Dimethylacetamide → HCID 86694459, compound

HRID 1519543Notes

Reaction equation

HRID 1519543 reaction equation
[CH3:1][O:2][C:3](=[O:17])[CH2:4][C:5]1[CH:10]=[CH:9][C:8](Cl)=[C:7]([O:12][C:13]([F:16])([F:15])[F:14])[CH:6]=1.[CH3:18][N:19](C)C(=O)C>[Zn].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[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].[C-]#N.[C-]#N.[Zn+2]>[CH3:1][O:2][C:3](=[O:17])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([C:18]#[N:19])=[C:7]([O:12][C:13]([F:16])([F:15])[F:14])[CH:6]=1

Participants

7

Reactant 2

HCID 31374DimethylacetamideHCID 86694460HCID 86694460, compound

Product 1

HCID 86694459HCID 86694459, compound

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 23994ZincCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
120 °C

Procedure

A suspension of methyl(4-chloro-3-trifluoromethoxyphenyl)acetate (4.8 g, 17.8 mmol) in N,N-dimethylacetamide (50 mL) in a 250 mL round bottomed flask was degassed by bubbling nitrogen for 15 minutes. To this suspension was then added zinc dust (0.23 g, 3.55 mmol), DPPF (0.79 g, 1.42 mmol), Pd2(dba)3 (0.65 g, 0.71 mmol), and Zn(CN)2 (2.50 g, 21.3 mmol) at room temperature. The nitrogen purge was continued for another 15 minutes before the mixture was heated in a 120° C. oil bath for 12 hours. LC-MS indicated that the starting material was consumed to give the product. LC-MS (IE, m/z): 260 [M+1]+. The mixture was partitioned twice between water and ethyl acetate. The organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified on a silica gel column (5-20% ethyl acetate/hexanes) to yield the title product as a yellowish solid. 1H-NMR (500 MHz, CDCl3) δ ppm 3.77 (s, 2H), 3.78 (s, 3H), 7.39 (d, J=7.5 Hz, 1H), 7.40 (s, 1H), 7.72 (d, J=7.5 Hz, 1H).

Workup

  1. customwas degassed
  2. customby bubbling nitrogen for 15 minutes
  3. customat room temperature
  4. customThe nitrogen purge
  5. customwas consumed
  6. customto give the product
  7. customThe mixture was partitioned twice between water and ethyl acetate
  8. dry with materialThe organic layers were dried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified on a silica gel column (5-20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-f985ae419bf24f30bf87d437b5da9dfa
Source dataset
uspto-grants-2015_07
Patent number
US09073882B2

Reaction notes

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