Dimethylformamide → 5-Cyano-2-(3,4-Dichlorophenoxy)-Benzaldehyde

HRID 1839426Notes

Reaction equation

HRID 1839426 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([O:10][C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[C:13]([Cl:18])[CH:12]=2)=[C:6]([CH:9]=1)[CH:7]=[O:8].[CH3:19][N:20](C=O)C>[C-]#N.[Zn+2].[C-]#N.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:19]([C:2]1[CH:3]=[CH:4][C:5]([O:10][C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[C:13]([Cl:18])[CH:12]=2)=[C:6]([CH:9]=1)[CH:7]=[O:8])#[N:20]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 120170305-Bromo-2-(3,4-dichlorophenoxy)benzaldehyde

Product 1

HCID 120170505-Cyano-2-(3,4-Dichlorophenoxy)-Benzaldehyde

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst

Procedure

Under N2 in a flame-dried 3-neck round bottomed flask fitted with a reflux condenser and magnetic stirrer, a mixture of 5-bromo-2-(3,4-dichlorophenoxy)-benzaldehyde (3.0 g, 8.7 mmol), zinc (II) cyanide (1.5 g, 13 mmol) and tetrakis(triphenylphosphine) palladium (0) (1.5 g, 1.3 mmol) in anhydrous DMF (145 ml) was stirred at room temperature while degassing with N2 for 5 min. After heating at approximately 80° C. for 90 min., the reaction was judged complete by thin layer chromatography (50% CH2Cl2:hexanes) and was allowed to cool to room temperature. The reaction mixture was then diluted with water and ethyl acetate (EA) and stirred another 10 min. The water layer was separated, extracted twice with EA and combined with the original EA layer, and washed with an aqueous solution of Rochelle salt (potassium sodium tartrate tetrahydrate) followed by aqueous NaCl. The organic layer was dried with Na2SO4, filtered and concentrated in vacuo to an oil. The oil was flash chromatographed on a 15×5 cm column of silica gel, eluting with CH2Cl2:hexanes (1:1) to obtain the title product as a white solid, 1.5 g (60%), m.p. 122-126° C.

Workup

  1. customUnder N2 in a flame-dried 3-neck round bottomed flask fitted with a reflux condenser and magnetic stirrer
  2. customwhile degassing with N2 for 5 min
  3. temperatureAfter heating at approximately 80° C. for 90 min.
  4. temperatureto cool to room temperature
  5. additionThe reaction mixture was then diluted with water and ethyl acetate (EA)
  6. stirringstirred another 10 min
  7. customThe water layer was separated
  8. extractionextracted twice with EA
  9. washwashed with an aqueous solution of Rochelle salt (potassium sodium tartrate tetrahydrate)
  10. dry with materialThe organic layer was dried with Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo to an oil
  13. customchromatographed on a 15×5 cm column of silica gel
  14. washeluting with CH2Cl2:hexanes (1:1)

Sources & evidence

ORD record
ord-db887357ac454ab0b5c908349aabf2e0
Source dataset
uspto-grants-2004_01
Patent number
US06677378B2

Reaction notes

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