Ethyl Acetate → N-(5'-Bromo-4-(difluoromethyl)spiro[cyclohexane-1,2'-indene]-3'(1'H)-ylidene)-2-methylpropane-2-sulfinamide

HRID 539382Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 539382
[CH3:1][C:2]([S:5]([NH2:7])=[O:6])([CH3:4])[CH3:3].[Br:8][C:9]1[CH:17]=[C:16]2[C:12]([CH2:13][C:14]3([CH2:23][CH2:22][CH:21]([CH:24]([F:26])[F:25])[CH2:20][CH2:19]3)[C:15]2=O)=[CH:11][CH:10]=1.CCOC(C)=O.C([O-])(O)=O.[Na+]>CCCCCCC.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:8][C:9]1[CH:17]=[C:16]2[C:12](=[CH:11][CH:10]=1)[CH2:13][C:14]1([CH2:23][CH2:22][CH:21]([CH:24]([F:25])[F:26])[CH2:20][CH2:19]1)[C:15]2=[N:7][S:5]([C:2]([CH3:4])([CH3:3])[CH3:1])=[O:6]

Komponenten

7

Edukt 4

HCID 8857Ethyl Acetate2×HCID 516892Sodium BicarbonateHCID 3382465Tert-Butanesulfinamide2×HCID 679794786'-Bromo-4-(difluoromethyl)spiro[cyclohexane-1,2'-inden]-1'(3'H)-one2×

Produkt 1

HCID 67979575N-(5'-Bromo-4-(difluoromethyl)spiro[cyclohexane-1,2'-indene]-3'(1'H)-ylidene)-2-methylpropane-2-sulfinamideAusbeute 60,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 76524Titanium tetraethoxideKatalysator2×HCID 8900HeptaneLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

Titanium ethoxide (0.893 mL, 4.33 mmol), 2-methylpropane-2-sulfinamide (0.315 g, 2.60 mmol) and 6′-bromo-4-(difluoromethyl)spiro[cyclohexane-1,2′-inden]-1′(3′H)-one (Intermediate 91, 0.713 g, 2.17 mmol) were dissolved in 2-Me THF (5 mL) and heated to 90° C. overnight. 2-Methylpropane-2-sulfinamide (0.315 g, 2.60 mmol) and titanium ethoxide (0.893 mL, 4.33 mmol) were added and the reaction was refluxed for 7 h. Another portion of reagents was added and the mixture was refluxed overnight. The reaction was allowed to attain r.t. EtOAc (50 mL) was added followed by dropwise addition of NaHCO3 (10 mL). The mixture was stirred at r.t. for 2 h. The crude product was purified using flash chromatography (40 g SiO2, O-40% EtOAc in heptane) to give the title compound (564 mg, 60% yield): MS (ES+) m/z 432 [M+H]+.

Aufarbeitung

  1. temperaturethe reaction was refluxed for 7 h
  2. additionAnother portion of reagents was added
  3. temperaturethe mixture was refluxed overnight
  4. customto attain r.t
  5. customThe crude product was purified

Quellen und Nachweise

ORD-Eintrag
ord-9140d213f7f3431f894431291218d2ff
Quelldatensatz
uspto-grants-2014_10
Patentnummer
US08865911B2

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