Potassium Phosphate, Tribasic → Ethyl 2-[1-(2-ethoxy-3'-methylaminobiphenyl-4-yl)meth-(e)-ylidene]butyrate

HRID 390658Notes

Reaction equation

HRID 390658 reaction equation
C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2)CCCCC1.[CH2:26]([O:28][C:29]1[CH:30]=[C:31](/[CH:43]=[C:44](\[CH2:50][CH3:51])/[C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH:32]=[CH:33][C:34]=1OS(C(F)(F)F)(=O)=O)[CH3:27].[CH3:52][NH:53][C:54]1[CH:59]=[CH:58][CH:57]=[C:56](B2OC(C)(C)C(C)(C)O2)[CH:55]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>CN(C)C=O.[Cl-].[NH4+].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:26]([O:28][C:29]1[CH:30]=[C:31](/[CH:43]=[C:44](\[CH2:50][CH3:51])/[C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH:32]=[CH:33][C:34]=1[C:56]1[CH:57]=[CH:58][CH:59]=[C:54]([NH:53][CH3:52])[CH:55]=1)[CH3:27]

Participants

8

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 27342162-(Dicyclohexylphosphino)biphenylHCID 57976762N-Methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anilineHCID 87636882Ethyl 2-[1-(3-ethoxy-4-trifluoromethanesulfonyloxyphenyl)meth-(e)-ylidene]butyrate

Product 1

HCID 68957253Ethyl 2-[1-(2-ethoxy-3'-methylaminobiphenyl-4-yl)meth-(e)-ylidene]butyrateYield 37.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
92.5 °C

Procedure

45 mg (0.2 mmol) of palladium acetate and then 140 mg (0.4 mmol) of 2-(dicyclohexylphosphino)biphenyl are added to a mixture of 1.7 g (4 mmol) of ethyl 2-[1-(3-ethoxy-4-trifluoromethanesulfonyloxyphenyl)meth-(E)-ylidene]butyrate, 1.1 g (4.8 mmol) of methyl[3-(4,4,5,5-tetramethyl[1.3.2]dioxaborolan-2-yl)phenyl]amine (prepared according to Example 28a) and 2 mL of aqueous 2 M potassium phosphate solution in 8 mL of dimethylformamide. The reaction mixture is heated at 90-95° C. for 3 hours. The reaction medium is hydrolyzed in saturated ammonium chloride solution and extracted with ethyl acetate. The organic phases are combined, washed with saturated sodium chloride solution and dried over sodium sulfate. The solvent is evaporated off and the brown oil obtained (2.3 g) is purified by chromatography on a column of silica eluted with a 90/10 heptane/ethyl acetate mixture. 526 mg (15%) of ethyl 2-[1-(2-ethoxy-3′-methylaminobiphenyl-4-yl)meth-(E)-ylidene]butyrate are obtained in the form of a yellow oil.

Workup

  1. extractionextracted with ethyl acetate
  2. washwashed with saturated sodium chloride solution
  3. dry with materialdried over sodium sulfate
  4. customThe solvent is evaporated off
  5. customthe brown oil obtained (2.3 g)
  6. customis purified by chromatography on a column of silica
  7. washeluted with a 90/10 heptane/ethyl acetate mixture

Sources & evidence

ORD record
ord-af62b1e9ce644f949c32c41dacb2c043
Source dataset
uspto-grants-2013_02
Patent number
US08383652B2

Reaction notes

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