The Journal of Organic Chemistry
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7.7 Hz, 1H), 7.22 (t, J = 9.8 Hz, 1H), 5.03 (br s, 1H), 2.69 (d, J = 4.8 Hz,
3H); 13C {1H} NMR (125 MHz, CDCl3) δ 158.7 (C−F, 1JC−F = 253.9
Hz), 134.9 (C−F, 3JC−F = 8.6 Hz), 130.6, 126.6 (C−F, 3JC−F = 13.1 Hz),
124.4 (C−F, 4JC−F = 3.7 Hz), 116.8 (C−F, 2JC−F = 21.5 Hz), 29.1.
4-Fluoro-N-methylbenzenesulphonamide (3e).34 Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/100);
a white solid; 90% yield (85 mg); mp 68−69 °C; 1H NMR (500 MHz,
CDCl3) δ 7.92−7.88 (m, 2H), 7.21 (t, J = 8.5 Hz, 2H), 4.83 (br s, 1H),
2.66 (s, 3H); 13C {1H} NMR (125 MHz, CDCl3) δ 165.0 (C−F, 1JC−F
N-Methyl(phenyl)methanesulfonamide (3o).38 Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/100);
1
a white solid; 92% yield (85 mg); mp 110−111 °C; H NMR (500
MHz, CDCl3) δ 7.38 (s, 5H), 4.23 (s, 2H), 2.66 (s, 3H); 13C {1H}
NMR (125 MHz, CDCl3) δ 130.5, 129.2, 128.8, 128.6, 57.5, 29.6.
N-Methylmethanesulfonamide (3p).4d Purified by flash column
chromatography on silica gel (ethyl acetate/hexanes = 1/100); a yellow
oil; 94% yield (51 mg); 1H NMR (500 MHz, CDCl3) δ 2.90 (s, 3H),
2.75 (s, 3H); 13C {1H} NMR (125 MHz, CDCl3) δ 38.2, 29.2.
N,2-Dimethyl-2-propanesulfonamide (3q).15c Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/100);
a yellow oil; 93% yield (70 mg); 1H NMR (500 MHz, CDCl3) δ 3.16
(br s, 1H), 2.80 (d, J = 5.6 Hz, 3H), 1.17 (s, 9H); 13C {1H} NMR (125
MHz, CDCl3) δ 55.5, 31.4, 22.4.
= 254.7 Hz), 134.7, 129.8 (C−F, 3JC−F = 9.2 Hz), 116.2 (C−F, 2JC−F
=
22.6 Hz), 29.1.
3-Chloro-N-methylbenzenesulfonamide (3f).35 Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/100);
a white solid; 89% yield (92 mg); mp 44−45 °C; 1H NMR (500 MHz,
CDCl3) δ 7.86 (s, 1H), 7.76 (d, J = 7.7 Hz, 1H), 7.56 (d, J = 8.0 Hz,
1H), 7.48 (t, J = 8.0 Hz, 1H), 5.06-4.98 (br s, 1H), 2.68 (d, J = 5.1 Hz,
3H); 13C {1H} NMR (125 MHz, CDCl3) δ 140.4, 135.2, 132.7, 130.4,
127.1, 125.2, 29.2.
N-Methylcyclopropanesulfonamide (3r).15c Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/
100); a yellow oil; 89% yield (60 mg); 1H NMR (500 MHz, CDCl3) δ
4.82 (br s, 1H), 2.77 (d, J = 5.3 Hz, 3H), 2.40−2.36 (m, 1H), 1.11−1.09
(m, 2H), 0.97−0.94 (m, 2H); 13C {1H} NMR (125 MHz, CDCl3) δ
29.3, 28.4, 4.7.
4-Chloro-N-methylbenzenesulfonamide (3g).34 Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/100);
a white solid; 91% yield (94 mg); mp 44−45 °C; 1H NMR (500 MHz,
CDCl3) δ 7.81 (d, J = 8.6 Hz, 2H), 7.50 (d, J = 8.6 Hz, 2H), 4.98−4.88
(br s, 1H), 2.66 (d, J = 5.3 Hz, 3H); 13C {1H} NMR (125 MHz, CDCl3)
δ 139.1, 137.1, 129.3, 128.6, 29.1.
N-Methylaniline (5a).39 Purified by flash column chromatography
on silica gel (ethyl acetate/hexanes = 1/100); a yellow oil; 93% yield
(50 mg); 1H NMR (500 MHz, CDCl3) δ 7.19 (t, J = 7.9 Hz, 2H), 6.71
(t, J = 7.3 Hz, 1H), 6.61 (d, J = 7.9 Hz, 2H), 2.83 (s, 3H); 13C {1H}
NMR (125 MHz, CDCl3) δ 149.2, 129.1, 117.1, 112.3, 30.6.
N,4-Dimethylbenzenamine (5b).40 Purified by flash column
chromatography on silica gel (ethyl acetate/hexanes = 1/100); a
brown oil; 85% yield (51 mg); 1H NMR (500 MHz, CDCl3) δ 7.06 (d, J
= 8.3 Hz, 2H), 6.60 (d, J = 8.4 Hz, 2H), 2.85 (s, 3H), 2.30 (s, 3H); 13C
{1H} NMR (125 MHz, CDCl3) δ 147.0, 129.6, 126.4, 112.5, 31.0, 20.3.
4-Methoxy-N-methylbenzenamine (5c).41 Purified by flash column
chromatography on silica gel (ethyl acetate/hexanes = 1/100); a yellow
oil; 82% yield (56 mg); 1H NMR (500 MHz, CDCl3) δ 6.82 (d, J = 8.9
Hz, 2H), 6.61 (d, J = 8.9 Hz, 2H), 3.77 (s, 3H), 2.81 (s, 3H); 13C {1H}
NMR (125 MHz, CDCl3) δ 151.9, 143.6, 114.8, 113.5, 55.7, 31.5.
4-Fluoro-N-methylbenzenamine (5d).42 Purified by flash column
chromatography on silica gel (ethyl acetate/hexanes = 1/100); a yellow
oil; 86% yield (54 mg); 1H NMR (500 MHz, CDCl3) δ 6.90 (t, J = 8.8
Hz, 2H), 6.56-6.52 (m, 2H), 3.60 (br s, 1H), 2.80 (s, 3H); 13C {1H}
4-Bromo-N-methylbenzenesulfonamide (3h).32 Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/100);
1
a yellow solid; 92% yield (115 mg); mp 74−76 °C; H NMR (500
MHz, CDCl3) δ 7.74 (d, J = 8.6 Hz, 2H), 7.66 (d, J = 8.6 Hz, 2H), 5.17
(br s, 1H), 2.64 (s, 3H); 13C {1H} NMR (125 MHz, CDCl3) δ 137.6,
132.3, 128.7, 127.6, 29.1.
N-Methyl-2-(trifluoromethyl)benzenesulfonamide (3i).33 Purified
by flash column chromatography on silica gel (ethyl acetate/hexanes =
1/100); a white solid; 93% yield (111 mg); mp 96−97 °C; 1H NMR
(500 MHz, CDCl3) δ 8.25-8.22 (m, 1H), 7.93-7.90 (m, 1H), 7.78−7.74
(m, 2H), 4.88 (br s, 1H), 2.71 (d, J = 4.8 Hz, 3H); 13C {1H} NMR (125
3
MHz, CDCl3) δ 137.3, 132.7, 132.3, 131.7, 128.4 (C−F, JC−F = 6.3
Hz), 127.3 (C−F, 2JC−F = 33.1 Hz), 122.8 (C−F, 1JC−F = 273.7 Hz),
29.2.
N-Methyl-4-(trifluoromethyl)benzenesulfonamide (3j).4d Purified
by flash column chromatography on silica gel (ethyl acetate/hexanes =
1/100); a white solid; 91% yield (109 mg); mp 77−78 °C; 1H NMR
(500 MHz, CDCl3) δ 8.02 (d, J = 8.2 Hz, 2H), 7.80 (d, J = 8.2 Hz, 2H),
5.26 (br s, 1H), 2.69 (s, 3H); 13C {1H} NMR (125 MHz, CDCl3) δ
142.2, 134.2 (C−F, 2JC−F = 33.0 Hz), 127.6, 126.2 (C−F, 4JC−F = 3.7
Hz), 123.1 (C−F, 1JC−F = 273.0 Hz), 29.0.
1
NMR (125 MHz, CDCl3) δ 155.9 (C−F, JC−F = 234.3 Hz), 145.8,
115.7 (C−F, 2JC−F = 22.3 Hz), 113.2 (C−F, 3JC−F = 6.2 Hz), 31.4.
4-Chloro-N-methylbenzenamine (5e).43 Purified by flash column
chromatography on silica gel (ethyl acetate/hexanes = 1/100); a yellow
oil; 90% yield (64 mg); 1H NMR (500 MHz, CDCl3) δ 7.15 (d, J = 8.8
Hz, 2H), 6.53 (d, J = 8.8 Hz, 2H), 3.58 (br s, 1H), 2.81 (s, 3H); 13C
{1H} NMR (125 MHz, CDCl3) δ 147.8, 128.8, 121.6, 113.3, 30.7.
4-Bromo-N-methylbenzenamine (5f).15c Purified by flash column
chromatography on silica gel (ethyl acetate/hexanes = 1/100); a yellow
oil; 83% yield (77 mg); 1H NMR (500 MHz, CDCl3) δ 7.24 (d, J = 8.8
Hz, 2H), 6.45 (d, J = 8.8 Hz, 2H), 3.71 (br s, 1H), 2.77 (s, 3H); 13C
{1H} NMR (125 MHz, CDCl3) δ 148.2, 131.7, 113.8, 108.6, 30.6.
N-Methyl-4-(trifluoromethoxy)benzenamine (5g).15c Purified by
flash column chromatography on silica gel (ethyl acetate/hexanes = 1/
N-Methyl-4-(trifluoromethoxy)benzenesulfonamide (3k).4d Puri-
fied by flash column chromatography on silica gel (ethyl acetate/
1
hexanes = 1/100); a yellow oil; 91% yield (116 mg); H NMR (500
MHz, CDCl3) δ 7.96 (d, J = 8.8 Hz, 2H), 7.36 (d, J = 8.3 Hz, 2H), 2.66
(d, J = 5.2 Hz, 3H); 13C {1H} NMR (125 MHz, CDCl3) δ 152.0, 137.0,
129.2, 120.9, 120.1 (C−F, 1JC−F = 259.0 Hz), 29.0.
N-Methyl-4-nitrobenzenesulfonamide (3l).36 Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/
100); a light yellow solid; 84% yield (91 mg); mp 75−76 °C; 1H NMR
(500 MHz, CDCl3) δ 8.21 (d, J = 9.2 Hz, 2H), 6.96 (d, J = 9.2 Hz, 2H),
3.91 (s, 3H); 13C {1H} NMR (125 MHz, CDCl3) δ 164.5, 141.4, 125.8,
113.9, 55.8.
1
100); a pale yellow oil; 92% yield (88 mg); H NMR (500 MHz,
CDCl3) δ 7.05 (d, J = 8.4 Hz, 2H), 6.58 (d, J = 8.6 Hz, 2H), 3.51 (br s,
1H), 2.83 (s, 3H); 13C {1H} NMR (125 MHz, CDCl3) δ 147.7, 140.4,
122.2, 119.6 (C−F, 1JC−F = 254.3 Hz), 112.6, 30.8.
N-Methylnaphthalene-2-sulfonamide (3m).33 Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/100);
a purple solid; 93% yield (103 mg); mp 105−107 °C; 1H NMR (500
MHz, CDCl3) δ 8.45 (s, 1H), 7.98 (d, J = 7.3 Hz, 2H), 7.97-7.83 (m,
2H), 7.68−7.60 (m, 1H), 2.69 (d, J = 5.4 Hz, 3H); 13C {1H} NMR (125
MHz, CDCl3) δ 135.4, 134.7, 132.0, 129.4, 129.1, 128.7, 128.6, 127.8,
127.4, 122.2, 29.2.
3,5-Bis(trifluoromethyl)-N-methylaniline (5h).7a Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/100);
a yellow oil; 89% yield (108 mg); 1H NMR (500 MHz, CDCl3) δ 7.14
(s, 1H), 6.92 (s, 2H), 4.17 (br s, 1H), 2.89 (d, J = 4.5 Hz, 3H); 13C {1H}
NMR (125 MHz, CDCl3) δ 149.5, 132.2 (C−F, 2JC−F = 21.7 Hz), 123.5
(C−F, 1JC−F = 275.0 Hz), 111.3 (C−F, 4JC−F = 3.3 Hz), 109.9−109.7
(m), 30.2.
N-Methylthiophene-2-sulfonamide (3n).37 Purified by flash
column chromatography on silica gel (ethyl acetate/hexanes = 1/
100); a brown solid; 90% yield (80 mg); mp 78−81 °C; 1H NMR (500
MHz, CDCl3) δ 7.63−7.60 (m, 2H), 7.11 (t, J = 4.8 Hz, 1H), 4.70 (br s,
1H), 2.74 (d, J = 5.4 Hz, 3H); 13C {1H} NMR (125 MHz, CDCl3) δ
139.5, 132.2, 131.8, 127.3, 29.4.
Methyl-4-(methylamino)benzoate (5i).4d Purified by flash column
chromatography on silica gel (ethyl acetate/hexanes = 1/100); a white
solid; 81% yield (67 mg); mp 94−95 °C; 1H NMR (500 MHz, CDCl3)
δ 7.87 (d, J = 8.6 Hz, 2H), 6.55 (d, J = 8.6 Hz, 2H), 3.85 (s, 3H), 2.88 (s,
3H); 13C {1H} NMR (125 MHz, CDCl3) δ 167.3, 152.8, 131.4, 118.0,
110.9, 51.4, 30.0.
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J. Org. Chem. 2021, 86, 2621−2631