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(s, 3H); 13C NMR (75 MHz, CDCl3): d=174.7, 165.8, 154.7, 143.0,
140.0, 136.3, 131.3, 129.5, 128.9, 128.5, 127.7, 127.0, 113.2, 106.4,
97.8, 70.3, 50.1, 39.5, 32.0, 21.7 ppm; IR (KBr): n˜ =2919, 2067,
1620 cmÀ1; HRMS (ESI) calcd for C24H24N2O3SNa [M+Na]+, 443.1405,
found 443.1409.
1.33 (m, 2H), 0.97 ppm (t, J=7.3 Hz, 3H); 13C NMR (75 MHz, CDCl3):
d=174.7, 166.6, 153.5, 142.9, 140.1, 131.6, 129.5, 127.0, 112.8,
105.4, 96.2, 55.5, 51.5, 48.0, 31.7, 28.7, 21.7, 20.5, 14.1 ppm; IR (KBr):
n˜ =2925, 2854, 2067, 1621, 1456 cmÀ1; HRMS (ESI) calcd for
C21H27N2O3S [M+H]+ 387.1737, found 387.1736.
(E)-N-(7-((tert-butyldimethylsilyl)oxy)-1-methyl-2,3-dihydroquino-
lin-4(1H)-ylidene)-4-methylbenzenesulfonamide (4g): Yellow oil
(11 mg, 0.025 mmol, 24%); 1H NMR (300 MHz, CDCl3): d=7.91 (d,
J=8.7 Hz, 1H), 7.90 (d, J=8.1 Hz, 2H), 7.30 (d, J=8.1 Hz, 2H), 6.17
(dd, J=8.7, 2.1 Hz, 1H), 6.06 (d, J=2.1 Hz, 1H), 3.44–3.34 (m, 4H),
2.93 (s, 3H), 2.42 (s, 3H), 0.97 (s, 9H), 0.22 ppm (s, 6H); 13C NMR
(75 MHz, CDCl3): d=174.8, 163.5, 154.8, 143.0, 140.0, 131.1, 129.5,
127.0, 113.5, 111.3, 103.4, 50.1, 39.5, 32.0, 25.8, 21.7, 18.5,
À4.0 ppm; IR (KBr): n˜ =2927, 2067, 1614, 1547, 1497 cmÀ1; HRMS
(ESI) calcd for C23H33N2O3SSi [M+H]+, 445.1981, found 445.1988.
(E)-N-(1-hexyl-7-methoxy-2,3-dihydroquinolin-4(1H)-ylidene)-4-
methylbenzenesulfonamide (4n): Yellow solid (40.7 mg,
0.098 mmol, 87%); m.p. 118–1208C; H NMR (300 MHz, CDCl3): d=
1
7.95 (d, J=9.1 Hz, 1H), 7.89 (d, J=8.1 Hz, 2H), 7.30 (d, J=8.0 Hz,
2H), 6.21 (dd, J=9.0, 1.7 Hz, 1H), 6.06 (d, J=1.7 Hz, 1H), 3.82 (s,
3H), 3.39 (s, 4H), 3.31 (t, J=7.4 Hz, 2H), 2.43 (s, 3H), 1.64–1.58 (m,
2H), 1.38–1.30 (m, 6H), 0.90 ppm (t, J=5.1 Hz, 3H); 13C NMR
(75 MHz, CDCl3): d=174.6, 166.6, 153.5, 142.9, 140.1, 131.6, 129.5,
127.0, 112.8, 105.4, 96.2, 55.5, 51.8, 48.0, 31.8, 31.7, 27.0, 26.5, 22.8,
21.7, 14.2 ppm; IR (KBr): n˜ =2925, 2854, 1705, 1621, 1461 cmÀ1
;
HRMS (APCI) calcd for C23H31N2O3S [M+H]+ 415.2055, found
Synthesis of N-(7-hydroxy-1-methyl-2,3-dihydroquinolin-4(1H)-
ylidene)-4-methylbenzenesulfonamide (4g’): To a stirred solution
of 3-((tert-butyldimethylsilyl)oxy)-N-methyl-N-((1-tosyl- 1H-1,2,3-tria-
zol-4-yl)methyl)aniline (55 mg, 0.12 mmol) in DMF (6.00 mL) and
the resultant mixture was stirred for 20 minutes at 1208C. The re-
action mixture was concentrated to afford the crude product, then
quenched with a solution of NH4Cl, washed with ethyl acetate,
dried over MgSO4, filtered, and concentrated under reduced pres-
sure to afford the crude product, which was purified by silica-gel
column chromatography to afford the desired product (28 mg,
72%) as a yellow solid.
415.2065
(E)-N-(1-allyl-7-methoxy-2,3-dihydroquinolin-4(1H)-ylidene)-4-
methylbenzenesulfonamide
(4o):
Yellow
solid
(40 mg,
1
0.108 mmol, 86%); m.p. 138–1428C; H NMR (300 MHz, CDCl3): d=
7.96 (d, J=4.5 Hz, 1H), 7.90 (d, J=4.1 Hz, 2H), 7.31 (d, J=4.0 Hz,
2H), 6.24 (dd, J=9.2, 2.3 Hz, 1H), 6.09 (d, J=1.1 Hz, 1H), 5.90–5.76
(m, 1H), 5.28–5.20 (m, 2H), 3.96 (d, J=5.1 Hz, 2H), 3.80 (s, 3H),
3.42 (s, 4H), 2.43 ppm (s, 3H); 13C NMR (75 MHz, CDCl3): d=174.6,
166.6, 153.6, 143.0, 140.0, 132.1, 131.4, 129.5, 127.0, 117.9, 112.9,
106.0, 96.8, 55.6, 54.3, 48.0, 31.8, 31.1 (grease), 21.8 ppm; IR (KBr):
n˜ =2923, 2852, 1619, 1544, 1456 cmÀ1; HRMS (ESI) calcd for
C20H23N2O3S [M+H]+ 371.1429, found 371.1432.
N-(7-hydroxy-1-methyl-2,3-dihydroquinolin-4(1H)-ylidene)-4-
methylbenzenesulfonamide
(4g’):
Yellow
solid
(18 mg,
1
0.054 mmol, 51%); m.p. 165–1688C; H NMR (300 MHz, CDCl3): d=
7.89 (m, 3H), 7.31 (d, J=8.1 Hz, 2H), 6.16 (d, J=7.5 Hz, 1H), 6.07 (s,
1H), 3.44–3.30 (m, 4H), 2.93 (s, 3H), 2.43 ppm (s, 3H); 13C NMR
(75 MHz, CDCl3): d=174.8, 163.5, 155.1, 143.1, 139.9, 131.7, 129.6,
127.0, 113.0, 107.4, 98.5, 50.0, 39.5, 31.9, 21.8 ppm; IR (KBr): n˜ =
3432, 1621, 1556, 1498 cmÀ1; HRMS (ESI) calcd for C17H17N2O3S
[MÀH]À 329.0960, found 329.0959.
(E)-N-(1-ethyl-7-methoxy-2,3-dihydroquinolin-4(1H)-ylidene)-4-
methylbenzenesulfonamide (4k): Yellow solid (77 mg, 0.22 mmol,
73%); m.p. 189–1928C; 1H NMR (300 MHz, CDCl3): d=7.96 (d, J=
9.0 Hz, 1H), 7.89 (d, J=8.2 Hz, 2H), 7.30 (d, J=8.0 Hz, 2H), 6.22
(dd, J=9.0, 2.2 Hz, 1H), 6.09 (d, J=2.1 Hz, 1H), 3.82 ( s, 3H), 3.43
(q, J=7.1 Hz, 2H), 3.39 (s, 4H), 2.43 (s, 3H), 1.19 ppm (t, J=7.1 Hz,
3H); 13C NMR (75 MHz, CDCl3): d=174.7, 166.7, 153.2, 142.9, 140.1,
131.7, 129.5, 127.0, 113.0, 105.5, 96.3, 55.6, 47.2, 46.0, 31.7 (grease),
21.8, 14.3, 11.1 ppm; IR (KBr): n˜ =2075, 1644, 1496 cmÀ1; HRMS
(ESI) calcd for C19H22N2O3SNa [M+Na]+ 381.1249, found, 381.1259.
Synthesis of N-(7-(benzyloxy)-1-methyl-1,2,3,4-tetrahydroquino-
lin-4-yl)-4- methylbenzenesulfonamide (4s): To a stirred solution
of N-(7-(benzyloxy)-1-methyl-2,3-dihydroquinolin-4(1H)-ylidene)-4-
methylbenzenesulfonamide (90 mg, 0.21 mmol) in THF (10 mL) was
added NaBH4 (10 mg, 0.26 mmol) and MeOH (1 mL) at 08C, the re-
sultant mixture was stirred at room temperature for 1 h. The reac-
tion was evaporated under reduced pressure. The resultant residue
was dissolved in ethyl acetate, washed with H2O, dried over
MgSO4, filtered, and concentrated under reduced pressure to
afford the desired product (76 mg, 84%) as an off white solid.
N-(7-(benzyloxy)-1-methyl-1,2,3,4-tetrahydroquinolin-4-yl)-4-
methylbenzenesulfonamide
(4s):
Colorless
oil
(76 mg,
1
0.179 mmol, 84%); H NMR (300 MHz, CDCl3): d=7.81 (d, J=9.0 Hz,
2H), 7.40–7.24 (m, 7H), 6.43 (d, J=6.0 Hz, 1H), 6.18 (d, J=3.0 Hz,
1H), 6.12 (dd, J=3.0 Hz, 1H), 4.99 (s, 2H), 4.45 (d, J=6.0 Hz, 1H),
4.25–4.27 (m, 1H), 3.35–3.25 (m, 1H), 3.13–3.09 (m, 1H), 2.85 (s,
3H), 2.47 (s, 3H), 2.18–2.08 (m, 1H), 1.94–1.85 ppm (m, 1H);
13C NMR (75 MHz, CDCl3): d=160.3, 147.7, 143.7, 138.0, 137.3,
130.3, 130.0, 128.8, 128.1, 127.7, 127.5, 113.7, 102.4, 98.8, 70.1, 50.1,
46.2, 39.2, 29.4, 21.8 ppm; IR (KBr): n˜ =1616, 1572, 1510,
1454 cmÀ1; HRMS (ESI) calcd for C24H26N2O3SNa [M+Na]+ 445.1562,
found 445.1559.
(E)-N-(7-methoxy-1-propyl-2,3-dihydroquinolin-4(1H)-ylidene)-4-
methylbenzenesulfonamide (4l): Yellow solid (77 mg, 0.21 mmol,
70%); m.p. 141–1478C; 1H NMR (300 MHz, CDCl3): d=7.96 (d, J=
9.0 Hz, 1H), 7.89 (d, J=8.1 Hz, 2H), 7.30(d, J=8.1 Hz, 2H), 6.22 (dd,
J=9.0, 2.0 Hz, 1H), 6.06 (d, J=2.0 Hz, 1H), 3.82 (s, 3H), 3.50–3.33
(m, 4H), 3.28 (t, J=7.4 Hz, 2H), 2.43 (s, 3H), 1.7–1.5 (m, 2H),
0.98 ppm (t, J=7.4 Hz, 3H); 13C NMR (75 MHz, CDCl3): d=174.7,
166.6, 153.5, 142.9, 140.1, 131.6, 129.5, 127.0, 112.8, 105.3, 96.3,
55.5, 53.5, 48.0, 31.6, 21.8, 19.9, 11.7 ppm; IR (KBr): n˜ =2924, 2084,
1638 cmÀ1; HRMS (ESI) calcd for C20H25N2O3S [M+H]+, 373.1586,
found, 373.1579.
Synthesis of 7-(benzyloxy)-1-methyl-2,3-dihydroquinolin-4(1H)-
one (4t): A mixture of 1m HCl (2 mL) and 1,4-dioxane (8 mL) was
added to N-(7-(benzyloxy)-1-methyl-2,3-dihydroquinolin-4(1H)-yli-
dene)-4-methylbenzenesulfonamide (50 mg, 0.12 mmol) and
heated to 1008C for 2 h. The solution mixture was evaporated
under reduce pressure and diluted with H2O, extracted with ethyl
acetate, dried over MgSO4, filled, and concentrated under reduced
pressure to afford the crude product, which was purified by silica-
gel column chromatography to afford the desired product (23 mg,
72%) as a colorless oil.
(E)-N-(1-butyl-7-methoxy-2,3-dihydroquinolin-4(1H)-ylidene)-4-
methylbenzenesulfonamide (4m): Yellow solid (33.1 mg,
1
0.086 mmol, 71%); m.p. 148–1528C; H NMR (300 MHz, CDCl3): d=
7.95 (d, J=9.2 Hz, 1H), 7.89 (d, J=7.8 Hz, 2H), 7.30 (d, J=7.9 Hz,
2H), 6.21 (dd, J=9.1, 2.4 Hz, 1H), 6.06 (s, 1H), 3.82 (s, 3H), 3.39
(s,4H), 3.32, (t, J=7.3 Hz, 2H), 2.42 (s, 3H), 1.66–1.57 (m, 2H), 1.46–
7-(benzyloxy)-1-methyl-2,3-dihydroquinolin-4(1H)-one (4t): col-
1
orless oil (23 mg, 0.085 mmol, 72%); H NMR (300 MHz, CDCl3): d=
Chem. Asian J. 2016, 11, 757 – 765
763
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