E
H.-M. Vu et al.
Paper
Synthesis
1H NMR (400 MHz, CDCl3): δ = 8.25 (d, J = 7.5 Hz, 1 H), 7.84 (t, J = 7.2
Hz, 1 H), 7.67 (d, J = 8.0 Hz, 1 H), 7.57 (t, J = 7.5 Hz, 1 H), 7.37–7.28 (m,
1 H), 7.11–6.96 (m, 2 H), 2.44 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 164.23, 161.52, 159.39, 154.90,
147.06, 136.49, 132.17, 128.49, 128.19, 127.18, 116.81, 111.23,
110.66, 102.75, 55.87.
13C NMR (101 MHz, CDCl3): δ = 162.01, 159.47, 154.87, 146.24,
139.62, 136.66, 131.98, 129.13, 128.64, 127.31, 126.19, 120.34,
117.10, 113.45, 19.73.
19F NMR (471 MHz, CDCl3): δ = –105.44 (dd, J = 13.2, 8.1 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C15H11FNO3: 272.0717; found:
272.0721.
19F NMR (471 MHz, CDCl3): δ = –114.04 (dd, J = 9.5, 5.8 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C15H11FNO2: 256.0768; found:
2-[2-Fluoro-4-(trifluoromethyl)phenyl]-4H-benzo[d][1,3]oxazin-
4-one (2l)
256.0771.
Yield: 49 mg (53%); white solid; mp 88–91 °C.
1H NMR (400 MHz, CDCl3): δ = 8.26 (t, J = 7.0 Hz, 2 H), 7.86 (t, J = 7.7
Hz, 1 H), 7.72 (d, J = 8.1 Hz, 1 H), 7.61–7.46 (m, 3 H).
2-(2,6-Difluorophenyl)-4H-benzo[d][1,3]oxazin-4-one (2h)22a
Yield: 68 mg (86%); white solid; mp 115–119 °C.
1H NMR (400 MHz, CDCl3): δ = 8.26 (d, J = 7.8 Hz, 1 H), 7.85 (t, J = 7.1
Hz, 1 H), 7.70 (d, J = 8.1 Hz, 1 H), 7.59 (t, J = 7.3 Hz, 1 H), 7.51–7.43 (m,
1 H), 7.03 (t, J = 8.3 Hz, 2 H).
13C NMR (101 MHz, CDCl3): δ = 162.34, 159.72, 158.67, 153.51,
146.29, 136.82, 132.03, 129.34, 128.76, 127.67, 124.10, 122.43,
121.21, 117.14, 114.88.
13C NMR (101 MHz, CDCl3): δ = 162.12, 159.57, 158.94, 150.84,
146.17, 136.71, 129.42, 128.67, 128.27, 127.49, 117.24, 112.43,
111.39, 110.61.
19F NMR (471 MHz, CDCl3): δ = –63.28 (s), –106.44 (dd, J = 10.3, 7.3
Hz).
HRMS (ESI): m/z [M + H]+ calcd for C15H8F4NO2: 332.0305; found:
332.0310.
19F NMR (471 MHz, CDCl3): δ = –110.43 (t, J = 9.5 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C14H8F2NO2: 260.0518; found:
260.0521.
2-(2,4-Difluorophenyl)-4H-benzo[d][1,3]oxazin-4-one (2m)18b
Yield: 40 mg (52%); white solid; mp 154–157 °C.
1H NMR (400 MHz, CDCl3): δ = 8.27 (d, J = 7.9 Hz, 1 H), 8.19 (dd, J =
15.1, 8.5 Hz, 1 H), 7.87 (t, J = 7.7 Hz, 1 H), 7.72 (d, J = 8.1 Hz, 1 H), 7.57
(t, J = 7.6 Hz, 1 H), 7.11–6.94 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 166.66, 164.11, 160.87, 158.98,
154.05, 146.61, 136.67, 132.73, 128.70, 127.39, 116.94, 115.56,
112.03, 105.63.
2-(2-Fluoro-5-methylphenyl)-4H-benzo[d][1,3]oxazin-4-one (2i)
Yield: 22 mg (29%); white solid; mp 106–108 °C.
1H NMR (400 MHz, CDCl3): δ = 8.26 (dd, J = 7.9, 1.1 Hz, 1 H), 7.92 (dd,
J = 6.9, 1.9 Hz, 1 H), 7.88–7.81 (m, 1 H), 7.72 (d, J = 8.1 Hz, 1 H), 7.56 (t,
J = 7.6 Hz, 1 H), 7.37–7.29 (m, 1 H), 7.11 (dd, J = 10.8, 8.5 Hz, 1 H), 2.41
(s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 160.93, 159.23, 158.37, 155.04,
146.74, 136.56, 134.57, 133.94, 131.11, 130.88, 128.59, 127.39,
118.43, 116.75, 20.56.
19F NMR (471 MHz, CDCl3): δ = –101.11 to –101.23 (m), –102.28 (dt,
J = 19.3, 7.7 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C14H8F2NO2: 260.0518; found:
19F NMR (471 MHz, CDCl3): δ = –114.37 to –114.52 (m).
260.0520.
HRMS (ESI): m/z [M + H]+ calcd for C15H11FNO2: 256.0768; found:
256.0769.
2-(4-Chloro-2-fluorophenyl)-4H-benzo[d][1,3]oxazin-4-one (2n)
Yield: 52 mg (63%); white solid; mp 132–134 °C.
1H NMR (400 MHz, CDCl3): δ = 8.25 (dd, J = 8.0, 1.3 Hz, 1 H), 8.15–8.06
(m, 1 H), 7.87–7.82 (m, 1 H), 7.72 (t, J = 4.3 Hz, 1 H), 7.57 (t, J = 7.6 Hz,
1 H), 7.31–7.28 (m, 1 H), 7.10 (d, J = 7.5 Hz, 1 H).
13C NMR (101 MHz, CDCl3): δ = 162.57, 159.94, 158.88, 154.01,
146.54, 136.67, 131.92, 129.54, 128.92, 128.63, 127.47, 124.94,
118.05, 113.46.
2-(2-Fluoro-4-methylphenyl)-4H-benzo[d][1,3]oxazin-4-one (2j)
Yield: 38 mg (49%); white solid; mp 94–98 °C.
1H NMR (400 MHz, CDCl3): δ = 8.26 (dd, J = 7.9, 1.3 Hz, 1 H), 8.03 (t, J =
7.9 Hz, 1 H), 7.87–7.81 (m, 1 H), 7.71 (d, J = 7.9 Hz, 1 H), 7.58–7.48 (m,
1 H), 7.07 (dd, J = 20.7, 10.1 Hz, 2 H), 2.44 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 162.66, 160.07, 159.29, 155.01,
146.87, 145.60, 136.50, 130.86, 128.50, 127.46, 125.17, 117.70,
116.96, 116.06, 21.50.
19F NMR (471 MHz, CDCl3): δ = –106.19 (dd, J = 11.8, 7.9 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C14H8ClFNO2: 276.0222; found:
19F NMR (471 MHz, CDCl3): δ = –109.78 (dd, J = 11.9, 7.8 Hz).
276.0223.
HRMS (ESI): m/z [M + H]+ calcd for C15H11FNO2: 256.0768; found:
256.0772.
2-(4-Bromo-2-fluorophenyl)-4H-benzo[d][1,3]oxazin-4-one (2o)
Yield: 65 mg (68%); white solid; mp 129–131 °C.
1H NMR (400 MHz, CDCl3): δ = 8.25 (d, J = 7.9 Hz, 1 H), 8.03 (t, J = 8.2
Hz, 1 H), 7.85 (t, J = 7.7 Hz, 1 H), 7.71 (d, J = 7.9 Hz, 1 H), 7.57 (t, J = 7.6
Hz, 1 H), 7.48–7.40 (m, 2 H).
2-(2-Fluoro-4-methoxyphenyl)-4H-benzo[d][1,3]oxazin-4-one
(2k)
Yield: 42 mg (52%); white solid; mp 139–141 °C.
1H NMR (400 MHz, CDCl3): δ = 8.24 (dd, J = 7.9, 1.3 Hz, 1 H), 8.11 (t, J =
8.7 Hz, 1 H), 7.87–7.78 (m, 1 H), 7.69 (d, J = 8.0 Hz, 1 H), 7.55–7.49 (m,
1 H), 6.82 (dd, J = 8.9, 2.4 Hz, 1 H), 6.74 (dd, J = 12.9, 2.4 Hz, 1 H), 3.90
(s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 162.39, 159.75, 158.90, 154.10,
146.53, 136.74, 132.03, 129.06, 128.61, 127.57, 121.25, 120.99,
118.11, 117.01.
19F NMR (471 MHz, CDCl3): δ = –106.20 (dd, J = 17.9, 7.9 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C14H8BrFNO2: 319.9717; found:
319.9721.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–G