The Journal of Organic Chemistry
Article
m/z calculated for C24H21NNaO3S [M + Na]+ 426.1140, found
426.1135.
N-(2-((4,5-Dimethyl-2-(2-oxoethyl)phenyl)ethynyl)-4-methyl-
phenyl)-4-methylbenzenesulfonamide (10i). Pale yellow solid (105.7
mg, 49% yield); mp 120−122 °C; Rf = 0.69 (50% ethyl acetate in
petroleum ether); IR (KBr) 3262, 3031, 2974, 2926, 2824, 2730, 2204,
1720, 1597, 1494, 1452, 1396, 1337, 1278, 1162 cm−1; 1H NMR
(CDCl3, 300 MHz) δH 9.66 (t, J = 2.2 Hz, 1H), 7.68 (d, J = 8.1 Hz,
2H), 7.49−7.46 (m, 2H), 7.27 (s, 1H), 7.18−7.15 (m, 3H), 7.10−7.06
(m, 2H), 3.78 (d, J = 2.1 Hz, 2H), 2.34 (s, 3H), 2.30 (s, 3H), 2.28 (s,
3H), 2.26 (s, 3H); 13CNMR (CDCl3, 75 MHz) δC 198.9, 143.7, 138.7,
136.5, 136.3, 135.0, 134.4, 133.5, 132.5, 131.8, 130.7, 130.5, 129.5,
127.2, 120.8, 120.2, 114.7, 93.5, 88.1, 49.2, 21.5, 20.6, 19.8, 19.3;
HRMS (ESI+) m/z calculated for C26H25NNaO3S [M + Na]+
454.1453, found 454.1450.
N-(4-Methoxy-2-((2-(2-oxoethyl)phenyl)ethynyl)phenyl)-4-
methylbenzenesulfonamide (10c). Yellow gum (151.0 mg, 72%
yield); Rf = 0.56 (50% ethyl acetate in petroleum ether); IR (KBr)
3261, 3020, 2928, 2845, 2731, 2207, 1720, 1602, 1495, 1399, 1334,
1281, 1159 cm−1; 1H NMR (CDCl3, 300 MHz) δH 9.67 (s, 1H), 7.61
(d, J = 8.1 Hz, 2H), 7.53−7.46 (m, 2H), 7.41−7.28 (m, 5H), 7.13 (d, J
= 8.1 Hz, 2H), 6.87 (s, 1H), 3.84 (d, J = 2.4 Hz, 2H), 3.78 (s, 3H),
2.33 (s, 3H); 13C NMR (CDCl3, 75 MHz) δC 198.7, 156.8, 143.6,
136.4, 133.5, 132.5, 130.5, 129.5, 129.4, 127.7, 127.1, 124.4, 122.9,
117.1, 116.4, 116.2, 92.7, 89.1, 55.5, 49.6, 21.4; HRMS (EI+) m/z
calculated for C24H21NO4S [M]+ 419.1191, found 419.1188.
N-(4-Bromo-2-((2-(2-oxoethyl)phenyl)ethynyl)phenyl)-4-methyl-
benzenesulfonamide (10d). Yellow gum (142.8 mg, 61% yield); Rf =
0.60 (50% ethyl acetate in petroleum ether); IR (KBr) 3246, 2922,
2850, 2732, 2210, 1718, 1594, 1482, 1389, 1336, 1280, 1159 cm−1; 1H
NMR (CDCl3, 300 MHz) δH 9.69 (s, 1H), 7.74−7.72 (m, 3H), 7.53−
7.49 (m, 2H), 7.46−7.32 (m, 5H), 7.22 (d, J = 8.1 Hz, 2H), 3.89 (s,
2H), 2.37 (s, 3H); 13C NMR (CDCl3, 75 MHz) δC 198.3, 144.2,
136.9, 136.3, 134.7, 133.4, 132.8, 130.7, 129.9, 129.7, 127.9, 127.2,
122.6, 121.6, 117.0, 116.0, 94.6, 87.6, 49.8, 21.5; MS (EI+) m/z 467
[M]+.
N-(4-Bromo-2-((4,5-dimethyl-2-(2-oxoethyl)phenyl)ethynyl)-
phenyl)-4-methylbenzenesulfonamide(10j). Pale yellow solid (163.8
mg, 66% yield); mp 116−118 °C; Rf = 0.58 (50% ethyl acetate in
petroleum ether); IR (KBr) 3163, 2981, 2829, 2731, 2201, 1710, 1592,
1486, 1391, 1327, 1289, 1155 cm−1; 1H NMR (CDCl3, 300 MHz) δH
9.66 (t, J = 2.3 Hz, 1H), 7.74−7.72 (m, 3H), 7.49−7.46 (m, 2H), 7.37
(dd, J = 9.0, 2.1 Hz, 1H), 7.29 (s, 1H), 7.22 (d, J = 8.1 Hz, 2H), 7.10
(s, 1H), 3.81 (d, J = 2.1 Hz, 2H), 2.37 (s, 3H), 2.32 (s, 3H), 2.29 (s,
3H); 13C NMR (CDCl3, 75 MHz) δC 198.6, 144.1, 139.2, 136.8,
136.5, 136.3, 134.5, 133.6, 132.5, 131.9, 130.6, 129.7, 127.2, 121.5,
119.7, 116.9, 116.3, 95.1, 86.6, 49.4, 21.5, 19.8, 19.3; HRMS (EI+) m/
z calculated for C25H22BrNO3S [M]+ 495.0504, found 495.0508.
N-(2-((4-Fluoro-2-(2-oxoethyl)phenyl)ethynyl)phenyl)-4-methyl-
benzenesulfonamide (10k). Pale yellow gum (97.8 mg, 48% yield); Rf
= 0.46 (50% ethyl acetate in petroleum ether); IR (KBr) 3256, 3065,
2924, 2827, 2728, 2210, 1721, 1603, 1495, 1404, 1336, 1281, 1161
N-(4-Chloro-2-((2-(2-oxoethyl)phenyl)ethynyl)phenyl)-4-methyl-
benzenesulfonamide (10e). Yellow gum (110.2 mg, 52% yield); Rf =
0.50 (50% ethyl acetate in petroleum ether); IR (KBr) 3234, 2923,
2855, 2738, 2210, 1718, 1594, 1482, 1392, 1330, 1158 cm−1; 1H NMR
(CDCl3, 300 MHz) δH 9.69 (t, J = 2.2 Hz, 1H), 7.73−7.70 (m, 3H),
7.55−7.51 (m, 2H), 7.46−7.33 (m, 4H), 7.27−7.20 (m, 3H), 3.89 (d, J
= 2.1 Hz, 2H), 2.36 (s, 3H); 13C NMR (CDCl3, 75 MHz) δC 198.4,
144.2, 136.4, 136.3, 133.4, 132.8, 131.8, 130.7, 129.9, 129.8, 129.7,
127.9, 127.2, 122.6, 121.6, 115.9, 94.5, 87.8, 49.8, 21.6; HRMS (EI+)
m/z calculated for C23H18ClNO3S [M]+ 423.0696, found 423.0693.
N-(4-Fluoro-2-((2-(2-oxoethyl)phenyl)ethynyl)phenyl)-4-methyl-
benzenesulfonamide (10f). Yellow gum (116.1 mg, 57% yield)
[highly unstable]; Rf = 0.58 (50% ethyl acetate in petroleum ether); IR
(KBr) 3251, 3069, 2923, 2852, 2741, 2207, 1718, 1598, 1489, 1397,
1
cm−1; H NMR (CDCl3, 300 MHz) δH 9.71 (t, J = 1.9 Hz, 1H), 7.73
(d, J = 8.4 Hz, 2H), 7.57−7.49 (m, 3H), 7.37 (dd, J = 7.8, 0.9 Hz, 1H),
7.32−7.30 (m, 1H), 7.21 (d, J = 8.1 Hz, 2H), 7.10−7.04 (m, 3H), 3.89
(d, J = 1.8 Hz, 2H), 2.36 (s, 3H); 13C NMR (CDCl3, 75 MHz) δC
197.5, 162.8 (d, J = 250.9 Hz), 144.0, 137.7, 136.5, 136.2 (d, J = 8.2
Hz), 134.4 (d, J = 8.6 Hz), 132.3, 130.0, 129.6, 127.2, 124.4, 120.0,
119.1, 117.8 (d, J = 22.5 Hz), 115.2 (d, J = 21.8 Hz), 113.9, 92.7, 88.6,
49.5, 21.5; HRMS (EI+) m/z calculated for C23H18FNO3S [M]+
407.0991, found 407.0990.
1
1334, 1272, 1156 cm−1; H NMR (CDCl3, 300 MHz) δH 9.68 (t, J =
4-Methyl-N-(2-((2-(1-oxopropan-2-yl)phenyl)ethynyl)phenyl)-
benzenesulfonamide (10l). Pale yellow gum (127.1 mg, 63% yield);
Rf = 0.68 (50% ethyl acetate in petroleum ether); IR (KBr) 3262,
3064, 2929, 2876, 2725, 2210, 1721, 1600, 1490, 1451, 1403, 1338,
1282, 1162 cm−1; 1H NMR (CDCl3, 300 MHz) δH 9.63 (d, J = 1.5 Hz,
1H), 7.72 (d, J = 8.1 Hz, 2H), 7.63−7.53 (m, 3H), 7.46−7.30 (m,
5H), 7.19 (d, J = 8.1 Hz, 2H), 7.07 (t,J = 7.5 Hz, 1H), 4.11−4.06 (m,
1H), 2.35 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H); 13C NMR (CDCl3, 75
MHz) δC 200.6, 143.9, 139.0, 137.8, 136.5, 133.0, 132.3, 129.9, 129.7,
129.6, 127.9, 127.6, 127.2, 124.3, 122.6, 119.9, 114.0, 93.5, 89.0, 51.3,
21.5, 13.8; HRMS (EI+) m/z calculated for C24H21NO3S [M]+
403.1242, found 403.1245.
4-Methyl-N-(4-methyl-2-((2-(1-oxopropan-2-yl)phenyl)ethynyl)-
phenyl)benzenesulfonamide (10m). Yellow gum (98.1 mg, 47%
yield); Rf = 0.67 (50% ethyl acetate in petroleum ether); IR (KBr)
3303, 3180, 2922, 2851, 2739, 1711, 1598, 1497, 1415, 1325, 1285,
1154 cm−1; 1H NMR (CDCl3, 300 MHz) δH 9.63(d, J = 1.2 Hz, 1H),
7.68 (d, J = 8.1 Hz, 2H), 7.53−7.48 (m, 3H), 7.43−7.40 (m, 1H),
7.37−7.32 (m, 1H), 7.26−7.24 (m, 1H), 7.19−7.10 (m, 4H), 4.07−
4.05 (m, 1H), 2.34 (m, 3H), 2.28 (s, 3H), 1.51 (d, J = 7.2 Hz, 3H);
13C NMR (CDCl3, 75 MHz) δC 200.7, 143.8, 139.1, 136.5, 134.4,
2.3 Hz, 1H), 7.66 (d, J = 8.4 Hz, 2H), 7.59−7.48 (m, 3H), 7.43−7.32
(m, 3H), 7.18 (d, J = 8.1 Hz, 2H), 7.09−7.02 (m, 2H), 3.87 (d, J = 2.1
Hz, 2H), 2.35 (s, 3H); 13C NMR (CDCl3, 75 MHz): δC 198.4, 159.2
(d, J = 244.5 Hz), 143.9, 136.2, 133.8 (d, J = 2.6 Hz), 133.4, 132.6,
130.6, 129.8, 129.6, 127.8, 127.1, 123.5 (d, J = 8.9 Hz), 122.5, 118.5
(d, J = 24.5 Hz), 117.0 (d, J = 22.4 Hz), 93.9, 87.9, 49.7, 21.4.
Methyl 3-(4-Methylphenylsulfonamido)-4-((2-(2-oxoethyl)-
phenyl)ethynyl)benzoate (10g). Pale yellow gum (156.6 mg, 70%
yield); Rf = 0.35 (50% ethyl acetate in petroleum ether); IR (KBr)
3206, 2939, 2833, 2729, 1712, 1603, 1565, 1409, 1255, 1160 cm−1; 1H
NMR (CDCl3, 300 MHz) δH 9.70 (t, J = 2.4 Hz, 1H), 8.22 (d, J = 1.2
Hz, 1H), 7.84 (s, 1H), 7.78 (d, J = 8.4 Hz, 2H), 7.73 (dd, J = 8.0 Hz,
1.4 Hz, 1H), 7.57−7.54 (m, 1H), 7.46−7.42 (m, 2H), 7.40−7.34 (m,
2H), 7.22 (d, J = 8.1 Hz, 2H), 3.93−3.92 (m, 5H), 2.36 (s, 3H); 13C
NMR (CDCl3, 75 MHz) δC 198.4, 165.9, 144.2, 137.9, 136.3, 133.5,
132.9, 132.3, 131.1, 130.8, 130.0, 129.7, 127.9, 127.3, 125.1, 122.6,
120.7, 118.3, 96.0, 88.4, 52.5, 49.9, 21.6; HRMS (EI+) m/z calculated
for C25H21NO5S [M]+ 447.1140, found 447.1134.
N-(2-((4,5-Dimethyl-2-(2-oxoethyl)phenyl)ethynyl)phenyl)-4-
methylbenzenesulfonamide (10h). Pale yellow solid (125.2 mg, 60%
yield); mp 120−122 °C; Rf = 0.52 (50% ethyl acetate in petroleum
ether); IR (KBr) 3189, 2964, 2921, 2859, 2744, 2204, 1706, 1600,
1490, 1411, 1327, 1285, 1154 cm−1; 1H NMR (CDCl3, 300 MHz) δH
9.67 (s, 1H), 7.73 (d, J = 8.1 Hz, 2H), 7.64 (s, 1H), 7.58 (d, J = 8.1
Hz, 1H), 7.36 (d, J = 7.5 Hz, 1H), 7.30−7.26 (m, 2H), 7.19 (d, J = 8.1
Hz, 2H), 7.08−7.03 (m, 2H), 3.81 (d, J = 1.8 Hz, 2H), 2.36 (s, 3H),
2.31 (s, 3H), 2.29 (s, 3H); 13C NMR (CDCl3, 75 MHz) δC 198.8,
143.9, 138.8, 137.6, 136.5, 136.4, 133.5, 132.2, 131.9, 130.7, 129.6,
127.3, 124.3, 120.1, 119.9, 114.4, 94.1, 87.9, 49.3, 21.5, 19.8, 19.3;
HRMS (ESI+) m/z calculated for C25H23NNaO3S [M + Na]+
440.1296, found 440.1306.
133.0, 132.5, 130.8, 129.6, 129.5, 128.0, 127.6, 127.2, 122.7, 120.8,
115.3, 114.4, 93.0, 89.3, 51.3, 21.5, 20.6, 13.8; HRMS (ESI+) m/z
calculated for C25H23NNaO3S [M + Na]+ 440.1296, found 440.1295.
N-(4-Bromo-2-((2-(1-oxopropan-2-yl)phenyl)ethynyl)phenyl)-4-
methylbenzenesulfonamide (10n). Pale yellow solid (180.9 mg, 75%
yield); mp 96−98 °C; Rf = 0.73 (50% ethyl acetate in petroleum
ether); IR (KBr) 3266, 3071, 2923, 2855, 2712, 2209, 1723, 1591,
1
1482, 1376, 1333, 1167 cm−1; H NMR (CDCl3, 300 MHz) δH 9.59
(s, 1H), 7.74−7.71 (m, 3H), 7.54−7.50 (m, 2H), 7.47 (m, 1H), 7.43−
7.34 (m, 3H), 7.30−7.26 (m, 1H), 7.22 (d, J = 8.1 Hz, 2H), 4.07−4.04
(m, 1H), 2.37 (s, 3H), 1.54 (d, J = 6.9 Hz, 3H); 13C NMR (CDCl3, 75
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J. Org. Chem. XXXX, XXX, XXX−XXX