Toluene → 3-(1-ethyl-4,4,6-trimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-7-yl)-4-trifluoromethoxy-benzaldehyde

HRID 2239251

Reaktionsgleichung

Reaktionsgleichung von HRID 2239251
Br[C:2]1[C:3]([CH3:17])=[CH:4][C:5]2[C:10]([CH3:12])([CH3:11])[O:9][C:8](=[O:13])[N:7]([CH2:14][CH3:15])[C:6]=2[CH:16]=1.[F:18][C:19]([F:33])([F:32])[O:20][C:21]1[CH:26]=[CH:25][C:24]([CH:27]=[O:28])=[CH:23][C:22]=1B(O)O.C1(C)C=CC=CC=1.C([O-])([O-])=O.[K+].[K+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(O)C>[CH2:14]([N:7]1[C:6]2[CH:16]=[C:2]([C:26]3[CH:25]=[C:24]([CH:23]=[CH:22][C:21]=3[O:20][C:19]([F:18])([F:32])[F:33])[CH:27]=[O:28])[C:3]([CH3:17])=[CH:4][C:5]=2[C:10]([CH3:12])([CH3:11])[O:9][C:8]1=[O:13])[CH3:15]

Komponenten

7

Edukt 4

HCID 1140TolueneHCID 11430Potassium CarbonateHCID 219664285-Formyl-2-(trifluoromethoxy)benzeneboronic acidHCID 685829667-Bromo-1-ethyl-4,4,6-trimethyl-1,4-dihydro-benzo[d][1,3]oxazin-2-one

Produkt 1

HCID 866116793-(1-ethyl-4,4,6-trimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-7-yl)-4-trifluoromethoxy-benzaldehydeAusbeute 52 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 702EthanolLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A round bottom flask was charged with 0.5 g (1.67 mmol) of Compound 14D, 0.58 g (2,5 mmol) of 2-trifluoromethoxy-5-formylphenylboronic acid and 0.083 g of tetrakis(triphenylphosphine)palladium(0). The flask was sealed with a septa and 8.5 mL of toluene and 2.5 mL of ethanol was added. The resulting solution was stirred to dissolve the reactants and then 1.7 mL of 2M K2CO3 was added via syringe. The reaction mixture was heated to 80° C. for 4 hours. After cooling, the reaction mixture was partitioned between ethyl acatate (20 mL) and water (8 mL). The water layer was further extracted (2×10 mL) and the combined organic layers were washed with water (10 mL) followed by brine (10 mL), dried over magnesium sulfate, filtered and excess solvent removed on the rotary evaporator. The crude product was purified by flash chromatography (EtOAc/Hexanes; gradient 20% to 40%) to give 0.35 g (52%) of 3-(1-ethyl-4,4,6-trimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-7-yl)-4-trifluoromethoxy-benzaldehyde as yellow solid. MS (electrospray): mass calculated for C21H20F3NO4, 407.13; m/z found 408 [M+H]+.

Aufarbeitung

  1. additionwas added
  2. dissolutionto dissolve the reactants
  3. temperatureAfter cooling
  4. customthe reaction mixture was partitioned between ethyl acatate (20 mL) and water (8 mL)
  5. extractionThe water layer was further extracted (2×10 mL)
  6. washthe combined organic layers were washed with water (10 mL)
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customexcess solvent removed on the rotary evaporator
  10. customThe crude product was purified by flash chromatography (EtOAc/Hexanes; gradient 20% to 40%)

Quellen und Nachweise

ORD-Eintrag
ord-c0042d7720d44d08978f2de0f3d5c9b2
Quelldatensatz
uspto-grants-2010_05
Patentnummer
US07723326B2

Verknüpfte Notizen

Wird geladen…