Potassium Phosphate, Tribasic → HCID 86663672, compound

HRID 879078Notes

Reaction equation

HRID 879078 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[CH:14]=[CH:13][C:12](OS(C(F)(F)F)(=O)=O)=[C:11]([CH:23]=[O:24])[CH:10]=1.[CH:25]1(B(O)O)[CH2:27][CH2:26]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[Br-].[Na+]>O.C(OCC)(=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[CH:14]=[CH:13][C:12]([CH:25]2[CH2:27][CH2:26]2)=[C:11]([CH:23]=[O:24])[CH:10]=1

Participants

9

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 253881Sodium BromideHCID 2760897Cyclopropylboronic acidHCID 86663671HCID 86663671, compound

Product 1

HCID 86663672HCID 86663672, compoundYield 54%

Reagents, catalysts & solvents 4

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of trifluoromethanesulfonic acid 2′,4′-dichloro-3-formylbiphenyl-4-yl ester (30.0 g, 0.075 mol), cyclopropyl boronic acid (8.50 g, 0.097 mol), potassium phosphate (56.30 g, 0.27 mol) and sodium bromide (7.7 g, 0.075 mol) is added toluene (300 ml) then distilled water (30 ml) under a nitrogen atmosphere. To this mixture is then added tetrakis(triphenylphosphine) palladium (9.30 g, 0.0081 mol) in one portion, and the mixture is then heated at 100° C. overnight. After cooling to room temperature the mixture is diluted with distilled water (500 ml) and ethyl acetate (500 ml), and the two layers are separated. The aqueous phase is extracted again with ethyl acetate (2×500 ml), then all organic fractions are combined, then washed with distilled water (1 L) then brine (1 L). After drying over magnesium sulfate the suspension is filtered and the filtrate is concentrated in vacuo. The crude product is purified by flash column chromatography on silica gel (2-10% ethyl acetate in hexanes as eluant), then additionally by flash column chromatography on basic alumina (10% ethyl acetate in hexane as eluant) to afford 2′,4′-dichloro-4-cyclopropylbiphenyl-3-carbaldehyde (11.7 g, 54%).

Workup

  1. customthe two layers are separated
  2. extractionThe aqueous phase is extracted again with ethyl acetate (2×500 ml)
  3. washwashed with distilled water (1 L)
  4. dry with materialAfter drying over magnesium sulfate the suspension
  5. filtrationis filtered
  6. concentrationthe filtrate is concentrated in vacuo
  7. customThe crude product is purified by flash column chromatography on silica gel (2-10% ethyl acetate in hexanes as eluant)

Sources & evidence

ORD record
ord-4458de8af0f740cdbaa78d8d53dfba4e
Source dataset
uspto-grants-2015_03
Patent number
US08987476B2

Reaction notes

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