Ethyl Acetate → Methyl 4-[4-(hydroxymethyl)-2-methoxy-5-nitrophenoxy]butanoate

HRID 33988Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 33988
[BH4-].[Na+].[CH3:3][O:4][C:5](=[O:23])[CH2:6][CH2:7][CH2:8][O:9][C:10]1[CH:15]=[C:14]([N+:16]([O-:18])=[O:17])[C:13]([CH:19]=[O:20])=[CH:12][C:11]=1[O:21][CH3:22].CCOC(C)=O>C1COCC1>[CH3:3][O:4][C:5](=[O:23])[CH2:6][CH2:7][CH2:8][O:9][C:10]1[CH:15]=[C:14]([N+:16]([O-:18])=[O:17])[C:13]([CH2:19][OH:20])=[CH:12][C:11]=1[O:21][CH3:22]

Komponenten

5

Edukt 3

HCID 8857Ethyl AcetateHCID 4311764Sodium borohydrideHCID 11033807Butanoic acid, 4-(4-formyl-2-methoxy-5-nitrophenoxy)-, methyl ester

Produkt 1

HCID 15334312Methyl 4-[4-(hydroxymethyl)-2-methoxy-5-nitrophenoxy]butanoateAusbeute 64,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

Sodium borohydride (2.69 g, 71.3 nmol) was added to a stirred solution of the ester (49)(10.0 g, 33.6 mmol) in THF (50 mL) under an N2 atmosphere at room temperature. Effervescence was observed upon addition of the reducing agent. TLC (EtOAc) after 16 hours revealed the complete loss of starting material. The solution was concentrated and redissolved in EtOAc (100 mL). The organic layer was washed with sat. NH4Cl (5×100 mL) and concentrated in vacuo. Purification by flash chromatography (1% MeOH/CHCl3) yielded the product (50) as a yellow solid (6.46 g, 64%). MP=98-102° C. 1H NMR (250 MHz, CDCl3) δ 7.70 (s, 1H), 7.16 (s, 1H), 4.95 (d, J=6.5 Hz, 2H), 4.12 (t, J=6.2 Hz, 2H), 3.98 (s, 3H), 3.70 (s, 3H), 2.71 (t, J=6.5 Hz, 1H), 2.56 (t, J=7.1 Hz, 2H), 2.19 (pent, J=6.7 Hz, 2H). 13C NMR (67.8 MHz, CDCl3) 173.9 (C12), 154.6 (Cquat.), 147.3 (Cquat.), 139.6 (Cquat.), 133.2 (Cquat.), 111.0 (C6), 109.8 (C3), 68.6 (C9), 62.7 (C1), 56.7 (C8), 52.1 (C13), 30.7 (C11), 24.6 (C10). IR (cm−1) 3286, 2937, 2881, 1737, 1577, 1533, 1368, 1332, 1282, 1162, 1008, 979, 950, 872, 821, 755, 651. MS (M+) 299.0. Anal. Calcd for C13H17NO7: C, 52.17; H, 5.73; N, 4.68. Found: C, 52.41; H, 5.86; N, 4.67.

Aufarbeitung

  1. additionEffervescence was observed upon addition of the reducing agent
  2. concentrationThe solution was concentrated
  3. dissolutionredissolved in EtOAc (100 mL)
  4. washThe organic layer was washed with sat. NH4Cl (5×100 mL)
  5. concentrationconcentrated in vacuo
  6. customPurification by flash chromatography (1% MeOH/CHCl3)

Quellen und Nachweise

ORD-Eintrag
ord-c32eeb0bb8d745feac6412ebb2bee818
Quelldatensatz
uspto-grants-2008_09
Patentnummer
US07429658B2

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