Potassium Carbonate → Methyl 8-bromo-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-2-carboxylate

HRID 627835ノート

反応式

HRID 627835 の反応式
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2=[C:6]([CH:15]=1)[O:7][CH2:8][CH2:9][C:10]([CH:13]=O)=[C:11]2Cl.C(=O)([O-])[O-].[K+].[K+].[C:22]([O:26][CH3:27])(=[O:25])[CH2:23][SH:24]>CN(C=O)C.O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11]3[S:24][C:23]([C:22]([O:26][CH3:27])=[O:25])=[CH:13][C:10]=3[CH2:9][CH2:8][O:7][C:6]=2[CH:15]=1

参加物

6

反応物 3

HCID 11430Potassium CarbonateHCID 16907Methyl ThioglycolateHCID 57900258(Z)-8-bromo-5-chloro-2,3-dihydrobenzo[b]oxepine-4-carbaldehyde

生成物 1

HCID 56833843Methyl 8-bromo-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-2-carboxylate収率 78%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
50 °C

実験手順

(Z)-8-Bromo-5-chloro-2,3-dihydrobenzo[b]oxepine-4-carbaldehyde 9 was dissolved in 10 mL DMF and treated sequentially with potassium carbonate (2.20 g, 16.6 mmol) and methyl thioglycolate (0.83 mL). The whole was heated at 50° C. overnight, cooled to room temperature, diluted with water and extracted with ethylacetate. The combined organics were washed with brine, dried over sodium sulfate and concentrated. The crude residue was purified by flash column chromatography (20-50% ethylacetate in hexanes) to give 2.20 g (78% yield) 10 as a colorless solid. 1H NMR (DMSO-d6, 500 MHz) 7.70 (s, 1H), 7.67 (d, J=8.5 Hz, 1H), 7.31-7.28 (m, 2H), 4.32 (t, J=5.0 Hz, 2H), 3.84 (s, 3H), 3.21 (t, J=5.0 Hz, 2H).

後処理

  1. temperaturecooled to room temperature
  2. extractionextracted with ethylacetate
  3. washThe combined organics were washed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe crude residue was purified by flash column chromatography (20-50% ethylacetate in hexanes)

出典と根拠

ORDレコード
ord-8a8886ea7f3b48a68e76825b1159d923
出典データセット
uspto-grants-2016_04
特許番号
US09309265B2

反応ノート

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