F.-X. Felpin et al.
171.4 ppm; IR (KBr) n=1523, 1666, 2933, 3095, 3205 cmÀ1; HRMS (ESI):
m/z calcd for C19H21NO3Na: 334.1413 [M+Na+]; found: 334.1414.
(KBr) n=1597, 1679, 2943, 3064, 3212 cmÀ1; HRMS (ESI): m/z calcd for
C16H16NO: 238.1226 [M+]; found: 238.1226.
3-(4-Methoxycarbonylbenzyl)-6,7-dimethoxy-3,4-dihydro-1H-quinolin-2-
one (8 f): Purification by flash chromatography (30% EtOAc/CH2Cl2)
gave a white solid (259.2 mg, 73%). M.p. 1718C; 1H NMR (CDCl3,
300 MHz): d=2.51–2.59 (m, 1H), 2.66–2.82 (m, 3H), 3.39 (dd, J=3.0,
13.2 Hz, 1H), 3.80 (s, 3H), 3.84 (s, 3H), 3.90 (s, 3H), 6.43 (s, 1H), 6.56 (s,
1H), 7.27 (d, J=8.3 Hz, 2H), 7.97 (d, J=7.5 Hz, 2H), 9.21 ppm (brs,
1H); 13C NMR (CDCl3, 75 MHz): d=29.4, 35.3, 41.7, 52.0, 56.1, 56.3,
100.2, 111.8, 113.9, 128.4, 129.2, 129.7, 130.2, 144.7, 144.8, 148.4, 166.9,
173.0 ppm; IR (KBr) n=1670, 1721, 2951, 3095, 3206 cmÀ1; HRMS (ESI):
m/z calcd for C20H21NO5Na: 378.1311 [M+Na+]; found: 378.1315.
3-Methyl-3,4-dihydro-1H-quinolin-2-one (11g): Purification by flash chro-
matography (40% EtOAc/petroleum ether) gave a white solid (135.2 mg,
84%). M.p. 1298C [Lit.[21] 129–1308C]; 1H NMR (CDCl3, 300 MHz): d=
1.28 (d, J=6.6 Hz, 3H), 2.59–2.79 (m, 2H), 2.93–3.07 (m, 1H), 6.82 (d,
J=7.5 Hz, 1H), 6.99 (t, J=7.5 Hz, 1H), 7.14–7.20 (m, 2H), 8.73–
8.88 ppm (m, 1H); 13C NMR (CDCl3, 75 MHz): d=15.3, 33.3, 34.8, 115.3,
122.7, 123.3, 127.3, 127.9, 137.2, 175.1 ppm; IR (KBr) n=1594, 1667,
2926, 2988, 3071, 3197 cmÀ1; HRMS (ESI): m/z calcd for C10H12NO:
162.0913 [M+]; found: 162.0913.
3-Methyl-6,7-dimethyl-3,4-dihydro-1H-quinolin-2-one (11h): Purification
General procedure for the preparation of 2-quinolones by sequential
HRC reactions: Acrylate (2 mmol) and PdACTHNUTRGNEUNG(OAc)2 (5 mol%) were added
by flash chromatography (40% EtOAc/petroleum ether) gave a white
1
solid (107.7 mg, 57%). M.p. 1868C; H NMR (CDCl3, 300 MHz): d=1.28
to a solution of diazonium salt (1 mmol) in 1,4-dioxane (5 mL). The reac-
tion was stirred for 12 h at 608C (508C for methyl acrylate 10a, 258C and
6 h for g-butyrolactone 10 f), then charcoal (110 mg) was added and the
resulting mixture was stirred under H2 for 24 h at 508C. After filtration,
the crude material was purified by flash chromatography to give the cor-
responding 2-quinolone.
(d, J=6.4 Hz, 3H), 2.20 (s, 3H), 2.21 (s, 3H), 2.61–2.70 (m, 2H), 2.89–
2.99 (m, 1H), 6.63 (s, 1H), 6.90 (s, 1H), 8.98 ppm (brs, 1H); 13C NMR
(CDCl3, 75 MHz): d=15.4, 19.0, 19.4, 32.9, 35.1, 116.4, 120.6, 129.1, 130.9,
134.9, 135.6, 174.9 ppm; IR (KBr) n=1668, 2931, 3094, 3191 cmÀ1
;
HRMS (ESI): m/z calcd for C12H16NO: 190.1226 [M+]; found: 190.1228.
3-(2-Hydroxyethyl)-7-methoxy-3,4-dihydro-1H-quinolin-2-one (11i): Pu-
rification by flash chromatography (60% THF/petroleum ether) gave a
white solid (88.4 mg, 40%). M.p. 958C; 1H NMR (CDCl3, 250 MHz): d=
1.71–1.81 (m, 1H), 1.98–2.12 (m, 1H), 2.65–2.80 (m, 2H), 2.88–3.00 (m,
1H), 3.66–3.86 (m, 6H), 6.38 (d, J=2.4 Hz, 1H), 6.52 (dd, J=2.4, 8.3 Hz,
1H), 7.02 (d, J=8.3 Hz, 1H), 9.18 ppm (brs, 1H); 13C NMR (CDCl3,
62.5 MHz): d=30.9, 32.9, 38.6, 55.3, 60.8, 101.5, 108.4, 115.4, 128.7, 137.5,
3,4-Dihydro-1H-quinolin-2-one (11a): Purification by flash chromatogra-
phy (60% EtOAc/petroleum ether) gave a white solid (138.2 mg, 94%).
M.p. 1648C [Lit.[21] 164–1668C]; 1H NMR (CDCl3, 250 MHz): d=2.64 (t,
J=7.9 Hz, 2H), 2.96 (t, J=7.3 Hz, 2H), 6.87–7.00 (m, 2H), 7.13–7.19 (m,
2H), 9.86 ppm (brs, 1H); 13C NMR (CDCl3, 75 MHz): d=25.2, 30.6,
115.6, 123.0, 123.5, 127.4, 127.8, 137.3, 172.5 ppm; IR (KBr) n=1594,
1682, 2944, 2975, 3054, 3090, 3193 cmÀ1; HRMS (ESI): m/z calcd for
C9H10NO: 148.0756 [M+]; found: 148.0754.
159.2, 175.1 ppm; IR (KBr) n=1596, 1678, 2931, 3109, 3215, 3371 cmÀ1
;
HRMS (ESI): m/z calcd for C12H15NO3Na: 244.0944 [M+Na+]; found:
7-Trifluoromethyl-3,4-dihydro-1H-quinolin-2-one (11b): Purification by
flash chromatography (40% EtOAc/petroleum ether) gave a white solid
(154.8 mg, 72%). M.p. 1788C; 1H NMR (CDCl3, 250 MHz): d=2.69 (dd,
J=7.2, 9.3 Hz, 2H), 3.04 (t, J=7.2 Hz, 2H), 7.07 (s, 1H), 7.22–7.30 (m,
2H), 9.34 ppm (brs, 1H); IR (KBr) n=1597, 1684, 2937, 2977, 3051,
3116, 3203 cmÀ1; HRMS (ESI): m/z calcd for C10H9NOF3: 216.0630 [M+];
found: 216.0641.
244.0940.
7-Hydroxy-3,4-dihydro-1H-quinolin-2-one (11j): Purification by flash
chromatography (50% THF/petroleum ether) gave
a white solid
(107.6 mg, 66%). M.p. 2328C [Lit.[22] 228–2308C]; 1H NMR (Acetone,
250 MHz): d=2.47 (dd, J=7.1, 9.1 Hz, 2H), 2.82 (app t, J=7.1 Hz, 2H),
6.10–6.47 (m, 2H), 6.97 (d, J=7.9 Hz, 1H), 8.32 (s, 1H), 9.14 ppm (brs,
1H); 13C NMR (Acetone, 62.5 MHz): d=25.4, 31.9, 103.3, 109.9, 115.5,
129.4, 140.3, 157.7, 171.3 ppm; IR (KBr) n=1658, 2958, 3281 cmÀ1
;
7-Methoxy-3,4-dihydro-1H-quinolin-2-one (11c): Purification by flash
chromatography (60% EtOAc/petroleum ether) gave
a white solid
HRMS (ESI): m/z calcd for C9H9NO2Na: 186.0525 [M+Na+]; found:
(154.6 mg, 93%). M.p. 1458C [Lit.[22] 145–1468C]; 1H NMR (CDCl3,
250 MHz): d=2.69 (dd, J=7.0, 8.9 Hz, 2H), 2.89 (t, J=7.0 Hz, 2H), 3.78
(s, 3H), 6.39 (d, J=2.4 Hz, 1H), 7.07 (dd, J=2.4, 8.3 Hz, 1H), 7.04 (d,
J=8.2 Hz, 1H), 9.03 ppm (brs, 1H); 13C NMR (CDCl3, 75 MHz): d=
24.5, 31.0, 55.4, 101.6, 108.2, 115.7, 128.5, 138.2, 159.2, 172.5 ppm; IR
(KBr) n=1593, 1625, 1682, 2927, 2955, 3056, 3107, 3197 cmÀ1; HRMS
(ESI): m/z calcd for C10H11NO2Na: 200.0681 [M+Na+]; found: 200.0680.
186.0524.
3-Phenylquinolin-2-one (13): Purification by flash chromatography (20%
EtOAc/CH2Cl2) gave a white solid (165.7 mg, 75%). M.p. 2348C [Lit.[24]
231–2328C]; 1H NMR (CDCl3, 300 MHz): d=7.22 (t, J=7.9 Hz, 1H),
7.38–7.52 (m, 5H), 7.61 (d, J=7.1 Hz, 1H), 7.83 (d, J=6.8 Hz, 2H), 7.93
(s, 1H), 12.2 ppm (brs, 1H); 13C NMR (CDCl3, 75 MHz): d=115.6, 120.3,
122.6, 127.8, 128.2, 128.3, 128.9, 130.3, 132.4, 136.2, 138.0, 138.5,
163.2 ppm; IR (KBr) n=1657, 2895, 3029 cmÀ-1; HRMS (ESI): m/z calcd
for C15H12NO: 222.0913 [M+]; found: 222.0914.
6,7-Dimethyl-3,4-dihydro-1H-quinolin-2-one (11d): Purification by flash
chromatography (20% EtOAc/CH2Cl2) gave a white solid (117.3 mg,
67%). M.p. 2008C [Lit.[23] 199–2028C]; 1H NMR (CDCl3, 300 MHz): d=
2.20 (s, 6H), 2.62 (t, J=7.2 Hz, 2H), 2.90 (t, J=7.2 Hz, 2H), 6.66 (s, 1H),
6.91 (s, 1H), 9.53 ppm (brs, 1H); 13C NMR (CDCl3, 75 MHz): d=19.0,
19.3, 24.8, 30.9, 116.7, 120.7, 128.9, 131.0, 135.0, 135.7, 172.4 ppm; IR
(KBr) n=1678, 2946, 3074, 3201 cmÀ1; HRMS (ESI): m/z calcd for
C11H14NO: 176.1069 [M+]; found: 176.1070.
Methyl 3-(4-methoxycarbonylphenyl)propanoate (16): A solution of (E)-
methyl 4-methoxycarbonylcinnamate (110 mg, 0.5 mmol) and reused Pd/
C (first reuse, 5 mol%) in MeOH (3 mL) was stirred at room tempera-
ture for 12 h under H2. After filtration, the crude showed excellent purity
(108.8 mg, 98%). 1H NMR (CDCl3, 250 MHz): d=2.64 (t, J=7.9 Hz,
2H), 2.99 (t, J=7.5 Hz, 2H), 3.65 (s, 3H), 3.89 (s, 3H), 7.26 (d, J=
8.1 Hz, 2H), 7.95 ppm (d, J=8.1 Hz, 2H); 13C NMR (CDCl3, 50 MHz):
d=30.8, 35.1, 51.7, 52.0, 128.3, 129.8, 145.9, 166.9, 172.9 ppm.
3-Phenyl-3,4-dihydro-1H-quinolin-2-one (11e): Purification by flash chro-
matography (20% EtOAc/CH2Cl2) gave a white solid (156.1 mg, 70%).
M.p. 1658C; 1H NMR (CDCl3, 250 MHz): d=3.24–3.27 (m, 2H), 3.88
(dd, J=7.2, 8.5 Hz, 1H), 6.81 (d, J=7.9 Hz, 1H), 7.00 (t, J=6.9 Hz, 1H),
7.15–7.36 (m, 7H), 8.83 ppm (brs, 1H); 13C NMR (CDCl3, 75 MHz): d=
33.5, 46.5, 115.4, 123.1, 127.2, 127.6, 127.9, 128.1, 128.6, 137.0, 138.4,
172.4 ppm; IR (KBr) n=1597, 1682, 1713, 2945, 3064, 3217 cmÀ1; HRMS
(ESI): m/z calcd for C15H13NONa: 246.0889 [M+Na+]; found: 246.0885.
Dibenzyl (18): A solution of trans-stilbene (90 mg, 0.5 mmol) and reused
Pd/C (first reuse, 5 mol%) in MeOH (3 mL) was stirred at room temper-
ature for 12 h under H2. After filtration, the crude showed excellent
purity (89.2 mg, 98%). 1H NMR (CDCl3, 250 MHz): d=3.01 (s, 4H),
7.26–7.40 ppm (m, 10H); 13C NMR (CDCl3, 75 MHz): d=37.9, 125.9,
128.3, 128.4, 141.7 ppm.
3-(2-Methylphenyl)-3,4-dihydro-1H-quinolin-2-one (11 f): Purification by
Biphenyl (20): A solution of 4-bromobiphenyl (116 mg, 0.5 mmol) and
reused Pd/C (first reuse, 5 mol%) in MeOH (3 mL) was stirred at room
temperature for 12 h under H2. After filtration, the crude showed excel-
lent purity (75.8 mg, 98%). 1H NMR (CDCl3, 250 MHz): d=7.36–7.52
(m, 6H), 7.63–7.67 ppm (m, 4H); 13C NMR (CDCl3, 75 MHz): d=127.1,
127.2, 128.7, 141.2 ppm.
flash chromatography (20% EtOAc/CH2Cl2) gave
a white solid
(168.3 mg, 71%). M.p. 1758C; 1H NMR (CDCl3, 300 MHz): d=2.41 (s,
3H), 3.11–3.29 (m, 2H), 4.10 (dd, J=7.1, 11.3 Hz, 1H), 6.82 (d, J=
7.5 Hz, 1H), 6.99 (t, J=7.2 Hz, 1H), 7.13–7.26 (m, 6H), 9.35 ppm (brs,
1H); 13C NMR (CDCl3, 75 MHz): d=19.8, 33.0, 43.1, 115.4, 123.0, 123.4,
126.3, 127.1, 127.6, 127.6, 127.8, 130.6, 136.3, 137.0, 137.2, 172.5 ppm; IR
7244
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 7238 – 7245