Boron tribromide → HCID 25149592, compound

HRID 1170977Notes

Reaction equation

HRID 1170977 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:14]=[C:15]([Cl:29])[C:16]=1[O:17][C:18]1[CH:23]=[CH:22][C:21]([O:24]C)=[C:20]([CH:26]([CH3:28])[CH3:27])[CH:19]=1)[CH2:5][P:6](=[O:13])([O:10]CC)[O:7]CC.Br[Si](C)(C)C.B(Br)(Br)Br>C(Cl)Cl>[Cl:29][C:15]1[CH:14]=[C:4]([CH:3]=[C:2]([Cl:1])[C:16]=1[O:17][C:18]1[CH:23]=[CH:22][C:21]([OH:24])=[C:20]([CH:26]([CH3:27])[CH3:28])[CH:19]=1)[CH2:5][P:6](=[O:7])([OH:10])[OH:13]

Participants

5

Reactant 3

HCID 25134Boron tribromideHCID 76113BromotrimethylsilaneHCID 25149509HCID 25149509, compound

Product 1

HCID 25149592HCID 25149592, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of diethyl 3,5-dichloro-4-(3′-iso-propyl-4′-methoxyphenoxy)benzylphosphonate (0.59 g, 1.28 mmol) in CH2Cl2 (10.0 mL) at −30° C. was added bromotrimethylsilane (2.53 mL, 19.2 mmol). The reaction mixture was stirred at room temperature for 16 h and the solvent was removed under reduced pressure. The residue was dissolved in dichloromethane (25.0 mL), cooled to −78° C. and to it was added BBr3 (19.0 mL, 19.0 mmol, 1.0 M solution in CH2Cl2). The reaction mixture was stirred at −78° C. for 10 min, allowed to warm to room temperature and stirred for 16 h. The reaction mixture was poured into ice, concentrated and extracted with ethyl acetate. The organic layer was washed with water (20 mL×2), dried over MgSO4 and filtered. The solvent was removed under reduced pressure to afford 3,5-dichloro-4-(3′-iso-propyl-4′-hydroxyphenoxy)benzylphosphonic acid as a brown solid (0.20 g, 40%): mp: 178-181° C.; LC-MS m/z=391 [C16H17Cl2O5P−H]−; 1H NMR (300 MHz, DMSO-d6): δ 9.08 (s, 1 H), 7.48 (s, 2 H), 6.72 (m, 2 H), 6.25 (m, 1 H), 3.18 (m, 1 H), 3.00 (d, J=21.0 Hz, 2 H), 3.11 (m, 1 H), 1.14 (d, J=6.0 Hz, 6 H); Anal. Calcd for (C16H17Cl2O5P+0.2 C4H8O2+0.5H2O): C, 48.30; H, 4.73. Found: C, 48.69, H, 5.16.

Workup

  1. customthe solvent was removed under reduced pressure
  2. dissolutionThe residue was dissolved in dichloromethane (25.0 mL)
  3. temperaturecooled to −78° C. and to it
  4. stirringThe reaction mixture was stirred at −78° C. for 10 min
  5. temperatureto warm to room temperature
  6. stirringstirred for 16 h
  7. additionThe reaction mixture was poured into ice
  8. concentrationconcentrated
  9. extractionextracted with ethyl acetate
  10. washThe organic layer was washed with water (20 mL×2)
  11. dry with materialdried over MgSO4
  12. filtrationfiltered
  13. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-84f6d09108c548b79b1e5317a1ca7e88
Source dataset
uspto-grants-2010_11
Patent number
US07829552B2

Reaction notes

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