N,N'-Dimethylethylenediamine → HCID 57411802, compound

HRID 2046201Notes

Reaction equation

HRID 2046201 reaction equation
[O:1]([CH2:8][C:9]1[CH:18]=[C:12]2[C:13](=[O:17])[NH:14][CH2:15][CH2:16][N:11]2[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[C:20]1[CH:25]=[CH:24][C:23]([F:26])=[CH:22][C:21]=1[F:27].CNCCNC.C([O-])([O-])=O.[K+].[K+]>C1(C)C=CC=CC=1.[Cu]I>[F:26][C:23]1[CH:22]=[C:21]([F:27])[CH:20]=[CH:25][C:24]=1[N:14]1[CH2:15][CH2:16][N:11]2[N:10]=[C:9]([CH2:8][O:1][C:2]3[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=3)[CH:18]=[C:12]2[C:13]1=[O:17]

Participants

7

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium CarbonateHCID 676741-Bromo-2,4-difluorobenzeneHCID 57411799HCID 57411799, compound

Product 1

HCID 57411802HCID 57411802, compoundYield 443.5%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
120 °C

Procedure

Copper (I) iodide (6.6 mg, 0.033 mmol) was added to a suspension of 2-phenoxymethyl-6,7-dihydro-5H-pyrazolo[1,5-a]pyrazin-4-one (40 mg, 0.16 mmol), 1-bromo-2,4-difluorobenzene (63 mg, 0.033 mmol), N,N′-dimethylethylenediamine (0.01 mL, 0.09 mmol) and K2CO3 (45 mg, 0.033 mmol) in toluene (2 mL). The reaction mixture was stirred at 120° C. for 16 hours. The mixture was filtered through a pad of diatomaceous earth which was washed with AcOEt. The filtrate was evaporated in vacuo. The crude product was purified by flash column chromatography (silica; AcOEt in DCM 0/100 to 20/80). The desired fractions were collected and the solvents evaporated in vacuo to yield 5-(2,4-difluoro-phenyl)-2-phenoxymethyl-6,7-dihydro-5H-pyrazolo[1,5-a]pyrazin-4-one (52 mg, 92% yield) as a white solid. 1H NMR (500 MHz, CDCl3) δ ppm 4.02-4.15 (m, 2H), 4.50-4.62 (m, 2H), 5.13 (s, 2H), 6.91-6.99 (m, 3H), 7.01 (d, J=8.4 Hz, 2H), 7.04 (s, 1H), 7.27-7.32 (m, 2H), 7.35 (td, J=8.7, 6.1 Hz, 1H).

Workup

  1. filtrationThe mixture was filtered through a pad of diatomaceous earth which
  2. washwas washed with AcOEt
  3. customThe filtrate was evaporated in vacuo
  4. customThe crude product was purified by flash column chromatography (silica; AcOEt in DCM 0/100 to 20/80)
  5. customThe desired fractions were collected
  6. customthe solvents evaporated in vacuo

Sources & evidence

ORD record
ord-77d9009db3c44e88be29a97a51779563
Source dataset
uspto-grants-2013_11
Patent number
US08592422B2

Reaction notes

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