P-Chloroacetophenone → HCID 86619548, compound

HRID 919027Notes

Reaction equation

HRID 919027 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:5]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])=[CH:4][CH:3]=1.[CH3:15][C:16]([C:18]1[CH:23]=[CH:22][C:21]([Cl:24])=[CH:20][CH:19]=1)=[O:17].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CC([O-])(C)C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1COCC1>[Cl:24][C:21]1[CH:22]=[CH:23][C:18]([C:16](=[O:17])[CH2:15][C:2]2[CH:14]=[CH:13][C:5]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])=[CH:4][CH:3]=2)=[CH:19][CH:20]=1

Participants

7

Reactant 4

HCID 7467P-ChloroacetophenoneHCID 634876Binap, (A+-)-HCID 11334366Tert-butyl 4-bromobenzoateHCID 23676156Sodium t-butoxide

Product 1

HCID 86619548HCID 86619548, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A THF solution (200 ml) containing t-butyl 4-bromobenzoate (19.9 g, 77.6 mmol), 4-chloroacetophenone (10 g, 64.7 mmol), Pd2dba3 (1.19 g, 1.29 mmol), BINAP (1.6 g, 2.58 mmol) and NaOtBu (8.7 g, 90.6 mmol) was refluxed under an argon atmosphere for approximately 5 hours. The solution was concentrated and then partitioned between EtOAc and water. The organic phase was washed with water, brine and dried over Na2SO4. The filtered solution was concentrated and the residue purified by silica gel chromatography using a hexanes/EtOAc gradient to give the title compound. 1H NMR (500 MHz, CDCl3): δ 7.95 (d, J=8.5 Hz, 2 H); 7.93 (d, J=8.7 Hz, 2 H); 7.43 (d, J=8.3 Hz, 2 H); 7.29 (d, J=8.2 Hz, 2 H); 4.30 (s, 2 H); 1.58 (s, 9 H). LC1 4.01 min. (M-tBu+H)=275

Workup

  1. temperaturewas refluxed under an argon atmosphere for approximately 5 hours
  2. concentrationThe solution was concentrated
  3. custompartitioned between EtOAc and water
  4. washThe organic phase was washed with water, brine
  5. dry with materialdried over Na2SO4
  6. concentrationThe filtered solution was concentrated
  7. customthe residue purified by silica gel chromatography

Sources & evidence

ORD record
ord-7437bf4c293c440783c9b98f5c74df06
Source dataset
uspto-grants-2016_03
Patent number
US09272999B2

Reaction notes

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