Sodium Carbonate → 4-(Chloromethyl)-2-nitroanisole
Reaction equation
[CH3:1][O:2][C:3]1[CH:10]=[CH:9][C:6]([CH2:7]O)=[CH:5][C:4]=1[N+:11]([O-:13])=[O:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cl:33]N1C(=O)CCC1=O.C(=O)([O-])[O-].[Na+].[Na+]>ClCCl>[CH3:1][O:2][C:3]1[CH:10]=[CH:9][C:6]([CH2:7][Cl:33])=[CH:5][C:4]=1[N+:11]([O-:13])=[O:12]Participants
Conditions
- Temperature
- 0 °C
Procedure
To a solution of 4-methoxy-3-nitrobenzyl alcohol (4.9 g, 24.4 mmol) in 150 mL of dichloromethane was added triphenylphosphine (4.2 g, 31.7 mmol). The reaction was cooled to 0° C. and N-chlorosuccinimide (8.3 g, 31.7 mmol) was added. The reaction was warmed to room temperature and then heated gently to 50° C. for 2 h. The reaction was poured into aqueous sodium carbonate solution and the aqueous layer was extracted with dichloromethane and then ethyl acetate. Combined organics were dried over anhydrous MgSO4, filtered, concentrated onto silica gel and purified by flash chromatography with ethyl acetate/hexanes as the eluent to give 4-methoxy-3-nitrobenzyl chloride (3.09 g, 63%). 1H NMR (400 MHz, CDCl3) δ ppm 7.98 (d, J=2.4 Hz, 1H), 7.73 (d, J=8.8, 2.4 Hz, 1H), 7.37 (d, J=8.8 Hz, 1H), 4.78 (s, 2H), 3.91 (s, 3H).
Workup
- temperatureThe reaction was warmed to room temperature
- temperatureheated gently to 50° C. for 2 h
- extractionthe aqueous layer was extracted with dichloromethane
- dry with materialCombined organics were dried over anhydrous MgSO4
- filtrationfiltered
- concentrationconcentrated onto silica gel
- custompurified by flash chromatography with ethyl acetate/hexanes as the eluent
Sources & evidence
- ORD record
- ord-184f94b7c559441ea1546f4d86214c6c
- Source dataset
- uspto-grants-2011_07
- Patent number
- US07981903B2
Reaction notes
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