Diisopropylamine → 2-Ethynyl-1-fluoro-4-nitrobenzene

HRID 1593067Notes

Reaction equation

HRID 1593067 reaction equation
[Si]([C:5]#[CH:6])(C)(C)C.Br[C:8]1[CH:9]=[C:10]([N+:15]([O-:17])=[O:16])[CH:11]=[CH:12][C:13]=1[F:14].C(NC(C)C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-].C1COCC1>C1COCC1.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.[Cu]I>[C:5]([C:8]1[CH:9]=[C:10]([N+:15]([O-:17])=[O:16])[CH:11]=[CH:12][C:13]=1[F:14])#[CH:6]

Participants

8

Reactant 4

HCID 7912DiisopropylamineHCID 66111TrimethylsilylacetyleneHCID 696992-Bromo-1-fluoro-4-nitrobenzeneHCID 11078149TBAF tetrahydrofuran

Product 1

HCID 126873612-Ethynyl-1-fluoro-4-nitrobenzene

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of bis(benzonitril)dichloropalladium(II) (53 mg, 0.14 mmol) and copper (I) iodide (26 mg, 0.14 mmol) in 6 mL dry THF was purged with argon for 3 minutes, then was added tri(tert-butyl phosphine) (69 ul, 0.28 mmol), TMS acetylene (0.77 ml, 5.5 mmol), 3-bromo-4-fluoronitrobenzene 505 mg, 2.295 mmol), and di-isopropylamine (0.77 ml, 5.5 mmol). The mixture was stirred at room temperature for 5 hours under argon. To the reaction mixture was added 7 mL 1 M TBAF/THF and the mixture was stirred at room temperature for 10 minutes. Workup and purification by column chromatography (silica, 5%-35% EtOAc/hexane) give 2-ethynyl-1-fluoro-4-nitro-benzene.

Workup

  1. customwas purged with argon for 3 minutes
  2. stirringthe mixture was stirred at room temperature for 10 minutes
  3. customWorkup and purification by column chromatography (silica, 5%-35% EtOAc/hexane)

Sources & evidence

ORD record
ord-dcda741809ff4ee49973b6b0b2411136
Source dataset
uspto-grants-2007_11
Patent number
US07294635B2

Reaction notes

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