2,4-Difluoroaniline → HCID 58677639, compound

HRID 1012649Notes

Reaction equation

HRID 1012649 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[NH2:9].Br[C:11]1[CH:16]=[CH:15][C:14]([C:17]([C:19]2[CH:24]=[C:23]([O:25][CH2:26][C:27]3[CH:32]=[CH:31][C:30]([O:33][CH3:34])=[CH:29][CH:28]=3)[CH:22]=[CH:21][C:20]=2[CH3:35])=[O:18])=[C:13]([N+:36]([O-:38])=[O:37])[CH:12]=1.C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.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]>[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[NH:9][C:11]1[CH:16]=[CH:15][C:14]([C:17]([C:19]2[CH:24]=[C:23]([O:25][CH2:26][C:27]3[CH:32]=[CH:31][C:30]([O:33][CH3:34])=[CH:29][CH:28]=3)[CH:22]=[CH:21][C:20]=2[CH3:35])=[O:18])=[C:13]([N+:36]([O-:38])=[O:37])[CH:12]=1

Participants

7

Reactant 4

HCID 97092,4-DifluoroanilineHCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 67314788HCID 67314788, compound

Product 1

HCID 58677639HCID 58677639, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

2,4-Difluoro-phenylamine (26 μL, 0.25 mmol) was dissolved in dry 1,4-dioxane (3 mL) in a vial under an argon atmosphere. Compound 504 (114 mg, 0.25 mmol) was added and dissolved in the solvent. Rac-BINAP (7.0 mg, 0.012 mmol), Pd2(dba)3 (7.0 mg, 0.008 mmol) and Cs2CO3 (114 mg, 0.35 mmol) were added, and the reaction mixture was stirred under an argon atmosphere at 100° C. for 16 h. The reaction mixture was filtered through Celite and then purified by continuous gradient flash chromatography using EtOAc/petroleum ether (40-60) (v:v=1:9 to 1:3) as the eluent to afford the title compound as curry yellow solid. 13C NMR (CDCl3) δ 194.5, 159.6 (dd), 159.5, 156.1, 155.9 (dd), 149.6, 147.1, 137.2, 132.8, 131.8, 131.7, 129.2, 128.5, 126.8, 124.8 (dd), 123.8 (dd), 117.9, 117.1, 114.1, 111.8 (dd), 109.5, 105.2 (dd), 70.1, 55.3, 19.9

Workup

  1. dissolutiondissolved in the solvent
  2. filtrationThe reaction mixture was filtered through Celite
  3. custompurified by continuous gradient flash chromatography

Sources & evidence

ORD record
ord-b91385ee08cf4f96aa4dac1dd7e37050
Source dataset
uspto-grants-2011_07
Patent number
US07977387B2

Reaction notes

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