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

HRID 989335ノート

反応式

HRID 989335 の反応式
[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

参加物

6

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 23925Iron触媒HCID 887Methanol溶媒HCID 962Water溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-0cfcb586c1b947f4b5eda110998be8ba
出典データセット
uspto-grants-2003_10
特許番号
US06638929B2

反応ノート

読み込み中…