Potassium Phosphate, Tribasic → HCID 59457676, compound

HRID 1711104Notes

Reaction equation

HRID 1711104 reaction equation
Cl[C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[C:9]([C:11]3[N:12]=[CH:13][N:14]([CH3:16])[CH:15]=3)[S:10][C:3]=12.[F:17][C:18]1[CH:24]=[C:23]([N+:25]([O-:27])=[O:26])[CH:22]=[CH:21][C:19]=1[NH2:20].C1CCC(P(C2C(C3C=CC=CC=3)=CC=CC=2)C2CCCCC2)CC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[F:17][C:18]1[CH:24]=[C:23]([N+:25]([O-:27])=[O:26])[CH:22]=[CH:21][C:19]=1[NH:20][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[C:9]([C:11]3[N:12]=[CH:13][N:14]([CH3:16])[CH:15]=3)[S:10][C:3]=12

Participants

7

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 1012542-Fluoro-4-nitroanilineHCID 27342162-(Dicyclohexylphosphino)biphenylHCID 594245247-Chloro-2-(1-methyl-1H-imidazol-4-yl)thieno[3,2-b]pyridine

Product 1

HCID 59457676HCID 59457676, compoundYield 50.1%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

A suspension of 175 (500 mg, 2.00 mmol, scheme 35), 416 (406 mg, 2.60 mmol), Pd2(dba)3 (73 mg, 0.08 mmol), (2-biphenyl)dicyclohexylphosphine (56 mg, 0.16 mmol), and K3PO4 (638 mg, 3.00 mmol) in toluene (20 ml) was degassed for 15 min with nitrogen, and then heated at 110° C. for 22 hrs in a sealed flask [ J. P. Wolfe, H. Tomori J. P. Sadighi J. Yin, S. L. Buchwald J. Org. Chem. 2000, 65, 1158-1174]. After cooling to room temperature the reaction mixture was filtered, the filtrate was concentrated and the residue was adsorbed on silica gel and subjected to flash column chromatography (eluents MeOH/CH2Cl2: 2/98 to 10/90). Fractions containing the product were combined, concentrated and treated with AcOEt/hexanes to afford title compound 417 (370 mg, 50% yield) as a yellow-orange solid. 1H NMR (400 MHz, DMSO-d6) δ (ppm): 9.57 (bs, 1H), 8.45 (d, J=5.1 Hz, 1H), 8.22 (dd, J=11.3, 2.5 Hz, 1H), 8.06 (dd, J=8.9, 2.3 Hz, 1H), 7.83 (d, J=1.2 Hz, 1H), 7.70 (d, J=1.2 Hz, 1H), 7.63 (s, 1H), 7.24 (t, J=8.7 Hz, 1H), 6.94 (bd, J=4.7 Hz, 1H), 3.71 (s, 3H). LCMS: 370.0 (M+H)+.

Workup

  1. customwas degassed for 15 min with nitrogen
  2. temperatureAfter cooling to room temperature the reaction mixture
  3. filtrationwas filtered
  4. concentrationthe filtrate was concentrated
  5. additionFractions containing the product
  6. concentrationconcentrated
  7. additiontreated with AcOEt/hexanes

Sources & evidence

ORD record
ord-9a027e6b434641f1b47e66f73643c2e1
Source dataset
uspto-grants-2010_09
Patent number
US07790729B2

Reaction notes

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