Sodium Carbonate → Benzene, 4-methoxy-1-(1-methylethenyl)-2-nitro-

HRID 1772498Notes

Reaction equation

HRID 1772498 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[CH3:13][C:14]1(C)[C:18](C)(C)OB(C(C)=C)O1.C(=O)([O-])[O-].[Na+].[Na+].O1CCOCC1.O>O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:9][O:8][C:5]1[CH:6]=[CH:7][C:2]([C:14]([CH3:18])=[CH2:13])=[C:3]([N+:10]([O-:12])=[O:11])[CH:4]=1

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 251404-Chloro-3-nitroanisoleHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolaneHCID 218864351,4-Dioxane--water (1/1)

Product 1

HCID 10583925Benzene, 4-methoxy-1-(1-methylethenyl)-2-nitro-Yield 53%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

To 1-chloro-4-methoxy-2-nitrobenzene (5.03 g, 26.8 mmol), 4,4,5,5-tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane (5.41 g, 32.2 mmol), bis(triphenylphosphine)palladium(II) chloride (1.50 g, 2.15 mmol), and sodium carbonate (3.41 g, 32.2 mmol) was added dioxane/water (4:1, 100 mL:25 mL). The reaction was heated at 80° C. for 5 hours. The reaction was cooled to room temperature overnight. The reaction mixture was diluted with water, extracted with ethyl acetate (3×), dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using 0-5% ethyl acetate/hexanes as eluent followed by drying in vacuum oven provided the title compound as an orange oil (2.74 g, 53%): 1H NMR (400 MHz, CDCl3) δ 7.37 (d, J=2.7 Hz, 1H), 7.23 (d, J=8.6 Hz, 1H), 7.08 (dd, J=8.5, 2.6 Hz, 1H), 5.24-4.75 (m, 2H), 3.86 (s, 3H), 2.19-1.88 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 158.79, 148.61, 142.53, 131.41, 131.32, 119.24, 115.20, 108.64, 55.84, 23.38; EIMS m/z 193 ([M]+).

Workup

  1. temperatureThe reaction was cooled to room temperature overnight
  2. extractionextracted with ethyl acetate (3×)
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by flash column chromatography
  7. customby drying in vacuum oven

Sources & evidence

ORD record
ord-910889d064d2448a9dacacd0dade43ce
Source dataset
uspto-grants-2016_02
Patent number
US09249133B2

Reaction notes

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