Sodium Carbonate → ethyl (Z)-2-ethoxy-3-(3'-methylaminobiphenyl-4-yl)acrylate

HRID 390682Notes

Reaction equation

HRID 390682 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[C:9](\[O:15][CH2:16][CH3:17])/[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Na+].[Na+].[CH3:24][NH:25][C:26]1[CH:31]=[CH:30][CH:29]=[C:28](B2OC(C)(C)C(C)(C)O2)[CH:27]=1>C1(C)C=CC=CC=1.C(O)C.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:16]([O:15]/[C:9](=[CH:8]\[C:5]1[CH:6]=[CH:7][C:2]([C:28]2[CH:29]=[CH:30][CH:31]=[C:26]([NH:25][CH3:24])[CH:27]=2)=[CH:3][CH:4]=1)/[C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH3:17]

Participants

8

Reactant 3

HCID 10340Sodium CarbonateHCID 57976762N-Methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anilineHCID 68960230ethyl (Z)-3-(4-bromophenyl)-2-ethoxyacrylate

Product 1

HCID 86626079ethyl (Z)-2-ethoxy-3-(3'-methylaminobiphenyl-4-yl)acrylateYield 94%

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 702EthanolSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 10.8 g (36.1 mmol) of ethyl (Z)-3-(4-bromophenyl)-2-ethoxyacrylate prepared beforehand as described in Example 1c and 108 mL (217 mmol) of aqueous 2 M sodium carbonate solution in 120 mL of toluene, 1.5 g (1.8 mmol) of dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium are added. The reaction medium is stirred and a solution of 9.25 g (39.7 mmol) of methyl[3-(4,4,5,5-tetramethyl[1.3.2]dioxaborolan-2-yl)phenyl]amine in 90 mL of ethanol is then added dropwise. After stirring at 80° C. for 2 hours, the reaction medium is hydrolyzed and diluted with ethyl acetate. After separation of the phases by settling, the ethyl acetate phase is washed with saturated sodium chloride solution, dried over magnesium sulfate, filtered and evaporated. The residue obtained is purified by chromatography on a column of silica eluted with a 90/10 and then 80/20 heptane/ethyl acetate mixture. 10.5 g (94%) of ethyl (Z)-2-ethoxy-3-(3′-methylaminobiphenyl-4-yl)acrylate are obtained in the form of a yellow oil. After taking up the product in pentane, 9.5 g (85%) of ethyl (Z)-2-ethoxy-3-(3′-methylaminobiphenyl-4-yl)acrylate are obtained in the form of a pale yellow solid with a melting point of 52° C.

Workup

  1. additionare added
  2. stirringAfter stirring at 80° C. for 2 hours
  3. customAfter separation of the phases
  4. washthe ethyl acetate phase is washed with saturated sodium chloride solution
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue obtained
  9. customis purified by chromatography on a column of silica
  10. washeluted with a 90/10

Sources & evidence

ORD record
ord-3358cfc0fc0e46f696702c14a115f559
Source dataset
uspto-grants-2013_02
Patent number
US08383652B2

Reaction notes

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