Water → Ethyl 3-(bromomethyl)benzyl(methyl)phosphinate
Reaction equation
Br[CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([CH2:9][Br:10])[CH:4]=1.[CH3:11][P:12]([O:16]CC)[O:13][CH2:14][CH3:15].O>CN(C=O)C>[Br:10][CH2:9][C:5]1[CH:4]=[C:3]([CH:8]=[CH:7][CH:6]=1)[CH2:2][P:12]([CH3:11])(=[O:16])[O:13][CH2:14][CH3:15]Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 150 °C
Procedure
To a solution of α,α′-Bisbromo-m-xylene (7.75 g, 29.38 mmol) in DMF (10 mL) was added diethyl methylphosphonite (2.0 g, 14.69 mmol) via syringe. The mixture was heated to 150° C. for 2 minutes in a microwave. The reaction mixture was poured into water and product extracted with ethyl acetate (3×25 mL). The combined organics were washed with water (2×50 mL) and brine (50 mL), and dried over Na2SO4. Reduced volume in vacuo and purified product by flash column eluting 20-100% ethyl acetate in hexanes to give 1.89 g mg (44%) 65 as a colorless oil. 1H NMR (300 MHz, CDCl3) δ 1.24 (t, 3H), 1.33 (d, 3H), 3.08 (d, 2H), 3.97 (dt, 2H), 4.44 (s, 2H), 7.25 (m, 4H). LCMS: m/z for C11H16BrO2P++H observed 291.0 and 293.0 at 2.09 minutes of a 3.5 minute run, gradient 5-95% CH3CN in H2O.
Workup
- extractionextracted with ethyl acetate (3×25 mL)
- washThe combined organics were washed with water (2×50 mL) and brine (50 mL)
- dry with materialdried over Na2SO4
- custompurified product by flash column
- washeluting 20-100% ethyl acetate in hexanes
Sources & evidence
- ORD record
- ord-426d1d3b096c45459a79773d33a786f5
- Source dataset
- uspto-grants-2012_12
- Patent number
- US08338593B2
Reaction notes
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