Dimethylformamide → 1-(2,2-Dimethoxyethyl)-3-methyl-2-nitrobenzene

HRID 751481Notes

Reaction equation

HRID 751481 reaction equation
[N+:1]([C:4]1[C:9]([CH3:10])=[CH:8][CH:7]=[CH:6][C:5]=1[CH3:11])([O-:3])=[O:2].[CH3:12][O:13][CH:14]([O:18][CH3:19])N(C)C.CN(C)C=O.C[Si](Cl)(C)C>C(OCC)(=O)C.CO>[CH3:12][O:13][CH:14]([O:18][CH3:19])[CH2:11][C:5]1[CH:6]=[CH:7][CH:8]=[C:9]([CH3:10])[C:4]=1[N+:1]([O-:3])=[O:2]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 6397ChlorotrimethylsilaneHCID 66722,6-DimethylnitrobenzeneHCID 78373Dimethylformamide dimethyl acetal

Product 1

HCID 692699561-(2,2-Dimethoxyethyl)-3-methyl-2-nitrobenzeneYield 14%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

Combine 2-nitro-meta-xylene (5 mL, 0.037 mol), N,N-dimethylformamide dimethylacetal (5.4 mL, 1.1 eq) and N,N-dimethylformamide (60 mL) in a flask and reflux under nitrogen for 2 days. Let cool to room temperature then concentrate to approximately one-half volume. Add methanol (40 mL) and trimethylsilylchloride (6.6 mL, 1.4 eq). Reflux overnight. Dilute with ethyl acetate after cooling to room temperature then extract with saturated sodium bicarbonate followed by brine. Dry over magnesium sulfate, filter and concentrate. Purification by column chromatography (9:1 Hexanes:ethyl acetate) gives 1.15 g (14%) product as a light yellow oil. 1H NMR (400 MHz, DMSO-d6) δ 2.23 (s, 3H), 2.80 (d, J=5.36 Hz, 2H), 3.19 (s, 6H), 4.45 (m, 1H), 7.32 (m, 2H), 7.42 (m, 1H).

Workup

  1. concentrationthen concentrate to approximately one-half volume
  2. temperatureReflux overnight
  3. temperatureafter cooling to room temperature
  4. extractionthen extract with saturated sodium bicarbonate
  5. dry with materialDry over magnesium sulfate
  6. filtrationfilter
  7. concentrationconcentrate
  8. customPurification by column chromatography (9:1 Hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-b2c7e790db074372a74aaf68d083ad01
Source dataset
uspto-grants-2008_07
Patent number
US07405305B2

Reaction notes

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