Pyridine → Benzo[b]thiophene-6-carbonitrile

HRID 402115

反応式

HRID 402115 の反応式
Br[C:2]1[S:6][C:5]2[CH:7]=[CH:8][CH:9]=[CH:10][C:4]=2[CH:3]=1.[N:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[Cu]C#N.C(N)CN>CN(C)C=O.O>[C:12]([C:10]1[C:4]2[CH:3]=[CH:2][S:6][C:5]=2[CH:7]=[CH:8][CH:9]=1)#[N:11].[C:16]([C:15]1[CH:14]=[CH:13][C:12]2[CH:3]=[CH:2][S:6][C:5]=2[CH:4]=1)#[N:11]

参加物

8

反応物 4

HCID 1049PyridineHCID 3301EthylenediamineHCID 947862-Bromobenzo(b)thiopheneHCID 178418546HCID 178418546、化合物

生成物 2

HCID 21816574Benzo[b]thiophene-6-carbonitrile収率 41%HCID 218165751-Benzothiophene-4-carbonitrile収率 39%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
60 °C

実験手順

To a solution of the isomeric bromobenzo[b]thiophene (14.2 g, 66.5 mmol) from Step B above in N,N-dimethylformamide (130 mL) were added pyridine (7.5 mL) and copper(I) cyanide (7.75 g). The reaction mixture was heated under reflux for 20 hours. The reaction solution was then cooled to 60° C. and poured into a solution of ethylene diamine in water. The resultant mixture was stirred for 30 minutes and extracted with diethyl ether and ethyl acetate. The combined organic extract was washed with 1:1 brine/water, dried over sodium sulfate and concentrated under reduced pressure. The crude product obtained was purified by flash column chromatography (95:5 to 91:9 hexanes/ethyl acetate) to give 4-cyanobenzo[b]thiophene (4.15 g, 39%) as a light yellow solid, and 6-cyanobenzo[b]thiophene (4.34 g, 41%) as a reddish oil: 1H NMR for 4-cyanobenzo[b]thiophene (CDCl3, 500 MHz) δ 8.10 (d, J=8.2 Hz, 1H), 7.74-7.70 (m, 2H), 7.62 (dd, J=5.5, 0.6 Hz, 1H), 7.43 (d, J=7.8 Hz, 1H); 1H NMR for 6-cyanobenzo[b]thiophene (CDCl3, 500 MHz) δ8.22 (app s, 1H), 7.90 (d, J=8.3 Hz, 1H), 7.72 (d, J=5.4 Hz, 1H), 7.59 (d, J=8.3 Hz, 1H), 7.42 (dd, J=5.4, 0.5 Hz, 1H).

後処理

  1. temperatureThe reaction mixture was heated
  2. temperatureunder reflux for 20 hours
  3. extractionextracted with diethyl ether and ethyl acetate
  4. extractionThe combined organic extract
  5. washwas washed with 1:1 brine/water
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe crude product obtained
  9. customwas purified by flash column chromatography (95:5 to 91:9 hexanes/ethyl acetate)

出典と根拠

ORDレコード
ord-9c5a366155954af7a8f295b14ef41331
出典データセット
uspto-grants-2014_06
特許番号
US08741901B2

関連ノート

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