Ammonium Chloride → ethyl (E)-3-(2-ethoxy-3' methylaminobiphenyl-4-yl)-2-methylacrylate

HRID 390654Notes

Reaction equation

HRID 390654 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](\[CH3:50])/[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].[CH3:51][NH:52][C:53]1[CH:58]=[CH:57][CH:56]=[C:55](B2OC(C)(C)C(C)(C)O2)[CH:54]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[Cl-].[NH4+]>CN(C)C=O.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](\[CH3:50])/[C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH:32]=[CH:33][C:34]=1[C:55]1[CH:56]=[CH:57][CH:58]=[C:53]([NH:52][CH3:51])[CH:54]=1)[CH3:27]

Participants

8

Reactant 5

HCID 25517Ammonium ChlorideHCID 62657Potassium Phosphate, TribasicHCID 27342162-(Dicyclohexylphosphino)biphenylHCID 57976762N-Methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anilineHCID 86626100ethyl (E)-3-(3-ethoxy-4-trifluoromethanesulfonyloxyphenyl)-2-methylacrylate

Product 1

HCID 86626102ethyl (E)-3-(2-ethoxy-3' methylaminobiphenyl-4-yl)-2-methylacrylateYield 25.5%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

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 1.65 g (4 mmol) of ethyl (E)-3-(3-ethoxy-4-trifluoromethanesulfonyloxyphenyl)-2-methylacrylate, 1.1 g (4.8 mmol) of methyl[3-(4,4,5,5-tetramethyl[1.3.2]dioxaborolan-2-yl)phenyl]amine (prepared as described in 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 4 hours. The medium is hydrolyzed with 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 (2.7 g) is purified by chromatography on a column of silica eluted with a 90/10 heptane/ethyl acetate mixture. 346 mg (17%) of ethyl (E)-3-(2-ethoxy-3′ methylaminobiphenyl-4-yl)-2-methylacrylate 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 (2.7 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-1ecd4859918647fa9eda5321f2b14a48
Source dataset
uspto-grants-2013_02
Patent number
US08383652B2

Reaction notes

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