Nitric Acid → 1-Chloro-5-methoxy-2-methyl-4-nitrobenzene

HRID 272680Notes

Reaction equation

C(OC(=O)C)(=O)C.[N+:8]([O-:11])(O)=[O:9].[Cl:12][C:13]1[CH:18]=[C:17]([O:19][CH3:20])[CH:16]=[CH:15][C:14]=1[CH3:21]>O>[Cl:12][C:13]1[CH:18]=[C:17]([O:19][CH3:20])[C:16]([N+:8]([O-:11])=[O:9])=[CH:15][C:14]=1[CH3:21]

Participants

Conditions

Temperature: -5 °C

Procedure

Acetic anhydride (10 mL) at −10° C. was treated with concentrated nitric acid (>69% pure, 1 mL) and then treated portionwise with 2-chloro-4-methoxy-1-methylbenzene (0.78 g, 5 mmol) at a rate that maintained the internal temperature lower than −5° C. The solution was stirred for additional one hour while warming to room temperature, poured into an ice and water mixture, and extracted with ethyl acetate several times. The organic layers were combined, washed with 10% Na2CO3 and brine, dried (MgSO4), and concentrated under vacuum. The residue was purified by flash column chromatography on silica gel eluting with 9:1 hexanes/ethyl acetate to provide 0.75 g (71%) of the desired product. MS (DCI) m/e 219 (M+NH4)+; 1H NMR (CDCl3, 300 MHz) δ 7.78 (s, 1H), 7.09 (s, 1H), 3.94 (s, 3H), 2.35 (s, 3H).

Workup

temperaturewhile warming to room temperature
extractionextracted with ethyl acetate several times
washwashed with 10% Na2CO3 and brine
dry with materialdried (MgSO4)
concentrationconcentrated under vacuum
customThe residue was purified by flash column chromatography on silica gel eluting with 9:1 hexanes/ethyl acetate

Sources & evidence

ORD record: ord-1aa7025d750e4edb970f742dc689a65a
Source dataset: uspto-grants-2008_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07456169B2

Reaction notes

Loading…