Terephthalic acid monomethylester chloride → Methyl 4-(7-bromo-5-cyanobenzo[d]oxazol-2-yl)benzoate

HRID 2066828Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2066828
[Cl-].[CH3:2][O:3][C:4](=[O:14])[C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=O)=[CH:7][CH:6]=1.[NH2:15][C:16]1[CH:17]=[C:18]([CH:21]=[C:22]([Br:25])[C:23]=1O)[C:19]#[N:20]>O1CCOCC1>[Br:25][C:22]1[C:23]2[O:11][C:9]([C:8]3[CH:7]=[CH:6][C:5]([C:4]([O:3][CH3:2])=[O:14])=[CH:13][CH:12]=3)=[N:15][C:16]=2[CH:17]=[C:18]([C:19]#[N:20])[CH:21]=1

Komponenten

4

Edukt 2

HCID 53442854Terephthalic acid monomethylester chlorideHCID 671407903-Amino-5-bromo-4-hydroxybenzonitrile

Produkt 1

HCID 68411439Methyl 4-(7-bromo-5-cyanobenzo[d]oxazol-2-yl)benzoateAusbeute 89,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

To a 3-l round-bottom flask fitted with a stir bar and a Claisen adapter fitted with a thermocouple and a condenser blanketed with nitrogen was added terephthalic acid monomethyl ester chloride (37.3 g) and a solution of 3-amino-5-bromo-4-hydroxybenzonitrile (40 g, Step B) in dioxane (675 ml). The mixture was heated to reflux and stirred at this temperature overnight. The mixture was then cooled to room temperature and the dioxane was removed in vacuo. The flask was fitted with a Dean-Stark trap and p-toluenesulfonic acid monohydrate (35.8 g) and toluene (2.5 l) were added. The mixture was heated to reflux and stirred at this temperature overnight. The mixture was then allowed to cool, transferred to a new 5-l flask, and concentrated to a brown solid. The crude product was triturated with methanol to provide 55.5 g (83%) of the title compound. 1H NMR (500 MHz, DMSO-d6): δ 8.50 (s, 1H), 8.34 (d, J=8.0 Hz, 2H), 8.29 (s, 1H), 8.19 (d, J=8.0 Hz, 2H), 3.91 (s, 3H).

Aufarbeitung

  1. customTo a 3-l round-bottom flask fitted with a stir bar
  2. customa Claisen adapter fitted with a thermocouple and a condenser
  3. temperatureThe mixture was heated
  4. temperatureto reflux
  5. customthe dioxane was removed in vacuo
  6. customThe flask was fitted with a Dean-Stark trap and p-toluenesulfonic acid monohydrate (35.8 g) and toluene (2.5 l)
  7. additionwere added
  8. temperatureThe mixture was heated
  9. temperatureto reflux
  10. stirringstirred at this temperature overnight
  11. temperatureto cool
  12. customtransferred to a new 5-l flask
  13. concentrationconcentrated to a brown solid
  14. customThe crude product was triturated with methanol

Quellen und Nachweise

ORD-Eintrag
ord-5a0fc097c9184880b1a177400fd084bb
Quelldatensatz
uspto-grants-2012_10
Patentnummer
US08293721B2

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