Dimethylacetamide → HCID 58847064, compound

HRID 1966308Notes

Reaction equation

HRID 1966308 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([N:10]2[CH2:15][CH:14]([CH3:16])[O:13][CH:12]([CH3:17])[CH2:11]2)=[C:6]([CH:9]=1)[CH:7]=[O:8].C[C:19]([N:21](C)C)=O>CP(C)[C-]1C=CC=C1.[C-]1(P(C)C)C=CC=C1.[Fe+2].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].[Zn].[C-]#N.[Zn+2].[C-]#N>[CH3:17][C@H:12]1[O:13][C@@H:14]([CH3:16])[CH2:15][N:10]([C:5]2[CH:4]=[CH:3][C:2]([C:19]#[N:21])=[CH:9][C:6]=2[CH:7]=[O:8])[CH2:11]1

Participants

7

Reactant 2

HCID 31374DimethylacetamideHCID 18455603HCID 18455603, compound

Product 1

HCID 58847064HCID 58847064, compound

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 23994ZincCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 145821890HCID 145821890, compoundCatalyst

Conditions

Temperature
120 °C

Procedure

A mixture of 5-bromo-2-(2,6-dimethylmorpholin-4-yl)benzaldehyde (0.298 g, 1.00 mmol), 1,1′-bis(dimethylphosphino)ferrocene [dppf] (0.022 g, 0.040 mmol), tris(dibenzylideneacetone)dipalladium [Pd2(dba)3] (0.018 g, 0.020 mmol), zinc dust (0.008 g, 0.12 mmol) and zinc cyanide (0.070 g, 0.60 mmol) in dimethylacetamide (2 mL) is heated 120° C. for 4 h. The reaction mixture is cooled and partitioned between dilute ammonium hydroxide and ethyl acetate. The phases are separated. The organic layer is extracted with an additional portion of ethyl acetate. The combined organic layers are dried (NaSO4) and then concentrated. The resulting residue is purified by silica gel chromatography using ethyl acetate-methylene chloride-heptane (0.5:4.0:5.5) as the eluent to afford, 172 mg (70%) of the cyano aldehyde. 1H NMR (400 MHz, CDCl3) δ 10.05, 7.97, 7.64, 7.01, 3.92-3.79, 3.14, 2.70, 1.17.

Workup

  1. temperatureThe reaction mixture is cooled
  2. custompartitioned between dilute ammonium hydroxide and ethyl acetate
  3. customThe phases are separated
  4. extractionThe organic layer is extracted with an additional portion of ethyl acetate
  5. dry with materialThe combined organic layers are dried (NaSO4)
  6. concentrationconcentrated
  7. customThe resulting residue is purified by silica gel chromatography
  8. customto afford

Sources & evidence

ORD record
ord-5a740c57ccc24c959159d7d0d084405f
Source dataset
uspto-grants-2013_04
Patent number
US08420646B2

Reaction notes

Loading…