10.1002/chem.201905595
Chemistry - A European Journal
FULL PAPER
Reaction time: 48 h, column chromatography (isohexane/ethyl acetate, 1–
3%, 1 h, 3–8%, 0.5 h, 8–15%, 20 min). Biaryl 3g (44.2 mg, 139 μmol, 69%)
was obtained as a colorless solid. M.p. 126.5 °C; UV (MeOH): λ = 231,
286, 335 nm; fluorescence (MeOH): λex = 231 nm, λem = 411 nm; IR (ATR):
푣̃ = 3058, 3028, 2936, 2920, 2844, 1590, 1495, 1465, 1438, 1378, 1332,
1276, 1227, 1147, 1099, 1063, 1030, 953, 918, 903, 867, 817, 751, 726,
676, 635 cm–1; 1H NMR (600 MHz, CDCl3): δ = 1.55 (m, 6 H), 2.32 (s, 3 H),
2.89 (m, 4 H), 7.13 (d, J = 8.3 Hz, 1 H), 7.21 (m, 2 H), 7.30 (d, J = 8.7 Hz,
1 H), 7.34 (m, 1 H), 7.38 (m, 1 H), 7.77 (d, J = 9.0 Hz, 1 H), 7.82 (m, 2 H)
ppm; 13C NMR and DEPT (151 MHz, CDCl3): δ = 20.81 (CH3), 23.93 (CH2),
26.22 (2 CH2), 53.72 (2 CH2), 118.69 (CH), 121.02 (CH), 121.31 (C),
123.14 (CH), 125.60 (CH), 126.06 (CH), 128.26 (CH), 129.15 (CH), 129.34
(CH), 130.16 (C), 131.19 (C), 132.63 (C), 133.63 (C), 135.87 (CH), 148.09
(C), 151.83 (C) ppm; ESI-MS (+10 V): m/z = 318.2 [M+H]+; elemental
analysis (%) calcd for C22H23NO: C 83.24, H 7.30, N 4.41; found: C 83.44,
H 7.42, N 4.35.
6-Bromo-1-(2-(dimethylamino)-5-methoxyphenyl)naphthalen-2-ol (3j): 4-
Methoxy-N,N-dimethylaniline (90.7 mg, 600 µmol), dichloromethane (6
mL), 6-bromo-2-naphthol (268 mg, 1.20 mmol), methanesulfonic acid
(23.2 mg, 241 µmol), FePcF16 (5.1 mg, 6.0 µmol). Reaction time: 24 h,
column chromatography (isohexane/ethyl acetate, 2–8%, 1.5 h, 8–15%,
20 min). Biaryl 3j (196 mg, 526 μmol, 88%) was obtained as a dark yellow
solid. M.p. 169 °C; UV (MeOH): λ = 235, 282, 348 nm; fluorescence
(MeOH): λex = 235 nm, λem = 422 nm; IR (ATR): 푣̃ = 3058, 3021, 2985,
2949, 2924, 2850, 2830, 2790, 1736, 1679, 1630, 1574, 1490, 1451, 1415,
1360, 1331, 1290, 1233, 1203, 1163, 1068, 1038, 1003, 953, 925, 877,
813, 769, 672, 615 cm–1 1H NMR (600 MHz, CDCl3): δ = 2.67 (s, 6 H),
;
3.75 (s, 3 H), 6.91 (d, J = 3.0 Hz, 1 H), 6.98 (dd, J = 8.7, 3.0 Hz, 1 H), 7.23
(d, J = 8.7 Hz, 1 H), 7.30 (d, J = 9.0 Hz, 1 H), 7.42 (dd, J = 9.0, 2.3 Hz, 1
H), 7.69 (d, J = 6.0 Hz, 1 H), 7.70 (d, J = 6.4 Hz, 1 H), 7.96 (d, J = 2.3 Hz,
1 H), 10.51 (br s, 1 H) ppm; 13C NMR and DEPT (151 MHz, CDCl3): δ =
44.30 (2 CH3), 55.78 (CH3), 114.54 (CH), 116.91 (C), 119.56 (CH), 119.98
(CH), 120.83 (C), 122.09 (CH), 127.18 (CH), 128.74 (CH), 129.45 (CH),
130.20 (CH), 131.16 (C), 131.83 (C), 132.07 (C), 143.11 (C), 152.79 (C),
155.56 (C) ppm; ESI-MS (+10 V): m/z = 372.1 [M+H]+; ESI-MS (–10 V):
m/z = 369.9 [M‒H]–, elemental analysis (%) calcd for C19H18BrNO2: C
61.30, H 4.87, N 3.76; found: C 60.97, H 4.83, N 3.52.
4a (49.0 mg, 171 μmol, 28%).
1-(5-Methyl-2-morpholinophenyl)naphthalen-2-ol
(3h):
4-(4-
Tolyl)morpholine (70.9 mg, 400 µmol), dichloromethane (4 mL), 2-
naphthol (2a) (346 mg, 2.40 mmol), methanesulfonic acid (15.5 mg, 161
µmol), FePcF16 (3.4 mg, 4.0 µmol). Reaction time: 24 h, column
chromatography (isohexane/ethyl acetate, 2–5%, 1 h, 5–8%, 45 min, 8–
15%, 0.5 h). Biaryl 3h (90.3 mg, 283 μmol, 71%) was obtained as a brown
solid. M.p. 94 °C; UV (MeOH): λ = 230, 288, 334 nm; fluorescence
(MeOH): λex = 334 nm, λem = 412 nm; IR (ATR): 푣̃ = 3055, 2960, 2912,
2851, 1726, 1618, 1593, 1497, 1450, 1362, 1334, 1298, 1275, 1227, 1154,
1113, 1068, 1045, 954, 916, 877, 815, 749, 730, 676, 662, 635, 613 cm–1;
1H NMR (600 MHz, CDCl3): δ = 2.34 (s, 3 H), 2.99 (m, 4 H), 3.68 (m, 4 H),
7.18 (d, J = 8.3 Hz, 1 H), 7.23 (dd, J = 17.4, 1.5 Hz, 2 H), 7.32 (d, J =
8.7 Hz, 1 H), 7.36 (m, 1 H), 7.38 (m, 1 H), 7.73 (d, J = 8.3 Hz, 1 H), 7.79
(d, J = 8.7 Hz, 1 H), 7.83 (dd, J = 7.9, 1.5 Hz, 1 H), 9.69 (br s, 1 H) ppm;
13C NMR and DEPT (151 MHz, CDCl3): δ = 20.84 (CH3), 52.49 (2 CH2),
66.84 (2 CH2), 118.52 (CH), 120.60 (CH), 120.64 (C), 123.45 (CH), 125.35
(CH), 126.40 (CH), 128.34 (CH), 129.58 (CH), 129.77 (CH), 130.12 (C),
130.44 (C), 133.40 (C), 133.73 (C), 135.97 (CH), 146.26 (C), 151.42
(C) ppm; ESI-MS (+10 V): m/z = 320.2 [M+H]+; ESI-MS (–10 V): m/z =
1-(5-Chloro-2-(dimethylamino)phenyl)naphthalen-2-ol (3k): 4-Chloro-N,N-
dimethylaniline (93.4 mg, 600 µmol), dichloromethane (6 mL), 2-naphthol
(2a) (347 mg, 2.41 mmol), methanesulfonic acid (23.1 mg, 240 µmol),
FePcF16 (5.1 mg, 6.0 µmol). Reaction time: 24 h, column chromatography
(isohexane/ethyl acetate, 1–3%, 0.5 h, 3–7%, 1.5 h, 7–15%, 20 min).
Biaryl 3k (63.8 mg, 214 μmol, 36%) was obtained as a brownish yellow
solid. M.p. 128 °C; UV (MeOH): λ = 230, 282, 333 nm; fluorescence
(MeOH): λex = 230 nm, λem = 364, 422 nm; IR (ATR): 푣̃ = 3051, 2959, 2916,
2876, 2845, 2797, 2056, 1701, 1632, 1592, 1510, 1474, 1455, 1391, 1358,
1336, 1299, 1272, 1234, 1176, 1150, 1127, 1112, 1038, 997, 952, 924,
890, 849, 815, 787, 746, 721, 686, 640, 624 cm–1 1H NMR (600 MHz,
;
CDCl3): δ = 2.67 (s, 6 H), 7.20 (d, J = 8.7 Hz, 1 H), 7.27 (d, J = 8.8 Hz, 1
H), 7.37 (m, 2 H), 7.40 (d, J = 2.4 Hz, 1 H), 7.42 (m, 1 H), 7.76 (d, J =
8.5 Hz, 1 H), 7.81 (d, J = 8.8 Hz, 1 H), 7.83 (m, 1 H), 9.66 (br s, 1 H) ppm;
13C NMR and DEPT (151 MHz, CDCl3): δ = 43.72 (2 CH3), 119.62 (CH),
119.85 (C), 120.70 (CH), 123.51 (CH), 124.97 (CH), 126.72 (CH), 128.33
(C), 128.39 (CH), 128.40 (CH), 130.04 (C), 130.09 (CH), 132.50 (C),
133.13 (C), 134.81 (CH), 148.72 (C), 152.26 (C) ppm; ESI-MS (+10 V):
m/z = 298.1 [M+H]+; elemental analysis (%) calcd for C18H16ClNO: C 72.60,
H 5.42, N 4.70; found: C 72.63, H 5.50, N 4.39.
+
318.1 [M‒H]–, HRMS (ESI) calcd for C21H22NO2 ([M+H]+): 320.1651;
found: 320.1654.
4a (116 mg, 405 μmol, 34%).
1-(2-(Dimethylamino)-5-methoxyphenyl)naphthalen-2-ol (3i): 4-Methoxy-
N,N-dimethylaniline (90.7 mg, 600 µmol), dichloromethane (6 mL), 2-
naphthol (2a) (177 mg, 1.23 mmol), methanesulfonic acid (23.3 mg, 241
µmol), FePcF16 (5.1 mg, 6.0 µmol). Reaction time: 24 h, column
chromatography (isohexane/ethyl acetate, 2–8%, 1.5 h, 8–15%, 20 min).
Biaryl 3i (144 mg, 491 μmol, 82%) was obtained as a colorless solid. M.p.
4a (90.5 mg, 316 μmol, 26%).
1,1-Bis(2-(dimethylamino)-4-(triisopropylsilyloxy)phenyl)naphthalen-
2(1H)-one (6): N,N-Dimethyl-3-(triisopropylsilyloxy)aniline (5) (173 mg,
589 μmol), dichloromethane (6 mL), 2-naphthol (2a) (173 mg, 1.20 mmol),
methanesulfonic acid (23.1 mg, 240 µmol), FePcF16 (10.5 mg, 12.3 µmol).
Reaction time: 24 h, column chromatography (isohexane/ethyl acetate, 1–
3%,1 h, 3–15%, 0.5 h, 15%, 20 min). Compound 6 was obtained as a pale
yellow solid (78.2 mg, 108 μmol, 37%). M.p. 261 °C; UV (MeOH): λ = 219,
259, 293 nm; fluorescence (MeOH): λex = 259 nm, λem = 443 nm; IR (ATR):
푣̃ = 2942, 2886, 2864, 2790, 1738, 1690, 1651, 1606, 1557, 1542, 1508,
1453, 1423, 1356, 1255, 1185, 1122, 1091, 998, 922, 882, 798, 752, 680,
641 cm–1; 1H NMR (500 MHz, CDCl3): δ = 0.83 (d, J = 7.6 Hz, 9 H), 0.88
(d, J = 7.6 Hz, 9 H), 0.94 (d, J = 7.6 Hz, 9 H), 1.01 (d, J = 7.6 Hz, 9 H),
1.06 (m, 3 H), 1.33 (m, 3 H), 2.86 (s, 6 H), 2.87 (s, 6 H), 5.94 (d, J = 10.1 Hz,
1 H), 6.04 (m, 2 H), 6.13 (d, J = 2.2 Hz, 1 H), 6.21 (br d, J = 9.1 Hz, 2 H),
6.75 (m, 2 H), 6.97 (d, J = 10.1 Hz, 1 H), 7.09 (m, 1 H), 7.19 (m, 2 H) ppm;
13C NMR and DEPT (125 MHz, CDCl3): δ = 13.23 (3 CH), 13.61 (3 CH),
18.09 (3 CH3), 18.19 (3 CH3), 18.29 (3 CH3), 18.42 (3 CH3), 40.49 (2 CH3),
41.50 (2 CH3), 63.91 (C), 103.24 (CH), 104.23 (CH), 104.86 (CH), 105.03
(CH), 116.07 (C), 119.06 (C), 126.57 (CH), 127.37 (CH), 128.28 (CH),
128.76 (CH), 129.52 (CH), 130.43 (CH), 132.33 (C), 133.29 (CH), 139.09
141.5 °C; UV (MeOH): λ = 233, 287, 336 nm; fluorescence (MeOH): λex
=
233 nm, λem = 412 nm; IR (ATR): 푣̃ = 3045, 3004, 2972, 2954, 2919, 2873,
2829, 2790, 1619, 1594, 1558, 1542, 1500, 1460, 1408, 1361, 1337, 1308,
1292, 1238, 1192, 1168, 1037, 1005, 954, 922, 879, 861, 816, 754, 724,
698, 675, 636, 605 cm–1 1H NMR (600 MHz, CDCl3): δ = 2.67 (s, 6 H),
;
3.75 (s, 3 H), 6.98 (m, 2 H), 7.24 (d, J = 8.3 Hz, 1 H), 7.29 (d, J = 8.7 Hz,
1 H), 7.34 (m, 1 H), 7.38 (m, 1 H), 7.80 (d, J = 8.7 Hz, 1 H), 7.83 (m, 2 H),
10.49 (br s, 1 H) ppm; 13C NMR and DEPT (151 MHz, CDCl3): δ = 44.26
(2 CH3), 55.78 (CH3), 114.33 (CH), 119.40 (CH), 120.11 (CH), 120.65 (C),
120.94 (CH), 123.25 (CH), 125.30 (CH), 126.31 (CH), 128.33 (CH), 129.70
(CH), 129.99 (C), 132.30 (C), 133.49 (C), 143.20 (C), 152.39 (C), 155.44
(C) ppm; ESI-MS (+10 V): m/z = 294.1 [M+H]+; elemental analysis (%)
calcd for C19H19NO2: C 77.79, H 6.53, N 4.77; found: C 77.76, H 6.81, N
4.77.
4a (34.2 mg, 120 μmol, 20%).
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