Nitric Acid → HCID 67403353, compound

HRID 468006Notes

Reaction equation

[CH3:1][C:2]1([CH3:13])[O:7][B:6]([OH:8])[C:5]2[CH:9]=[CH:10][CH:11]=[CH:12][C:4]=2[CH2:3]1.[N+:14]([O-])([OH:16])=[O:15]>[N+](C1C=CC=CC=1)([O-])=O>[CH3:1][C:2]1([CH3:13])[O:7][B:6]([OH:8])[C:5]2[CH:9]=[C:10]([N+:14]([O-:16])=[O:15])[CH:11]=[CH:12][C:4]=2[CH2:3]1

Participants

Conditions

Temperature: -45 °C

Procedure

A solution of 3,3-dimethyl-3,4-dihydro-benzo[c][1,2]oxaborinin-1-ol (0.82 g, 4.7 mmol) in nitrobenzene (2.5 mL) was added dropwise to fuming nitric acid (10 mL) maintained at −45° C. The reaction was stirred for 45 minutes at this temperature, and then poured onto wet ice (400 mL). This mixture was allowed to stand for 90 minutes, gradually warming to room temperature. The resultant aqueous suspension was extracted with dichloromethane (3×50 mL). The combined organic portions were washed with water (2×50 mL) until the aqueous portion showed a pH of 7. The dichloromethane solution was then dried over sodium sulfate and concentrated to dryness. The resulting oil was triturated with heptane to produce 3,3-Dimethyl-7-nitro-3,4-dihydro-benzo[c][1,2]oxaborinin-1-ol as a white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.25 (s, 6H) 3.02 (s, 2H) 7.47 (d, J=8.4 Hz, 1H) 8.25 (dd, J=8.3, 2.6 Hz, 1H) 8.47 (d, J=2.5 Hz, 1H) 8.85 (s, 1H). Amount obtained: 468 mg, 45% yield.

Workup

waitto stand for 90 minutes
temperaturegradually warming to room temperature
extractionThe resultant aqueous suspension was extracted with dichloromethane (3×50 mL)
washThe combined organic portions were washed with water (2×50 mL) until the aqueous portion
dry with materialThe dichloromethane solution was then dried over sodium sulfate
concentrationconcentrated to dryness
customThe resulting oil was triturated with heptane

Sources & evidence

ORD record: ord-e7afc021f8c740a9b3182855a0dea3a1
Source dataset: uspto-grants-2014_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08623911B2

Reaction notes

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