1,3-Bis(diphenylphosphino)propane → HCID 68488910, compound

HRID 1470886Notes

Reaction equation

HRID 1470886 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][CH:9]=2)=[CH:4][C:3]=1[CH:15]1[C:20](=[O:21])[C:19]([CH3:23])([CH3:22])[O:18][C:17]([CH3:25])([CH3:24])[C:16]1=[O:26].O.[OH-].[Li+].[C:30]1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:31]=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.COCCOC>[Cl:14][C:11]1[CH:10]=[CH:9][C:8]([C:5]2[CH:6]=[CH:7][C:2]([CH:30]=[CH2:31])=[C:3]([CH:15]3[C:16](=[O:26])[C:17]([CH3:25])([CH3:24])[O:18][C:19]([CH3:23])([CH3:22])[C:20]3=[O:21])[CH:4]=2)=[CH:13][CH:12]=1

Participants

6

Reactant 3

HCID 812191,3-Bis(diphenylphosphino)propaneHCID 168937Lithium hydroxide, monohydrateHCID 49787146HCID 49787146, compound

Product 1

HCID 68488910HCID 68488910, compoundYield 275.7%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

A solution of 4-(4-bromo-4′-chlorobiphenyl-3-yl)-2,2,6,6-tetramethylpyran-3,5-dione (0.314 g, 0.72 mmol), vinylboronic anhydride pyridine complex (0.175 g, 0.73 mmol), lithium hydroxide monohydrate (0.177 g, 4.22 mmol), 1,3-bis(diphenylphosphino)propane (0.015 g, 0.036 mmol) and palladium acetate (0.010 g, 0.044 mmol) is stirred in a mixed solvent system of 1,2-dimethoxyethane (5 ml) and distilled water (1 ml) at 80° C. for 3 hours. After cooling to room temperature the mixture is filtered through diatomaceous earth, followed by washing with ethyl acetate and distilled water. The aqueous phase is acidified with 2M aqueous hydrochloric acid to pH3, then the organic phase is separated and the aqueous phase extracted again with ethyl acetate. All organic fractions are combined, then dried over anhydrous magnesium sulphate and filtered. After concentration in vacuo the crude oil is purified by preparative reverse phase HPLC then triturated with hexanes to afford 4-(4′-chloro-4-vinylbiphenyl-3-yl)-2,2,6,6-tetramethylpyran-3,5-dione (0.038 g) as a white solid.

Workup

  1. distillationdistilled water (1 ml) at 80° C. for 3 hours
  2. filtrationis filtered through diatomaceous earth
  3. washby washing with ethyl acetate
  4. distillationdistilled water
  5. customthe organic phase is separated
  6. extractionthe aqueous phase extracted again with ethyl acetate
  7. dry with materialdried over anhydrous magnesium sulphate
  8. filtrationfiltered
  9. concentrationAfter concentration in vacuo the crude oil
  10. customis purified by preparative reverse phase HPLC
  11. customthen triturated with hexanes

Sources & evidence

ORD record
ord-84956db348ad43de9756f69274322df0
Source dataset
uspto-grants-2015_04
Patent number
US09006429B2

Reaction notes

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