Arkivoc 2019, v, 0-0
Abd El-Aal, H. A.K. et al.
2
-(2-(N-Benzyl-N-methylamino)-4-methyl-5-phenylthiophen-3-yl)acetic acid (7). Colourless plates; 74%, mp
-1 1
120-23 ºC (AcOH); IR (KBr) max 3070, 2930, 2612, 1725, 1590, 1580, 1440, 1384, 1248 cm ; H NMR (400
MHz, CDCl3, ppm), δ 2.33 (3H, s, CH3), 2.92 (3H, s, N-CH3), 3.87 (2H, s, CH2), 4.60 (2H, s, Ph-CH2), 7.08 (1H,
1
3
dddd, J 8.1, 7.9, 2.0, 1.6 Hz), 7.17-7.31 (7H, m), 7.37 (2H, dddd, J 7.9, 1.8, 1.6, 0.5 Hz), 10.45 (1H, s, COOH); C
NMR (100 MHz, CDCl3, δ, ppm): 14.2 (1C, -CH3), 32.6 (1C, -CH2), 44.8 (1C, N-CH3), 53.6 (1C, PhCH2), 127.1(2C,
Ar., C‐2'', C‐6''), 127.9 (2C, Ar., C‐2', C‐6'), 128.5 (2C, Ar., C-3'', C-5''), 128.9 (2C, Ar., C-4', C-4''), 129.0 (2C, Ar.,
C-3', C-5'), 132.1 (1C, Ar., C-1'), 133.0 (1C, Ar., C-3), 133.1 (1C, Ar., C-4), 136.7 (1C, Ar., C-5), 137.5 (1C, Ar., C-2),
+
1
40.1 (1C, Ar., C-1''), 174.0 (1C, -COOH); MS (EI, 70 eV) m/z (%), 351 (M , 22), 306 (100), 292 (50), 263 (30), 171
(
80), 105 (41), 77 (8). Anal. Calcd. for C21H21NO2S (351); C, 71.79; H, 5.98; N, 3.98; S, 9.11. Found; C, 71.64; H,
6.19; N, 4.11; S, 8.85%.
2
-(2-(N-Methyl-N-((pyridin-2-yl)methyl)amino)-4-methyl-5-phenylthiophen-3-yl)acetic acid (7c). Yellow
-
crystals; 77%; mp 204 dec.ºC, (AcOH); IR (KBr) max 3070, 2948, 2740, 1715, 1600, 1570, 1455, 1330, 1245 cm
1
1
;
H NMR (400 MHz, CDCl3, ppm), δ 2.33 (3H, s, CH3), 3.02 (3H, s, N-CH3), 3.87 (2H, s, CH2), 4.81 (2H, s, Ph-
CH2), 7.09 (1H, dddd, J 8.1, 7.9, 2.0, 1.6 Hz), 7.17-7.29 (4H, m), 7.37 (2H, dddd, J 7.9, 1.8, 1.6, 0.5 Hz), 7.63 (1H,
1
3
ddd, J 7.6, 7.4, 1.9 Hz), 8.51 (1H, ddd, J 4.5, 1.9, 0.5 Hz), 10.52 (1H, s, COOH); C NMR (100 MHz, CDCl3, δ,
ppm): 14.2 (1C, -CH3), 32.6(1C, -CH2), 44.8 (1C, N-CH3), 49.2 (1C, pyridyl-CH2), 123.3 (1C, Ar., C-4'), 123.5 (1C,
Ar., C-4''), 127.1 (2C, Ar., C‐2', C‐6'), 128.9 (1C, Ar., C-2''), 129.0 (2C, Ar., C-3', C-5'), 132.1 (1C, Ar., C-3''), 133.0
(
1C, Ar., C-1'), 133.1 (1C, Ar., C-3), 137.5 (1C, Ar., C-4), 137.7 (1C, Ar., C-5), 140.1 (1C, Ar., C-2), 149.0 (1C, Ar.,
+
+
C-5''), 160.1 (1C, Ar., C-1''), 174.0 (1C, -COOH); MS (EI, 70 eV) m/z (%), 354 (M +2, 9), 353 (22), 337 (M , 29),
07 (100), 292 (32), 278 (27), 201 (42), 172 (70), 106 (55), 77 (27). Anal. Calcd. for C20H20N2O2S (352); C, 68.18;
H, 5.68; N, 7.95; S, 9.09. Found; C, 68.16; H, 5.92; N, 7.85; S, 9.27%.
3
3
-(2-(N-Methyl-N-phenylamino)-4-methyl-5-phenylthiophen-3-yl)propanoic acid (7d). Colourless plates;
-1 1
80%, mp 140-43 ºC (methanol); IR (KBr) max 3110, 2974, 2642, 1723, 1600, 1585, 1440, 1374, 1230 cm ; H
NMR (400 MHz, CDCl3, ppm), δ 2.29 (3H, s, CH3), 2.64 (2H, t, J 7.4 Hz, CβH2), 2.96 (2H, t, J 7.4 Hz, CH2), 3.14
(
(
1
3H, s, N-CH3), 6.89 (1H, tt, J 8.1, 1.2 Hz), 7.08 (2H, dtd, J 8.2, 1.2, 0.5 Hz), 7.12 (H, tdd, J 7.7, 2.0, 1.6 Hz),7.27
2H, dddd, J 8.2, 8.1, 1.4, 0.5 Hz), 7.34 (2H, dddd, J 7.9, 7.7, 1.3, 0.6 Hz), 7.47 (2H, dddd, J 7.9, 1.9, 1.6, 0.5 Hz),
0.66 (1H, s, COOH); C NMR (100 MHz, CDCl3, δ, ppm): 14.2 (1C, -CH3), 30.0 (1C, -CβH2), 34.2 (1C, -CH2), 52.9
1
3
(
1C, N-CH3), 122.1 (2C, Ar., C‐2'', C‐6''), 124.7 (1C, Ar., C-4''), 127.1 (2C, Ar., C‐2', C‐6'), 128.9 (1C, Ar., C-4'),
129.0 (2C, Ar., C-3'', C-5''), 129.2 (2C, Ar., C-3', C-5'), 132.1 (1C, Ar., C-1'), 133.0 (1C, Ar., C-3), 133.1 (1C, Ar., C-
4
), 137.5 (1C, Ar., C-5), 140.1 (1C, Ar., C-2), 144.7 (1C, Ar., C-1''), 177.7 (1C, -COOH); MS (EI, 70 eV) m/z (%), 352
+
+
(
(
M +1, 18), 351 (M , 32), 306 (100), 292 (19), 278 (48), 172 (64), 106 (25), 77 (12). Anal. Calcd. for C21H21NO2S
351); C, 71.79; H, 5.98; N, 3.98; S, 9.11. Found; C, 71.88; H, 6.05; N, 3.90; S, 9.04%.
3
-(2-(N-Benzyl-N-methylamino)-4-methyl-5-phenylthiophen-3-yl)propanoic acid (7e). Yellow crystals; 82%;
-1 1
mp 118-20 ºC (acetone); IR (KBr) max 3065, 2970, 2550, 1710, 1600, 1590, 1440, 1338, 1280 cm ; H NMR
400 MHz, CDCl3, ppm), δ 2.30 (3H, s, CH3), 2.54 (2H, t, J 7.4 Hz, CβH2), 2.94 (2H, t, J 7.4 Hz, CH2), 2.92 (3H, s,
N-CH3), 4.60 (2H, s, Ph-CH2), 7.08 (1H, tdd, J 8.1, 2.0, 1.6 Hz), 7.17-7.31 (7H, m), 7.37 (2H, dddd, J 7.9, 1.8, 1.6,
(
1
3
0.5 Hz), 11.08 (1H, s, COOH); C NMR (100 MHz, CDCl3, δ, ppm): 14.2 (1C, -CH3), 30.0 (1C, -CβH2), 34.2 (1C, -
CH2), 44.8 (1C, PhCH2), 53.6 (1C, N-CH3), 127.1 (2C, Ar., C‐2', C‐6'), 127.9 (2C, Ar., C-4', C-4''), 128.5 (2C, Ar.,
C‐2'', C‐6''), 128.9 (2C, Ar., C-3'', C-5''), 129.0 (2C, Ar., C-3', C-5'), 132.1 (1C, Ar., C-1'), 133.0 (1C, Ar., C-3), 133.1
(
1C, Ar., C-4), 136.7 (1C, Ar., C-5), 137.5 (1C, Ar., C-2), 140.1 (1C, Ar., C-1''), 177.7 (1C, -COOH); MS (EI, 70 eV)
+
+
m/z (%), 365 (M , 26), 364 (M -1, 14), 306 (100), 292 (19), 277 (40), 172 (45), 105 (27), 77 (10). Anal. Calcd. for
C22H23NO2S (365); C, 72.32; H, 6.30; N, 3.83; S, 8.76. Found; C, 72.36; H, 6.44; N, 4.05; S, 8.64%.
3-(2-(N-Methyl-N-((pyridin-2-yl)methyl)amino)-4-methyl-5-phenylthiophen-3-yl)propanoic
acid
(7f).
Colourless crystals; 75%; mp 185-88 ºC (AcOEt); IR (KBr) max 3090, 2966, 2653, 1720, 1600, 1590, 1480, 1360,
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