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The Journal of Organic Chemistry
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4.2 Hz, 1H), 7.37 (t, J = 7.5 Hz, 1H), 7.28 (d, J = 7.2 Hz, 1H),
7.11 – 6.98 (m, 4H), 6.95 – 6.79 (m, 1H), 4.37 (s, 2H), 2.33 (s,
3H); 13C {1H} NMR (125 MHz, CDCl3) δ 159.2, 149.3, 137.0,
136.1, 135.4, 130.4, 130.0, 127.5, 126.1, 122.3, 119.5, 32.8, 19.3.
2-((2-Chlorobenzyl)thio)pyridine (3ae). Colorless oil (82.4
mg, 70%).9d 1H NMR (500 MHz, CDCl3) δ 8.48 (d, J = 4.5
Hz, 1H), 7.59 – 7.43 (m, 2H), 7.39 – 7.30 (m, 1H), 7.22 –
7.09 (m, 3H), 7.11 – 6.94 (m, 1H), 4.59 (s, 2H); 13C {1H} NMR
(125 MHz, CDCl3) δ 158.3, 149.1, 136.3 135.8, 134.3, 131.0,
129.6, 128.5, 126.8, 122.5, 119.7, 32.1.
1H), 6.95 – 6.90 (m, 1H), 4.35 (s, 2H); C {1H} NMR (125
MHz, CDCl3) δ 157.6, 150.3, 149.5, 148.3, 136.5, 136.1, 134.4,
123.3, 122.3, 119.9, 31.3;. HRMS (ESI) for C11H11N2S (M+H)
Calcd: 203.0643; found: 203.0666.
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2-(Phenethylthio)pyridine (3am). Colorless oil (44.8 mg,
42%).21 1H NMR (500 MHz, CDCl3) δ 8.45 (d, J = 4.5 Hz,
1H), 7.46 (t, J = 8.0 Hz, 1H), 7.37 – 7.09 (m, 6H), 7.04 –
6.84 (m, 1H), 3.43 (t, J = 7.5 Hz, 2H), 3.01 (t, J = 7.5 Hz, 2H) ;
13C {1H} NMR (125 MHz, CDCl3) δ 159.0, 149.4, 140.6, 135.9,
128.6, 128.4, 126.4, 122.4, 119.3, 35.9, 31.5.
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2-((4-nitrobenzyl)thio)pyridine (3af). Colorless oil (84.0
mg, 68%). 1H NMR (600 MHz, CDCl3) δ 8.45 (d, J = 4.2 Hz,
1H), 8.12 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 8.4 Hz, 2H), 7.49 (t,
J = 7.2 Hz, 1H), 7.17 (d, J = 8.4 Hz, 1H), 7.09 – 6.93 (m, 1H),
2-(Octylthio)pyridine (3an). Colorless oil, (42.1 mg, 38%).22
1H NMR (500 MHz, CDCl3) δ 8.42 (t, J = 4.5 Hz, 1H), 7.47
(dt, J = 7.5, 5.5 Hz, 1H), 7.25 – 7.11 (m, 1H), 7.07 – 6.85 (m,
1H), 3.20 – 3.13 (m, 2H), 1.75 – 1.65 (m, 2H), 1.50 – 1.40 (m,
2H), 1.37 – 1.15 (m, 8H), 0.87 (t, J = 6.5 Hz, 3H); 13C {1H}
NMR (125 MHz, CDCl3) δ 159.7, 149.2, 136.0, 122.2, 119.2,
31.8, 30.3, 29.3, 29.1, 28.9, 22.6, 14.0.
2-(Benzhydrylthio)pyridine (3ao). White solid, m.p. 69-70
oC, (111.0 mg, 80%).23 1H NMR (500 MHz, CDCl3) δ 8.37 (s,
1H), 7.51 – 7.36 (m, 5H), 7.33 – 7.16 (m, 6H), 7.11 (dd, J = 7.5,
4.5 Hz, 1H), 6.98 – 6.90 (m, 1H), 6.35 (d, J = 4.5 Hz, 1H); 13C
{1H} NMR (125 MHz, CDCl3) δ 158.3, 149.2, 141.3, 136.3,
128.6, 128.5, 127.1, 122.5, 119.9, 52.9.
2-((1-Phenylethyl)thio)pyridine (3ap). White solid, 47-49
oC, (66.1 mg, 62%).9d 1H NMR (500 MHz, CDCl3) δ 8.45 (d,
J = 4.5 Hz, 1H), 7.44 (t, J = 6.5 Hz, 3H), 7.29 (t, J = 7.5 Hz,
2H), 7.21 (t, J = 7.5 Hz, 1H), 7.11 (d, J = 8.0 Hz, 1H), 7.06 –
6.85 (m, 1H), 5.13 (q, J = 7.0 Hz, 1H), 1.74 (d, J = 7.0 Hz, 3H);
13C {1H} NMR (125 MHz, CDCl3) δ 158.8, 149.2, 143.2, 136.3,
128.5, 127.4, 127.2, 123.1, 119.7, 43.8, 22.6.
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4.52 (s, 2H); C {1H} NMR (150 MHz, CDCl3) δ 157.1, 149.3,
147.0, 146.5, 136.3, 129.8, 123.6, 122.4, 120.1, 33.4. HRMS (ESI)
for C12H11N2O2S (M+H) Calcd: 247.0541; found: 247.0520.
2-((4-fluorobenzyl)thio)pyridine (3ag). Colorless oil (89.8
mg, 82%). 1H NMR (600 MHz, CDCl3) δ 8.44 (d, J = 4.8 Hz,
1H), 7.44 (t, J = 7.8 Hz, 1H), 7.35 (dd, J = 7.8, 6.0 Hz, 2H),
7.14 (d, J = 7.8 Hz, 1H), 6.96 (dt, J = 13.2, 7.8 Hz, 3H), 4.40
(s, 2H); 13C {1H} NMR (150 MHz, CDCl3) δ 162.0 (d, J = 245.3
Hz), 158.4 (s), 149.4 (s), 136.1 (s), 133.9 (d, J = 3.2 Hz), 130.5
(d, J = 8.1 Hz), 122.2 (s), 119.7 (s), 115.3 (d, J = 21.4 Hz), 33.6
(s). HRMS (ESI) for C12H11FNS (M+H) Calcd: 220.0596;
found: 220.0608.
2-((4-Bromobenzyl)thio)pyridine (3ah). Colorless oil (109.0
mg, 78%).20 1H NMR (500 MHz, CDCl3) δ 8.44 (d, J = 4.5
Hz, 1H), 7.46 (t, J = 7.5 Hz, 1H), 7.38 (d, J = 8.5 Hz, 2H),
7.27 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 8.0 Hz, 1H), 7.03 – 6.93
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(m, 1H), 4.39 (s, 2H); C {1H} NMR (125 MHz, CDCl3) δ
2-(Benzylthio)-3-fluoropyridine (3ba). Colorless oil, (83.5
mg, 76%).9d 1H NMR (500 MHz, CDCl3) δ 8.28 (s, 1H), 7.41
(d, J = 7.5 Hz, 2H), 7.31 – 7.31 (m, 4H), 7.01 (dd, J = 7.5, 4.0
158.1, 149.2, 137.3, 136.3, 131.5, 130.7, 122.4, 121.0, 119.8, 33.8.
1-((Naphthalen-1-ylmethyl)thio)pyridine (3ai). White solid,
113-115 C (75.0 mg, 60%).9d 1H NMR (500 MHz, CDCl3) δ
Hz, 1H), 4.48 (s, 2H); C {1H} NMR (125 MHz, CDCl3) δ
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8.51 (d, J = 4.0 Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 7.84 (d, J =
8.0 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 7.0 Hz, 1H),
7.52 – 7.42 (m, 3H), 7.37 (t, J = 7.5 Hz, 1H), 7.13 (d, J = 8.0
Hz, 1H), 7.03 – 6.94 (m, 1H), 4.93 (s, 2H); 13C {1H} NMR
(125 MHz, CDCl3) δ 159.0, 149.2, 136.2, 134.0, 133.2, 131.8,
128.8, 128.2, 127.6, 126.3, 125.8, 125.4, 124.0, 122.4, 119.7, 32.4.
2-((Naphthalen-1-ylmethyl)thio)pyridine (3aj). White solid,
156.1 (d, J = 256.0 Hz), 147.5 (d, J = 17.8 Hz), 144.8 (d, J =
5.0 Hz), 129.1 (s), 128.5 (s), 127.2 (s), 121.1 (d, J = 18.0 Hz),
120.1 (d, J = 2.8 Hz), 33.3 (s).
2-(Benzylthio)-3-chloropyridine (3ca). Colorless oil, (93.0
mg, 79%).9d 1H NMR (500 MHz, CDCl3) δ 8.36 (d, J = 4.5
Hz, 1H), 7.52 (d, J = 80 Hz, 1H), 7.42 (d, J = 7.5 Hz, 2H),
7.34 – 7.17 (m, 3H), 6.95 (dd, J = 8.0, 4.5 Hz, 1H), 4.46 (s,
2H); 13C {1H} NMR (125 MHz, CDCl3) δ 157.3, 146.8, 137.5,
135.9, 129.2, 129.0, 128.5, 127.2, 119.8, 34.7.
2-(Benzylthio)-4-methylpyridine (3da). Colorless oil, (91.5
mg, 85%).9d 1H NMR (500 MHz, CDCl3) δ 8.30 (d, J = 5.1
Hz, 1H), 7.39 (d, J = 7.4 Hz, 2H), 7.32 – 7.17 (m, 3H), 6.98
(s, 1H), 6.80 (d, J = 5.0 Hz, 1H), 4.42 (s, 2H), 2.24 (s, 3H);
13C {1H} NMR (125 MHz, CDCl3) δ 158.6, 149.1, 147.3, 138.2,
129.1, 128.6, 127.1, 122.7, 121.1, 34.5, 20.9.
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124-125 C, (101.5 mg, 81%). H NMR (600 MHz, CDCl3) δ
8.46 (d, J = 4.2 Hz, 1H), 7.83 (s, 1H), 7.76 (t, J = 7.8 Hz, 3H),
7.51 (d, J = 8.4 Hz, 1H), 7.45 – 7.34 (m, 3H), 7.14 (d, J = 8.4
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Hz, 1H), 7.00 – 6.84 (m, 1H), 4.60 (s, 2H); C {1H} NMR
(150 MHz, CDCl3) δ 158.7, 149.3, 136.2, 135.4, 133.4, 132.7,
128.3, 127.8, 127.7, 127.6, 127.2, 126.2, 125.8, 122.3, 119.7, 34.8.
HRMS (ESI) for C16H14NS (M+H) Calcd: 252.0847; found:
252.0864.
2-((Thiophen-2-ylmethyl)thio)pyridine (3ak). Colorless oil,
(79.0, 76%).9d 1H NMR (500 MHz, CDCl3) δ 8.50 (d, J = 4.0
Hz, 1H), 7.53 (t, J = 7.0 Hz, 1H), 7.21 (d, J = 8.0 Hz, 1H), 7.15
(dd, J = 5.0, 1.0 Hz, 1H), 7.09 – 6.97 (m, 2H), 6.89 (dd, J =
5.0, 3.5 Hz, 1H), 4.70 (s, 2H); 13C {1H} NMR (125 MHz,
CDCl3) δ 157.9, 148.8, 140.7, 136.8, 126.7, 126.6, 125.0, 122.8,
120.0, 29.3.
2-(Benzylthio)isonicotinonitrile (3ea). White solid, 78-79
oC, (69.5 mg, 61%).9d 1H NMR (500 MHz, CDCl3) δ 8.57 (d,
J = 5.0 Hz, 1H), 7.38 (d, J = 7.5 Hz, 2H), 7.34 – 7.19 (m, 4H),
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7.14 (d, J = 5.0 Hz, 1H), 4.44 (s, 2H); C {1H} NMR (125
MHz, CDCl3) δ 161.3, 150.1, 137.0, 129.0, 128.6, 127.4, 123.7,
120.4, 120.2, 116.2, 34.5.
2-(Benzylthio)-5-methoxypyridine (3fa). Colorless oil, (62.5
mg, 54%).9d 1H NMR (500 MHz, CDCl3) δ 8.18 (s, 1H), 7.31
(d, J = 7.5 Hz, 2H), 7.26 – 7.09 (m, 6H), 4.42 (s, 2H), 3.79
(s, 3H); 13C {1H} NMR (125 MHz, CDCl3) δ 154.3, 148.5, 137.2,
133.9, 129.0, 128.5, 127.3, 125.3, 124.9, 56.2, 36.6.
2-((pyridin-3-ylmethyl)thio)pyridine (3al). Colorless oil,
(16.0 mg, 16%). 1H NMR (500 MHz, CDCl3) δ 8.57 (d, J = 1.8
Hz, 1H), 8.42 – 8.32 (m, 2H), 7.68 – 7.64 (m, 1H), 7.45 –
7.34 (m, 1H), 7.13 (dd, J = 7.2, 4.8 Hz, 1H), 7.12 – 7.05 (m,
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