Ammonium Chloride → 8-Amino-4-(3-bromoanilino)-[1]benzothieno[3,2-b]pyridine-3-carbonitrile

HRID 2213780Notes

Reaction equation

HRID 2213780 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:24]=[CH:25][CH:26]=1)[NH:5][C:6]1[C:11]([C:12]#[N:13])=[CH:10][N:9]=[C:8]2[C:14]3[CH:20]=[C:19]([N+:21]([O-])=O)[CH:18]=[CH:17][C:15]=3[S:16][C:7]=12.[Cl-].[NH4+]>CO.O.[Fe]>[NH2:21][C:19]1[CH:18]=[CH:17][C:15]2[S:16][C:7]3[C:8](=[N:9][CH:10]=[C:11]([C:12]#[N:13])[C:6]=3[NH:5][C:4]3[CH:24]=[CH:25][CH:26]=[C:2]([Br:1])[CH:3]=3)[C:14]=2[CH:20]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 102242324-(3-Bromoanilino)-8-nitro[1]benzothieno[3,2-b]pyridine-3-carbonitrile

Product 1

HCID 102719978-Amino-4-(3-bromoanilino)-[1]benzothieno[3,2-b]pyridine-3-carbonitrileYield 21.4%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

A mixture of 436 mg (1.03 mmol) of 4-(3-bromoanilino)-8-nitro[1]benzothieno[3,2-b]pyridine-3-carbonitrile, 291 mg (5.19 mmol) of iron powder and 416 mg (7.77 mmol) of ammonium chloride in 160 mL of methanol and 110 mL of water is heated at reflux for 5.5 hours. The reaction mixture is filtered hot and the solid residue is extracted with several portions of hot ethyl acetate followed by hot methanol. All the organic layers are combined and washed with water. The organic layer is dried over magnesium sulfate, filtered and concentrated in vacuo. Diethyl ether and hexane are added and the solid is collected by filtration to provide 87 mg of 8-amino-4-(3-bromoanilino)-[1]benzothieno[3,2-b]pyridine-3-carbonitrile. The filtrate is concentrated and purified by flash chromatography, eluting with a gradient of 1:1 hexane/ethyl acetate to 100% ethyl acetate to give an additional 56 mg of 8-amino-4-(3-bromoanilino)-[1]benzothieno[3,2-b]pyridine-3-carbonitrile as a bright yellow solid, mp 295–300° C. dec.

Workup

  1. temperatureis heated
  2. temperatureat reflux for 5.5 hours
  3. filtrationThe reaction mixture is filtered hot
  4. extractionthe solid residue is extracted with several portions of hot ethyl acetate
  5. washwashed with water
  6. dry with materialThe organic layer is dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. additionDiethyl ether and hexane are added
  10. filtrationthe solid is collected by filtration

Sources & evidence

ORD record
ord-b0909352cc654dc8917680c9585f5b26
Source dataset
uspto-grants-2006_09
Patent number
US07105531B2

Reaction notes

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