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The Journal of Organic Chemistry
The Journal of Organic Chemistry
Article
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NMR (75.41 MHz, 23.0 °C, DMSO-d6): δ 166.7, 136.9,
134.4, 130.9, 130.6, 126.9, 122.0 ppm. Anal. Calcd for
C7H6BrNO:C, 42.03; H, 3.02; N, 7.00; Found: C, 42.03; H,
3.02; N, 7.00. HRMS (ESI) m/z: [M+H] Calcd for
C7H7BrNO 199.9711; Found: 199.9718.
HRMS (ESI) m/z: [M+H] Calcd for C17H22N 240.1752;
Found: 240.1758.
N-(4-methoxybenzyl)aniline (4e):15 white solid, mp 62-
64ꢀ°C ; 100 mg, 94% yield. Purification by column chroma-
tography on silica gel (pentane/ethyl ether = 30/1). 1H
NMR (299.86 MHz, 23.0 °C, CDCl3): δ 7.32 (d, J = 8.3 Hz,
2H), 7.21 (t, J = 7.5 Hz, 2H), 6.91 (d, J = 8.0 Hz, 2H), 6.75
(t, J = 7.3 Hz, 1H), 6.67 (d, J = 7.7 Hz, 2H), 4.28 (s, 2H),
3.97 (bs, 1H), 3.83 (s, 3H) ppm; 13C{1H} NMR (75.41
MHz, 23.0 °C, CDCl3): δ 158.8, 148.2, 131.3, 129.2, 128.8,
117.4, 114.0, 112.8, 55.3, 47.7 ppm. Anal. Calcd for
C14H15NO: C, 78.84; H, 7.09; N, 6.57; Found: C, 78.95; H,
7.11; N, 6.62. HRMS (ESI) m/z: [M+H] Calcd for
C14H16NO 214.1232; Found: 214.1236.
Thiophene-2-carboxamide (3n):14 white solid, 50 mg,
78% yield. Purification by column chromatography on sili-
ca gel (pentane/ethyl ether = 1/2, DCM 10%, CH3OH 10%).
1H NMR (299.86 MHz, 23.0 °C, DMSO-d6): δ 7.99 (s, 1H),
7.76-7.74 (m, 2H), 7.39 (s, 1H), 7.14-7.12 (m, 1H) ppm;
13C{1H} NMR (75.41 MHz, 23.0 °C, DMSO-d6): δ 163.3,
140.8, 131.4, 129.1, 128.4 ppm. Anal. Calcd for C5H5NOS:
C, 47.23; H, 3.96; N, 11.02; Found: C, 47.71; H, 3.52; N,
11.13. HRMS (ESI) m/z: [M+H] Calcd for C5H6NOS
128.0170; Found: 128.0175.
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N-(2-methoxybenzyl)aniline (4f):15 white solid; mp 92-
94ꢀ°C ; 76 mg, 71% yield. Purification by column chroma-
tography on silica gel (pentane/ethyl ether = 30/1). 1H
NMR (299.86 MHz, 23.0 °C, CDCl3): δ 7.22 (d, J = 7.4 Hz,
1H), 7.16 (t, J = 8.1 Hz, 1H), 7.08 (dd, J = 11.3, 4.3 Hz,
2H), 6.82 (dd, J = 16.1, 7.9 Hz, 2H), 6.69 – 6.46 (m, 3H),
4.25 (s, 2H), 4.03 (bs, 1H), 3.77 (s, 3H) ppm; 13C{1H}
NMR (75.41 MHz, 23.0 °C, CDCl3): δ 157.4, 148.5,
129.224, 128.934, 128.344, 127.4, 120.6, 117.4, 113.1,
110.3, 55.34 43.5 ppm. Anal. Calcd for C14H15NO: C,
78.84; H, 7.09; N, 6.57; Found: C, 78.74; H, 7.17; N, 6.56.
HRMS (ESI) m/z: [M+H] Calcd for C14H16NO 214.1232;
Found: 214.1237.
N-benzylaniline (4a):15 light yellow oil, 85 mg, 93%
yield. Purification by column chromatography on silica gel
(pentane/ethyl ether = 20/1). 1H NMR (299.86 MHz,
23.0 °C, CDCl3): δ 7.40 – 7.14 (m, 5H), 7.09 (t, J = 7.6 Hz,
2H), 6.63 (t, J = 7.2 Hz, 1H), 6.55 (d, J = 8.1 Hz, 2H), 4.23
(s, 2H), 3.94 (bs, 1H) ppm; 13C{1H} NMR (75.41 MHz,
23.0 °C, CDCl3): δ 148.1, 139.4, 129.2, 128.6, 127.5, 127.2,
117.5, 112.8, 48.3 ppm. Anal. Calcd for C13H13N: C, 85.21;
H, 7.15; N, 7.64; Found: C, 85.45; H, 7.26; N, 7.42. HRMS
(ESI) m/z: [M+H] Calcd for C13H14N 184.1126; Found:
184.1128.
N-(3-methylbenzyl)aniline (4b):15 yellow oil, 89 mg,
90% yield. Purification by column chromatography on sili-
ca gel (pentane/ethyl ether = 30/1). 1H NMR (299.86 MHz,
23.0 °C, CDCl3): δ 7.41-7.31 (m, 5H), 7.25 (d, J = 7.2 Hz,
1H), 6.88 (t, J = 7.3 Hz, 1H), 6.78 (d, J = 7.6 Hz, 2H), 4.41
(s, 2H), 4.09 (bs, 1H), 2.51 (s, 3H) ppm; 13C{1H} NMR
(75.41 MHz, 23.0 °C, CDCl3): δ 148.1, 139.3, 138.2, 129.1,
128.4, 128.2, 127.9, 124.5, 117.4, 112.7, 48.2, 21.3 ppm.
Anal. Calcd for C14H15N: C, 85.24; H, 7.66; N, 7.10; Found:
C, 85.31; H, 7.42; N, 7.15. HRMS (ESI) m/z: [M+H] Calcd
for C14H16N 198.1283; Found: 198.1279.
N-(4-chlorobenzyl)aniline (4g):15 light yellow oil, 93 mg,
86% yield. Purification by column chromatography on sili-
ca gel (pentane/ethyl ether = 20/1). 1H NMR (299.86 MHz,
23.0 °C, CDCl3): δ 7.35 (d, J = 3.8 Hz, 4H), 7.30 – 7.18 (m,
2H), 6.87 – 6.72 (m, 1H), 6.72 – 6.57 (m, 2H), 4.35 (s, 2H),
4.09 (bs, 1H) ppm; 13C{1H} NMR (75.41 MHz, 23.0 °C,
CDCl3): δ 147.7, 137.9, 132.7, 129.2, 128.7, 128.6, 117.7,
112.8, 47.5 ppm. Anal. Calcd for C13H12ClN:C, 71.73; H,
5.56; N, 6.43; Found: C, 71.64; H, 5.75; N, 6.52. HRMS
(ESI) m/z: [M+H] Calcd for C13H13ClN 218.0737; Found:
218.0737.
N-(2-methylbenzyl)aniline (4c):15 yellow oil, 72 mg,
73% yield. Purification by column chromatography on sili-
ca gel (pentane/ethyl ether = 30/1). 1H NMR (299.86 MHz,
23.0 °C, CDCl3): δ 7.43 (d, J = 6.1 Hz, 1H), 7.39 – 7.26 (m,
5H), 6.96 – 6.78 (m, 1H), 6.77 – 6.63 (m, 2H), 4.35 (s, 2H),
3.90 (bs, 1H), 2.47 (d, J = 1.7 Hz, 3H) ppm; 13C{1H} NMR
(75.41 MHz, 23.0 °C, CDCl3): δ 148.2, 136.9, 136.3, 130.3,
129.2, 128.2, 127.3, 126.1, 117.4, 112.6, 46.3, 18.9 ppm.
Anal. Calcd for C14H15N: C, 85.24; H, 7.66; N, 7.10; Found:
C, 85.45; H, 7.42; N, 7.18. HRMS (ESI) m/z: [M+H] Calcd
for C14H16N 198.1283; Found: 198.1280.
N-(4-bromobenzyl)aniline (4h):15 yellow oil, 106 mg,
81% yield. Purification by column chromatography on sili-
ca gel (pentane/ethyl ether = 20/1). 1H NMR (299.86 MHz,
23.0 °C, CDCl3): δ 7.52-7.49 (m, 2H), 7.37 – 7.18 (m, 4H),
6.81-6.76 (m, 1H), 6.66 (d, J = 7.1 Hz, 2H), 4.34 (s, 2H),
4.09 (bs, 1H) ppm; 13C{1H} NMR (75.41 MHz, 23.0 °C,
CDCl3): δ 147.7, 138.5, 131.6, 129.3, 129.0, 120.9, 117.8,
112.8, 47.6 ppm. Anal. Calcd for C13H12BrN: C, 59.56; H,
4.61; N, 5.34; Found: C, 59.73; H, 4.59; N, 5.44. HRMS
(ESI) m/z: [M+H] Calcd for C13H13BrN 262.0231; Found:
262.0237.
N-(4-(tert-butyl)benzyl)aniline (4d):15 white solid, mp
38–40ꢀ°C ; 110 mg, 92% yield. Purification by column
chromatography on silica gel (pentane/ethyl ether = 30/1).
1H NMR (299.86 MHz, 23.0 °C, CD2Cl2): δ 7.36 (dd, J =
19.9, 8.3 Hz, 4H), 7.20 (t, J = 6.2 Hz, 2H), 6.74 (t, J = 7.3
Hz, 1H), 6.67 (d, J = 7.8 Hz, 2H), 4.31 (s, 2H), 4.01 (bs,
1H), 1.35 (s, 9H) ppm; 13C{1H} NMR (75.41 MHz, 23.0 °C,
CD2Cl2): δ 150.1, 148.4, 136.6, 129.1, 127.2, 125.4, 117.2,
112.7, 47.7, 34.4, 31.1 ppm. Anal. Calcd for C17H21N: C,
85.30; H, 8.84; N, 5.85; Found: C, 85.41; H, 8.72; N, 5.90.
N-(naphthalen-1-ylmethyl)aniline (4i):15 white solid, mp
67-69ꢀ°C ; 84 mg, 72% yield. Purification by column chro-
matography on silica gel (pentane/ethyl ether = 30/1, DCM
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2%). H NMR (299.86 MHz, 23.0 °C, CDCl3): δ 8.25-8.23
(m, 1H), 8.10-8.07 (m, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.75
– 7.67 (m, 3H), 7.66 – 7.55 (m, 1H), 7.42 (t, J = 7.8 Hz,
2H), 6.98 (t, J = 7.3 Hz, 1H), 6.83 (d, J = 7.9 Hz, 2H), 4.85
(s, 2H), 4.08 (bs, 1H) ppm; 13C{1H} NMR (75.41 MHz,
23.0 °C, CDCl3): δ 148.2, 134.3, 133.8, 131.5, 129.3, 128.7,
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