Dimethyl oxalate → HCID 69655528, Verbindung

HRID 2214643Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2214643
[F:1][C:2]1[CH:20]=[CH:19][C:5]([CH2:6][N:7]([CH2:11][C:12]2[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=2)[C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1.[CH3:21][O:22][C:23](=[O:28])[C:24](OC)=[O:25].[Li+].C[Si]([N-][Si](C)(C)C)(C)C>C1COCC1>[CH3:21][O:22][C:23](=[O:28])[C:24]([OH:25])=[CH:9][C:8](=[O:10])[N:7]([CH2:11][C:12]1[CH:13]=[CH:14][C:15]([F:18])=[CH:16][CH:17]=1)[CH2:6][C:5]1[CH:4]=[CH:3][C:2]([F:1])=[CH:20][CH:19]=1

Komponenten

5

Edukt 3

HCID 11120Dimethyl oxalateHCID 2733832Lithium HexamethyldisilazideHCID 21947396HCID 21947396, Verbindung

Produkt 1

HCID 69655528HCID 69655528, VerbindungAusbeute 53 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

N,N-Bis-(4-fluoro-benzyl)-acetamide (15.0 grams, 54.5 mmol) and dimethyloxalate (9.6 grams, 81.3 mmol) were dissolved in 54 mL of THF. After cooling to 0° C. 108 mL of 1N LiHMDS (THF) was added dropwise. The reaction mixture was stirred 1 hr then quenched with 1N HCl. The resulting mixture was extracted with CH2Cl2, dried over Na2SO4, filtered and the solvent removed under vacuum. The product was purified by flash column chromatography (SiO2, 80:20 hexanes/EtOAc) to yield 10 grams (53% yield) of 3-[bis-(4-fluoro-benzyl)-carbamoyl]-2-hydroxy-acrylic acid methyl ester as a solid. Mp=118–120° C. Anal. calcd for C19H17F2NO4: C, 63.15; H, 4.74; N, 3.87. found: C, 62.97; H, 4.72; N, 3.81. 1H NMR (500 MHz, CDCl3) δ: 3.87 (s, 3), 4.46 (s, 2), 4.58 (s, 2), 6.32 (s, 1), 7.00–7.26 (overlapping m, 8). 13C NMR (125 MHz, CDCl3) δ: 47.34, 49.35, 53.03, 93.34, 115.66, 115.83, 116.00, 116.18, 128.45, 128.52, 130.03, 130.10, 131.09, 131.93, 131.95, 160.29, 161.44, 161.51, 163.10, 163.41, 163.47, 171.36.

Aufarbeitung

  1. customthen quenched with 1N HCl
  2. extractionThe resulting mixture was extracted with CH2Cl2
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. customthe solvent removed under vacuum
  6. customThe product was purified by flash column chromatography (SiO2, 80:20 hexanes/EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-35d684e30ce548869cdcb96c9bef2c9e
Quelldatensatz
uspto-grants-2006_09
Patentnummer
US07109186B2

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