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

HRID 500657

Reaktionsgleichung

Reaktionsgleichung von HRID 500657
[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]

Komponenten

7

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418851HCID 178418851, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-1f2bc02933cb4315b946d63359534b3e
Quelldatensatz
uspto-grants-2010_08
Patentnummer
US07772238B2

Verknüpfte Notizen

Wird geladen…