Hydrochloric Acid → 5-Methoxy-2-nitro-4-(trifluoromethyl)benzene acetonitrile

HRID 840541Notes

Reaction equation

[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[CH:5][C:4]=1[C:12]([F:15])([F:14])[F:13].ClC1C=CC(O[CH2:22][C:23]#[N:24])=CC=1.CC([O-])(C)C.[K+].Cl>CN(C=O)C>[CH3:1][O:2][C:3]1[C:4]([C:12]([F:13])([F:14])[F:15])=[CH:5][C:6]([N+:9]([O-:11])=[O:10])=[C:7]([CH2:22][C:23]#[N:24])[CH:8]=1

Participants

Conditions

Temperature: -10 °C

Procedure

A mixture of 1-methoxy-4-nitro-2-trifluoromethylbenzene (93 g, 0.421 mol) and 4-chlorophenoxyacetonitrile (77.55 g, 0.463 mol) in dry DMF (500 ml) was added dropwise over 0.75 h to a stirred solution of KOtBu (103.85 g, 0.927 mol) in dry DMF (400 ml) at −10° C. After complete addition the resulting purple solution was maintained at −10° C. for 1 h then poured into a mixture of ice/water (1.5 l) and 5 M aqueous HCl (1.5 l). The resulting mixture was extracted with dichloromethane (3×1 l). The combined extracts were washed with water (3 l), dried (Na2SO4) and evaporated under reduced pressure. The residue was chromatographed on silica using 10-40% ethyl acetate/petroleum ether as eluant to give the crude product which was recrystallised from ethyl acetate/petroleum ether to afford the title compound (85.13 g, 78%) as a white solid. Mp 103-104° C.

Workup

additionAfter complete addition the resulting purple solution
extractionThe resulting mixture was extracted with dichloromethane (3×1 l)
washThe combined extracts were washed with water (3 l)
dry with materialdried (Na2SO4)
customevaporated under reduced pressure
customThe residue was chromatographed on silica using 10-40% ethyl acetate/petroleum ether as eluant
customto give the crude product which
customwas recrystallised from ethyl acetate/petroleum ether

Sources & evidence

ORD record: ord-c9089e495eef4c4c9c7ed67f6d6f68ae
Source dataset: uspto-grants-2002_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06369060B1

Reaction notes

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