Acetone → 1-Allyl-2-allyloxy-3-nitrobenzene

HRID 1041143Notes

Reaction equation

HRID 1041143 reaction equation
[CH2:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[C:5]=1[OH:13])[CH:2]=[CH2:3].[CH3:14][C:15]([CH3:17])=O.C(=O)([O-])[O-].[K+].[K+].ICC=C>C(OCC)(=O)C>[CH2:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[C:5]=1[O:13][CH2:17][CH:15]=[CH2:14])[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 180AcetoneHCID 11166Allyl iodideHCID 11430Potassium CarbonateHCID 113098672-Allyl-6-nitrophenol

Product 1

HCID 112182621-Allyl-2-allyloxy-3-nitrobenzeneYield 80%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Into a microwave vial was placed 1-allyloxy-2-nitrobenzene (0.5 g, 0.003 mol). The yellow-green oil was heated neat in the microwave at 180° C. for 30 min producing a black solid. 1H NMR of the crude solid showed desired product plus impurities. The reaction mixture was purified by ISCO chromatography on silica gel using 5-20% ethyl acetate-hexane. Product, 2-allyl-6-nitrophenol, was isolated as a yellow oil (0.1 g, 20%). 1H NMR (CDCl3, 400 MHz) δ 10.95 (s, 1H), 8.00 (d, 1H, J=8.59 Hz), 7.47 (d, 1H, J=7.58 Hz), 6.93 (t, 2H, J=8.59, 7.58 Hz), 5.97 (m, 1H), 5.12 (m, 2H), 3.49 (d, 2H, J=6.31 Hz), 861c) To a stirred solution of 2-allyl-6-nitrophenol (100 mg, 0.0006 mol) in acetone (4 mL, 0.06 mol) at 0° C. in an ice bath was added potassium carbonate (0.092 g, 0.00067 mol) followed by 3-iodo-1-propene (0.11 g, 0.00067 mol) under an atmosphere of nitrogen. The reaction mixture was stirred for 1 h at 0° C. then warmed to room temperature overnight. The reaction mixture was diluted with ethyl acetate and washed with 10% HCl, water, dried over magnesium sulfate and concentrated in vacuo. The reaction mixture was purified by ISCO chromatography on silica gel (12 g) using ethyl acetate-hexane (10%-50%) to give 1-allyl-2-allyloxy-3-nitrobenzene as a yellow oil (93 mg, 80%). 1H NMR (400 MHz, CDCl3) δ 7.69 (d, 1H, J=8.0 Hz), 7.44 (d, 1H, J=7.8 Hz), 7.16 (t, 1H, J=8.08, 7.8 Hz), 5.90-6.13 (m, 2H), 5.40 (d, 1H, J=17 Hz), 5.29 (d, 1H, J=10 Hz), 5.15 (d, 1H, J=10 Hz), 5.09 (d, 1H, J=17 Hz), 4.50 (d, 2H, J=5.8 Hz), 3.49 (d, 2H, J=6.3 Hz).

Workup

  1. temperaturethen warmed to room temperature overnight
  2. washwashed with 10% HCl, water
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated in vacuo
  5. customThe reaction mixture was purified by ISCO chromatography on silica gel (12 g)

Sources & evidence

ORD record
ord-77b52c891768463cb678ff34a522bcde
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

Loading…