Hydrochloric Acid → 3-[3-(4,4-Dimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-6-yl)Phenyl]propynenitrile

HRID 413167Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 413167
[I-].[Na+].[C:3]([C:5]1[CH:6]=[C:7]([C:11]2[CH:23]=[CH:22][C:14]3[NH:15][C:16](=[O:21])[O:17][C:18]([CH3:20])([CH3:19])[C:13]=3[CH:12]=2)[CH:8]=[CH:9][CH:10]=1)#[CH:4].Cl[Si](C)(C)C.Cl.[C:30](#[N:32])C>O.CS(C)=O>[CH3:19][C:18]1([CH3:20])[O:17][C:16](=[O:21])[NH:15][C:14]2[CH:22]=[CH:23][C:11]([C:7]3[CH:6]=[C:5]([C:3]#[C:4][C:30]#[N:32])[CH:10]=[CH:9][CH:8]=3)=[CH:12][C:13]1=2

Komponenten

8

Edukt 5

HCID 313Hydrochloric AcidHCID 5238Sodium IodideHCID 6342AcetonitrileHCID 6397ChlorotrimethylsilaneHCID 98141916-(3-Ethynyl-phenyl)-4,4-dimethyl-1,4-dihydro-benzo[d][1,3]oxazin-2-one

Produkt 1

HCID 98575553-[3-(4,4-Dimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-6-yl)Phenyl]propynenitrileAusbeute 4,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 679Dimethyl SulfoxideLösungsmittelHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

To a stirred mixture of DMSO, acetonitrile and water (9 mL/3 mL/0.5 mL) was added at rt under nitrogen cuprous cyanide (0.193 g, 2.2 mmol), sodium iodide (11 mg, 0.072 mmol), and 6-(3-ethynyl-phenyl)-4,4-dimethyl-1,4-dihydro-benzo[d][1,3]oxazin-2-one (0.2 g, 0.72 mmol). Chlorotrimethylsilane was then added to the above mixture in a dropwise manner. After addition, the mixture was heated at 50° C. for 72 hours. The reaction mixture was then cooled to rt and treated with 0.5 N aqueous HCl cold solution (50 mL). The precipitate obtained was collected on a filter and washed with water. The solid was purified on a silica gel column (hexane:ethyl acetate/2:1) to give the title compound as an off-white solid (10 mg, 4.6 %): mp 212-213° C.; 1H-NMR (CHCl3-d6) δ7.96 (s, 1H), 7.77 (s, 1H), 7.65 (d, 1H, J=7.8 Hz), 7.60 (d, 1H, J=7.69 Hz), 7.51 (d, 1H, J=7.77 Hz), 7.45 (dd, 1H, J=8.67, 2.21 Hz), 7.31 (d, 1H, J=1.55 Hz), 6.91 (d, 1H, J=8.19 Hz), 1.8 (s, 6H); MS (EI) m/z 302 ([M+], 30%).

Aufarbeitung

  1. additionwas added at rt under nitrogen cuprous cyanide (0.193 g, 2.2 mmol)
  2. additionAfter addition
  3. temperatureThe reaction mixture was then cooled to rt
  4. customThe precipitate obtained
  5. customwas collected on
  6. filtrationa filter
  7. washwashed with water
  8. customThe solid was purified on a silica gel column (hexane:ethyl acetate/2:1)

Quellen und Nachweise

ORD-Eintrag
ord-085541000f1a4ce79b6ec1dc0e5f6c35
Quelldatensatz
uspto-grants-2003_05
Patentnummer
US06566358B2

Notizen zur Reaktion

Wird geladen…