Potassium Carbonate → 2-(3-Chloropropoxy)-1-methoxy-4-nitrobenzene

HRID 1593760Notes

Reaction equation

HRID 1593760 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[OH:12].C1(C)C=CC(S(O[CH2:23][CH2:24][CH2:25][Cl:26])(=O)=O)=CC=1.C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O>[Cl:26][CH2:25][CH2:24][CH2:23][O:12][C:4]1[CH:5]=[C:6]([N+:9]([O-:11])=[O:10])[CH:7]=[CH:8][C:3]=1[O:2][CH3:1]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 694343-Chloropropyl p-toluenesulfonateHCID 694712-Methoxy-5-nitrophenol

Product 1

HCID 133001802-(3-Chloropropoxy)-1-methoxy-4-nitrobenzeneYield 19.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 2-methoxy-5-nitrophenol (16.90 g, 100 mmol), 3-chloropropyl p-toluenesulfonate (29.2 g, 120 mmol) and potassium carbonate (27.0 g, 195 mmol) in 160 mL of N,N-dimethylformamide was heated at 80° C. for 2 hours. The reaction mixture was cooled to room temperature and partitioned between water and ethyl acetate. The organic layer was washed with saturated sodium bicarbonate, dried over magnesium sulfate and filtered. The solution was concentrated in vacuo and recrystallized from hexane and ethyl acetate to give 4.68 g of 2-(3-chloropropoxy)-1-methoxy-4-nitrobenzene as a first crop of off-white crystals. A second crop of 11.10 g was obtained from the mother liquor. The remaining solution was concentrated in vacuo and purified by flash column chromatography, eluting with 4:1 hexane:ethyl acetate, to provide 1.31 g of 2-(3-chloropropoxy)-1-methoxy-4-nitrobenzene as off-white crystals, mp 85-87° C.; 1H NMR (400 MHz, DMSO-d6) δ 2.23 (m, 2H), 3.79 (t, J=6 Hz, 2H), 3.92 (s, 3H), 4.21 (t, J=6 Hz, 2H), 7.19 (d, J=9 Hz, 1H), 7.77 (d, J=2 Hz, 1H), 7.92 (dd, J=9, 2 Hz, 1H); MS (ES) m/z246.1, 248.1 (M+H)+

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. custompartitioned between water and ethyl acetate
  3. washThe organic layer was washed with saturated sodium bicarbonate
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationThe solution was concentrated in vacuo
  7. customrecrystallized from hexane and ethyl acetate

Sources & evidence

ORD record
ord-5378c60bd5e14dd390f14f511e0fe5cf
Source dataset
uspto-grants-2007_11
Patent number
US07297795B2

Reaction notes

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