Diisopropylamine → HCID 59252689, compound

HRID 388538Notes

Reaction equation

HRID 388538 reaction equation
Br[C:2]1[CH:8]=[C:7]([F:9])[CH:6]=[CH:5][C:3]=1N.[CH3:10][S:11]([C:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1)(=[O:13])=[O:12].CC1C(P(C2C(C)=CC(C)=C(S([O-])(=O)=O)C=2)C2C(C)=CC(C)=C(S([O-])(=O)=O)C=2)=CC(S([O-])(=O)=O)=C(C)C=1.O.[Na+].[Na+].[Na+].C([NH:67]C(C)C)(C)C>CN(C=O)C.O.CCOC(C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[F:9][C:7]1[CH:8]=[C:2]([NH2:67])[C:3]([C:17]2[CH:18]=[CH:19][C:14]([S:11]([CH3:10])(=[O:13])=[O:12])=[CH:15][CH:16]=2)=[CH:5][CH:6]=1

Participants

8

Reactant 4

HCID 7912DiisopropylamineHCID 2428732-Bromo-4-fluoroanilineHCID 27343644-(Methanesulfonyl)phenylboronic acidHCID 72376407HCID 72376407, compound

Product 1

HCID 59252689HCID 59252689, compoundYield 95%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 8857Ethyl AcetateSolventHCID 21962138N,N-Dimethylformamide--water (1/1)Solvent

Conditions

Temperature
50 °C

Procedure

To a solution of 2-bromo-4-fluoroaniline (5.0 g, 26.3 mmol) in DMF/water (80/20 v/v, 65.8 ml) under an atmosphere of nitrogen were added 4-(methanesulfonyl)phenylboronic acid (7.9 g, 39.5 mmol), tris(4,6-dimethyl-3-sulfanatophenyl)phosphine trisodium salt hydrate (2.6 g, 4.0 mmol), palladium(II) acetate (0.3 g, 1.3 mmol), and diisopropyl amine (11.3 ml, 79.0 mmol). The reaction was allowed to stir at 50° C. for 2.5 h. The reaction was diluted with EtOAc and washed with 3M LiCl (3×), water, and brine. The organic portion was dried over sodium sulfate, filtered, and concentrated in vacuo to afford 4-fluoro-4′-(methylsulfonyl)-1,1′-biphenyl-2-amine as a yellow solid (95%). LCMS (M+H) 266.1. 1H NMR (400 MHz, CD3OD) δ 8.02 (m, 2H), 7.65 (m, 2H), 7.05 (dd, J=8.6, 6.2 Hz, 1H), 6.57-6.47 (m, 2H), 3.86 (s, 2H), 3.11 (s, 3H).

Workup

  1. washwashed with 3M LiCl (3×), water, and brine
  2. dry with materialThe organic portion was dried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-54af6552f9534c67941a1594577af076
Source dataset
uspto-grants-2013_02
Patent number
US08377954B2

Reaction notes

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