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Liu AP, et al. Sci China Chem January (2013) Vol.56 No.1
4-Bromo-2-(4-chlorophenyl)-1-((2-fluoroethoxy)-methyl)-
7.45–7.54 (m, 4H, Ph H); MS (70 eV) m/z: Calcd. 448,
found 448; Anal. calcd for C17H13BrClF3N2O2: C 45.41, H
2.91, N 6.23; found C 45.25, H 2.97, N 6.25.
5-(trifluoromethyl)pyrrole-3-carbonitrile (6d). White solid,
1
m.p. 86.6–88.8 °C; H NMR (CDCl3, 300 MHz) : 3.60 (t,
4-Bromo-2-(4-chlorophenyl)-1-((prop-2-yn-1-yloxy)
methoxy)methyl-5-(trifluoromethyl)pyrrole-3-carbonitrile (7f).
White solid, m.p. 139.3–140.7 °C; H NMR (CDCl3, 300
MHz) : 2.42 (s, 1H, CH), 4.11 (s, 2H, CH2), 4.73 (s, 2H,
CH2), 5.33 (s, 2H, CH2), 7.46–7.55 (m, 4H, Ph H); MS (70
eV) m/z: Calcd. 446, found 446; Anal. calcd for
C17H11BrClF3N2O2: C 45.61, H 2.48, N 6.26; found C 45.64,
H 2.56, N 6.15.
J = 4.2 Hz, 2H, CH2), 4.43 (t, J = 4.2 Hz, 2H, CH2), 5.27 (s,
2H, CH2), 7.49–7.55 (m, 4H, Ph H); MS (70 eV) m/z: Calcd.
424, found 424; Anal. calcd for C15H10BrClF4N2O: C 42.33,
H 2.37, N 6.58; found C 42.42, H 2.33, N 6.52.
1
4-Bromo-1-((2-bromoethoxy)methyl)-2-(4-chlorophenyl)-
5-(trifluoromethyl)pyrrole-3-carbonitrile (6e). White solid,
1
m.p. 91.7–94.2 °C; H NMR (CDCl3, 300 MHz) : 3.40 (t,
J = 5.7 Hz, 2H, CH2), 3.73 (t, J = 5.7 Hz, 2H, CH2), 5.26 (s,
2H, CH2), 7.49–7.55 (m, 4H, Ph H); 13C NMR (CDCl3, 75
MHz) δ: 144.41, 137.40, 131.12, 129.68, 124.77, 121.71,
118.12, 113.25, 103.74, 99.25, 75.18, 68.94, 29.31; MS (70
eV) m/z: Calcd. 484, found 484; Anal. calcd for
C15H10Br2ClF3N2O: C 37.03, H 2.07, N 5.76; found C 37.07,
H 2.11, N 5.72.
4-Bromo-2-(4-chlorophenyl)-1-((methoxymethoxy)methyl)-
5-(trifluoromethyl)pyrrole-3-carbonitrile (7a). White solid;
1H NMR (CDCl3, 300 MHz) : 3.29 (s, 3H, CH3), 4.60 (s,
2H, CH2), 5.29 (s, 2H, CH2), 7.50–7.52 (m, 4H, Ph H); MS
(70 eV) m/z: Calcd. 422, found 422; Anal. calcd for
C15H11BrClF3N2O2: C 42.53, H 2.62, N 6.61; found C 42.54,
H 2.50, N 6.67.
4-Bromo-2-(4-chlorophenyl)-1-((ethoxymethoxy)methyl)-
5-(trifluoromethyl)pyrrole-3-carbonitrile (7b). White solid,
m.p. 115.8–116.8 °C; 1H NMR (CDCl3, 300 MHz) : 1.08–
1.13 (t, J = 7.2 Hz, 3H, CH3), 3.46 (q, J = 7.0 Hz, 2H, CH2),
4.63 (s, 2H, CH2), 5.31 (s, 2H, CH2), 7.477.55 (m, 4H, Ph
H); 13C NMR (CDCl3, 75 MHz) : 144.48, 137.29, 131.26,
129.51, 125.04, 121.76, 118.18, 113.31, 103.68, 99.28,
93.60, 73.24, 64.28, 14.79; MS (70 eV) m/z: Calcd. 436,
found 436; Anal. calcd for C16H13BrClF3N2O2: C 43.91, H
2.99, N 6.40; found C 43.95, H 3.03, N 6.25.
4-Bromo-2-(4-chlorophenyl)-1-((propoxymethoxy)methyl)-
5-(trifluoromethyl)pyrrole-3-carbonitrile (7c). White solid,
m.p. 109.7–111.2 °C; 1H NMR (CDCl3, 300 MHz) δ: 0.83 (t,
J = 6.6 Hz, 3H, CH3), 1.43 (m, 2H, CH2), 3.36 (t, J = 7.5
Hz, 2H, CH2), 4.62 (s, 2H, CH2), 5.31 (s, 2H, CH2),
7.46–7.55 (m, 4H, Ph H); MS (70 eV) m/z: Calcd. 450,
found 450; Anal. calcd for C17H15BrClF3N2O2: C 45.21, H
3.35, N 6.20; found C 45.33, H 3.33, N 6.18.
4-Bromo-2-(4-chlorophenyl)-1-((2-methoxyethoxy)
methyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (7g). White
1
solid, m.p. 102.1–103.7 °C; H NMR (CDCl3, 300 MHz)
: 3.31 (s, 3H, CH3), 3.49–3.50 (m, 2H, CH2), 3.51–3.52 (m,
2H, CH2), 5.26 (s, 2H, CH2), 7.52 (s, 4H, Ph H); MS (70 eV)
m/z: Calcd. 436, found 436; Anal. calcd for
C16H13BrClF3N2O2: C 43.91, H 2.99, N 6.40; found C 43.90,
H 2.96, N 6.51.
1-((2-(Allyloxy)ethoxy)methyl-4-bromo-2-(4-chlorophenyl)-
5-(trifluoromethyl)pyrrole-3-carbonitrile (7h). White solid,
1
m.p. 77.3–80.2 °C; H NMR (CDCl3, 300 MHz) : 3.52–
3.58 (m, 4H, CH2CH2), 3.93 (d, J = 8.4 Hz, 2H, CH2), 5.17
(s, 2H, CH2), 5.25 (s, 2H, CH2), 5.78–5.88 (m, 1H, CH),
7.52–7.56 (m, 4H, Ph H); 13C NMR (CDCl3, 75 MHz) δ:
144.34, 137.11, 134.84, 131.21, 129.60, 125.03, 121.70,
118.12, 117.30, 113.36, 103.38, 98.92, 75.83, 72.13, 69.06,
68.33; MS (70 eV) m/z: Calcd. 462, found 462; Anal. calcd
for C18H15BrClF3N2O2: C 46.63, H 3.26, N 6.04; found C
46.69, H 3.43, N 6.09.
4-Bromo-2-(4-chlorophenyl)-1-((2-(prop-2-yn-1-yl)oxy)
ethoxy)methyl-5-(trifluoromethyl)pyrrole-3-carbonitrile (7i).
White solid, m.p. 78.1–80.6 °C; 1H NMR (CDCl3, 300 MHz)
δ: 2.08 (s, 1H, CH), 3.56–3.65 (m, 4H, CH2CH2), 4.12 (s,
2H, CH2), 5.26 (s, 2H, CH2), 7.53 (s, 4H, Ph H); 13C NMR
(CDCl3, 75 MHz) δ: 144.39, 137.17, 131.26, 129.55, 125.05,
121.75, 118.17, 113.39, 103.52, 98.83, 78.99, 75.83, 74.90,
68.82, 68.18, 58.39; MS (70 eV) m/z: Calcd. 460, found 460;
Anal. calcd for C18H13BrClF3N2O2: C 46.83, H 2.84, N 6.07;
found C 46.83, H 2.93, N 6.00.
4-Bromo-2-(4-chlorophenyl)-1-((methylthio)methoxy)
methyl-5-(trifluoromethyl)pyrrole-3-carbonitrile (8a). Yel-
low solid, m.p. 145.9–146.7 °C; 1H NMR (CDCl3, 300 MHz)
δ: 2.09 (s, 3H, CH3), 4.55 (s, 2H, CH2), 5.35 (s, 2H, CH2),
7.46–7.56 (m, 4H, Ph H); MS (70 eV) m/z: Calcd. 438,
found 438; Anal. calcd for C15H11BrClF3N2OS: C 40.98, H
2.52, N 6.37; found C 40.85, H 2.61, N 6.34.
4-Bromo-2-(4-chlorophenyl)-1-((isopropoxymethoxy)
methyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (7d). White
solid, m.p. 74.976.9 °C; 1H NMR (CDCl3, 300 MHz) : 1.04
(d, J = 9.3 Hz, 6H, 2CH3), 3.72–3.78 (m, 1H, CH), 4.64 (s,
2H, CH2), 5.32 (s, 2H, CH2), 7.46–7.54 (m, 4H, Ph H); MS
(70 eV) m/z: Calcd. 450, found 450; Anal. calcd for
C17H15BrClF3N2O2: C 45.21, H 3.35, N 6.20; found C 45.09,
H 3.30, N 6.29.
4-Bromo-2-(4-chlorophenyl)-1-((ethylthio)methoxy)
methyl-5-(trifluoromethyl)pyrrole-3-carbonitrile (8b). White
1
solid, m.p. 97.6–98.8 °C; H NMR (CDCl3, 300 MHz) δ:
1-((2-Allyloxy)methoxy)methyl-4-bromo-2-(4-chlorophe-
nyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (7e). White
solid, m.p. 116.0–118.1 °C; 1H NMR (CDCl3, 300 MHz) :
3.95 (d, J = 5.7 Hz, 2H, CH2), 4.65 (s, 2H, CH2), 5.15–5.18
(m, 2H, CH2), 5.33 (s, 2H, CH2), 5.70–5.83 (m, 1H, CH),
1.20 (t, J = 7.2 Hz, 3H, CH3), 2.49 (q, J = 7.2 Hz, 2H, CH2),
4.58 (s, 2H, CH2), 5.35 (s, 2H, CH2), 7.44–7.55 (m, 4H, Ph
H); 13C NMR (CDCl3, 75 MHz) δ: 144.49, 137.45, 131.19,
129.62, 124.90, 121.71, 118.13, 113.24, 103.80, 99.27,
72.80, 71.14, 24.89, 14.49; MS (70 eV) m/z: Calcd. 452,