Phosphorus oxychloride → Ethyl 4-chloro-2-methylpyrimidine-5-carboxylate

HRID 1930386Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1930386
P(Cl)(Cl)([Cl:3])=O.O[C:7]1[C:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:11][N:10]=[C:9]([CH3:18])[N:8]=1>C(N(CC)CC)C>[Cl:3][C:7]1[C:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:11][N:10]=[C:9]([CH3:18])[N:8]=1

Komponenten

4

Edukt 2

HCID 24813Phosphorus oxychlorideHCID 178469783HCID 178469783, Verbindung

Produkt 1

HCID 12677176Ethyl 4-chloro-2-methylpyrimidine-5-carboxylateAusbeute 53 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8471TriethylamineLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

In cold (˜0° C.) phosphorous oxychloride (40 mL) was carefully added triethylamine (1.87 mL) with stirring. To this was added, in parts, ethyl 4-hydroxy-2-methylpyrimidine-5-carboxylate (5.00 g, 27.4 mmol). The mixture then warmed to 40° C. and stirred under Argon for 2 hours. The mixture was evaporated free of phosphorous oxychloride, diluted with chloroform (150 mL) and poured carefully into ice (400 mL) and allowed to warm to RT. The organic phase was separated, washed with saturated sodium bicarbonate (75 mL), then brine (100 mL) and dried over sodium sulfate. The solvents evaporated to give a thick oil which was purified by chromatography (Biotage Si-40 column, 15-40% ethyl acetate/hexane) to give ethyl 4-chloro-2-methylpyrimidine-5-carboxylate as a clear oil (2.96 g, 53% yield). 1H NMR (400 MHz, DMSO-d6): δ 1.31 (t, 3 H), 2.66 (s, 3 H), 4.34 (q, 2 H), 9.06 (s, 1 H); MS (ESI) m/z: 201.0 (M+H+).

Aufarbeitung

  1. stirringstirred under Argon for 2 hours
  2. customThe mixture was evaporated free of phosphorous oxychloride
  3. additiondiluted with chloroform (150 mL)
  4. additionpoured carefully into ice (400 mL)
  5. temperatureto warm to RT
  6. customThe organic phase was separated
  7. washwashed with saturated sodium bicarbonate (75 mL)
  8. dry with materialbrine (100 mL) and dried over sodium sulfate
  9. customThe solvents evaporated
  10. customto give a thick oil which
  11. customwas purified by chromatography (Biotage Si-40 column, 15-40% ethyl acetate/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-2b2f35e8fb4846e9a8ad201e00d0f4d2
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08188113B2

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