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

HRID 500657

反応式

HRID 500657 の反応式
[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]

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 178418851HCID 178418851、化合物触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-1f2bc02933cb4315b946d63359534b3e
出典データセット
uspto-grants-2010_08
特許番号
US07772238B2

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