Nitric Acid → 4-Methoxybenzyl 1-hydroxy-4-nitronaphthalene-2-carboxylate

HRID 366798Notes

Reaction equation

[OH:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][C:3]=1[C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=1)=[O:13].[N+:24]([O-])([OH:26])=[O:25]>CC(O)=O>[OH:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([N+:24]([O-:26])=[O:25])=[CH:4][C:3]=1[C:12]([O:14][CH2:15][C:16]1[CH:17]=[CH:18][C:19]([O:22][CH3:23])=[CH:20][CH:21]=1)=[O:13]

Participants

Conditions

Temperature: 25 °C

Procedure

A warm vigorously stirred solution of 2 (25.4 g, 0.082 mmol) in AcOH (260 mL) was cooled to 25° C. and treated in one portion with a solution of HNO3 (70% w/w, 18.6 g, 0.20 mmol) in AcOH (25 mL). The temperature rose to 35° C. (controlled with external cooling) and a solid separated. After stirring for a further 10 min at 30° C., the mixture was cooled to 0° C. The precipitate was collected, washed with cold AcOH and iPr2O, and recrystallised from CH2Cl2 /petroleum ether to give 4-methoxybenzyl 1-hydroxy-4-nitronaphthalene-2-carboxylate (3) (17.9 g, 61%) mp 163-164° C. 1H NMR [(CD3)2SO] δ 12.46 (br s, 1H, OH), 8.60 (s, 1H, H-3), 8.60 (d, J=8.6 Hz, 1H, H-5), 8.47 (d, J=8.3 Hz, 1H, H-8), 7.97 (br t, J=7.8 Hz, 1H, H-6), 7.79 (br t, J=7.7 Hz, 1H, H-7), 7.50 (d, J=8.6 Hz, 2H, H-2',6'), 7.00 (d, J=8.7 Hz, 2H, H-3',5'), 5.32 (s, 2H, CH2), 3.78 (s, 3H, OCH3). Anal. Calculated for C19H15NO6 : C, 64.6; H, 4.3; N, 4.0. Found: C, 64.7; H, 4.0; N, 4.2%.

Workup

customrose to 35° C.
temperature(controlled with external cooling)
customa solid separated
temperaturethe mixture was cooled to 0° C
customThe precipitate was collected
washwashed with cold AcOH and iPr2O
customrecrystallised from CH2Cl2 /petroleum ether

Sources & evidence

ORD record: ord-d79f6bf68fee4e66b5746b8d561220a6
Source dataset: uspto-grants-2000_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06130237

Reaction notes

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