Ammonium Chloride → methyl (Z)-3-(2-butoxy-3'-methylaminobiphenyl-4-yl)-2-methoxyacrylate

HRID 390644Notes

Reaction equation

HRID 390644 reaction equation
[CH2:1]([O:5][C:6]1[CH:7]=[C:8](/[CH:13]=[C:14](\[O:19][CH3:20])/[C:15]([O:17][CH3:18])=[O:16])[CH:9]=[CH:10][C:11]=1I)[CH2:2][CH2:3][CH3:4].[CH3:21][NH:22][C:23]1[CH:28]=[CH:27][CH:26]=[C:25](B2OC(C)(C)C(C)(C)O2)[CH:24]=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.C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2)CCCCC1>[CH2:1]([O:5][C:6]1[CH:7]=[C:8](/[CH:13]=[C:14](\[O:19][CH3:20])/[C:15]([O:17][CH3:18])=[O:16])[CH:9]=[CH:10][C:11]=1[C:25]1[CH:26]=[CH:27][CH:28]=[C:23]([NH:22][CH3:21])[CH:24]=1)[CH2:2][CH2:3][CH3:4]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 62657Potassium Phosphate, TribasicHCID 57976762N-Methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anilineHCID 59574929methyl (Z)-3-(3-butoxy-4-iodophenyl)-2-methoxyacrylate

Product 1

HCID 86626095methyl (Z)-3-(2-butoxy-3'-methylaminobiphenyl-4-yl)-2-methoxyacrylateYield 75.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 27342162-(Dicyclohexylphosphino)biphenylCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
92.5 °C

Procedure

In a manner similar to that of Example 25c, 4 mg (0.018 mmol) of palladium acetate and then 13 mg (0.036 mmol) of 2-(dicyclohexylphosphino)biphenyl are added to a mixture of 0.7 g (1.8 mmol) of methyl (Z)-3-(3-butoxy-4-iodophenyl)-2-methoxyacrylate prepared as in Example 24c, 0.5 g (2.15 mmol) of methyl[3-(4,4,5,5-tetramethyl[1.3.2]dioxaborolan-2-yl)phenyl]amine and 1.8 mL of aqueous 2M potassium phosphate solution in 10 mL of dimethylformamide. The reaction mixture is heated at 90-95° C. for 1 hour. The reaction medium is hydrolyzed with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic phases are combined, washed with saturated sodium chloride solution and dried over magnesium sulfate. The solvent is evaporated off and the residue is purified by chromatography on a column of silica eluted with a 60/40 heptane/ethyl acetate mixture. 0.5 g (71%) of methyl (Z)-3-(2-butoxy-3′-methylaminobiphenyl-4-yl)-2-methoxyacrylate are obtained.

Workup

  1. extractionextracted with ethyl acetate
  2. washwashed with saturated sodium chloride solution
  3. dry with materialdried over magnesium sulfate
  4. customThe solvent is evaporated off
  5. customthe residue is purified by chromatography on a column of silica
  6. washeluted with a 60/40 heptane/ethyl acetate mixture

Sources & evidence

ORD record
ord-35d8bb8ca66142369a1fd4caa4ac6cce
Source dataset
uspto-grants-2013_02
Patent number
US08383652B2

Reaction notes

Loading…