Hydrochloric Acid → 4-Propyl-3',5'-difluoro-4'-cyanotolan

HRID 1034109Notes

Reaction equation

HRID 1034109 reaction equation
[F:1][C:2]1[CH:7]=[C:6](I)[CH:5]=[C:4]([F:9])[C:3]=1[C:10]#[N:11].[CH2:12]([C:15]1[CH:20]=[CH:19][C:18]([C:21]#[CH:22])=[CH:17][CH:16]=1)[CH2:13][CH3:14].Cl>CN(C)C=O.[Pd](Cl)Cl.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>[CH2:12]([C:15]1[CH:16]=[CH:17][C:18]([C:21]#[C:22][C:6]2[CH:7]=[C:2]([F:1])[C:3]([C:10]#[N:11])=[C:4]([F:9])[CH:5]=2)=[CH:19][CH:20]=1)[CH2:13][CH3:14]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 27751331-Ethynyl-4-propylbenzeneHCID 190230682,6-Difluoro-4-iodobenzonitrile

Product 1

HCID 678200934-Propyl-3',5'-difluoro-4'-cyanotolanYield 27.3%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

5.6 g of this 1,3-difluoro-2-cyano-5-iodobenzene was dissolved in 35 ml of N,N-dimethylformamide, to which was added 7.3 mg of bis(triphenylphosphine) palladium (II) chloride and 34 m of cuprous iodide. Next, 3 g of the 4-propylphenylacetylene obtained in Step 2 was added and allowed to react at 50° to 60° C. for 0.5 hour. After completion of the reaction, 35 ml of 9% hydrochloric acid was added to the reaction solution. After being extracted with chloroform, the crystals were washed with water three times to distill off the chloroform. The residue was purified by silica gel-chloroform column chromatography, followed by recrystallization with a mixed solvent of acetone and methanol to obtain 1.6 g of 4-propyl-3',5'-difluoro-4'-cyanotolan. The melting (C-I) point of this compound was 83.3° C.

Workup

  1. customto react at 50° to 60° C. for 0.5 hour
  2. additionwas added to the reaction solution
  3. extractionAfter being extracted with chloroform
  4. washthe crystals were washed with water three times
  5. distillationto distill off the chloroform
  6. customThe residue was purified by silica gel-chloroform column chromatography
  7. customfollowed by recrystallization with a mixed solvent of acetone and methanol

Sources & evidence

ORD record
ord-96dca59ae695483485b56915baabee13
Source dataset
uspto-grants-1994_05
Patent number
US05314640

Reaction notes

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