Hydroxylamine, sulfate (1:1) → ((R)-1-benzyloxymethyl-3-butenyloxy)acetaldehyde oxime

HRID 538018

Reaktionsgleichung

Reaktionsgleichung von HRID 538018
C(O[CH:4](OCC)[CH2:5][O:6][C@H:7]([CH2:17][CH:18]=[CH2:19])[CH2:8][O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)C.S(O)(O)(=O)=O.[NH2:28][OH:29].C([O-])(=O)C.[Na+]>C(O)=O.O.C(O)C>[CH2:10]([O:9][CH2:8][C@H:7]([O:6][CH2:5][CH:4]=[N:28][OH:29])[CH2:17][CH:18]=[CH2:19])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Komponenten

7

Edukt 3

HCID 159255Hydroxylamine, sulfate (1:1)HCID 517045Sodium AcetateHCID 59281174[(R)-2-(2,2-diethoxyethoxy)-4-pentenyloxymethyl]benzene

Produkt 1

HCID 86640913((R)-1-benzyloxymethyl-3-butenyloxy)acetaldehyde oxime

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 284Formic AcidLösungsmittel2×HCID 702EthanolLösungsmittelHCID 962WaterLösungsmittel2×

Versuchsvorschrift

A solution of C2 (234 g, 0.759 mol) in formic acid (400 mL) and water (100 mL) was stirred at room temperature for 2 hours. As LCMS analysis revealed a small amount of remaining starting material, formic acid (50 mL) was added and the reaction mixture was stirred for a further 30 minutes. The reaction mixture was diluted with ethanol (1 L) and water (400 mL). Hydroxylamine sulfate (435 g, 2.65 mol) and sodium acetate (217 g, 2.64 mol) were added and the reaction was stirred at room temperature for 18 hours. The reaction mixture was then filtered and concentrated in vacuo. The residue was partitioned between ethyl acetate (500 mL) and water (1 L), and the aqueous layer was extracted with ethyl acetate (3×500 mL). The combined organic layers were washed with saturated aqueous sodium chloride solution (2×500 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure to provide the product as an orange oil. By 1H NMR, this material consisted of a roughly 1:1 mixture of oxime isomers. Yield: 234 g, which was taken directly to the following step. LCMS m/z 250.1 [M+H]+. 1H NMR (400 MHz, CDCl3), characteristic peaks: δ [7.52 (t, J=5.5 Hz) and 6.96 (t, J=3.6 Hz), total 1H], 7.28-7.39 (m, 5H), 5.74-5.87 (m, 1H), 5.04-5.14 (m, 2H), 4.55 and 4.56 (2 s, total 2H), {4.45-4.55 (m) and [4.27 (dd, half of ABX pattern, J=13.2, 5.4 Hz) and 4.21 (dd, half of ABX pattern, J=13.2, 5.6 Hz)], total 2H}, 2.30-2.37 (m, 2H).

Aufarbeitung

  1. additionwas added
  2. stirringthe reaction was stirred at room temperature for 18 hours
  3. filtrationThe reaction mixture was then filtered
  4. concentrationconcentrated in vacuo
  5. customThe residue was partitioned between ethyl acetate (500 mL) and water (1 L)
  6. extractionthe aqueous layer was extracted with ethyl acetate (3×500 mL)
  7. washThe combined organic layers were washed with saturated aqueous sodium chloride solution (2×500 mL)
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-5092a31d82784b75b5a4c4376aff1c72
Quelldatensatz
uspto-grants-2014_10
Patentnummer
US08865706B2

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