B. Schmidt, N. Elizarov, N. Riemer, F. Hölter
FULL PAPER
24.3 ppm. 19F NMR (282 MHz, CDCl3): δ = –112.7 (dd, J = 12.9,
Procedure under basic conditions: yellow solid, m.p. 93 °C. 1H
8.3 Hz) ppm. IR (ATR): ν = 3341 (w), 1690 (s), 1419 (s), 1275 (s), NMR (300 MHz, [D6]DMSO): δ = 9.98 (s, 1 H), 7.58 (d, J =
˜
1176 (s) cm–1. MS (EI): m/z (%) = 237 (35), 195 (57), 163 (100),
136 (35), 106 (13). HRMS (EI): calcd. for C12H12NO3F [M]+
237.0796; found 237.0796.
8.6 Hz, 2 H), 7.51 (d, J = 8.5 Hz, 2 H), 7.47 (d, J = 8.5 Hz, 2 H),
7.09 (d, J = 16.5 Hz, 1 H), 7.01 (d, J = 16.5 Hz, 1 H), 6.93 (d, J =
8.8 Hz, 1 H), 3.77 (s, 3 H), 2.05 (s, 3 H) ppm. 13C NMR (75 MHz,
[D6]DMSO): δ = 168.7, 139.4, 137.7, 132.3, 129.1, 128.5, 127.8,
Methyl (E)-3-(4-Acetamido-3-fluorophenyl)acrylate (11fa): Com-
pounds 2f (100 mg, 0.37 mmol) and 10a (67 μL, 0.74 mmol) were
converted into 11fa (67 mg, 0.28 mmol, 76%) by the General Pro-
cedure: colourless solid, m.p. 188 °C. 1H NMR (300 MHz, [D6]-
DMSO): δ = 9.89 (s, 1 H), 8.04 (dd, J = 8.3, 8.3 Hz, 1 H), 7.70
(dd, J = 12.3, 1.7 Hz, 1 H), 7.60 (d, J = 16.0 Hz, 1 H), 7.50 (dd, J
= 8.4, 1.5 Hz, 1 H), 6.62 (d, J = 16.0 Hz, 1 H), 3.72 (s, 3 H), 2.11
(s, 3 H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 168.9, 166.6,
152.8 (d, J = 245.6 Hz), 143.0, 130.6 (d, J = 7.1 Hz), 128.4 (d, J =
11.8 Hz), 125.0 (d, J = 2.9 Hz), 143.0, 117.8, 114.8 (d, J = 20.5 Hz),
51.4, 23.6 ppm. 19F NMR (282 MHz, [D6]DMSO): δ = –125.0 (dd,
127.4, 127.3, 126.7, 119.5, 55.6, 24.5 ppm. IR (ATR): ν = 3283 (w),
˜
1659 (m), 1509 (s), 1243 (s), 1031 (s) cm–1. MS (EI): m/z (%) = 267
(100), 225 (33), 135 (49), 43 (90). HRMS (EI): calcd. for
C17H17NO2 [M]+ 267.1259; found 267.1250. C17H17NO2 (267.33):
calcd. C 76.4, H 6.4, N 5.2; found C 76.1, H 6.4, N 5.3.
(E)-N-[4-(4-Chlorostyryl)phenyl]acetamide (p-11af): Compounds p-
2a (80 mg, 0.32 mmol) and 10f (41 μL, 0.32 mmol) were converted
into p-11af (44 mg, 0.16 mmol, 51%) by the General Procedure:
yellow solid, m.p. Ͼ 250 °C. 1H NMR (300 MHz, [D6]DMSO): δ
= 10.01 (s, 1 H), 7.60 (d, J = 8.3 Hz, 2 H), 7.58 (d, J = 8.6 Hz, 2
H), 7.52 (d, J = 8.6 Hz, 2 H), 7.40 (d, J = 8.4 Hz, 2 H), 7.21 (d, J
= 16.5 Hz, 1 H), 7.12 (d, J = 16.5 Hz, 1 H), 2.05 (s, 3 H) ppm. 13C
NMR (75 MHz, [D6]DMSO): δ = 168.7, 139.6, 136.7, 132.0, 129.4,
J = 9.3, 9.3 Hz) ppm. IR (ATR): ν = 3258 (w), 1703 (s), 1521 (s),
˜
1427 (s), 1178 (s) cm–1. HRMS (EI): calcd. for C12H12NO3F [M +
H]+ 238.0874; found 238.0876.
(E)-N-(4-Styrylphenyl)acetamide (p-11ab):[83] Compounds p-2a
(80 mg, 0.32 mmol) and 10b (37 μL, 0.32 mmol) were converted
into p-11ab (50 mg, 0.21 mmol, 66%) by the General Procedure:
yellow solid, m.p. 230 °C. 1H NMR (300 MHz, [D6]DMSO): δ =
10.01 (s, 1 H), 7.65–7.50 (m, 6 H), 7.36 (dd, J = 7.5, 7.5 Hz, 2 H),
7.25 (tm, J = 7.5 Hz, 1 H), 7.20 (d, J = 16.1 Hz, 1 H), 7.13 (d, J =
16.5 Hz, 1 H), 2.06 (s, 3 H) ppm. 13C NMR (75 MHz, [D6]DMSO):
δ = 168.7, 139.4, 137.7, 132.3, 129.1, 128.5, 127.8, 127.4, 127.3,
129.1, 129.1, 128.3, 127.5, 126.0, 119.5, 24.5 ppm. IR (ATR): ν =
˜
3291 (w), 1660 (s), 1595 (s), 1510 (s), 1316 (m) cm–1. MS (EI): m/z
(%) = 271 (77), 229 (70), 165 (30), 43 (100). HRMS (EI): calcd. for
C16H14NOCl [M]+ 271.0758; found 271.0749. C16H14ClNO
(271.74): calcd. C 70.7, H 5.2, N 5.2; found C 70.5, H 5.1, N 5.3.
(E/Z)-N-[4-(4-Nitrostyryl)phenyl]acetamide (p-11ag): Compounds
p-2a (80 mg, 0.32 mmol) and 10g (48 mg, 0.32 mmol) were con-
verted into p-11ag (90 mg, 0.32 mmol, quant) by the General Pro-
cedure: inseparable mixtures of E and Z isomers (ratios 3:1–4:1);
yellow oil.
126.7, 119.5, 24.5 ppm. IR (ATR): ν = 3299 (w), 1663 (m), 1321
˜
(m), 969 (s), 823 (s) cm–1. MS (EI): m/z (%) = 237 (56), 195 (65),
165 (31), 43 (100). HRMS (EI): calcd. for C16H15NO [M]+
237.1154; found 237.1141. C16H15NO (237.30): calcd. C 76.4, H
6.4, N 5.2; found C 76.1, H 6.4, N 5.3.
1
NMR Data for the Major Isomer (E)-p-11ag: H NMR (300 MHz,
[D6]DMSO): δ = 10.08 (s, 1 H), 8.21 (d, J = 8.8 Hz, 2 H), 7.82 (d,
J = 8.8 Hz, 2 H), 7.65 (d, J = 8.9 Hz, 2 H), 7.58 (d, J = 8.9 Hz, 2
(E)-N-[4-(4-Methylstyryl)phenyl]acetamide (p-11ac):[84] Compounds
p-2a (80 mg, 0.32 mmol) and 10c (42 μL, 0.32 mmol) were con-
verted into p-11ac (41 mg, 0.16 mmol, 51%) by the General Pro-
cedure: yellow solid, m.p. 242–244 °C. 1H NMR (300 MHz, [D6]-
DMSO): δ = 9.99 (s, 1 H), 7.59 (d, J = 8.5 Hz, 2 H), 7.51 (d, J =
8.6 Hz, 2 H), 7.46 (d, J = 8.0 Hz, 2 H), 7.17 (d, J = 7.9 Hz, 2 H),
7.08 (d, J = 16.8 Hz, 1 H), 7.14 (d, J = 16.8 Hz, 1 H), 2.30 (s, 3
H), 2.05 (s, 3 H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 168.7,
139.2, 137.1, 134.9, 132.4, 129.7, 127.5, 127.3, 127.2, 126.6, 119.5,
H), 7.44 (d, J = 16.6 Hz, 1 H), 7.29 (d, J = 16.4 Hz, 2 H) ppm. 13
C
NMR (75 MHz, [D6]DMSO): δ = 168.9, 146.4, 144.8, 140.3, 133.4,
131.5, 129.6, 128.2, 127.4, 125.2, 119.5, 24.5 ppm.
Selected 1H-NMR Data for the Minor Isomer (Z)-p-11ag: 1H NMR
(300 MHz, [D6]DMSO): δ = 10.00 (s, 1 H), 8.13 (d, J = 8.8 Hz, 2
H), 7.15 (d, J = 8.6 Hz, 2 H), 6.78 (d, J = 12.3 Hz, 1 H), 6.64 (d,
J = 12.3 Hz, 1 H) ppm.
24.5, 21.3 ppm. IR (ATR): ν = 3296 (w), 1662 (s), 1593 (s), 1315
˜
General Procedure for the Azo Coupling of Acetamidoarene Diazo-
nium Salts 2a: The appropriate coupling partner 12 (1.20 mmol)
and NaOAc (30 mg, 0.35 mmol) were added to a solution of one
of the arenediazonium salts m-2a or p-2a (237 mg, 1.00 mmol) in
methanol (6 mL) and water (3 mL). The solution was stirred at
ambient temperature for 2 h, diluted with water (15 mL) and ex-
tracted three times with ethyl acetate (60 mL total volume). The
combined organic layers were dried with Na2SO4, filtered and con-
centrated under reduced pressure. The residue was purified by col-
umn chromatography on silica.
(s), 1260 (m) cm–1. MS (EI): m/z (%) = 251 (97), 209 (100), 194
(28), 165 (28). HRMS (EI): calcd. for C17H17NO [M]+ 251.1310;
found 251.1324.
(E)-N-[4-(3-Methylstyryl)phenyl]acetamide (p-11ad): Compounds p-
2a (80 mg, 0.32 mmol) and 10d (42 μL, 0.32 mmol) were converted
into p-11ad (40 mg, 0.16 mmol, 50%) by the General Procedure:
yellow solid, m.p. 142–143 °C. 1H NMR (300 MHz, [D6]DMSO):
δ = 10.00 (s, 1 H), 7.64 (d, J = 8.6 Hz, 2 H), 7.56 (d, J = 8.6 Hz, 2
H), 7.43 (s, 1 H), 7.39 (d, J = 7.9 Hz, 1 H), 7.28 (dd, J = 7.6,
7.6 Hz, 1 H), 7.21 (d, J = 16.5 Hz, 1 H), 7.13 (d, J = 16.6 Hz, 1
H), 7.10 (d, J = 7.1 Hz, 1 H), 2.32 (s, 3 H), 2.07 (s, 3 H) ppm. 13C
NMR (75 MHz, [D6]DMSO): δ = 168.7, 139.3, 138.2, 137.6, 132.3,
129.0, 128.5, 128.3, 127.4, 127.3, 127.2, 124.0, 119.5, 24.5,
(E)-N-(3-{[4-(Dimethylamino)phenyl]diazenyl}phenyl)acetamide (m-
13aa):[86] Compounds m-2a (249 mg, 1.00 mmol) and 12a (145 mg,
1.20 mmol) were converted into m-13aa (230 mg, 0.82 mmol, 82%)
by the General Procedure: red solid, m.p. 189 °C. 1H NMR
(300 MHz, [D6]DMSO): δ = 10.12 (s, 1 H), 8.05 (s, 1 H), 7.78 (d,
J = 9.1 Hz, 2 H), 7.62 (ddd, J = 7.3, 2.1, 2.1 Hz, 1 H), 7.44–7.39
(m, 2 H), 6.83 (d, J = 9.2 Hz, 2 H), 3.06 (s, 6 H), 2.07 (s, 3 H) ppm.
13C NMR (75 MHz, [D6]DMSO): δ = 168.9, 153.3, 152.9, 142.9,
140.6, 129.8, 125.2, 120.4, 117.9, 112.0, 111.9, 24.5 ppm. IR (ATR):
21.5 ppm. IR (ATR): ν = 3277 (w), 1660 (s), 1526 (s), 1369 (m),
˜
1261 (m) cm–1. MS (EI): m/z (%) = 251 (97), 209 (87), 165 (33),
43 (100). HRMS (EI): calcd. for C17H17NO [M]+ 251.1310; found
251.1315.
(E)-N-[4-(4-Methoxystyryl)phenyl]acetamide (p-11ae):[85] Com-
pounds p-2a (80 mg, 0.32 mmol) and 10e (43 μL, 0.32 mmol) were
converted into p-11ae (56 mg, 0.21 mmol, 66%) by the General
ν = 3301 (w), 2926 (w), 1598 (s), 1360 (s), 1148 (s) cm–1. MS (EI):
˜
m/z (%) = 282 (23), 148 (100), 120 (20), 105 (18). HRMS (EI):
5836
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Eur. J. Org. Chem. 2015, 5826–5841