Trimethylsilylacetylene → HCID 68997715, compound

HRID 578785Notes

Reaction equation

HRID 578785 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[C:4]([NH:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH:3]=1.[CH3:17][Si:18]([C:21]#[CH:22])([CH3:20])[CH3:19]>C(NC(C)C)(C)C.C(OCC)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[C:13]([O:12][C:10]([NH:9][C:4]1[CH:3]=[C:2]([C:22]#[C:21][Si:18]([CH3:20])([CH3:19])[CH3:17])[CH:7]=[CH:6][C:5]=1[F:8])=[O:11])([CH3:16])([CH3:15])[CH3:14]

Participants

7

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 58022041HCID 58022041, compound

Product 1

HCID 68997715HCID 68997715, compound

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 3283Diethyl EtherSolventHCID 7912DiisopropylamineSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-bromo-2-(tert-butoxycarbonylamino)-1-fluorobenzene (0.57 g), trimethylsilylacetylene (0.55 mL), tetrakis(triphenylphosphine)palladium(0) (23 mg)and copper (I) iodide (7 mg) in N,N-diisopropylamine (5.7 mL) was stirred at 80° C. overnight. The reaction mixture was cooled to room temperature, and the mixture was diluted with diethyl ether. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=15/1) to give 1-(tert-butoxy -carbonylamino)-2-fluoro-5-trimethylsilylethynylbenzene (0.6 g). This material was dissolved in tetrahydrofuran (10 mL). To the solution was added tetra(n-butyl)ammonium fluoride (1 mol/L tetrahydrofuran solution, 2.4 mL), and the mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=20/1 -10/1) to give the title compound (0.34 g).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customThe insoluble material was removed by filtration
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. customThe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=15/1)

Sources & evidence

ORD record
ord-f2ce6d732788410887b078703e9e2046
Source dataset
uspto-grants-2015_05
Patent number
US09040693B2

Reaction notes

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