Dimethylformamide → 3-Formyl-5-(trifluoromethyl)benzonitrile

HRID 2071092Notes

Reaction equation

HRID 2071092 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:9]=1)[CH:5]=[O:6].[CH3:14][N:15](C=O)C>CCOCC.[C-]#N.[Zn+2].[C-]#N.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>[CH:5]([C:4]1[CH:3]=[C:2]([CH:9]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:7]=1)[C:14]#[N:15])=[O:6]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 161154383-Bromo-5-(trifluoromethyl)benzaldehyde

Product 1

HCID 116225163-Formyl-5-(trifluoromethyl)benzonitrile

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
90 °C

Procedure

To 3-bromo-5-(trifluoromethyl)benzaldehyde (1.0 gm, 3.95 mmol) in DMF (10 ml), zinc cyanide (278 mg, 2.37 mmol) was added followed by Pd(PPh3)4 (365 mg, 0.32 mmol) was added and heated at 90° C. for 5 h. Then the reaction mixture was cooled, diluted with ether and quenched with aqueous ammonium hydroxide solution. Then the reaction mixture was partitioned between water and ether. Organic layer was dried, evaporated and column purified (10% ethylacetate/90% hexanes) to yield 400 mg of 3-formyl-5-(trifluoromethyl)benzonitrile.

Workup

  1. additionwas added
  2. temperatureThen the reaction mixture was cooled
  3. customquenched with aqueous ammonium hydroxide solution
  4. customThen the reaction mixture was partitioned between water and ether
  5. customOrganic layer was dried
  6. customevaporated
  7. customcolumn purified (10% ethylacetate/90% hexanes)

Sources & evidence

ORD record
ord-2df94e69a9714e079c8890eda1738e15
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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