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16), 133.1 (Cq, C-2), 129.5 (Cq, C-4), 126.6 (CH, C-15), 125.3 (CH,
C-7), 121.0 (CH, C-3), 119.6 (Cq, C-6), 115.9 (CH, C-14), 82.9
(CH, C-1), 55.8 (CH2, C-9), 47.8 (CH2, C-10), 34.4 (Cq, C-17), 31.8
(CH3, C-18), 29.3 (CH2, C-8), 24.5 (CH2, C-12), 23.8 (CH2, C-11);
HRMS (EI+) calcd m/z for [C33H38N2O•+] 478.2979; found
478.2971; IR (neat) 2947, 2801, 1609, 1510, 1493, 1464, 1436,
1329, 1274, 1236, 1181, 1145, 1124, 1011, 880, 825, 736 cm−1.
8,8′-((4-Methoxyphenoxy)methylene)bis(1,2,5,6-tetrahydro-4H-
pyrrolo[3,2,1-ij]quinoline) (3na): According to GPD, from 2a-BF4
(24.4 mg, 0.0586 mmol) and 1n-K (11.3 mg, 0.0696 mmol) in
DMSO (5 mL), a grayish solid was obtained (37.0 mg). The sample
contained residual amounts of water: 1H NMR (400 MHz, CD2Cl2) δ
= 6.92 (s, 2 H, 3-H), 6.88−6.83 (m, 2 H, 14-H), 6.81 (s, 2 H, 7-H),
6.77−6.73 (m, 2 H, 15-H), 5.85 (s, 1 H, 1-H), 3.71 (s, 3 H, 16-OMe),
3.23−3.20 (m, 4 H, 9-H), 2.95−2.92 (m, 4 H, 10-H), 2.85−2.81 (m,
4 H, 8-H), 2.66−2.59 (m, 4 H, 12-H), 2.09−1.99 (m, 4 H, 11-H);
13C{1H} NMR (101 MHz, CD2Cl2) δ = 154.1 (Cq, C-16), 153.1 (Cq,
the solvent, the crude product was purified by chromatography (SiO2,
20% pentane in ethyl acetate, Rf = 0.71) to obtain 3cn (92.4 mg,
80%): H NMR (300 MHz, CDCl3) δ = 8.17−8.10 (m, 2 H, 8-H),
1
7.33−7.29 (m, 4 H, 3-H), 7.21−7.18 (m, 4 H, 4-H), 7.04−7.01 (m, 2
H, 9-H), 6.29 (s, 1 H, 1-H), 2.36 (s, 6 H, 6-H); 13C{1H} NMR (75.5
MHz, CDCl3) δ = 163.3 (Cq, C-7), 141.6 (Cq, C-10), 138.1 (Cq, C-
5), 137.2 (Cq, C-2), 129.6 (CH, C-4), 126.8 (CH, C-3), 125.9 (CH,
C-9), 116.1 (CH, C-8), 82.4 (CH, C-1), 21.2 (CH3, C-6); HRMS
(EI+) calcd m/z for [C21H19NO3•+] 333.1359; found 333.1366.
4,4′-((2-Nitrophenoxy)methylene)bis(methylbenzene) (3dn): In a
flame-dried flask under nitrogen were dissolved 1d-NBu4 (124 mg,
0.325 mmol) and 2n-Br (50 mg, 0.182 mmol) in MeCN (10 mL) and
stirred for 4 h at room temperature to yield a yellow solution. After
removal of the solvent, the crude product was purified by flash column
chromatography (SiO2, 1−10% pentane in ethyl acetate, Rf = 0.68) to
1
yield 3dn as a pale yellow oil (42.8 mg, 71%): H NMR (400 MHz,
CDCl3) δ = 7.82 (dd, J = 8.1 Hz, J = 1.7 Hz, 1 H, 11-H), 7.40−7.38
(m, 4 H, 3-H), 7.36−7.33 (m, 1 H, 9-H), 7.17−7.14 (m, 4 H, 4-H),
7.06 (dd, J = 8.6 Hz, J = 1.2 Hz, 1 H, 8-H), 6.97−6.93 (m, 1 H, 10-
H), 6.33 (s, 1 H, 1-H), 2.32 (s, 6 H, 6-H); 13C{1H} NMR (101 MHz,
CDCl3) δ = 151.2 (Cq, C-7), 140.7 (Cq, C-12), 137.9 (Cq, C-5),
137.6 (Cq, C-2), 133.8 (CH, C-9), 129.6 (CH, C-4), 126.5 (CH, C-
3), 125.6 (CH, C-11), 120.4 (CH, C-10), 116.4 (CH, C-8), 82.7
(CH, C-1), 21.2 (CH3, C-6); HRMS (EI+) calcd m/z for
[C21H19NO3•+] 333.1359; found 333.1371; IR (neat) 3024, 2912,
1604, 1582, 1519, 1482, 1451, 1248, 1304, 1274, 1248, 1178, 1164,
1089, 1043, 1007, 861, 829, 805, 763, 742, 667 cm−1.
4,4′-((3-Nitrophenoxy)methylene)bis(methylbenzene) (3en): 1e-
NBu4 (124 mg, 0.325 mmol) and 2n-Br (50 mg, 0.182 mmol) were
dissolved in MeCN (10 mL) and stirred for 4 h at room temperature
to yield a yellow solution. After removal of the solvent, the crude
product was purified by flash column chromatography (SiO2, 5%
pentane in ethyl acetate, Rf = 0.92) to yield 3en as a yellow oil (48.7
mg, 80%): 1H NMR (599 MHz, CDCl3) δ = 7.80 (app t, J = 2.3 Hz, 1
H, 12-H), 7.77 (ddd, J = 8.0 Hz, J = 2.2 Hz, J = 0.9 Hz, 1 H, 10-H),
7.36 (app t, J = 8.2 Hz, 1 H, 9-H), 7.31−7.30 (m, 4 H, 3-H), 7.28
(ddd, J = 8.3 Hz, J = 2.5 Hz, J = 1.0 Hz, 1 H, 8-H), 7.18−7.16 (m, 4
H, 4-H), 6.25 (s, 1 H, 1-H), 2.34 (s, 6 H, 6-H); 13C{1H} NMR (151
MHz, CDCl3) δ = 158.7 (Cq, C-7), 149.2 (Cq, C-11), 138.0 (Cq, C-
5), 137.4 (Cq, C-2), 130.0 (CH, C-9), 129.6 (CH, C-4), 126.9 (CH,
C-3), 122.8 (CH, C-8), 116.0 (CH, C-10), 111.0 (CH, C-12), 82.3
(CH, C-1), 21.3 (CH3, C-6); HRMS (EI+) calcd m/z for
[C21H19NO3•+] 333.1359; found 333.1351; IR (neat) 3022, 2931,
1618, 1580, 1524, 1477, 1450, 1247, 1318, 1283, 1234, 1177, 1013,
822, 804, 763, 736, 671 cm−1.
4-(Di-p-tolylmethoxy)benzonitrile (3fn): 1f-NBu4 (292 mg, 0.810
mmol) and 2n-Br (106 mg, 0.385 mmol) were dissolved in MeCN
(ca. 20 mL) and stirred for 4 h. After removal of the solvent, the crude
product was purified by chromatography (SiO2, 20% pentane in ethyl
acetate, Rf = 0.53) to obtain 3fn (118 mg, 98%) as a yellowish oil: 1H
NMR (300 MHz, CDCl3) δ = 7.54−7.49 (m, 2 H, 9-H), 7.32−7.28
(m, 4 H, 3-H), 7.20−7.15 (m, 4 H, 4-H), 7.05−6.99 (m, 2 H, 8-H),
6.24 (s, 1 H, 1-H), 2.36 (s, 6 H, 6-H); 13C{1H} NMR (75.5 MHz,
CDCl3) δ = 161.5 (Cq, C-7), 138.0 (Cq, C-5), 137.4 (Cq, C-2), 133.9
(CH, C-9), 129.6 (CH, C-4), 126.8 (CH, C-3), 119.3 (Cq, 10-CN),
116.8 (CH, C-8), 104.1 (Cq, C-10), 82.0 (CH, C-1), 21.2 (CH3, C-
6); HRMS (EI+) calcd m/z for [C22H19NO•+] 313.1461; found
313.1460.
C-13), 150.1 (Cq, C-5), 133.1 (Cq, C-2), 129.4 (Cq, C-4), 125.3 (CH,
C-7), 120.9 (CH, C-3), 119.5 (Cq, C-6), 117.4 (CH, C-14), 114.8
(CH, C-15), 83.6 (CH, C-1), 56.1 (CH3, 16-OMe), 55.7 (CH2, C-9),
47.8 (CH2, C-10), 29.2 (CH2, C-8), 24.5 (CH2, C-12), 23.7 (CH2, C-
+
11); HRMS (EI+) calcd m/z for [C30H33N2O2 ] [M + H+] 453.2537;
found 453.2536.
4-(Bis(1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinolin-8-yl)-
methyl)-2,6-di-tert-butylphenol (4oa): According to GPD, from 2a-
BF4 (27.6 mg, 0.0663 mmol) and 1o-K (24.3 mg, 0.0994 mmol) in
DMSO (2 mL), a grayish solid was obtained (31.0 mg). The
precipitated material contained residual phenol 1o-H (26%), and 4oa
1
was obtained in a yield of 64% (22.8 mg, 0.0426 mmol). The H
NMR spectrum (in CD2Cl2) agreed with that detected for the crude
reaction mixture of 2a + 1o-K in DMSO-d6 (see the Supporting
Information) but comprised additional resonances for 1o-H: HRMS
(ESI+) calcd m/z for [C37H47N2O+] [M + H+] 535.3683; found
535.3680.
Reactions of 2n-Br with Phenolate Anions in Acetonitrile.
4,4′-((2,4-Dinitrophenoxy)methylene)bis(methylbenzene) (3an):
1a-NBu4 (138 mg, 0.325 mmol) and 2n-Br (50 mg, 0.182 mmol)
were dissolved in MeCN (10 mL) and stirred for 4 h at room
temperature to yield a yellow solution. After removal of the solvent,
the crude product was purified by flash column chromatography
(SiO2, 20% pentane in ethyl acetate, Rf = 0.88) to yield 3an as a
1
colorless oil (68.8 mg, 99%): H NMR (400 MHz, CDCl3) δ = 8.72
(d, J = 2.8 Hz, 1 H, 11-H), 8.25 (dd, J = 9.3 Hz, J = 2.8 Hz, 1 H, 9-H),
7.36−7.34 (m, 4 H, 3-H), 7.20−7.16 (m, 5 H, 4-H and 8-H), 6.43 (s,
1 H, 1-H), 2.32 (s, 6 H, 6-H); 13C{1H} NMR (101 MHz, CDCl3) δ =
155.7 (Cq, C-7), 140.1 (Cq, C-10), 139.7 (Cq, C-12), 138.6 (Cq, C-5),
136.2 (Cq, C-2), 129.9 (CH, C-4), 128.8 (CH, C-9), 126.4 (CH, C-
3), 121.9 (CH, C-11), 116.4 (CH, C-8), 84.2 (CH, C-1), 21.3 (CH3,
C-6); IR (neat) 3093, 3025, 2921, 1603, 1522, 1484, 1418, 1340,
1273, 1178, 1121, 1066, 998, 974, 907, 833, 819, 804, 773, 763, 742,
724 cm−1.
4,4′-((Perfluorophenoxy)methylene)bis(methylbenzene) (3bn):
1b-NBu4 (138 mg, 0.325 mmol) and 2n-Br (50 mg, 0.182 mmol)
were dissolved in MeCN (10 mL) and stirred for 4 h at room
temperature. After removal of the solvent, the crude product was
filtered through silica (SiO2, 1% pentane in ethyl acetate, Rf = 1) to
1
yield 3bn as a colorless oil (56.6 mg, 82%): H NMR (400 MHz,
CDCl3) δ = 7.32−7.30 (m, 4 H, 3-H), 7.16−7.15 (m, 4 H, 4-H), 6.34
(s, 1 H, 1-H), 2.34 (s, 3 H, 6-H); 13C{1H} NMR (101 MHz, CDCl3)
δ = 138.4 (Cq, C-5), 136.8 (Cq, C-2), 129.3 (CH, C-4), 127.2 (CH,
C-3), 87.2 (CH, C-1), 21.3 (CH3, C-6); the resonances of the
perfluorophenyl ring could not be clearly assigned; 19F NMR (377
MHz, CDCl3) δ = −154.15 to −154.24 (m, 2 F, 8-F), −163.00 to
−163.13 (m, 1 F, 10-F), −163.57 to −163.72 (m, 2 F, 9-F); HRMS
(EI+) calcd m/z for [C21H14F5O•+] 377.0959; found 377.0971; IR
(neat) 3026, 3923, 1508, 1465, 1302, 1181, 1152, 1018, 992, 950,
923, 806, 786, 774, 806, 786, 762 cm−1.
4,4′-((2-(Trifluoromethyl)phenoxy)methylene)bis-
(methylbenzene) (3gn): 1g-NBu4 (131 mg, 0.325 mmol) and 2n-Br
(50 mg, 0.182 mmol) were dissolved in MeCN (10 mL) and stirred
for 4 h at room temperature to yield a pale yellow solution. After
removal of the solvent, the crude product was purified by flash column
chromatography (SiO2, 5% pentane in ethyl acetate, Rf = 0.87) to
1
yield 3gn as a pale yellow oil (50.9 mg, 78%): H NMR (400 MHz,
CDCl3) δ = 7.58 (dd, J = 7.7 Hz, J = 1.7 Hz, 1 H, 11-H), 7.36−7.34
(m, 4 H, 3-H), 7.32−7.30 (m, 1 H, 9-H), 7.15−7.13 (m, 4 H, 4-H),
6.96−6.91 (m, 2 H, 8-H and 10-H), 6.28 (s, 1 H, 1-H), 2.31 (s, 6 H,
6-H); 13C{1H} NMR (101 MHz, CDCl3) δ = 155.7 (Cq, q, JC,F = 1.8
Hz, C-7), 138.2 (Cq, C-2), 137.6 (Cq, C-5), 133.1 (CH, C-9), 129.5
4,4′-((4-Nitrophenoxy)methylene)bis(methylbenzene) (3cn): 1c-
NBu4 (235 mg, 0.618 mmol) and 2n-Br (95.0 mg, 0.345 mmol) were
dissolved in MeCN (ca. 20 mL) and stirred for 4 h. After removal of
R
J. Org. Chem. XXXX, XXX, XXX−XXX