Dichloromethane → HCID 136387211, compound

HRID 1038146Notes

Reaction equation

HRID 1038146 reaction equation
Br[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[C:8]([N+:11]([O-:13])=[O:12])[CH:9]=2)[N:4]([C:14]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[N:3]=1.CC1(C)C(C)(C)OB([C:41]2[CH:42]=[N:43][NH:44][CH:45]=2)O1.ClCCl.P([O-])([O-])([O-])=O.[K+].[K+].[K+].O1CCOCC1.S([O-])([O-])(=O)=O.[Mg+2]>[Cr].CCOC(C)=O.CCCCCC>[N+:11]([C:8]1[CH:9]=[C:10]2[C:5](=[CH:6][CH:7]=1)[N:4]([C:14]([C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[N:3]=[C:2]2[C:41]1[CH:42]=[N:43][NH:44][CH:45]=1)([O-:13])=[O:12]

Participants

9

Reactant 6

HCID 6344DichloromethaneHCID 24083Sulfuric acid magnesium salt (1:1)HCID 312751,4-DioxaneHCID 62657Potassium Phosphate, TribasicHCID 27740104-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 589464433-bromo-5-nitro-1-trityl-1H-indazole

Product 1

HCID 136387211HCID 136387211, compoundYield 38.2%

Reagents, catalysts & solvents 2

HCID 23976ChromiumCatalystHCID 21226206Ethyl acetate hexaneSolvent

Conditions

Temperature
80 °C

Procedure

To a vial containing 3-bromo-5-nitro-1-trityl-1H-indazole (1.45 g, 3.00 mmol), 4-(4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLAN-2-YL)-1H-PYRAZOLE (0.873 g, 4.50 mmol) [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (1:1) (0.245 g, 0.300 mmol) and Potassium phosphate (1.59 g, 7.50 mmol) in a mixture of 1,4-Dioxane (25 mL, 320 mmol) Water (12 mL, 670 mmol) was degassed under an atmosphere of Nitrogen. This r×n mixture was heated at 80° C. overnight under an atmosphere of Nitrogen. TLC (20% EtOAc/hexane) showed starting material. MS showed (M+H) at 472. The r×n was diluted with EtOAc and Water (50/50 mL) and filtered through Celite. The org. layer was washed with water, dried over Magnesium sulfate (2 g, 20 mmol) and rotavap to give a crude, 2.2 g. The crude was chrom. (30% EtOAc/Hexane) on Biotage (40 L) to obtain the product (fraction 2), M+H at 472, 5-nitro-3-(1H-pyrazol-4-yl)-1-trityl-1H-indazole (0.54 g; Yield=38%)

Workup

  1. customwas degassed under an atmosphere of Nitrogen
  2. additionThe r×n was diluted with EtOAc and Water (50/50 mL)
  3. filtrationfiltered through Celite
  4. washlayer was washed with water
  5. customto give a crude, 2.2 g

Sources & evidence

ORD record
ord-c885dded874f4011b3a25729967f650a
Source dataset
uspto-grants-2013_10
Patent number
US08546404B2

Reaction notes

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