Azobisisobutyronitrile → Diethyl 4-(bromomethyl)phenylphosphonate
Reaction equation
[C:1]1([CH3:15])[CH:6]=[CH:5][C:4]([P:7](=[O:14])([O:11][CH2:12][CH3:13])[O:8][CH2:9][CH3:10])=[CH:3][CH:2]=1.N(C(C)(C)C#N)=NC(C)(C)C#N.[Br:28]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl>[Br:28][CH2:15][C:1]1[CH:2]=[CH:3][C:4]([P:7](=[O:14])([O:8][CH2:9][CH3:10])[O:11][CH2:12][CH3:13])=[CH:5][CH:6]=1Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 10 °C
Procedure
To the suspension of diethyl p-tolylphosphonate (0.73 g, 3.2 mmol) was added a small amount of azobisisobutyronitrile (0.016 g, 0.1 mmol, in portions) and N-bromosuccinimide (0.57 g, 3.2 mmol) in anhydrous CCl4 (30 mL). The mixture was refluxed for 4 h, then cooled to 10° C. and filtered to remove succinimide. The filtrate was washed with water (30 mL) and brine (30 mL) and then dried over anhydrous Na2SO4. After filtration, the crude product was obtained via evaporation of solvent and purified by chromatography on silica gel (hexene/ethyl acetate: 2/1 as eluent) to provide diethyl 4-(bromomethyl)phenylphosphonate as a colorless oil. 1H NMR (500 MHz, CD3Cl): δ 7.79-7.83 (m, 2H), 7.50-7.52 (m, 2H), 4.51 (s, 2H), 4.09-4.18 (m, 4H), 1.33-1.36 (t, 6H).
Workup
- temperatureThe mixture was refluxed for 4 h
- filtrationfiltered
- customto remove succinimide
- washThe filtrate was washed with water (30 mL) and brine (30 mL)
- dry with materialdried over anhydrous Na2SO4
- filtrationAfter filtration
- customthe crude product was obtained via evaporation of solvent
- custompurified by chromatography on silica gel (hexene/ethyl acetate: 2/1 as eluent)
Sources & evidence
- ORD record
- ord-39d89588eb9d4d8ba23a3b44cbc12ad6
- Source dataset
- uspto-grants-2015_03
- Patent number
- US08987710B2
Reaction notes
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