The Journal of Organic Chemistry
Article
1H), 8.06 (dt, J = 7.8, 1.0 Hz, 1H), 7.88−7.86 (m, 2H), 7.85−7.81
(m, 1H), 7.48−7.41 (m, 1H), 7.23 (d, J = 7.9 Hz, 2H), 5.56 (dd, J =
8.8, 5.2 Hz, 1H), 4.13 (t, J = 7.1 Hz, 2H), 3.85 (dd, J = 17.9, 8.8 Hz,
1H), 3.63 (dd, J = 17.9, 5.2 Hz, 1H), 2.38 (s, 3H), 1.13 (t, J = 7.1 Hz,
3H); 13C{1H} NMR (101 MHz, CDCl3) δ (ppm): 196.4, 196.3,
170.4, 152.4, 149.1, 144.2, 137.0, 133.8, 129.3, 128.4, 127.4, 122.5,
61.4, 47.7, 37.8, 21.7, 13.9; HRMS (ESI) m/z: [M + H]+ Calcd for
C19H20NO4 326.1392; Found 326.1386.
128.3, 41.2, 40.8, 34.8, 21.7, 20.7, 14.2; HRMS (ESI) m/z: [M + H]+
Calcd for C20H23O2 295.1698; Found 295.1692.
2-(2-Oxo-2-(p-tolyl)ethyl)-3,4-dihydronaphthalen-1(2H)-one
(5d). Pale yellow viscous liquid; 22% yield (12 mg); Rf value = 0.4
[EtOAc/petroleum ether = 1:9 (v/v)]; FTIR νmax (neat): 1681, 1608,
1405 cm−1; 1H NMR (400 MHz, CDCl3) δ (ppm): 8.04 (dd, J = 7.8,
1.2 Hz, 1H), 7.94 (d, J = 8.2 Hz, 2H), 7.48 (td, J = 7.5, 1.4 Hz, 1H),
7.33−7.25 (m, 4H), 3.84 (dd, J = 17.5, 4.6 Hz, 1H), 3.32 (ddt, J =
13.3, 7.3, 4.5 Hz, 1H), 3.18 (ddd, J = 17.0, 12.7, 4.5 Hz, 1H), 3.01−
2.93 (m, 2H), 2.42 (s, 3H), 2.32−2.26 (m, 1H), 1.97 (qd, J = 13.0,
4.3 Hz, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ (ppm): 199.3,
198.3, 144.3, 144.0, 134.6, 133.5, 132.4, 129.4, 128.9, 128.4, 127.6,
126.7, 44.3, 38.9, 29.7, 29.5, 21.8; HRMS (ESI) m/z: [M + H]+ Calcd
for C19H19O2 279.1385; Found 279.1391.
Diethyl 2-(2-Oxo-2-(p-tolyl)ethyl)malonate (4l).26b Pale yellow
viscous liquid; 54% yield (32 mg); Rf value = 0.6 [EtOAc/petroleum
1
ether = 1:9 (v/v)]; FTIR νmax (neat): 1747, 1730, 1684 cm−1; H
NMR (400 MHz, CDCl3) δ (ppm): 7.88−7.86 (m, 2H), 7.25 (dd, J =
7.3, 1.2 Hz, 2H), 4.22 (ddt, J = 10.7, 7.1, 3.6 Hz, 4H), 4.04 (t, J = 7.1
Hz, 1H), 3.59 (d, J = 7.1 Hz, 2H), 2.40 (s, 3H), 1.28 (t, J = 7.1 Hz,
6H); 13C{1H} NMR (101 MHz, CDCl3) δ (ppm): 196.3, 169.2,
144.5, 133.8, 129.4, 128.4, 61.8, 47.4, 37.8, 21.8, 14.1.
2-(2-Oxo-2-(p-tolyl)ethyl)cyclohexan-1-one (5e).42 White solid;
mp: 67−69 °C; 12% yield (6 mg); Rf value = 0.4 [EtOAc/petroleum
ether = 1:9 (v/v)]; FTIR νmax (KBr plate): 1711, 1685, 1605 cm−1;
1H NMR (400 MHz, CDCl3) δ (ppm): 7.88 (d, J = 8.2 Hz, 2H), 7.24
(d, J = 8.0 Hz, 2H), 3.56 (dd, J = 17.6, 6.5 Hz, 1H), 3.14 (dq, J =
12.2, 6.0 Hz, 1H), 2.66 (dd, J = 17.6, 5.8 Hz, 1H), 2.44−2.39 (m,
2H), 2.39 (s, 3H), 2.15 (dddd, J = 15.9, 11.7, 6.6, 3.4 Hz, 2H), 1.90−
1.85 (m, 1H), 1.78 (ddd, J = 12.8, 9.2, 3.7 Hz, 1H), 1.73−1.60 (m,
1H), 1.48−1.38 (m, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ
(ppm): 211.8, 198.4, 143.9, 134.7, 129.3, 128.3, 46.5, 42.1, 38.3, 34.4,
28.1, 25.5, 21.7.
Di-tert-butyl 2-(2-Oxo-2-(p-tolyl)ethyl)malonate (4m).26b Pale
yellow viscous liquid; 62% yield (43 mg); Rf value = 0.7 [EtOAc/
petroleum ether = 1:9 (v/v)]; FTIR νmax (neat): 1723, 1683, 1422
1
cm−1; H NMR (400 MHz, CDCl3) δ (ppm):) 7.88 (d, J = 8.2 Hz,
2H), 7.25 (d, J = 8.6 Hz, 2H), 3.87 (t, J = 7.1 Hz, 1H), 3.48 (d, J = 7.1
Hz, 2H), 2.40 (s, 3H), 1.47 (s, 18H); 13C{1H} NMR (101 MHz,
CDCl3) δ (ppm): 196.6, 168.6, 144.2, 134.1, 129.4, 128.4, 81.9, 49.4,
37.8, 28.1, 21.8.
1-(tert-Butyl) 3-Ethyl 2-(2-oxo-2-(p-tolyl)ethyl)malonate (4n).26b
Pale yellow viscous liquid; 66% yield (42 mg); Rf value = 0.6 [EtOAc/
petroleum ether = 1:9 (v/v)]; FTIR νmax (neat): 1741, 1726, 1384
3-Benzoyl-1-(p-tolyl)pentane-1,4-dione (5f).43 Pale yellow syrup;
20% yield (12 mg); Rf value = 0.5 [EtOAc/petroleum ether = 1:9 (v/
v)]; FTIR νmax (neat): 1720, 1680, 1611 cm−1; 1H NMR (400 MHz,
CDCl3) δ (ppm): 8.07 (dd, J = 8.4, 1.3 Hz, 1H), 7.97 (ddd, J = 6.9,
4.3, 1.5 Hz, 2H), 7.87−7.85 (m, 1H), 7.60−7.58 (m, 1H), 7.50 (dd, J
= 8.2, 7.0 Hz, 1H), 7.43 (t, J = 7.6 Hz, 1H), 7.30 (d, J = 7.9 Hz, 1H),
7.23 (d, J = 7.9 Hz, 1H), 5.28 (dd, J = 9.0, 4.1 Hz, 1H), 3.77 (ddd, J =
18.0, 11.0, 6.9 Hz, 1H), 3.57 (dt, J = 18.2, 6.5 Hz, 1H), 2.40 (d, J =
12.4 Hz, 3H), 2.22 (d, J = 1.6 Hz, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ (ppm): 202.5, 197.0, 196.5, 196.4, 195.9, 144.9, 144.5,
136.2, 136.1, 133.9, 133.7, 133.6, 133.5, 129.7, 129.4, 129.1, 129.0,
128.9, 128.7, 128.4, 128.2, 56.9, 56.7, 38.1, 38.0, 29.6, 29.5, 21.8, 21.7.
N,2-Dimethyl-4-oxo-N-phenyl-4-(p-tolyl)butanamide (5g).
Brown gummy liquid; 43% yield (25 mg); Rf value = 0.3 [EtOAc/
petroleum ether = 3:7 (v/v)]; FTIR νmax (neat): 1685, 1657, 1599
1
cm−1; H NMR (400 MHz, CDCl3) δ (ppm): 7.85 (d, J = 8.3 Hz,
2H), 7.22 (d, J = 7.9 Hz, 2H), 4.24−4.15 (m, 2H), 3.93 (t, J = 7.1 Hz,
1H), 3.52 (d, J = 6.8 Hz, 2H), 2.37 (s, 3H), 1.44 (s, 9H), 1.26 (t, J =
7.1 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ (ppm): 196.3,
169.5, 168.1, 144.2, 133.9, 129.3, 128.3, 82.1, 61.5, 48.3, 37.7, 27.9,
21.7, 14.1.
Diethyl 2-Methyl-2-(2-oxo-2-(p-tolyl)ethyl)malonate (4o).26b
Pale yellow viscous liquid; 28% yield (17 mg); Rf value = 0.6
[EtOAc/petroleum ether = 1:9 (v/v)]; FTIR νmax (neat): 1736, 1686,
1
1607 cm−1; H NMR (400 MHz, CDCl3) δ (ppm): 7.85 (d, J = 8.2
Hz, 2H), 7.24 (d, J = 7.9 Hz, 2H), 4.19 (q, J = 7.1 Hz, 4H), 3.63 (s,
2H), 2.39 (s, 3H), 1.58 (s, 3H), 1.23 (t, J = 7.1 Hz, 6H); 13C{1H}
NMR (101 MHz, CDCl3) δ (ppm): 196.2, 171.8, 144.2, 134.3, 129.4,
128.2, 61.6, 51.6, 44.2, 21.7, 20.6, 14.0.
1
cm−1; H NMR (400 MHz, CDCl3) δ (ppm): 7.84 (d, J = 8.2 Hz,
1-(4-Methoxyphenyl)-4-(p-tolyl)butane-1,4-dione (5a).40 Color-
less gummy syrup; 33% yield (19 mg); Rf value = 0.3 [EtOAc/
petroleum ether = 1:9 (v/v)]; FTIR νmax (neat): 1672, 1615, 1551,
2H), 7.45 (q, J = 8.5 Hz, 4H), 7.36−7.34 (m, 1H), 7.21 (d, J = 8.0
Hz, 2H), 3.62 (dd, J = 17.8, 9.7 Hz, 1H), 3.26 (s, 3H), 3.05 (ddd, J =
9.9, 7.0, 4.0 Hz, 1H), 2.77 (dd, J = 17.8, 4.0 Hz, 1H), 2.37 (s, 3H),
1.05 (d, J = 7.0 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ
(ppm): 198.6, 175.9, 144.2, 143.8, 134.3, 129.7, 129.2, 128.2, 127.9,
127.8, 43.1, 37.7, 32.4, 21.7, 18.0; HRMS (ESI) m/z: [M + Na]+
Calcd for C19H21NNaO2 318.1470; Found 318.1487.
1
1401 cm−1; H NMR (400 MHz, CDCl3) δ (ppm): 8.02 (d, J = 9.0
Hz, 2H), 7.94 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 7.7 Hz, 2H), 6.95 (d, J
= 9.0 Hz, 2H), 3.87 (s, 3H), 3.41 (dd, J = 3.9, 3.0 Hz, 4H), 2.42 (s,
3H); 13C{1H} NMR (101 MHz, CDCl3) δ (ppm): 198.7, 197.5,
163.7, 144.0, 134.5, 130.5, 130.1, 129.4, 128.4, 113.9, 55.6, 32.7, 32.4,
21.8.
N,N-Diisopropyl-2-methyl-4-oxo-4-(p-tolyl)butanamide (5h).
Brown gummy liquid; 35% yield (20 mg); Rf value = 0.3 [EtOAc/
petroleum ether = 3:7 (v/v)]; FTIR νmax (neat): 1875, 1683, 1645
4-(4-Oxo-4-(p-tolyl)butanoyl)benzonitrile (5b).41 Colorless solid;
mp: 134−136 °C; 46% yield (25 mg); Rf value = 0.4 [EtOAc/
petroleum ether = 1:9 (v/v)]; FTIR νmax (KBr plate): 2235, 1695,
1621, 1405 cm−1; 1H NMR (400 MHz, CDCl3) δ (ppm): 8.12 (d, J =
8.6 Hz, 2H), 7.92 (d, J = 8.2 Hz, 2H), 7.79 (d, J = 8.6 Hz, 2H), 7.28
(d, J = 7.9 Hz, 2H), 3.47 (ddd, J = 6.1, 5.0, 1.4 Hz, 2H), 3.43−3.40
(m, 2H), 2.42 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ (ppm):
197.9, 197.8, 144.4, 140.0, 134.2, 132.7, 129.5, 128.7, 128.4, 118.1,
116.5, 32.9, 32.7, 21.8.
1
cm−1; H NMR (400 MHz, CDCl3) δ (ppm): 7.86 (d, J = 8.2 Hz,
2H), 7.21 (d, J = 8.0 Hz, 2H), 4.20−4.17 (m, 1H), 3.56 (dd, J = 17.6,
8.0 Hz, 1H), 3.43 (s, 1H), 3.37−3.28 (m, 1H), 2.87 (dd, J = 17.6, 5.0
Hz, 1H), 2.37 (s, 3H), 1.34 (d, J = 6.8 Hz, 3H), 1.31 (d, J = 6.8 Hz,
3H), 1.29 (d, J = 6.7 Hz, 3H), 1.23 (d, J = 6.7 Hz, 3H), 1.15 (d, J =
7.0 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ (ppm): 198.9,
174.7, 143.7, 134.7, 129.2, 128.3, 48.4, 45.7, 42.8, 32.7, 21.7, 21.2,
21.1, 20.8, 20.6, 18.2; HRMS (ESI) m/z: [M + Na]+ Calcd for
C18H27NNaO2 312.1939; Found 312.1918.
1-Phenyl-2-propyl-4-(p-tolyl)butane-1,4-dione (5c). Pale yellow
oil; 52% yield (31 mg); Rf value = 0.5 [EtOAc/petroleum ether = 1:9
2-Methyl-1-(pyrrolidin-1-yl)-4-(p-tolyl)butane-1,4-dione (5i).
1
(v/v)]; FTIR νmax (neat): 1681, 1608, 1416 cm−1; H NMR (400
Gummy liquid; 57% yield (30 mg); Rf value = 0.3 [EtOAc/petroleum
1
MHz, CDCl3) δ (ppm): 8.07 (d, J = 7.1 Hz, 2H), 7.87 (d, J = 8.2 Hz,
2H), 7.55 (d, J = 7.4 Hz, 1H), 7.48 (dd, J = 8.1, 6.8 Hz, 2H), 7.25 (t, J
= 6.3 Hz, 2H), 4.15 (dddd, J = 10.3, 7.2, 6.3, 4.2 Hz, 1H), 3.69 (dd, J
= 17.9, 9.1 Hz, 1H), 3.15 (dd, J = 17.9, 4.2 Hz, 1H), 2.39 (s, 3H),
1.73 (dt, J = 6.6, 4.2 Hz, 1H), 1.58−1.49 (m, 1H), 1.42−1.31 (m,
2H), 0.90 (t, J = 7.3 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ
(ppm) 203.7, 198.4, 144.0, 137.1, 134.3, 132.9, 129.3, 128.7, 128.6,
ether = 3:7 (v/v)]; FTIR νmax (neat): 1681, 1624, 1445 cm−1; H
NMR (400 MHz, CDCl3) δ (ppm): 7.84 (d, J = 8.1 Hz, 2H), 7.21 (d,
J = 8.2 Hz, 2H), 3.77 (dt, J = 9.9, 7.0 Hz, 1H), 3.59 (dd, J = 17.8, 8.8
Hz, 1H), 3.52−3.36 (m, 3H), 3.20 (ddd, J = 8.6, 6.9, 4.6 Hz, 1H),
2.90 (dd, J = 17.8, 4.5 Hz, 1H), 2.37 (s, 3H), 2.00−1.94 (m, 2H),
1.87−1.82 (m, 2H), 1.18 (d, J = 7.0 Hz, 3H); 13C{1H} NMR (101
MHz, CDCl3) δ (ppm): 198.9, 174.5, 143.9, 134.4, 129.2, 128.3, 46.5,
H
J. Org. Chem. XXXX, XXX, XXX−XXX