2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → 2-(2,6-Difluoro-3,5-dimethoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

HRID 1778654Notes

Reaction equation

HRID 1778654 reaction equation
[F:1][C:2]1[C:7](I)=[C:6]([F:9])[C:5]([O:10][CH3:11])=[CH:4][C:3]=1[O:12][CH3:13].C([Mg]Cl)(C)C.C(O[B:23]1[O:27][C:26]([CH3:29])([CH3:28])[C:25]([CH3:31])([CH3:30])[O:24]1)(C)C>C1COCC1>[F:1][C:2]1[C:3]([O:12][CH3:13])=[CH:4][C:5]([O:10][CH3:11])=[C:6]([F:9])[C:7]=1[B:23]1[O:27][C:26]([CH3:29])([CH3:28])[C:25]([CH3:31])([CH3:30])[O:24]1

Participants

5

Reactant 3

HCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 867228052,4-Difluoro-3-iodo-1,5-dimethoxybenzeneHCID 178418918HCID 178418918, compound

Product 1

HCID 867228062-(2,6-Difluoro-3,5-dimethoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 2,4-difluoro-3-iodo-1,5-dimethoxybenzene (1.50 g, 5.00 mmol) in tetrahedrofuran (THF, 20 mL) was slowly added 2.0 M isopropyl magnesium chloride in THF (2.87 mL, 5.75 mmol) at −10° C. under an atmosphere of nitrogen. After 10 min., 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.27 mL, 6.25 mmol)(Aldrich, Cat. No. 417149) was added. The reaction mixture was then stirred at ambient temperature for 2 h. The mixture was quenched with sat. NH4Cl, and extracted with ethyl acetate. The combined organic layers were washed with water and brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue (solid) was treated with ethyl ether, filtered, and dried under reduced pressure to afford the desired product (1.20 g, 80%). 1H-NMR (400 MHz, CDCl3): 6.70 (t, J=8.2 Hz, 1H), 3.85 (s, 6H), 1.38 (s, 12H). LCMS (M+H)+=301.1.

Workup

  1. customat −10° C.
  2. addition417149) was added
  3. customThe mixture was quenched with sat. NH4Cl
  4. extractionextracted with ethyl acetate
  5. washThe combined organic layers were washed with water and brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. additionThe residue (solid) was treated with ethyl ether
  10. filtrationfiltered
  11. customdried under reduced pressure

Sources & evidence

ORD record
ord-f1759dab77ba43aab9e81c7341510c0b
Source dataset
uspto-grants-2016_02
Patent number
US09266892B2

Reaction notes

Loading…