Notes
Bull. Korean Chem. Soc. 2012, Vol. 33, No. 4 1339
7.53; N, 5.97.
Found: C, 82.57; H, 6.03; N, 4.97.
Compound 3c-Z: 96%; white solid, mp 125-127 C; IR
o
Compound 2b: 62%; white solid, mp 140-142 C; IR
o
−1
1
−1
1
(KBr) 3335, 3263, 1702 cm ; H NMR (CDCl3, 300 MHz)
δ 1.83 (s, 3H), 1.93-2.04 (m, 1H), 2.15-2.25 (m, 1H), 2.45-
2.55 (m, 1H), 2.67-2.77 (m, 1H), 4.71 (br s, OH), 6.99-7.02
(m, 2H), 7.09-7.21 (m, 3H), 7.34-7.43 (m, 3H), 7.62-7.65
(KBr) 3183, 2957, 1690, 1361 cm ; H NMR (CDCl3, 300
MHz) δ 0.91 (t, J = 7.2 Hz, 3H), 1.31-1.50 (m, 4H), 1.95 (s,
3H), 2.33 (dt, J = 7.8 and 7.2 Hz, 2H), 5.14 (t, J = 7.8 Hz,
1H), 7.26-7.31 (m, 2H), 7.36-7.48 (m, 3H), 9.17 (br s, NH);
13
(m, 2H), 7.79 (br s, NH); C NMR (CDCl3, 75 MHz) δ
13
C NMR (CDCl3, 75 MHz) δ 9.06, 13.84, 22.37, 27.47,
9.54, 29.75, 38.62, 90.08, 125.87, 128.30, 128.32, 128.48,
128.55, 128.80, 128.94, 132.22, 141.15, 154.21, 173.79;
31.50, 115.35, 128.24, 128.31, 128.68, 129.44, 132.16,
+
137.69, 144.30, 172.29; ESIMS m/z 242 (M +H). Anal.
+
ESIMS m/z 294 (M +H). Anal. Calcd for C19H19NO2: C,
Calcd for C16H19NO: C, 79.63; H, 7.94; N, 5.80. Found: C,
79.91; H, 8.08; N, 5.83.
77.79; H, 6.53; N, 4.77. Found: C, 77.71; H, 6.42; N, 4.56.
o
Compound 2c: 80%; white solid, mp 114-116 C; IR
o
Compound 3d-Z: 93%; white solid, mp 207-209 C; IR
−1
1
−1
1
(KBr) 3401, 3293, 2953, 1700, 1649 cm ; H NMR (CDCl3,
300 MHz) δ 0.77 (t, J = 6.6 Hz, 3H), 1.05-1.20 (m, 5H),
1.25-1.34 (m, 1H), 1.62-1.72 (m, 1H), 1.80-1.90 (m, 1H),
1.82 (s, 3H), 4.80 (br s, OH), 7.33-7.44 (m, 3H), 7.58-7.64
(KBr) 3175, 3028, 1680 cm ; H NMR (CDCl3, 300 MHz)
δ 1.95 (s, 3H), 5.24 (d, J = 9.9 Hz, 1H), 5.62 (d, J = 9.9 Hz,
1H), 7.16-7.33 (m, 12H), 7.39-7.48 (m, 3H), 9.22 (br s, NH);
13
C NMR (CDCl3, 75 MHz) δ 9.15, 49.13, 115.95, 126.69,
13
(m, 3H); C NMR (CDCl3, 75 MHz) δ 9.46, 13.82, 22.31,
128.25, 128.42, 128.46, 128.68, 129.38, 129.42, 131.86,
+
137.82, 143.15, 144.72, 172.39; ESIMS m/z 352 (M +H).
22.81, 31.53, 36.65, 90.35, 128.36, 128.54, 128.64, 128.75,
+
132.44, 154.15, 173.68; ESIMS m/z 260 (M +H). Anal.
Anal. Calcd for C25H21NO: C, 85.44; H, 6.02; N, 3.99.
Found: C, 85.78; H, 6.32; N, 3.85.
Calcd for C16H21NO2: C, 74.10; H, 8.16; N, 5.40. Found: C,
74.44; H, 8.37; N, 5.19.
Typical Procedure for the Synthesis of 5a-Z. A stirred
solution of compound 3a (85 mg, 0.4 mmol), benzyl bromide
(103 mg, 0.6 mmol), and K2CO3 (83 mg, 0.6 mmol) in
CH3CN (1.0 mL) was heated to reflux for 15 h. After the
aqueous extractive workup and column chromatographic
purification process (hexanes/EtOAc/CH2Cl2, 6:1:1), com-
pound 5a-Z was obtained as colorless oil, 109 mg (90%).
Other compounds 5c-Z and 5d-Z were synthesized similarly,
and the spectroscopic data including 4a are as follows.
Compound 5a-Z: 90%; colorless oil; IR (film) 2964,
o
Compound 2d: 75%; white solid, mp 106-108 C; IR
−1
1
(KBr) 3313, 3301, 1699, 1493 cm ; H NMR (CDCl3, 300
MHz) δ 1.76 (s, 3H), 2.50 (dd, J = 14.4 and 8.7 Hz, 1H),
2.62 (dd, J = 14.4 and 5.7 Hz, 1H), 4.04 (br s, OH), 4.15 (dd,
J = 8.7 and 5.7 Hz, 1H), 5.90 (br s, NH), 7.04-7.24 (m, 10H),
13
7.32-7.38 (m, 3H), 7.45-7.51 (m, 2H); C NMR (CDCl3, 75
MHz) δ 9.60, 42.23, 46.27, 89.31, 126.28, 126.57, 127.41,
127.93, 128.35, 128.56, 128.58, 128.65, 128.76, 128.92,
132.10, 143.90, 144.64, 153.74, 172.36; ESIMS m/z 370
+
(M +H). Anal. Calcd for C25H23NO2: C, 81.27; H, 6.27; N,
−1
1
1691, 1439 cm ; H NMR (CDCl3, 300 MHz) δ 0.78 (t, J =
7.5 Hz, 3H), 1.96 (s, 3H), 2.15-2.25 (m, 2H), 4.96 (t, J = 8.1
Hz, 1H), 5.13 (s, 2H), 7.13-7.17 (m, 2H), 7.20-7.35 (m, 5H),
3.79. Found: C, 81.06; H, 6.44; N, 3.68.
Typical Procedure for the Synthesis of 3a-Z. A stirred
solution of compound 2a (116 mg, 0.5 mmol) and p-TsOH
(27 mg, 0.15 mmol) in 1,2-dichloroethane (1.0 mL) was
13
7.36-7.48 (m, 3H); C NMR (CDCl3, 75 MHz) δ 9.53,
14,47, 20.40, 44.74, 118.18, 125.82, 126.81, 126.88, 128.22,
128.24, 128.59, 129.72, 132.41, 137.78, 138.31, 145.62,
o
heated to 60 C for 1 h. After the aqueous extractive workup
+
171.43; ESIMS m/z 304 (M +H). Anal. Calcd for C21H21NO:
and column chromatographic purification process (CH2Cl2/
Et2O, 20:1), compound 3a-Z was obtained as a white solid,
103 mg (97%). Other compounds were synthesized similar-
ly, and the spectroscopic data of 3a-d are as follows.
C, 83.13; H, 6.98; N, 4.62. Found: C, 83.23; H, 7.12; N,
4.46.
Compound 5c-Z: 89%; colorless oil; IR (film) 2957,
o
Compound 3a-Z: 97%; white solid, mp 102-104 C; IR
−1
1
2925, 1694, 1441 cm ; H NMR (CDCl3, 300 MHz) δ 0.71
(t, J = 7.2 Hz, 3H), 1.04-1.14 (m, 4H), 1.96 (s, 3H), 2.17 (dt,
J = 7.8 and 7.2 Hz, 2H), 4.98 (t, J = 7.8 Hz, 1H), 5.14 (s,
2H), 7.12-7.17 (m, 2H), 7.19-7.37 (m, 5H), 7.38-7.47 (m,
−1
1
(KBr) 3183, 1686 cm ; H NMR (CDCl3, 300 MHz) δ 1.09
(t, J = 7.5 Hz, 3H), 1.95 (s, 3H), 2.29-2.39 (m, 2H), 5.12 (t, J
= 7.8 Hz, 1H), 7.26-7.31 (m, 2H), 7.37-7.48 (m, 3H), 8.91
13
(br s, NH); C NMR (CDCl3, 75 MHz) δ 9.10, 13.94, 21.13,
13
3H); C NMR (CDCl3, 75 MHz) δ 9.47, 13.61, 22.16,
116.62, 128.29, 128.33, 128.73, 129.44, 132.10, 137.12,
26.71, 32.14, 44.71, 116.89, 125.76, 126.62, 126.82, 128.16,
128.18, 128.53, 129.65, 132.39, 138.03, 138.26, 145.56,
+
144.45, 172.20; ESIMS m/z 214 (M +H). Anal. Calcd for
+
171.39; ESIMS m/z 332 (M +H). Anal. Calcd for
C14H15NO: C, 78.84; H, 7.09; N, 6.57. Found: C, 78.79; H,
7.35; N, 6.41.
C23H25NO: C, 83.34; H, 7.60; N, 4.23. Found: C, 83.39; H,
7.85; N, 4.32.
o
Compound 3b-Z: 91%; white solid, mp 160-162 C; IR
−1 1
(KBr) 3190, 1682 cm ; H NMR (CDCl3, 300 MHz) δ 1.94
o
Compound 5d-Z: 92%; yellow solid, mp 96-98 C; IR
−1
1
(s, 3H), 3.72 (d, J = 8.1 Hz, 2H), 5.33 (t, J = 8.1 Hz, 1H),
(KBr) 3027, 1695, 1444 cm ; H NMR (CDCl3, 300 MHz)
δ 1.99 (s, 3H), 5.03 (s, 2H), 5.05 (d, J = 10.8 Hz, 1H), 5.44
(d, J = 10.8 Hz, 1H), 6.75-6.79 (m, 4H), 7.08-7.24 (m, 9H),
13
7.16-7.31 (m, 7H), 7.33-7.45 (m, 3H), 9.79 (br s, NH);
C
NMR (CDCl3, 75 MHz) δ 9.12, 33.91, 113.25, 126.34,
13
7.26-7.46 (m, 7H); C NMR (CDCl3, 75 MHz) δ 9.64,
128.32, 128.35, 128.55, 128.61, 129.22, 129.42, 131.92,
+
138.18, 139.46, 144.55, 172.76; ESIMS m/z 276 (M +H).
44.64, 47.60, 117.12, 125.58, 126.50, 127.23, 127.68,
127.76, 128.37, 128.39, 128.59, 129.02, 129.65, 132.06,
Anal. Calcd for C19H17NO: C, 82.88; H, 6.22; N, 5.09.