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Double Addition
KOREAN CHEMICAL SOCIETY
J = 8.4 Hz, 1H), 7.21 (d, J = 2.4 Hz, 1H), 7.20–7.14 (m,
2H), 7.06 (t, J = 8.7 Hz, 2H), 6.92 (t, J = 8.7 Hz, 2H),
5.65 (s, 2H), 4.03 (t, J = 7.2 Hz, 2H), 3.89–3.84 (m, 5H),
3.16–3.07 (m, 4H); 13C NMR (125 MHz, CDCl3) δ
(FAB+) m/z calcd for C25H24Cl2NO+ [M - Br−] 424.1229,
found 424.1222.
7-Methoxy-2-(3-methoxybenzyl)-1-(3-methoxyphe-
nethyl)-3,4-dihydroisoquinolin-2-ium bromide (3l): 1a
(100 mg, 0.571 mmol) and 3-methoxybenzyl bromide
(573 mg, 2.85 mmol) were used. Yield: 78% (221 mg,
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179.0, 163.4 (d, JC-F = 157.8 Hz), 161.4 (d,1JC-
= 154.2 Hz) 159.2, 133.6 4 (d, JC-F = 3.1 Hz), 130.7
F
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4 (d, JC-F = 8.3 Hz), 130.2 4 (d, JC-F = 7.8 Hz), 129.5,
129.2, 127.2 (d, JC-F = 3.1 Hz), 127.1, 122.9, 116.5 (d,
JC-F = 21.8 Hz), 115.8, 115.7 (d, JC-F = 21.2 Hz), 60.1,
56.1, 51.4, 34.2, 33.5, 25.4; LC/MS m/z 392.2 [M - Br−];
HRMS (FAB+) m/z calcd for C25H24F2NO+ [M - Br−]
392.1820, found 392.1855.
0.445 mmol), yellow solid. H NMR (300 MHz, CDCl3) δ
4.14 (d, J = 2.1 Hz, 1H), 7.31 (d, J = 8.7 Hz, 2H),
7.37–7.30 (m, 2H), 7.26–7.16 (m, 3H), 7.20–7.16 (m, 1H),
6.93–6.90 (m, 2H), 6.77 (d, J = 6.9 Hz, 2H), 6.71–6.68 (m,
2H), 5.60 (s, 2H), 4.12 (t, J = 7.2 Hz, 2H), 3.85 (s, 3H),
3.82 (s, 3H), 3.80–3.71 (m, 5H), 3.15–3.07 (m, 4H); 13C
NMR (125 MHz, CDCl3) δ 179.1, 160.4, 160.0, 159.4,
139.4, 132.9, 130.7, 130.1, 129.5, 129.3, 127.2, 122.9,
120.5, 119.7, 115.6, 114.7, 114.2, 114.0, 112.6, 61.1, 56.0,
55.6, 55.4, 51.3, 51.8, 34.3, 34.1, 25.5; LC/MS m/z 416.2
2-(3-Fluorobenzyl)-1-(3-fluorophenethyl)-7-methoxy-
3,4-dihydroisoquinolin-2-ium
bromide
(3i):
1a
(100 mg, 0.571 mmol) and 2-methylbenzyl bromide
(527 mg, 2.85 mmol) were used. Yield: 83% (221 mg,
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+
0.476 mmol), yellow solid. H NMR (300 MHz, CDCl3)
[M - Br−]; HRMS (FAB+) m/z calcd for C27H30NO3 [M -
δ 7.45 (d, J = 2.4 Hz, 1H), 7.33–7.25 (m, 3H), 7.23–7.07
(m, 5H), 6.95 (t, J = 6.9 Hz, 2H), 5.55 (s, 2H), 4.07 (t,
J = 7.8 Hz, 2H), 3.87 (s, 3H), 3.67 (t, J = 7.5 Hz, 2H),
3.21–3.10 (m, 4H), 2.39 (s, 3H), 2.25 (s, 3H); 13C NMR
(125 MHz, CDCl3) δ 179.8, 159.5, 137.0, 136.3, 135.8,
131.5, 130.9, 129.7, 129.6, 129.4,129.3, 128.8, 127.6,
127.3, 126.9, 126.7, 126.4, 123.0, 115.4, 59.4, 56.0, 53.5,
51.7, 32.9, 31.9, 25.5, 19.7, 19.3; LC/MS m/z 384.2 [M -
Br−]; HRMS (FAB+) m/z calcd for C27H30NO+ [M - Br−]
384.2322, found 384.2347.
Br−] 416.2220, found 416.2199.
2-Benzyl-1-phenethyl-3,4-dihydroisoquinolin-2-ium
bromide (3m): 1b (100 mg, 0.689 mmol) and benzyl bro-
mide (590 mg, 3.45 mmol) were used. Yield: 91%
(255 mg, 0.628 mmol), slightly yellow solid.1H NMR
(300 MHz, CDCl3) δ 7.97 (d, J = 7.8 Hz, 1H), 7.65 (t,
J = 8.0 Hz, 1H), 7.46 (t, J = 7.7 Hz, 1H), 7.36–7.32 (m,
4H), 7.31–7.17 (m, 5H), 7.10 (dd, J = 7.6, 1.7 Hz, 2H),
5.52 (s, 2H), 4.06 (t, J = 7.4 Hz, 2H), 3.77 (t, J = 7.8 Hz,
2H), 3.17 (t, J = 7.4 Hz, 2H), 3.08 (t, J = 7.8 Hz, 2H); 13C
NMR (125 MHz, CDCl3) δ 178.9, 137.9, 137.5, 136.9,
131.5, 130.8, 129.7, 129.5, 129.1, 128.7, 128.6, 128.3,
128.1, 127.4, 126.4, 61.1, 51.3, 34.4, 34.0, 26.3; LC/MS
m/z 326.5 [M - Br−]; HRMS (FAB+) m/z calcd for
C24H24N+ [M - Br−] 326.1903, found 326.1895.
2-(3-Fluorobenzyl)-1-(3-fluorophenethyl)-7-methoxy-
3,4-dihydroisoquinolin-2-ium bromide (3j): 1a (100 mg,
0.571 mmol) and 3-fluorobenzyl bromide (412 mg,
2.85 mmol) were used. Yield: 81% (218 mg, 0.462 mmol),
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yellow solid. H NMR (300 MHz, CDCl3) δ 7.41–7.28 (m,
3H), 7.26–7.06 (m, 5H), 6.96 (d, J = 7.8 Hz, 1H),
6.91–6.86 (m, 2H), 5.69 (s, 2H), 4.09 (t, J = 7.2 Hz, 2H),
3.88–3.83 (m, 5H), 3.16–3.12 (m, 4H); 13C NMR
2-Benzyl-6-methoxy-1-phenethyl-3,4-dihydroisoquinolin-
2-ium bromide (3n): 1d (100 mg, 0.571 mmol) and ben-
zyl bromide (488 mg, 2.85 mmol) were used. Yield: 81%
(202 mg, 0.462 mmol), slightly yellow solid. 1H NMR
(300 MHz, CDCl3) δ 7.99 (d, J = 9.0 Hz, 1H), 7.42–7.32
(m, 3H), 7.31–7.20 (m, 5H), 7.19–7.10 (m, 2H), 6.97 (dd,
J = 8.9, 2.5 Hz, 1H), 6.91 (d, J = 2.3 Hz, 1H), 5.40
(s, 2H), 4.03 (t, J = 7.4 Hz, 2H), 3.93 (s, 3H), 3.69 (t, J =
7.7 Hz, 2H), 3.19 (t, J = 7.4 Hz, 2H), 3.11 (t, J = 7.7 Hz,
2H); 13C NMR (125 MHz, CDCl3) δ 176.8, 166.6, 140.9,
138.0, 133.8, 131.9, 129.6, 129.3, 129.1, 128.4, 127.9,
127.3, 118.9, 114.7, 113.9, 60.1, 56.3, 50.8, 34.6,
33.5, 26.8; LC/MS m/z 326.5 [M - Br−]; HRMS (FAB+) m/z
calcd for C25H26NO+ [M - Br−] 356.2009, found 356.1993.
2-Benzyl-6,7-dimethoxy-1-phenethyl-3,4-dihydroiso-
quinolin-2-ium bromide (3o): 1d (100 mg, 0.487 mmol)
and benzyl bromide (417 mg, 2.44 mmol) were used.
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(125 MHz, CDCl3) δ 179.4, 163.9 (d, JC-F = 25.6 Hz),
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161.9 (d, JC-F = 23.6 Hz), 159.4, 140.3 (d, JC-F = 7.2 Hz),
133.91 (d, JC-F = 7.2 Hz), 131.4 (d, JC-F = 8.2 Hz), 130.6
(d, JC-F = 8.2 Hz), 129.6, 129.4, 127.1, 124.2 (d, JC-
= 2.6 Hz), 124.2 (d, JC-F = 2.9 Hz), 123.1, 116.5 (d, JC-
F
= 20.6 Hz), 115.7, 115.3 (d, JC-F = 21.2 Hz), 115.0 (d,
F
JC-F = 22.2 Hz), 114.3 (d, JC-F = 20.9 Hz), 60.7, 56.0,
51.9, 34.0 (d, JC-F = 10.8 Hz), 25.5; LC/MS m/z 392.1
[M - Br−]; HRMS (FAB+) m/z calcd for C25H24F2NO+
[M - Br−] 392.1820, found 392.1855.
2-(3-Chlorobenzyl)-1-(3-chlorophenethyl)-7-methoxy-
3,4-dihydroisoquinolin-2-ium bromide (3k): 1a (100 mg,
0.571 mmol) and 3-chlorobenzyl bromide (580 mg,
2.85 mmol) were used. Yield: 80% (230 mg, 0.456 mmol),
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1
yellow solid. H NMR (300 MHz, CDCl3) δ 7.36–7.34 (m,
Yield: 78% (177 mg, 0.380 mmol), yellow solid. H NMR
6H), 7.30–7.06 (m, 5H), 5.71 (s, 2H), 4.09 (t, J = 7.2 Hz,
2H), 3.85–3.80 (m, 5H), 3.18–3.09 (m, 4H); 13C NMR
(125 MHz, CDCl3) δ 179.4, 159.4, 139.9, 135.5, 134.6,
133.6, 131.1, 130.4, 129.7, 129.6, 129.4, 128.4, 128.0,
127.5, 127.2, 126.8, 126.6, 123.2, 115.7, 60.8, 56.1, 51.9,
34.0, 33.9, 25.5; LC/MS m/z 424.1 [M - Br−]; HRMS
(300 MHz, CDCl3) δ 7.43–7.35 (m, 3H), 7.31–7.21 (m,
6H), 7.12 (dd, J = 7.5, 1.8 Hz, 2H), 6.91 (s, 1H), 5.40 (s,
2H), 4.07–3.98 (m, 5H), 3.88 (s, 3H), 3.76 (t, J = 7.5 Hz,
2H), 3.14 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 177.0,
156.7, 148.8, 138.2, 133.9, 131.9, 129.6, 129.3, 129.1,
128.5, 127.8, 127.4, 118.8, 112.8, 110.9, 60.2, 56.9, 56.8,
Bull. Korean Chem. Soc. 2019
© 2019 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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