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

HRID 1725057Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1725057
[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) δ 7.96 (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-6d306f74c2f741699e3376043271942e
Quelldatensatz
uspto-grants-2009_02
Patentnummer
US07488822B2

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