Dimethylformamide → HCID 68672414, compound

HRID 2071167Notes

Reaction equation

HRID 2071167 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH:11]=[C:10]([N:12]([CH3:14])[CH3:13])[N:9]=[C:8](Cl)[CH:7]=1)(=[O:3])[CH3:2].C(OCC)(=O)C.[NH4+].[OH-].[CH3:24][N:25](C=O)C>[C-]#N.[C-]#N.[Zn+2].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>[C:1]([O:4][CH2:5][C:6]1[CH:11]=[C:10]([N:12]([CH3:14])[CH3:13])[N:9]=[C:8]([C:24]#[N:25])[CH:7]=1)(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 8857Ethyl AcetateHCID 14923Ammonium HydroxideHCID 86647438HCID 86647438, compound

Product 1

HCID 68672414HCID 68672414, compound

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst2×

Conditions

Temperature
80 °C

Procedure

To a solution of 1.17 g (5.10 mmol) of (2-chloro-6-(dimethylamino)pyridin-4-yl)methyl acetate in 10 mL of DMF (degassed) was added 488 mg (4.16 mmol) of Zn(CN)2 and 519 mg (0.449 mmol) of Pd(PPh3)4. The mixture was stirred at 80° C. and more Pd(PPh3)4 was added in the following quantities at various intervals in a period of 10 h: 486 mg (50 min.), 708 mg (3 h), 657 mg (6 h). The temperature was increased to 100° C. and stirring was continued for about 11 h. Ethyl acetate and 50 mL of 10% NH4OH solution were added. The aqueous layer was extracted with EtOAc, and the combined extracts were washed with brine. The aqueous layer (brine) was extracted with EtOAc, and the combined extracts were dried over Na2SO4, filtered, and concentrated. Purification by flash silica gel chromatography (30% EtOAc/hexanes) provided 284 mg of (2-cyano-6-(dimethylamino)pyridin-4-yl)methyl acetate as a pale yellow solid.

Workup

  1. custom486 mg (50 min.), 708 mg (3 h), 657 mg (6 h)
  2. temperatureThe temperature was increased to 100° C.
  3. stirringstirring
  4. extractionThe aqueous layer was extracted with EtOAc
  5. washthe combined extracts were washed with brine
  6. extractionThe aqueous layer (brine) was extracted with EtOAc
  7. dry with materialthe combined extracts were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification by flash silica gel chromatography (30% EtOAc/hexanes)

Sources & evidence

ORD record
ord-d3bf7b53973c461a9af89a4c7fcf06f6
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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