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Benzylamine → Methyl 4-(benzylamino)-2-(4-fluoroanilino)benzoate

HRID 2191684
Notes
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Reaction equation

HRID 2191684 reaction equation
[F:1][C:2]1[CH:19]=[CH:18][C:5]([NH:6][C:7]2[CH:16]=[C:15](I)[CH:14]=[CH:13][C:8]=2[C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=1.[CH2:20]([NH2:27])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(O)(=O)C.C1(C)C=CC=CC=1>[CH2:20]([NH:27][C:15]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[C:7]([NH:6][C:5]2[CH:18]=[CH:19][C:2]([F:1])=[CH:3][CH:4]=2)[CH:16]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 4

HCID 7504BenzylamineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 57667861Methyl 2-(4-fluoroanilino)-4-iodobenzoate

Product 1

HCID 57667993Methyl 4-(benzylamino)-2-(4-fluoroanilino)benzoate

Reagents, catalysts & solvents 3

HCID 9811564
Bis(dibenzylideneacetone)palladium
Catalyst
HCID 176Acetic AcidSolvent
HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To toluene 3.0 mL solution of methyl 2-(4-fluoroanilino)-4-iodobenzoate 0.30 g were added benzylamine 0.13 mL, rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl 0.050 g, tris(dibenzylideneacetone)dipalladium(0) 0.022 g and sodium tert-butoxide 0.093 g at room temperature, and it was stirred under nitrogen atmosphere at 80° C. for 1 hour. After the reaction mixture was cooled to room temperature, acetic acid 1.0 mL was added to it, and the solvent was removed under reduced pressure. The obtained residue was refined by silica gel column chromatography [eluent; hexane:ethyl acetate=5:1] to give methyl 4-(benzylamino)-2-(4-fluoroanilino)benzoate 0.24 g of brown oil.

Workup

  1. temperatureAfter the reaction mixture was cooled to room temperature
  2. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-ec1fe47e645c4442a1ac0d67f199fabd
Source dataset
uspto-grants-2012_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08327467B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes