Triethylamine → HCID 59787426, compound

HRID 1965976Notes

Reaction equation

HRID 1965976 reaction equation
[F:1][C:2]([F:25])([F:24])[C:3]([N:5]1[CH2:11][CH2:10][C:9]2[C:12](OS(C(F)(F)F)(=O)=O)=[CH:13][CH:14]=[CH:15][C:8]=2[CH2:7][CH2:6]1)=[O:4].C(N(CC)CC)C.[C:33]1([C:39]#[CH:40])[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C=O)C.CCOC(C)=O.CCCCCC.[Cu](I)I>[C:33]1([C:39]#[C:40][C:12]2[C:9]3[CH2:10][CH2:11][N:5]([C:3](=[O:4])[C:2]([F:25])([F:24])[F:1])[CH2:6][CH2:7][C:8]=3[CH:15]=[CH:14][CH:13]=2)[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 10821PhenylacetyleneHCID 22219607HCID 22219607, compound

Product 1

HCID 59787426HCID 59787426, compoundYield 98%

Reagents, catalysts & solvents 4

HCID 67553Tetrabutylammonium IodideCatalystHCID 83717Copper iodideCatalystHCID 6228DimethylformamideSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

Combine 3-(2,2,2-trifluoroacetyl)-6-trifluoromethanesulfonyloxy-2,3,4,5-tetrahydro-1H-benzo[d]azepine (300 mg, 0.75 mmol), dichlorobis(triphenylphosphine)-palladium(II) dichloromethane adduct (54 mg, 0.08 mmol), copper iodide (42 mg, 0.23 mmol) and tetrabutyl ammonium iodide (830 mg, 2.25 mmol) in DMF (3.3 mL) containing triethylamine (0.67 mL) and stir the mixture for 5 min at room temperature. Add phenylacetylene (0.17 mL, 1.5 mmol) and heat the mixture to 70° C. under nitrogen atmosphere for 16 h. Cool the reaction to room temperature and dilute with EtOAc/hexane (1:1, 250 mL). Filter the slurry through Celite®. Wash the filtrate with water (2×300 mL), dry the organic phase over Na2SO4, filter and concentrate in vacuo. Purify by chromatography on silica gel eluting with hexane/EtOAc (19:1 to 9:1) to afford 6-phenylethynyl-3-(2,2,2-trifluoroacetyl)-2,3,4,5-tetrahydro-1H-benzo[d]azepine (251 mg, 98%) as a yellow oil.

Workup

  1. temperatureCool
  2. customthe reaction to room temperature
  3. filtrationFilter the slurry through Celite®
  4. washWash the filtrate with water (2×300 mL)
  5. dry with materialdry the organic phase over Na2SO4
  6. filtrationfilter
  7. concentrationconcentrate in vacuo
  8. customPurify by chromatography on silica gel eluting with hexane/EtOAc (19:1 to 9:1)

Sources & evidence

ORD record
ord-f63968fd861c4a99918e76412ff23855
Source dataset
uspto-grants-2013_04
Patent number
US08420631B2

Reaction notes

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