Job/Unit: O43510
/KAP1
Date: 10-02-15 15:30:24
Pages: 11
Effective Nitration of Anilides and Acrylamides by tert-Butyl Nitrite
(500 MHz, CDCl3): δ = 11.21 (s, 1 H, NH), 9.06 (dd, J = 9.4, (ESI): calcd. for C14H11N2O3 [M – H]– 255.0770; found 255.0787.
5.1 Hz, 1 H, ArNH), 7.98–8.03 (m, 3 H, ArNH and ArCO), 7.63
N-(5-Methoxy-2-nitrophenyl)benzamide (2g) and N-(3-Methoxy-4-
(t, J = 7.5 Hz, 1 H, ArCO), 7.56 (t, J = 7.5 Hz, 2 H, ArCO), 7.48
nitrophenyl)benzamide (2gЈ): Data for 2g: Yellow solid (64% yield);
(t, J = 9.4 Hz, 1 H, ArNH) ppm. 13C NMR (125 MHz, CDCl3): δ
Rf = 0.79 (petroleum ether/ethyl acetate, 8:1 v/v). 1H NMR
= 165.7, 157.0 (d, J = 247.9 Hz), 136.6 (d, J = 9.3 Hz), 133.8, 132.8,
(500 MHz, CDCl3): δ = 11.83 (s, 1 H, NH), 8.69 (s, 1 H, ArNH),
132.0, 129.1, 127.3, 124.0 (d, J = 7.2 Hz), 123.7 (d, J = 22.1 Hz),
8.28 (d, J = 9.4 Hz, 1 H, ArNH), 8.02 (d, J = 7.3 Hz, 2 H, ArCO),
112.43 (d, J = 27.2 Hz) ppm. HRMS (ESI): calcd. for C13H8FN2O3
7.63 (t, J = 7.3 Hz, 1 H, ArCO), 7.56 (t, J = 7.3 Hz, 2 H, ArCO),
[M – H]– 259.0519; found 259.0538.
6.72 (d, J = 9.4 Hz, 1 H, ArNH), 3.98 (s, 3 H, OMe) ppm. 13C
NMR (125 MHz, CDCl3): δ = 166.1, 165.9, 138.3, 134.0, 132.7,
129.7, 129.1, 128.2, 127.4, 111.1, 104.1, 56.2 ppm. HRMS (ESI):
calcd. for C14H11N2O4 [M – H]– 271.0719; found 271.0739. Data
for 2gЈ: White solid (24% yield); Rf = 0.43 (petroleum ether/ethyl
N-(4-Chloro-2-nitrophenyl)benzamide (2c): Yellow solid (94%
yield); Rf = 0.72 (petroleum ether/ethyl acetate, 8:1 v/v). H NMR
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(500 MHz, CDCl3): δ = 11.28 (s, 1 H, NH), 9.04 (d, J = 9.1 Hz, 1
H, ArNH), 8.29 (s, 1 H, ArNH), 7.99 (d, J = 7.1 Hz, 2 H, ArCO),
7.68 (d, J = 9.1 Hz, 1 H, ArNH), 7.64 (t, J = 7.1 Hz, 1 H, ArCO),
7.56 (t, J = 7.1 Hz, 2 H, ArCO) ppm. 13C NMR (125 MHz,
CDCl3): δ = 165.7, 136.6, 136.1, 134.0, 133.7, 132.9, 129.1, 128.5,
127.4, 125.5, 123.4 ppm. HRMS (ESI): calcd. for C13H8ClN2O3
[M – H]– 275.0224; found 275.0244.
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acetate, 8:1 v/v). H NMR (500 MHz, [D6]acetone): δ = 10.11 (s, 1
H, NH), 7.93–8.05 (m, 4 H, ArCO and ArNH), 7.95 (d, J = 9.0 Hz,
1 H, ArNH), 7.62 (t, J = 7.4 Hz, 1 H, ArCO), 7.58–7.49 (m, 3 H,
ArCO and ArNH), 3.98 (s, 3 H, OMe) ppm. 13C NMR (125 MHz,
[D6]acetone): δ = 167.1, 155.1, 146.1, 135.5, 135.4, 133.0, 129.5,
128.6, 127.5, 111.9, 105.2, 56.9 ppm. HRMS (ESI): calcd. for
C14H11N2O4 [M – H]– 271.0719; found 271.0737.
N-(4-Ethoxy-2-nitrophenyl)benzamide (2d): Yellow solid (98%
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yield); Rf = 0.79 (petroleum ether/ethyl acetate, 8:1 v/v). H NMR
N-(1-Nitronaphthalen-2-yl)benzamide (2h): Yellow solid (70%
(500 MHz, CDCl3): δ = 11.10 (s, 1 H, NH), 8.89 (d, J = 9.3 Hz, 1
H, ArNH), 7.99 (d, J = 7.4 Hz, 2 H, ArCO), 7.74 (s, 1 H, ArNH),
7.61 (t, J = 7.4 Hz, 1 H, ArCO), 7.54 (t, J = 7.4 Hz, 2 H, ArCO),
7.30 (d, J = 9.3 Hz, 1 H, ArNH), 4.11 (q, J = 6.9 Hz, 2 H, CH2),
1.47 (t, J = 6.9 Hz, 3 H, CH3) ppm. 13C NMR (125 MHz, CDCl3):
δ = 165.6, 154.4, 137.1, 134.2, 132.4, 129.0, 128.9, 127.3, 124.0,
123.6, 109.4, 64.4, 14.6 ppm. HRMS (ESI): calcd. for C15H13N2O4
[M – H]– 285.0876; found 285.0891.
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yield); Rf = 0.74 (petroleum ether/ethyl acetate, 8:1 v/v). H NMR
(500 MHz, CDCl3): δ = 9.85 (s, 1 H, NH), 8.05–8.15 (m, 4 H,
ArCO and ArNH), 7.94 (d, J = 8.2 Hz, 1 H, ArNH), 7.88 (d, J =
9.0 Hz, 1 H, ArNH), 7.71 (t, J = 7.3 Hz, 1 H, ArNH), 7.60–7.69
(m, 2 H, ArCO and ArNH), 7.59 (t, J = 7.6 Hz, 2 H, ArCO) ppm.
13C NMR (125 MHz, CDCl3): δ = 166.5, 140.7, 136.1, 133.3, 132.8,
131.1, 129.8, 129.0, 128.9, 128.2, 127.7, 127.7, 127.5, 127.2,
120.2 ppm. HRMS (ESI): calcd. for C17H11N2O3 [M – H]–
291.0770; found 291.0790.
N-(5-Bromo-2-nitrophenyl)benzamide (2e) and N-(3-Bromo-4-
nitrophenyl)benzamide (2eЈ): Data for 2e: Yellow solid (46% yield);
Rf = 0.74 (petroleum ether/ethyl acetate, 6:1 v/v). 1H NMR
(500 MHz, CDCl3): δ = 11.42 (s, 1 H, NH), 9.33 (s, 1 H, ArNH),
8.17 (d, J = 9.0 Hz, 1 H, ArNH), 8.00 (d, J = 7.5 Hz, 2 H, ArCO),
7.64 (t, J = 7.5 Hz, 1 H, ArCO), 7.57 (t, J = 7.5 Hz, 2 H, ArCO),
7.36 (d, J = 9.0 Hz, 1 H, ArNH) ppm. 13C NMR (125 MHz,
CDCl3): δ = 165.7, 136.2, 135.0, 133.6, 132.9, 131.7, 129.1, 127.4,
127.0, 126.5, 124.7 ppm. HRMS (ESI): calcd. for C13H8BrN2O3
[M – H]– 318.9719; found 318.9738. Data for 2eЈ: Light yellow solid
N-(2-Methyl-4-nitrophenyl)benzamide (2iЈ): White solid (47%
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yield); Rf = 0.50 (petroleum ether/ethyl acetate, 6:1 v/v). H NMR
(500 MHz, [D6]acetone): δ = 8.13 (s, 1 H, ArNH), 8.03 (d, J =
7.1 Hz, 2 H, ArCO), 7.84 (d, J = 7.6 Hz, 1 H, ArNH), 7.68 (d, J
= 7.6 Hz, 1 H, ArNH), 7.62 (t, J = 7.1 Hz, 2 H, ArCO), 7.55 (d, J
= 7.1 Hz, 2 H, ArCO), 2.42 (s, 3 H, CH3) ppm. 13C NMR
(125 MHz, [D6]acetone): δ = 166.5, 143.9, 139.4, 135.9, 135.0,
133.0, 132.8, 129.5, 128.5, 127.9, 123.3, 18.4 ppm. HRMS (ESI):
calcd. for C14H11N2O3 [M – H]– 255.0770; found 255.0787.
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(27% yield); Rf = 0.38 (petroleum ether/ethyl acetate, 6:1 v/v). H
NMR (500 MHz, CDCl3): δ = 8.19 (s, 1 H, ArNH), 8.04 (s, 1 H,
NH), 8.01 (d, J = 8.9 Hz, 1 H, ArNH), 7.88 (d, J = 7.6 Hz, 2 H,
ArCO), 7.78 (d, J = 8.9 Hz, 1 H, ArNH), 7.63 (t, J = 7.6 Hz, 1 H,
ArCO), 7.53 (d, J = 7.6 Hz, 2 H, ArCO) ppm. 13C NMR
(125 MHz, [D6]acetone): δ = 167.1, 145.4, 144.9, 135.1, 133.2,
129.5, 128.6, 127.8, 125.8, 119.9, 115.4 ppm. HRMS (ESI): calcd.
for C13H8BrN2O3 [M – H]– 318.9719; found 318.9739.
N-(2-Nitrophenyl)isonicotinamide (2k) and N-(4-Nitrophenyl)iso
nicotinamide (2kЈ): Data for 2k: Yellow solid (42% yield); Rf =
0.63 (petroleum ether/ethyl acetate, 6:1 v/v). H NMR (500 MHz,
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CDCl3): δ = 11.46 (s, 1 H, NH), 8.99 (d, J = 8.5 Hz, 1 H, ArNH),
8.89 (d, J = 6.0 Hz, 2 H, pyridine), 8.33 (d, J = 7.8 Hz, 1 H,
ArNH), 7.84 (d, J = 6.0 Hz, 2 H, pyridine), 7.77 (t, J = 7.8 Hz, 1
H, ArNH), 7.30 (t, J = 8.5 Hz, 1 H, ArNH) ppm. 13C NMR
(125 MHz, CDCl3): δ = 163.8, 151.1, 141.1, 136.6, 136.4, 134.6,
126.1, 124.1, 122.2, 120.9 ppm. HRMS (ESI): calcd. for
C12H8N3O3 [M – H]– 242.0566; found 242.0582. Data for 2kЈ:
White solid (17% yield); Rf = 0.31 (petroleum ether/ethyl acetate,
6:1 v/v). This is a known compound.[26] 1H NMR (500 MHz, [D6]-
DMSO): δ = 11.05 (s, 1 H), 8.84 (dd, J = 4.8, 1.5 Hz, 2 H, pyridine),
8.28 (d, J = 9.2 Hz, 2 H, ArNH), 8.04 (d, J = 9.2 Hz, 2 H, ArNH),
7.86 (dd, J = 4.8, 1.5 Hz, 2 H, pyridine) ppm. HRMS (ESI): calcd.
for C12H8N3O3 [M – H]– 242.0566; found 242.0584.
N-(5-Methyl-2-nitrophenyl)benzamide (2f) and N-(3-Methyl-4-
nitrophenyl)benzamide (2fЈ): Data for 2f: Yellow solid (68% yield);
Rf = 0.69 (petroleum ether/ethyl acetate, 8:1 v/v). 1H NMR
(500 MHz, CDCl3): δ = 11.45 (s, 1 H, NH), 8.86 (s, 1 H, ArNH),
8.19 (d, J = 8.5 Hz, 1 H, ArNH), 8.01 (d, J = 7.2 Hz, 2 H, ArCO),
7.62 (t, J = 7.2 Hz, 1 H, ArCO), 7.56 (t, J = 7.2 Hz, 2 H, ArCO),
7.03 (d, J = 8.5 Hz, 1 H, ArNH), 2.50 (s, 3 H, CH3) ppm. 13C
NMR (125 MHz, CDCl3): δ = 165.8, 148.3, 135.3, 134.4, 134.1,
132.6, 129.0, 127.4, 125.9, 124.3, 122.0, 22.2 ppm. HRMS (ESI):
calcd. for C14H11N2O3 [M – H]– 255.0770; found 255.0786. Data
4-Fluoro-N-(2-nitrophenyl)benzamide (2l) and 4-Fluoro-N-(4-
nitrophenyl)benzamide (2lЈ): Data for 2l: Yellow solid (63% yield);
for 2fЈ: White solid (24% yield); Rf = 0.31 (petroleum ether/ethyl
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acetate, 8:1 v/v). H NMR (500 MHz, [D6]acetone): δ = 10.07 (s, 1 Rf = 0.77 (petroleum ether/ethyl acetate, 8:1 v/v). 1H NMR
H, NH), 8.07 (d, J = 8.7 Hz, 1 H, ArNH), 8.02 (d, J = 7.5 Hz, 2 (500 MHz, CDCl3): δ = 11.31 (s, 1 H, NH), 8.97 (d, J = 8.5 Hz, 1
H, ArCO), 7.92–7.97 (m, 2 H, ArNH), 7.61 (t, J = 7.5 Hz, 1 H,
H, ArNH), 8.28 (d, J = 8.5 Hz, 1 H, ArNH), 8.02 (dd, J = 8.0,
ArCO), 7.53 (t, J = 7.5 Hz, 2 H, ArCO), 2.60 (s, 3 H, CH3) ppm. 5.4 Hz, 2 H, ArCO), 7.72 (dd, J = 8.5, 8.0 Hz, 1 H, ArNH), 7.26–
13C NMR (125 MHz, [D6]acetone): δ = 167.0, 145.0, 144.7, 135.9,
7.19 (m, 3 H, ArCO and ArNH) ppm. 13C NMR (125 MHz,
135.5, 132.9, 129.4, 128.6, 126.9, 123.7, 118.6, 21.2 ppm. HRMS
CDCl3): δ = 165.4 (d, J = 250.0 Hz), 164.6, 136.5, 136.2, 135.2,
Eur. J. Org. Chem. 0000, 0–0
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