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

HRID 627835노트

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HRID 627835 반응식
[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

참가 물질

6

반응물 3

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

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매HCID 6228Dimethylformamide용매

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온도
50 °C

실험 절차

(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).

후처리

  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)

출처 및 근거

ORD 기록
ord-8a8886ea7f3b48a68e76825b1159d923
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09309265B2

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