2,4-Dichloroaniline → 4-(2,4-Dichloroanilino)-8-nitro[1]benzothieno[3,2-b]pyridine-3-carbonitrile

HRID 989333Notes

Reaction equation

HRID 989333 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:10]=[C:9]([Cl:11])[CH:8]=[CH:7][C:5]=1[NH2:6].Cl[C:13]1[C:18]([C:19]#[N:20])=[CH:17][N:16]=[C:15]2[C:21]3[CH:27]=[C:26]([N+:28]([O-:30])=[O:29])[CH:25]=[CH:24][C:22]=3[S:23][C:14]=12>CN(C)C=O>[Cl:3][C:4]1[CH:10]=[C:9]([Cl:11])[CH:8]=[CH:7][C:5]=1[NH:6][C:13]1[C:18]([C:19]#[N:20])=[CH:17][N:16]=[C:15]2[C:21]3[CH:27]=[C:26]([N+:28]([O-:30])=[O:29])[CH:25]=[CH:24][C:22]=3[S:23][C:14]=12

Participants

5

Reactant 3

HCID 111232,4-DichloroanilineHCID 24758Sodium hydrideHCID 109571994-Chloro-8-nitrobenzo[4,5]thieno[3,2-b]pyridine-3-carbonitrile

Product 1

HCID 102235624-(2,4-Dichloroanilino)-8-nitro[1]benzothieno[3,2-b]pyridine-3-carbonitrileYield 29%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 160 mg (4.00 mmol) of sodium hydride (60% dispersion in oil) and 648 mg (4.00 mmol) of 2,4-dichloroaniline in 10 mL of dimethylformamide is stirred at room temperature for 1 hour. 4-Chloro-8-nitrobenzo[4,5]thieno[3,2-b]pyridine-3-carbonitrile, 578 mg (2.00 mmol), is added and the suspension is heated at 130° C. overnight. The reaction mixture is cooled to room temperature and partitioned between ethyl acetate and water. The organic layer is washed with water then dried over magnesium sulfate, filtered and concentrated in vacuo. Diethyl ether is added to the residue and the resultant solid is collected by filtration. The solid is suspended in diethyl ether and filtered. The filtrate is concentrated to a small volume and filtered to give 80 mg (29%) of 4-(2,4-dichloroanilino)-8-nitro[1]benzothieno[3,2-b]pyridine-3-carbonitrile as an off-white solid, mp 210-213° C.

Workup

  1. temperaturethe suspension is heated at 130° C. overnight
  2. temperatureThe reaction mixture is cooled to room temperature
  3. custompartitioned between ethyl acetate and water
  4. washThe organic layer is washed with water
  5. dry with materialthen dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. additionDiethyl ether is added to the residue
  9. filtrationthe resultant solid is collected by filtration
  10. filtrationfiltered
  11. concentrationThe filtrate is concentrated to a small volume
  12. filtrationfiltered

Sources & evidence

ORD record
ord-d035525954a247caaeffeaaccca7050e
Source dataset
uspto-grants-2003_10
Patent number
US06638929B2

Reaction notes

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