Hydrochloric Acid → Methyl 2-chloro-3-[4-(2-hydroxyethyl)phenyl]propanoate

HRID 33813

Reaktionsgleichung

Reaktionsgleichung von HRID 33813
N[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][OH:10])=[CH:4][CH:3]=1.[ClH:11].N([O-])=O.[Na+].[C:16]([O:20][CH3:21])(=[O:19])[CH:17]=[CH2:18]>CC(C)=O.O.[Cu]I>[Cl:11][CH:17]([CH2:18][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][OH:10])=[CH:4][CH:3]=1)[C:16]([O:20][CH3:21])=[O:19]

Komponenten

8

Edukt 4

HCID 313Hydrochloric AcidHCID 7294Methyl AcrylateHCID 669044-Aminophenethyl alcoholHCID 23668193Sodium Nitrite

Produkt 1

HCID 86600802Methyl 2-chloro-3-[4-(2-hydroxyethyl)phenyl]propanoateAusbeute 49 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 180AcetoneLösungsmittelHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

2-(4-Aminophenyl)ethanol (11 g, 81 mmol) and 32 ml conc HCl was dissolved in acetone and cooled to 0° C. Sodium nitrite (5.6 g, 81 mmol) in 20 ml water was added dropwise. The temperature was kept under 0° C. After one hour, methyl acrylate (70 g, 808 mmol) and CuI (1.6 g, 8 mmol) were added (<0° C.). The reaction mixture was stirred at room temperature overnight. The solvent was evaporated and water was added. The water phase was extracted three times with EtOAc, the organic phases were pooled and washed with water, dried (MgSO4) and evaporated under reduced pressure. The crude product was purified by flash chromatography using a 65:35 mixture of EtOAc and heptane as eluent. Further purification by preparative HPLC (using a gradient of CH3CN/5% CH3CN-waterphase containing 0.1M NH4OAc as eluent) gave 9.7 g product (yield 49%) as an oil.

Aufarbeitung

  1. customwas kept under 0° C
  2. customThe solvent was evaporated
  3. additionwater was added
  4. extractionThe water phase was extracted three times with EtOAc
  5. washwashed with water
  6. dry with materialdried (MgSO4)
  7. customevaporated under reduced pressure
  8. customThe crude product was purified by flash chromatography
  9. additiona 65:35 mixture of EtOAc and heptane as eluent
  10. customFurther purification by preparative HPLC (
  11. additioncontaining 0.1M NH4OAc as eluent)

Quellen und Nachweise

ORD-Eintrag
ord-52e7e194b4d5420f8886f537fc483c0d
Quelldatensatz
uspto-grants-2008_09
Patentnummer
US07429675B2

Verknüpfte Notizen

Wird geladen…