N,N'-Dimethylethylenediamine → HCID 57779774, compound

HRID 1364202Notes

Reaction equation

HRID 1364202 reaction equation
C(=O)([O-])[O-].[K+].[K+].[F:7][C:8]1[C:18]2[CH2:17][CH:16]=[CH:15][C:14](=[O:19])[NH:13][C:12]=2[C:11]([F:20])=[CH:10][C:9]=1[F:21].Br[C:23]1C(F)=C(F)C=C(F)[C:24]=1N.CNCCNC.C(Br)=C>[Cu]I.C1(C)C=CC=CC=1>[F:7][C:8]1[C:18]2[CH2:17][CH2:16][CH2:15][C:14](=[O:19])[N:13]([CH:23]=[CH2:24])[C:12]=2[C:11]([F:20])=[CH:10][C:9]=1[F:21]

Participants

8

Reactant 5

HCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium CarbonateHCID 11641BromoetheneHCID 6148982-Bromo-3,4,6-trifluorobenzenamineHCID 66971943HCID 66971943, compound

Product 1

HCID 57779774HCID 57779774, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1140TolueneSolvent

Procedure

A heavy-walled sealable 100 mL tube containing copper (I) iodide (0.088 g, 0.46 mmol), potassium carbonate (1.57 g, 11.4 mmol) and 6,7,9-trifluoro-1,5-dihydro-benzo[b]azepin-2-one (1.02 g, 4.74 mmol, prepared from commercially available 2-bromo-3,4,6-trifluoroaniline via application of Steps 1-3 of the procedure used for the synthesis of Examples 73 and 74) was fitted with a stirbar and septa and flushed with nitrogen. Toluene (5.0 mL), N,N′-dimethylethylene diamine (0.10 mL, 0.93 mmol) and vinyl bromide (10.0 mL, 1.0 M solution in tetrahydrofuran (THF), 10.0 mmol) were then added, in that order. The septa was removed, the reaction vessel was sealed tightly with a teflon screwcap and then placed in a pre-heated 110° C. oil bath. After 24 hours, the reaction was cooled to room temperature, poured into 1:1 H2O:saturated aqueous NaCl solution (50 mL) and extracted with methylene chloride (3×30 mL). The organic extracts were combined, dried over MgSO4, filtered and concentrated in vacuo to give an oil that was purified via flash chromatography on silica gel (0% to 30% ethyl acetate/hexanes linear gradient) to give the desired product.

Workup

  1. customused for the synthesis of Examples 73 and 74)
  2. customwas fitted with a stirbar and septa
  3. customflushed with nitrogen
  4. customThe septa was removed
  5. customthe reaction vessel was sealed tightly with a teflon screwcap
  6. customplaced in a pre-heated 110° C.
  7. additionpoured into 1:1 H2O
  8. extractionsaturated aqueous NaCl solution (50 mL) and extracted with methylene chloride (3×30 mL)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customto give an oil that
  13. customwas purified via flash chromatography on silica gel (0% to 30% ethyl acetate/hexanes linear gradient)

Sources & evidence

ORD record
ord-c4407af5df57496698cc05a5205af2da
Source dataset
uspto-grants-2011_02
Patent number
US07888345B2

Reaction notes

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