40, 127.74, 122.46, 121.06, 76.20, 68.49,
calcd. for [M+] C26H31Cl4N2O: 527.1185, found 527.1194; IR 53.27, 50.48, 32.07, 30.39, 29.83, 29.79, 29.74, 29.65, 29.51,
(neat, cm-1) 3007.9, 2927.5, 2926.5, 2854.5, 1646.7, 1587.7, 29.12, 26.39, 22.84, 14.27. HRMS: (ESI) calcd. for [M+]
1561.3, 1467.4, 1379.8, 1338.7; Melting point: 131-134 °C.
C32H43Cl4N2O: 611.2128, found 611.2129; IR (neat, cm-1)
3149.2, 3054.9, 2922.5, 2852.5, 1589.7, 1561.5, 1467.7,
3-decyl-1-(2-((2,4-dichlorobenzyl)oxy)-2-(2,4-dichlorophenyl)
ethyl)-1H-imidazol-3-ium bromide (5d). A solution of (4) (100 1378.8, 1340.6; Melting point: 100-104°C.
mg, 0.24 mmol) and decylbromide (150 μL, 0.72 mmol) was
refluxed 12 hours in MeCN (1 mL). The solvent was evaporated 1-(2-((2,4-dichlorobenzyl)oxy)-2-(2,4-dichlorophenyl)ethyl)-3-
and the residue was triturated with EtOAc to remove any trace hexadecyl-1H-imidazol-3-ium bromide (5g). A solution of (4)
of decylbromide. Evaporation of the residual solvent afforded (100 mg, 0.24 mmol) and hexadecylbromide (220 μL, 0.72
the salt (5d) as a white powder (130 mg, 0.2 mmol, 85 %). 1H mmol) was refluxed 12 hours in MeCN (1 mL). The solvent was
NMR (CDCl3, 400 MHz) δ 10.59 (s, 1H), 7.53 – 7.41 (m, 3H), evaporated and the residue was triturated with EtOAc to
7.36 – 7.27 (m, 3H), 7.18 – 7.09 (m, 2H), 5.21 (dd, J = 7.3, 4.2 remove any trace of hexadecylbromide. Evaporation of the
Hz, 1H), 4.77 – 4.58 (m, 2H), 4.52 (d, J = 12.0 Hz, 1H), 4.43 (d, J residual solvent afforded the salt (5g) as a white powder (166
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= 12.0 Hz, 1H), 4.31 (dh, J = 20.9, 13.7, 7.4 Hz, 2H), 1.87 (t, 2H), mg, 0.23 mmol, 95 %). H NMR (CDCl3,400 MHz) δ 10.41 (s,
1.28 (d, J = 21.3 Hz, 14H), 0.88 (t, J = 6.9 Hz, 3H); 13C NMR (126 1H), 7.62 – 7.41 (m, 3H), 7.37 – 7.23 (m, 5H), 5.23 (s, 1H), 4.68
MHz, CDCl3) δ 138.76, 135.96, 135.05, 134.30, 133.77, 132.85, (s, 2H), 4.52 (d, J = 12.1 Hz, 1H), 4.44 (d, J = 11.9 Hz, 1H), 4.38 –
132.20, 131.52, 130.17, 129.41, 129.32, 128.39, 127.73, 4.23 (m, 2H), 1.86 (s, 2H), 1.26 (s, 26H), 0.89 (s, 3H).13C NMR
122.52, 121.16, 76.19, 68.47, 53.26, 50.46, 31.98, 30.39, 29.59, (126 MHz, CDCl3) δ 138.22, 135.75, 134.82, 134.07, 133.66,
29.50, 29.38, 29.11, 26.38, 22.80, 14.25; HRMS: (ESI) calcd. for 132.75, 132.13, 131.27, 129.97, 129.23, 129.15, 128.21,
[M+] C28H35Cl4N2O: 555.1498, found 555.1503; IR (neat, cm-1) 127.58, 122.59, 121.42, 76.04, 68.29, 53.08, 50.27, 31.92,
3055.12, 3009.9, 2926.8, 2854.1, 1640.9, 1589.3, 1466.5, 30.28, 29.69, 29.66, 29.61, 29.53, 29.39, 29.36, 29.00, 26.24,
1379.8, 1338.8; Melting point: 81-84 °C.
22.69, 14.13. HRMS: (ESI) calcd. for [M+] C34H47Cl4N2O:
1-(2-((2,4-dichlorobenzyl)oxy)-2-(2,4-dichlorophenyl)ethyl)-3- 639.2447, found 639.2442; IR (neat, cm-1) 3148.1, 3051,6,
dodecyl-1H-imidazol-3-ium bromide (5e). A solution of (4)
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