Isopropyl nitrate → 5-Methoxycarbonylmethyl-9-nitro-6,7-dihydro-1H, 5H-pyrido[1,2,3-de]quinoxaline-2,3-dione

HRID 52564Notes

Reaction equation

[CH3:1][O:2][C:3]([CH2:5][CH:6]1[N:11]2[C:12](=[O:20])[C:13](=[O:19])[NH:14][C:15]3[CH:16]=[CH:17][CH:18]=[C:9]([C:10]=32)[CH2:8][CH2:7]1)=[O:4].[N+:21]([O-])([O:23]C(C)C)=[O:22]>S(=O)(=O)(O)O>[CH3:1][O:2][C:3]([CH2:5][CH:6]1[N:11]2[C:12](=[O:20])[C:13](=[O:19])[NH:14][C:15]3[CH:16]=[C:17]([N+:21]([O-:23])=[O:22])[CH:18]=[C:9]([C:10]=32)[CH2:8][CH2:7]1)=[O:4]

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of 5-methoxycarbonylmethyl-6,7-dihydro-1H, 5H-pyrido[1,2,3-de]quinoxaline-2,3-dione (66 mg, 0.24 mmol) in concentrated sulfuric acid (1.5 mL) was added isopropyl nitrate (30 μL, 0.3 mmol) at 0° C. The mixture was stirred for 45 min at 0° C., poured into ice-water, and extracted with ethyl acetate (100 mL×2). The extracts were washed with brine, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography with 0.1% acetic acid/ethyl acetate to give 33 mg of the title compound (43%): mp 254°~256° C.; 1H NMR (270 MHz, DMSO-d6) δ12.23 (bs, 1H), 7.91 (d, 1H, J=2.6 Hz), 7.85 (d, 1H, J=2.6 Hz), 5.05~5.21 (m, 1H), 3.64 (s, 3H), 2.85~3.10 (m, 2H), 2.56~2.72 (m, 2H), 2.17 (dm, 1H, J=13.5 Hz), 1.80~2.00 (m, 1H).

Workup

extractionextracted with ethyl acetate (100 mL×2)
washThe extracts were washed with brine
dry with materialdried over magnesium sulfate
concentrationconcentrated
customThe residue was purified by silica gel column chromatography with 0.1% acetic acid/ethyl acetate

Sources & evidence

ORD record: ord-0966d8087d04421d83fa22e68e8d8795
Source dataset: uspto-grants-1997_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05616586

Reaction notes

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