4,4ꢀ-Dihydroxy-3,3ꢀ-dinitrodiphenyl Ether
165
Then the slurry was cooled to 5◦C and the precipitated orange-colored solid was collected.
The solid was extracted into EtOAc (100 mL) and washed with water. The combined
organic layer was dried over Na2SO4, and the solvent was removed under reduced pressure
to give 9.0 g (97%) of 4,4ꢀ-dihydroxy-3,3ꢀ-dinitrodiphenyl ether (4) as an orange-colored
solid, mp. 156–157◦C (lit:20 156–157◦C). The solid was sufficiently pure as confirmed by
its NMR, though recrystallization from methanol gave orange colored needles (91%, mp.
157–158◦C). 1H-NMR (400 MHz, DMSO): δ 7.17 (d, 2H, Ph), 7.35 (dd, 2H, Ph), 7.55 (d,
2H, Ph). 13C-NMR (100 MHz, DMSO): δ 114.42, 120.55, 126.27, 136.50, 148.10, 148.46.
m/z 291 (M-H).
1,3-bis(4-Hydroxy-3-nitrophenoxy)benzene (9)
1,3-bis(4-N-Acetylamino-3-nitrophenoxy)benzene (14.9 g, 32.0 mmol) was transformed
into 9 as described above [3.0 M NaOH aqueous solution was used instead of 1.5 M NaOH
aqueous solution. The reaction time was 5 h at 150◦C] to yield 12.3 g (100%) of 1,3-
bis(4-hydroxy-3-nitrophenoxy)benzene as an orange-colored solid, mp. 128–130◦C (lit.2
1
128.5–130◦C). H-NMR (400 MHz, DMSO): δ 6.67 (s, 1H, Ph), 6.73 (d, 2H, Ph), 7.17
(d, 2H, Ph), 7.36 (d, 2H, Ph), 7.39 (t, 1H, Ph), 7.58 (s, 2H, Ph), 10.88 (br s, 2H, OH).
13C-NMR (100 MHz, DMSO): δ 107.51, 112.37, 115.54, 120.60, 127.23, 131.28, 136.59,
147.00, 148.89, 158.48. m/z 383 (M-H).
1
The melting point, H-NMR and 13C-NMR are agreement with data given in the
literature.2
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