Sodium hydride → Di-tert-butyl [2-(ethoxycarbonyl)-1-benzothien-6-yl]malonate

HRID 500657

반응식

HRID 500657 반응식
[C:1]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])(=[O:10])[CH2:2][C:3]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])=[O:4].[H-].[Na+].Br[C:19]1[CH:32]=[CH:31][C:22]2[CH:23]=[C:24]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[S:25][C:21]=2[CH:20]=1.[NH4+].[Cl-]>C1COCC1.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH2:29]([O:28][C:26]([C:24]1[S:25][C:21]2[CH:20]=[C:19]([CH:2]([C:3]([O:5][C:6]([CH3:7])([CH3:8])[CH3:9])=[O:4])[C:1]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH:32]=[CH:31][C:22]=2[CH:23]=1)=[O:27])[CH3:30]

참가 물질

7

반응물 4

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 68324Di-tert-butyl malonateHCID 13567982Ethyl 6-bromo-1-benzothiophene-2-carboxylate

생성물 1

HCID 59424236Di-tert-butyl [2-(ethoxycarbonyl)-1-benzothien-6-yl]malonate수율 48%

시약·촉매·용매 2

HCID 178418851HCID 178418851, 화합물촉매HCID 8028Tetrahydrofuran용매2회

실험 절차

Di-tert-butyl malonate (1.5 g, 6.93 mmol) was dissolved in THF (6 mL) and sodium hydride (60% dispersion in mineral oil, 0.28 g, 7.00 mmol) was added. The mixture was stirred for 10 minutes before adding Pd(PtBu3)2 (0.1 g, 0.196 mmol) and a solution of ethyl 6-bromo-1-benzothiophene-2-carboxylate (1.8 g, 6.31 mmol) in THF (12 mL). The resulting mixture was heated to reflux under N2 for 18 hours. Room temperature was attained, saturated NH4Cl (150 mL) was added and the products extracted into EtOAc (2×125 mL). The combined organic extracts were dried over MgSO4 and concentrated in vacuo. Purification of the residue by MPLC gave 1.27 g of desired product (pale yellow solid, 48%). 1H NMR (DMSO-d6) δ 8.17 (s, 1H), 8.01 (s, 1H), 7.99 (d, J=8.4 Hz, 1H), 7.45 (dd, J=8.4, 1.8 Hz, 1H), 4.83 (s, 1H), 4.33 (q, J=7.2 Hz, 2H), 1.40 (s, 18H), 1.31 (t, J=7.2 Hz, 3H).

후처리

  1. temperatureThe resulting mixture was heated
  2. temperatureto reflux under N2 for 18 hours
  3. customRoom temperature
  4. extractionthe products extracted into EtOAc (2×125 mL)
  5. dry with materialThe combined organic extracts were dried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customPurification of the residue by MPLC

출처 및 근거

ORD 기록
ord-1f2bc02933cb4315b946d63359534b3e
출처 데이터셋
uspto-grants-2010_08
특허 번호
US07772238B2

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