Triethylamine → 5-Nitro-3-trimethylsilanylethynyl-1-trityl-1H-indazole

HRID 1038148Notes

Reaction equation

HRID 1038148 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.[C:33]([Si:35]([CH3:38])([CH3:37])[CH3:36])#[CH:34].C(N(CC)CC)C.C(OCC)(=O)C>CN(C=O)C.[Cu]I.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].O>[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:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[N:3]=[C:2]2[C:34]#[C:33][Si:35]([CH3:38])([CH3:37])[CH3:36])([O-:13])=[O:12]

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 66111TrimethylsilylacetyleneHCID 589464433-bromo-5-nitro-1-trityl-1H-indazole

Product 1

HCID 576858635-Nitro-3-trimethylsilanylethynyl-1-trityl-1H-indazoleYield 67.8%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 3-bromo-5-nitro-1-trityl-1H-indazole (4.83 g, 10 mmol), ethynyl-trimethyl-silane (1 g, 10 mmol), copper (I) iodide (91 mg, 0.5 mmol), PdCl2(dppf) (337 mg, 0.5 mmol) and triethylamine (1.2 g, 12 mmol) in DMF (50 mL) was stirred overnight at 80° C. under argon. Then ethyl acetate (100 mL) was added, followed by water. The organic layer was collected and aqueous layer was extracted three times with ethyl acetate. The combined organic fraction was washed with water and then brine. The solvent was removed under vacuum and the product was purified using chromatography (20% hexane in dichloromethane) to give desired product (3.4 g) in 67% yield.

Workup

  1. customThe organic layer was collected
  2. extractionaqueous layer was extracted three times with ethyl acetate
  3. washThe combined organic fraction was washed with water
  4. customThe solvent was removed under vacuum
  5. customthe product was purified

Sources & evidence

ORD record
ord-4e5b70f7ff1e4816a8379f21f48a784c
Source dataset
uspto-grants-2013_10
Patent number
US08546404B2

Reaction notes

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