NMR (400 MHz, CDCl3/TMS): d 8.58 (s, 1H), 6.95 (dd, J = 9.2,
2.4 Hz, 1H), 6.91 (d, J = 9.2 Hz, 1H), 6.83 (d, J = 2.4 Hz, 1H),
4.62 (s, 2H) ppm. 13C NMR (100 MHz, CDCl3+DMSO-d6/TMS):
169.6, 146.9, 133.2, 131.5, 127.4, 122.1, 120.6, 71.8 ppm.
3H), 4.45 (q, J = 4.4 Hz, 1H), 3.93–3.81 (m, 2H), 1.96–1.77 (m,
2H), 1.68–1.59 (m, 2H), 1.45–1.36 (m, 2H), 1.06 (t, J = 7.2 Hz, 3H),
0.97 (t, J = 7.2 Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3/TMS):
165.7, 142.7, 129.6, 127.3, 123.2, 118.3, 114.6, 78.1, 41.1, 29.0,
23.6, 19.9, 13.7, 9.3 ppm. MS (EI) m/z 267 (M+). Anal. Calcd for
C14H18ClNO2: C, 62.80; H, 6.78; N, 5.23; Found: C, 63.11; H, 6.71;
N, 5.01.
6-tert-Butyl-4-phenyl-(2◦H)-1,4-benzoxazin-3(4H)-one (3n).
A
white solid; Mp 116–118 C; IR (neat) nmax/cm-1 3060.3, 2962.2,
1695.1, 1604.6, 1507.5, 1360.3, 1280.2, 1046.4 cm-1. 1H NMR
(400 MHz, CDCl3/TMS): d 7.56–7.52 (m, 2H), 7.48–7.45 (m,
1H), 7.31–7.30 (m, 2H), 7.01 (dd, J = 8.8, 2.4 Hz 1H), 6.96 (d, J =
8.4 Hz, 1H), 6.43 (d, J = 2.0 Hz, 1H), 4.75 (s, 2H), 1.12 (s, 9H) ppm.
13C NMR (100 MHz, DMSO-d6/TMS): 164.4, 145.2, 142.7, 136.3,
130.4, 130.2, 129.3, 129.0, 120.8, 116.5, 113.4, 68.0, 34.3, 31.3 ppm.
MS (EI) m/z 281 (M+). Anal. Calcd for C18H19NO2: C, 76.84; H,
6.81; N, 4.98; Found: C, 77.05; H, 6.90; N, 5.12.
6-Fluoro-2-methyl-4-phenyl-(2H)-1,4-benzoxazin-3(4H)-one
(3t). A light yellow solid; Mp 96–98 ◦C; IR (neat) nmax/cm-1
3079.3, 2924.6, 1694.4, 1597.1, 1498.1, 1367.1, 1250.8, 1105.3 cm-1.
1H NMR (400 MHz, CDCl3/TMS): d 7.56–7.45 (m, 3H), 7.26 (d,
J = 6.8 Hz, 1H), 6.98 (dd, J = 8.8, 4.8 Hz, 1H), 6.70–6.65 (m,
1H), 6.15 (dd, J = 9.6, 3.2 Hz, 1H), 4.77 (q, J = 6.8 Hz, 1H), 1.64
(d, J = 6.8 Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3/TMS):
166.5, 157.9 (d, JCF = 238.9 Hz, 1C), 140.1 (d, JCF = 2.4 Hz, 1C),
135.8, 130.7 (d, JCF = 10.2 Hz, 1C), 130.1, 129.0, 128.5, 117.9 (d,
6-Methyl-4-phenyl-(2H)-1,4-benzoxazin-3(4H)-one (3o).
A
◦
white solid; Mp 112–114 C; IR (neat) nmax/cm-1 3053.3, 2917.5,
1689.8, 1589.7, 1510.7, 1366.0, 1272.9, 1055.0 cm-1. 1H NMR
(400 MHz, CDCl3/TMS): d 7.57–7.53 (m, 2H), 7.49–7.46 (m,
1H), 7.30–7.26 (m, 2H), 6.93 (d, J = 7.6 Hz, 1H), 6.79 (d, J =
8.0 Hz, 1H), 6.21 (s, 1H), 4.74 (s, 2H), 2.15 (s, 3H) ppm. 13C NMR
(100 MHz, CDCl3/TMS): 164.5, 142.7, 135.8, 132.3, 130.3, 130.0,
128.8, 128.7, 124.5, 117.3, 116.7, 68.2, 20.9 ppm. MS (EI) m/z
239 (M+). Anal. Calcd for C15H13NO2: C, 75.30; H, 5.48; N, 5.85;
Found: C, 75.21; H, 5.56; N, 5.68.
JCF = 9.2 Hz, 1C), 109.9 (d, JCF = 22.4 Hz, 1C), 104.2 (d, JCF
=
29.4 Hz, 1C), 73.9, 16.1 ppm. MS (EI) m/z 257 (M+). Anal. Calcd
for C15H12FNO2: C, 70.03; H, 4.70; N, 5.44; Found: C, 71.15; H,
4.78; N, 5.23.
Acknowledgements
This work was financially supported by the Natural Science
Foundation of China (No. 20572095) and the Specialized Research
Fund for the Doctoral Program Foundation of Higher Education
of China (No. 2060335036).
6-Chloro-4-phenyl-(2H)-1,4-benzoxazin-3(4H)-one
(3p).
A
light yellow solid; Mp 112–114 ◦C; IR (neat) nmax/cm-1 3079.3,
2922.7, 1687.1, 1598.1, 1492.1, 1363.4, 1260.2, 1055.8 cm-1. H
1
NMR (400 MHz, CDCl3 3/TMS): d 7.58–7.54 (m, 2H), 7.51–7.48
(m, 1H), 7.27 (d, J = 7.6 Hz, 2H), 6.99–6.92 (m, 2H), 6.40
(d, J = 1.5 Hz, 1H), 4.76 (s, 2H) ppm. 13C NMR (100 MHz,
CDCl3/TMS): 163.9, 143.4, 135.1, 131.5, 130.2, 129.2, 128.5,
127.6, 123.7, 118.0, 116.7, 68.0 ppm. MS (EI) m/z 259 (M+).
Anal. Calcd for C14H10ClNO2: C, 64.75; H, 3.88; N, 5.39; Found:
C, 64.44; H, 3.77; N, 5.18.
References
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6-tert-Butyl-4-butyl-(2H)-1,4-benzoxazin-3(4H)-one (3q).
A
colorless oil; IR (neat) nmax/cm-1 3073.3, 2958.1, 1683.7, 1608.0,
1514.8, 1437.1, 1382.1, 1276.1, 1047.9 cm-1.1H NMR (400 MHz,
CDCl3/TMS): d 7.02–7.00 (m, 2H), 6.91 (d, J = 8.4 Hz, 1H), 4.56
(s, 2H), 3.96 (t, J = 7.6 Hz, 2H), 1.70–1.63 (m, 2H), 1.48–1.38
(m, 2H), 1.32 (s, 9H), 0.99 (t, J = 7.2 Hz, 3H) ppm. 13C NMR
(100 MHz, CDCl3/TMS): 164.3, 148.7, 143.0, 127.8, 120.4, 116.3,
112.0, 67.6, 40.5, 34.4, 31.4, 29.0, 20.0, 13.7 ppm. MS (EI) m/z
261 (M+). Anal. Calcd for C16H23NO2: C, 73.53; H, 8.87; N, 5.36;
Found: C, 73.31; H, 8.18; N, 5.16.
6-Methyl-4-butyl-(2H)-1,4-benzoxazin-3(4H)-one (3r). A col-
orless oil;10h IR (neat) nmax/cm-1 3047.5, 2928.4, 1681.3, 1609.5,
1511.3, 1439.3, 1382.4, 1274.1, 1048.9 cm-1.1H NMR (400 MHz,
CDCl3/TMS): d 6.87 (d, J = 8.4 Hz, 1H), 6.79 (d, J = 6.8 Hz,
1H), 4.55 (s, 2H), 3.91 (t, J = 7.2 Hz, 2H), 2.34 (s, 3H), 1.68–1.61
(m, 2H), 1.46–1.37 (m, 2H), 0.97 (t, J = 7.2 Hz, 3H), ppm. 13C
NMR (100 MHz, CDCl3/TMS): 164.4, 143.1, 132.2, 128.2, 124.0,
116.7, 115.4, 67.6, 40.7, 29.1, 21.1, 20.0, 13.7 ppm.
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2008, 350, 2507; (b) W. L. Bao, Y. Y. Liu, X. LV and W. X. Qian, Org.
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2008, 73, 5159.
6-Chloro-4-butyl-2-ethyl-(2H)-1,4-benzoxazin-3(4H)-one (3s).
A light yellow solid; Mp 45–47 ◦C; IR (neat) nmax/cm-1
3079.6, 2954.4, 1677.3, 1603.8, 1494.8, 1433.5, 1351.2, 1255.1,
1116.2 cm-1.1H NMR (400 MHz, CDCl3/TMS): d 6.96–6.90 (m,
4072 | Org. Biomol. Chem., 2009, 7, 4067–4073
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