Nitric Acid → 4-(4-Methyl-3-nitrophenyl)-4-oxobutanoic acid

HRID 718809

Reaction equation

[N+:1]([O-:4])(O)=[O:2].[O:5]=[C:6]([C:12]1[CH:17]=[CH:16][C:15]([CH3:18])=[CH:14][CH:13]=1)[CH2:7][CH2:8][C:9]([OH:11])=[O:10]>OS(O)(=O)=O>[CH3:18][C:15]1[CH:14]=[CH:13][C:12]([C:6](=[O:5])[CH2:7][CH2:8][C:9]([OH:11])=[O:10])=[CH:17][C:16]=1[N+:1]([O-:4])=[O:2]

Participants

Conditions

Temperature: -5 °C

Procedure

HNO3 (65%) (2300 mL) was cooled to about 0° C. Fuming HNO3 (5700 mL) was carefully added maintaining an internal temperature of less than 15° C. The solution was cooled to about −5° C. and H2SO4 (800 mL) was added maintaining an internal temperature of less than 5° C. After cooling to about −8° C., 4-oxo-4-(p-tolyl)butanoic acid (72) (4000 g, 20.8 mol) was added portionwise maintaining the temperature below about 0° C. After completion of addition the mixture was allowed to warm to about 15-17° C. The solution was poured onto crushed ice with stirring. After about 2 h at rt, the solid was collected by filtration washing with water (3×10 L) and then dried to afford 4-(4-methyl-3-nitrophenyl)-4-oxobutanoic acid (73) (3400 g, 69% yield). 1H NMR (300 MHz, DMSO): δ 8.46 (s, 1H), 8.20 (d, J=8.4 Hz, 1H), 7.64 (d, J=8.0 Hz, 1H), 3.25 (m, 2H), 2.62 (m, 2H), 2.60 (s, 3H).

Workup

temperaturemaintaining an internal temperature of less than 15° C
temperaturemaintaining an internal temperature of less than 5° C
temperatureAfter cooling to about −8° C.
temperaturemaintaining the temperature below about 0° C
additionAfter completion of addition the mixture
temperatureto warm to about 15-17° C
additionThe solution was poured
customonto crushed ice
filtrationthe solid was collected by filtration
washwashing with water (3×10 L)
customdried

Sources & evidence

ORD record: ord-dc191878323f4981b331d38ebff37f3c
Source dataset: uspto-grants-2015_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09193744B2

Linked notes

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