Antimony trichloride → HCID 71114847, compound

HRID 1624032Notes

Reaction equation

HRID 1624032 reaction equation
[CH3:1][C:2]1([CH3:8])[C:6](=[O:7])[CH:5]=[CH:4][CH2:3]1.[Cl:9][C:10]1[CH:15]=[CH:14][C:13](B(O)O)=[C:12]([F:19])[CH:11]=1.C([O-])(=O)C.[Na+].[Sb](Cl)(Cl)Cl>CC([O-])=O.CC([O-])=O.[Pd+2].C(O)(=O)C>[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([CH:4]2[CH2:5][C:6](=[O:7])[C:2]([CH3:8])([CH3:1])[CH2:3]2)=[C:12]([F:19])[CH:11]=1

Participants

7

Reactant 4

HCID 24814Antimony trichlorideHCID 517045Sodium AcetateHCID 4193595(4-Chloro-2-fluorophenyl)boronic acidHCID 110733712-Cyclopenten-1-one, 5,5-dimethyl-

Product 1

HCID 71114847HCID 71114847, compoundYield 87.2%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 176Acetic AcidSolvent

Procedure

A solution of 5,5-dimethylcyclopent-2-en-1-one (42.0 g, 343.15 mmol), 4-chloro-2-fluorophenylboronic acid (94.47 g, 514.72 mmol), sodium acetate (56.30 g, 686.30 mmol), acetic acid (1130 mL), Pd(OAc)2 (7.70 g, 34.31 mmol), and antimony trichloride (7.83 g, 34.31 mmol) are stirred at ambient temperature for 16 hours. The solvent is evaporated to low volume and the residual acetic acid is removed using toluene. MTBE (500 mL) is added and the resulting precipitate is filtered off and discarded. The MTBE solution is washed with water (500 mL), aq. NaHCO3 (2×300 mL), dried over MgSO4, filtered, and concentrated to dryness. The residue is purified by silica gel flash chromatography, eluting with hexane to hexane 10% MTBE to give the title compound (72 g, 87%). 1H NMR (300.16 MHz, CDCl3) δ 7.21-7.06 (m, 3H), 3.67-3.59 (m, 1H), 2.81-2.72 (m, 1H), 2.41-2.31 (m, 1H), 2.21 (ddd, J=12.6, 6.3, 2.2 Hz, 1H), 1.89 (t, J=12.3 Hz, 1H), 1.159 (s, 3H), 1.137 (s, 3H).

Workup

  1. customThe solvent is evaporated to low volume
  2. customthe residual acetic acid is removed
  3. additionMTBE (500 mL) is added
  4. filtrationthe resulting precipitate is filtered off
  5. washThe MTBE solution is washed with water (500 mL), aq. NaHCO3 (2×300 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated to dryness
  9. customThe residue is purified by silica gel flash chromatography
  10. washeluting with hexane to hexane 10% MTBE

Sources & evidence

ORD record
ord-93208d0732a8490da23122490ecddb6c
Source dataset
uspto-grants-2014_07
Patent number
US08778984B2

Reaction notes

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