The Journal of Organic Chemistry
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167.9, 151.2, 137.9, 137.0, 132.9 (2C), 129.5 (2C), 129.4 (2C), 124.3,
120.3 (2C), 118.5, 115.5. HRMS for C15H10N3O2 [M − H]−:
calculated, 264.0779; found, 264.0772.
diethyl ether + 1% MeOH in CHCl3) as a colorless solid (103.4 mg,
0.330 mmol, 83%). Mp: 163−165 °C. 1H NMR (400 MHz, d6-
DMSO): δH (ppm) 11.21 (bs, 1H), 10.70 (bs, 1H), 8.12 (d, J = 8.4
Hz, AB-system, 2H), 8.08 (d, J = 8.4 Hz, AB system, 2H), 7.59 (m,
2H), 7.37 (m, 2H), 7.12 (m, 1H), 4.36 (q, J = 7.2 Hz, 2H), 1.35 (t, J =
7.2 Hz, 3H). 13C NMR (100 MHz, d6-DMSO): δC (ppm) 168.0,
165.0, 150.8, 137.5, 136.4, 133.4, 129.1 (2C), 129.0 (2C), 128.7 (2C),
123.8, 119.9 (2C), 61.2, 14.1. HRMS for C17H15N2O4 [M − H]−:
calculated, 311.1037; found, 311.1032.
4-Methyl-N-(phenylcarbamoyl)benzamide (11). The same
procedure as for 3-methyl-N-(phenylcarbamoyl)benzamide was applied,
using 4-bromotoluene (48.1 mg, 0.400 mmol). The title compound was
obtained after flash column chromatography (1−6% gradient of diethyl
ether in CHCl3) as a colorless solid (80.7 mg, 0.317 mmol, 79%). Mp:
1
195−196 °C. H NMR (400 MHz, CDCl3): δH (ppm) 10.90 (bs, 1H),
9.13 (bs, 1H), 7.88−7.91 (m, 2H), 7.59 (d, J = 8.4 Hz, 2H), 7.31−7.38
(m, 4H), 7.15 (t, J = 7.2 Hz, 1H), 2.46 (s, 3H). 13C NMR (100 MHz,
CDCl3): δC (ppm) 168.4, 151.8, 144.5, 137.4, 129.8 (2C), 129.4, 129.2
(2C), 128.0, 124.5 (2C), 120.6 (2C), 21.8. HRMS for C15H14N2NaO2
[M + Na]+: calculated, 277.0953; found, 277.0954. The same stoi-
chiometry of reagents and purification were used when 4-bromotoluene
was applied to synthesize the title compound in 79% isolated yield.
N-(Phenylcarbamoyl)-[1,1′-biphenyl]-4-carboxamide (12).
The same procedure as for 3-methyl-N-(phenylcarbamoyl)benzamide
was applied, using 4-bromobiphenyl (93.2 mg, 0.400 mmol) and
100 °C. The title compound was obtained after flash chromato-
graphy (10% MeOH, 20% acetone, 70% toluene) and a hot/cold
recrystallization in acetonitrile as a colorless solid (84.7 mg,
4-Acetyl-N-(phenylcarbamoyl)benzamide (17). The same
procedure as for 4-methoxy-N-(phenylcarbamoyl)benzamide was
applied, using 1-(4-bromophenyl)ethanone (199.0 mg, 0.400 mmol).
The title compound was obtained after flash chromatography (1−6%
gradient of MeOH in CHCl3) as a colorless solid (94.4 mg, 0.334
1
mmol, 84%). Mp: 230−233 °C. H NMR (400 MHz, d6-DMSO): δH
(ppm) 11.20 (bs, 1H), 10.73 (bs, 1H), 8.13 (d, J = 8.4 Hz, AB-system,
2H), 8.07 (d, J = 8.8 Hz, AB-system, 2 Hz), 7.59 (d, J = 8.8 Hz, 2H),
7.37 (t, J = 7.2 Hz, 2H), 7.12 (t, J = 7.2 Hz, 1H), 2.65 (s, 3H). 13C
NMR (100 MHz, d6-DMSO): δC (ppm) 197.7, 168.0, 150.9, 139.8,
137.5, 136.1, 129.4, 128.6 (2C), 128.6 (2C), 128.2 (2C), 123.8, 119.9
(2C), 27.1. HRMS for C16H13N2O3 [M − H]−: calculated, 281.0932;
found, 281.0925.
1
13C-Labeled 2,4-Dimethoxy-N-(phenylcarbamoyl)-
benzamide (18). When the 13C-labeled version was synthesized,
the same general method and purification were employed as for 14,
using the 13C-labeled counterpart of 1 (107.2 mg, 0.440 mmol). The
title compound was obtained as a colorless solid (121,2 mg, 0.388
0.268 mmol, 67%). Mp: 225−228 °C. H NMR (400 MHz, d6-DMSO):
δH (ppm) 11.07 (bs, 1H), 10.79 (bs, 1H), 8.14 (d, J = 8.8 Hz, 2H), 7.85 (d,
J = 8.4 Hz, 2H), 7.76−7.79 (m, 2H), 7.68 (dd, J = 1.2 Hz, J = 8.8 Hz, 2H),
7.50−7.54 (m, 2H), 7.42−7.46 (m, 1H), 7.35−7.39 (m, 2H), 7.10−7.14
(m, 1H). 13C NMR (100 MHz, d6-DMSO): δC (ppm) 168.8, 151.7, 144.9,
139.2, 138.1, 131.6, 129.6 (2C), 129.5 (2C), 129.4 (2C), 128.9, 127.4 (2C),
127.71 (2C), 124.2, 120.3 (2C). HRMS for C20H15N2O2 [M − H]−:
calculated, 315.1139; found, 315.1134.
1
mmol, 97%). Mp: 220−222 °C. H NMR (400 MHz, CDCl3): δH
(ppm) 10.96 (bs, 1H), 9.85 (bs, 1H), 8.18 (ddd, J = 1.2 Hz, J = 4.8 Hz,
J = 8.8 Hz, 1H), 7.59 (d, J = 8.8 Hz, 2H), 7.34 (t, J = 7.6 Hz, 2H), 7.11
(dt, J = 1.2 Hz, J = 8.2 Hz, 1H), 6.67 (dd, J = 2.4 Hz, J = 8.8 Hz, 1H),
6.53 (d, J = 1.2 Hz, 1H), 4.03 (s, 3H), 3.89 (s, 3H). 13C NMR (100
MHz, CDCl3): δC (ppm) 166.0, 165.4, 159.6, 151.4, 137.8, 134.6,
129.1 (2C), 124.1, 120.4 (2C), 112.7, 112.0, 106.4 (d, J = 4.3 Hz),
98.9, (d, J = 3.2 Hz), 56.5, 55.9. HRMS for C1513CH16N2NaO4 [M +
Na]+: calculated, 324.1041; found, 324.1042.
4-Methoxy-N-(phenylcarbamoyl)benzamide (13). The same
procedure as for 3-methyl-N-(phenylcarbamoyl)benzamide was
applied, using 4-iodoanisole (93.6 mg, 0.400 mmol) and cataCXium
PInCy (7.8 mg, 0.020 mmol). The title compound was obtained after
flash chromatography (0.5−4% MeOH in CHCl3) as a colorless
solid (109.1 mg, 0.400 mmol, 99%). Mp: 219−221 °C. 1H NMR
(400 MHz, d6-DMSO): δH (ppm) 10.93 (bs, 1H), 10.86 (bs, 1H), 8.06
(d, J = 8.8 Hz, 2H), 7.57−7.60 (m, 2H), 7.34−7.38 (m, 2H), 7.06−7.12
(m, 3H), 3.85 (s, 3H). 13C NMR (100 MHz, d6-DMSO): δC (ppm)
168.0, 163.1, 151.3, 137.7, 130.5 (2C), 129.0 (2C), 124.1, 123.7, 119.8
(2C), 113.9 (2C), 55.61. HRMS for C15H14N2NaO3 [M + Na]+:
calculated, 293.0902; found, 293.0903.
2,4-Dimethoxy-N-(phenylcarbamoyl)benzamide (14). The
same procedure as for 4-methoxy-N-(phenylcarbamoyl)benzamide
was applied, using 2,4-dimethoxyiodobenzene (105.6 mg, 0.400 mmol).
The title compound was obtained after flash chromatography (0.5−3%
gradient MeOH in CHCl31) as a colorless solid (111.0 mg, 0.370 mmol,
92%). Mp: 221−222 °C. H NMR (400 MHz, d6-DMSO): δH (ppm)
10.80 (bs, 1H), 10.09 (bs, 1H), 7.72 (d, J = 8.8 Hz, 1H), 7.57 (d, J =
8.4 Hz, 2H), 7.35 (t, J = 7.6 Hz, 2H), 7.11 (t, J = 7.6 Hz, 1H), 6.73 (m,
2H), 3.99 (s, 3H), 3.87 (s, 3H). 13C NMR (100 MHz, d6-DMSO): δC
(ppm) 166.2, 164.6, 159.3, 150.5, 137.6, 132.8, 129.0 (2C), 123.7, 119.7
(2C), 112.6, 106.7, 98.8, 56.6, 55.8. HRMS for C16H16N2NaO4 [M +
Na]+: calculated, 323.1008; found, 323.1003.
13C-Labeled Ethyl 4-((Phenylcarbamoyl)carbamoyl)-
benzoate (19). When the 13C-labeled version was synthesized, the
same general method and purification were employed as for 16, using
the 13C-labeled counterpart of 1 (107.2 mg, 0.440 mmol). Mp: 166−
1
168 °C. H NMR (400 MHz, d6-DMSO): δH (ppm) 11.21 (bs, 1H),
10.70 (bs, 1H), 8.13 (dd, J = 3.6 Hz, J = 8.4 Hz, 2H), 8.08 (d, J = 8.4
Hz, 2H), 7.59 (d, J = 8.4 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.12 (t, J =
7.6 Hz, 1H), 4.36 (q, J = 6.8 Hz, 2H), 1.35 (t, J = 6.8 Hz, 3H). 13C
NMR (100 MHz, d6-DMSO): δC (ppm) 168.0, 164.9, 150.8, 137.5,
136.3 (d, J = 65.1 Hz), 133.4, 129.1 (d, J = 4.4 Hz), 129.0, 128.7 (d,
J = 2.8 Hz), 123.8, 119.8 (2C), 61.2, 14.1. HRMS for C1613CH15N2O4
[M − H]−: calculated, 312.1071; found, 312.1065.
Triflumuron, 2-Chloro-N-((4-(trifluoromethoxy)phenyl)-
carbamoyl)benzamide (20).25 The same procedure as for 3-
methyl-N-(phenylcarbamoyl)benzamide was applied, using 2-chlor-
oiodobenzene (95.4 mg, 0.400 mmol) and 1-(4-(trifluoromethoxy)-
phenyl)urea (88.1 mg, 0.400 mmol). The title compound was obtained
after flash chromatography (1−3% gradient of diethyl ether in CHCl3) as
a colorless solid (89.4 mg, 0.249 mmol, 62%). Mp: 189−193 °C (lit.25 mp
4-(Methylamino)-N-(phenylcarbamoyl)benzamide (15). The
same procedure as for 4-methoxy-N-(phenylcarbamoyl)benzamide was
applied, using 4-iodo-N-methylaniline (133.3 mg, 0.560 mmol). The
title compound was obtained after flash chromatography (8−16%
gradient of diethyl ether in CHCl3) as a colorless solid (91.2 mg, 0.339
1
188−190 °C). H NMR (400 MHz, 1:1 d4-MeOH, CDCl3): δH (ppm0
10.50 (bs, 1H), 7.36−7.41 (m, 3H), 7.28−7.29 (m, 2H), 7.18−7.22
(m, 1H), 7.01 (d, J = 8.8 Hz, 2H). 13C NMR (100 MHz, 1:1 d4-MeOH,
CDCl3): δC (ppm) 168.9 (d, J = 4.2 Hz), 151.0 (d, J = 10.5 Hz), 145.3
(t, J = 1.5 Hz), 135.7, 135.6, 133.5, 132.1, 130.2, 128.9, 126.8, 121.5 (2C),
121.4, 120.4 (q, J = 254 Hz). 19F NMR (367 MHz, CDCl3): δF (ppm)
−58.66. HRMS for C15H10ClF3N2O3 [M + Na]+: calculated, 381.0230;
found, 381.0233.
1
mmol, 85%). Mp: 220−223 °C. H NMR (400 MHz, d6-DMSO): δH
(ppm) 11.15 (bs, 1H), 10.50 (bs, 1H), 7.89 (d, J = 8.0 Hz, 2H), 7.57
(d, J = 8.4 Hz, 2H), 7.34 (t, J = 7.6 Hz, 2H), 7.09 (t, J = 7.6 Hz, 1H),
6.64 (d, J = 4.4 Hz, 1H), 6.57 (d, J = 8.0 Hz, 2H), 2.75 (d, J = 4.0 Hz, 3H).
13C NMR (100 MHz, d6-DMSO): δC (ppm) 168.5, 154.3, 152.1, 138.3,
130.8 (2C), 129.4 (2C), 123.9, 120.1 (2C), 117.9, 111.0, 29.6. HRMS for
C15H15N3O2Na [M + Na]+: calculated, 292.1062; found, 292.1062.
Ethyl 4-((Phenylcarbamoyl)carbamoyl)benzoate (16). The
same procedure as for 4-methoxy-N-(phenylcarbamoyl)benzamide
was applied, using ethyl 4-iodobenzoate (110.4 mg, 0.400 mmol). The
title compound was obtained after flash chromatography (4−7%
13C-Labeled Triflumuron, 2-Chloro-N-((4-(trifluoromethoxy)-
phenyl)carbamoyl)benzamide (21). The same procedure as for
unlabeled triflumuron (20) was applied, using the 13C-labeled CO
precursor (107.2 mg, 0.440 mmol). The title compound was obtained
after flash chromatography (1−3% gradient of diethyl ether in CHCl3)
as a colorless solid (84.0 mg, 0.233 mmol, 58%). Mp: 190−193 °C. 1H
NMR (400 MHz, CDCl3): δH (ppm) 10.60 (bs, 1H), 8.54 (bs, 1H),
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dx.doi.org/10.1021/jo3000767 | J. Org. Chem. 2012, 77, 3793−3799