PAPER
Biomass-Involved Practical Approach to N-Aryl-1,4-benzoxazin-3-ones
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1H NMR (400 MHz, DMSO-d6): δ = 7.79 (d, J = 8.4 Hz, 2 H), 7.63
(dd, J = 8.4, 1.6 Hz, 1 H), 7.35 (d, J = 8.4 Hz, 2 H), 7.20 (d, J = 8.4
Hz, 1 H), 6.85 (d, J = 2.0 Hz, 1 H), 5.01 (q, J = 6.8 Hz, 1 H), 3.72
(s, 3 H), 1.54 (d, J = 6.8 Hz, 3 H).
13C NMR (100 MHz, DMSO-d6): δ = 165.5, 165.3, 147.8, 135.2,
133.1, 131.3, 130.6, 125.4, 123.8, 122.0, 117.3, 116.5, 73.5, 52.1,
16.2.
H), 5.15 (q, J = 6.8 Hz, 1 H), 3.60 (s, 6 H), 1.64 (d, J = 6.8 Hz, 3 H),
1.60 (d, J = 6.8 Hz, 3 H).
13C NMR (100 MHz, DMSO-d6): δ = 165.9, 165.7, 165.2, 147.9,
147.7, 134.2, 129.7, 128.8, 128.7, 128.0, 127.7, 127.6, 127.3, 126.9,
126.8, 126.3, 126.3, 125.5, 125.4, 122.2, 121.3, 117.3, 117.2, 116.4,
116.4, 73.8, 73.5, 52.0, 16.4, 16.2.
MS (EI): m/z (%) = 347 ([M]+, 69), 316 ([M – OCH3]+, 4), 304
(100), 77 (5).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C21H17NNaO4:
370.1050; found: 370.1054.
MS (EI): m/z (%) = 377 ([M + 2]+, 69), 375 ([M]+, 65), 346 ([M –
OCH3]+, 8), 334 (100), 332 (98), 253 (6).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C17H14BrNNaO4:
397.9998; found: 397.9998.
Methyl 4-(4-Nitrophenyl)-2-methyl-3-oxo-3,4-dihydro-2H-1,4-
benzoxazine-6-carboxylate (5e)
Gray solid; yield: 0.49 g (72%); mp 151–153 °C; Rf = 0.36 (EtOAc–
PE, 1:5).
1H NMR (400 MHz, DMSO-d6): δ = 8.43 (d, J = 8.8 Hz, 2 H), 7.71
(d, J = 8.4 Hz, 2 H), 7.65 (dd, J = 8.4, 2.0 Hz, 1 H), 7.24 (d, J = 8.4
Hz, 1 H), 6.87 (d, J = 1.6 Hz, 1 H), 5.01 (q, J = 6.8 Hz, 1 H), 3.70
(s, 3 H), 1.56 (d, J = 6.8 Hz, 3 H).
Acknowledgment
This work was supported by the National Natural Science Founda-
tion of China (21272280, 81201716, 81301890), Science & Tech-
nology Program of Guangdong Province and Guangzhou City
(2011A081401002, 2012J4300097), Guangdong Natural Science
Foundation (S2013010014278), National Significant New Drugs
Development (2011ZX09202-101-07). The authors also thank
Guangxi Wanshan Spice Co. Ltd for giving high-quality (–)-shi-
kimic acid as a gift.
MS (EI): m/z (%) = 342 ([M]+, 82), 311 ([M – OCH3]+, 9), 299
(100), 253 (41).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C17H14N2NaO6:
365.0744; found: 365.0746.
Supporting Information for this article is available online at
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Methyl 4-(4-Acetylphenyl)-2-methyl-3-oxo-3,4-dihydro-2H-1,4-
benzoxazine-6-carboxylate (5f)
Yellow solid; yield: 0.56 g (82%); mp 193–195 °C; Rf = 0.38
(EtOAc–PE, 1:4).
1H NMR (400 MHz, DMSO-d6): δ = 8.15 (d, J = 8.8 Hz, 2 H), 7.64
(dd, J1 = 8.4, 2.0 Hz, 1 H), 7.54 (d, J = 8.0 Hz, 2 H), 7.22 (d, J = 8.4
Hz, 1 H), 6.86 (d, J = 2.0 Hz, 1 H), 5.03 (q, J = 6.8 Hz, 1 H), 3.70
(s, 3 H), 2.65 (s, 3 H), 1.55 (d, J = 6.8 Hz, 3 H).
13C NMR (100 MHz, DMSO-d6): δ = 197.3, 165.4, 165.2, 147.9,
140.0, 136.9, 130.5, 129.9, 129.3, 125.5, 123.8, 117.3, 116.6, 73.5,
52.1, 26.9, 16.1.
MS (EI): m/z (%) = 339 ([M]+, 65), 308 ([M – OCH3]+, 8), 296
(100), 253 (8), 77 (9).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C19H17NNaO5:
362.0999; found: 362.1001.
References
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Methyl 4-(4′-Chlorobiphenyl-4-yl)-2-methyl-3-oxo-3,4-di-
hydro-2H-1,4-benzoxazine-6-carboxylate (5g)
White solid; yield: 0.71 g (87%); mp 202–204 °C; Rf = 0.55
(EtOAc–PE, 1:4).
1H NMR (400 MHz, DMSO-d6): δ = 7.88 (d, J = 8.4 Hz, 2 H), 7.80
(d, J = 8.4 Hz, 2 H), 7.64 (dd, J = 8.4, 2.0 Hz, 1 H), 7.55 (d, J = 8.4
Hz, 2 H), 7.45 (d, J = 8.0 Hz, 2 H), 7.21 (d, J = 8.4 Hz, 1 H), 6.93
(d, J = 1.6 Hz, 1 H), 5.04 (q, J = 6.8 Hz, 1 H), 3.68 (s, 3 H), 1.55 (d,
J = 6.8 Hz, 3 H).
13C NMR (100 MHz, DMSO-d6): δ = 165.9, 165.7, 148.1, 139.5,
138.0, 135.6, 133.1, 131.0, 129.8, 129.3, 128.9, 128.5, 125.7, 124.4,
117.6, 116.9, 73.8, 52.4, 16.5.
MS (EI): m/z (%) = 407 ([M]+, 73), 376 ([M – OCH3]+, 4), 364
(100).
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HRMS (ESI-TOF): m/z [M + Na]+ calcd for C23H18ClNNaO4:
430.0817; found: 430.0822.
Methyl 2-Methyl-4-(1-naphthyl)-3-oxo-3,4-dihydro-2H-1,4-
benzoxazine-6-carboxylate (5h)
Light pink solid; yield: 0.59 g (85%); mp 133–135 °C; Rf = 0.50
(EtOAc–PE, 1:4).
1H NMR (400 MHz, DMSO-d6): δ = 8.16–8.09 (m, 4 H), 7.75–7.45
(m, 12 H), 7.28 (d, J = 7.2 Hz, 1 H), 7.26 (d, J = 7.2 Hz, 1 H), 6.66
(d, J = 2.0 Hz, 1 H), 6.59 (d, J = 2.0 Hz, 1 H), 5.35 (q, J = 6.8 Hz, 1
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© Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 1167–1176