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Tetrahydrofuran → Ethyl 3-[2-[2-(5-cyanobenzo[b]thien-2-yl)ethyl]-4-ethoxy-5-methoxyphenyl]propionate

HRID 361907
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HRID 361907 반응식
O1CCCC1.[C:6]([C:8]1[CH:18]=[CH:17][C:11]2[S:12][C:13]([CH:15]=O)=[CH:14][C:10]=2[CH:9]=1)#[N:7].[Cl-].[CH2:20]([O:22][C:23]1[C:24]([O:56][CH3:57])=[CH:25][C:26]([CH2:49][CH2:50][C:51]([O:53][CH2:54][CH3:55])=[O:52])=[C:27]([C:29]2C=CC=CC=2[P+](C)(C2C=CC=CC=2)C2C=CC=CC=2)[CH:28]=1)[CH3:21].C1CCN2C(=NCCC2)CC1>C(O)C>[C:6]([C:8]1[CH:18]=[CH:17][C:11]2[S:12][C:13]([CH2:15][CH2:29][C:27]3[CH:28]=[C:23]([O:22][CH2:20][CH3:21])[C:24]([O:56][CH3:57])=[CH:25][C:26]=3[CH2:49][CH2:50][C:51]([O:53][CH2:54][CH3:55])=[O:52])=[CH:14][C:10]=2[CH:9]=1)#[N:7]
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참가 물질

6

반응물 4

HCID 8028TetrahydrofuranHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 135679662-Formylbenzo[b]thiophene-5-carbonitrileHCID 88305815HCID 88305815, 화합물

생성물 1

HCID 21844492Ethyl 3-[2-[2-(5-cyanobenzo[b]thien-2-yl)ethyl]-4-ethoxy-5-methoxyphenyl]propionate수율 34.2%

시약·촉매·용매 1

HCID 702
Ethanol
용매

실험 절차

9.3 g of ethyl 3-(4-ethoxy-3-methoxyphenyl)-propionate obtained in the above step c) was dissolved in 10 ml of acetic acid, followed by adding 7.4 g of chloromethyl methyl ether and subsequently stirring at room temperature for 22 hours. The resulting reaction solution was poured into ice water, extracted with ethyl acetate, washed with water and then dried to distill off the solvent. The residue thus obtained was dissolved in 10 ml of xylene, and the solution was mixed with 8.54 g of triphenylphosphine. The resulting mixture was stirred at room temperature for 18 hours and then at 70 to 80° C. for 5 hours. After cooling, xylene was removed by decantation, and the remaining portion was solidified by adding n-hexane to obtain 6.0 g of crude [5-ethoxy-2-(2-ethoxycarbonylethyl)-4-methoxyphenyl]methyltriphenylphosphonium chloride. e) To a mixture solution of 50 ml of tetrahydrofuran and 50 ml of ethanol were dissolved 1.5 g of 5-cyanobenzo[b]thiophene-2-carbaldehyde and 6.34 g of crude [5-ethoxy-2-(2-ethoxycarbonylethyl)-4-methoxyphenyl]-methyltriphenylphosphonium chloride obtained in the above step d). 1.83 g of 1,8-diazabicyclo[5.4.0]-7-undecene was added thereto, followed by stirring at room temperature for 18 hours. The resulting reaction solution was concentrated under a reduced pressure, and the residue was dissolved in a mixture solution of 20 ml of tetrahydrofuran and 20 ml of ethanol. The thus prepared solution was mixed with 1.70 g of 10% palladium carbon catalyst (50% wet type) and subjected to catalytic hydrogenation under normal pressure until hydrogen absorption was completed. After removing the catalyst by filtration, the solvent was distilled off. By subjecting the resulting residue to silica gel column chromatography, 1.2 g of oily ethyl 3-[2-[2-(5-cyanobenzo-[b]thien-2-yl)ethyl]-4-ethoxy-5-methoxyphenyl]propionate was obtained.

후처리

  1. customobtained in the above step d)
  2. customThe resulting reaction solution
  3. concentrationwas concentrated under a reduced pressure
  4. dissolutionthe residue was dissolved in a mixture solution of 20 ml of tetrahydrofuran and 20 ml of ethanol
  5. additionThe thus prepared solution was mixed with 1.70 g of 10% palladium carbon catalyst (50% wet type)
  6. customsubjected to catalytic hydrogenation under normal pressure until hydrogen absorption
  7. customAfter removing the catalyst
  8. filtrationby filtration
  9. distillationthe solvent was distilled off

출처 및 근거

ORD 기록
ord-56261a5d17f0412880c914fb8b2cd0f7
출처 데이터셋
uspto-grants-1999_02
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05866577

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