Sodium Bicarbonate → N-(6-Bromo-2-(2,2-dimethyltetrahydro-2H-pyran-4-yl)chroman-4-ylidene)-2-methylpropane-2-sulfinamide

HRID 1965128Notes

Reaction equation

HRID 1965128 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][CH:7]([CH:12]1[CH2:17][CH2:16][O:15][C:14]([CH3:19])([CH3:18])[CH2:13]1)[CH2:6][C:5]2=O.[CH3:21][C:22]([S:25]([NH2:27])=[O:26])([CH3:24])[CH3:23].C([O-])(O)=O.[Na+]>C1COCC1.CCOC(C)=O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][CH:7]([CH:12]1[CH2:17][CH2:16][O:15][C:14]([CH3:19])([CH3:18])[CH2:13]1)[CH2:6][C:5]2=[N:27][S:25]([C:22]([CH3:24])([CH3:23])[CH3:21])=[O:26]

Participants

7

Reactant 3

HCID 516892Sodium BicarbonateHCID 3382465Tert-ButanesulfinamideHCID 584239026-Bromo-2-(2,2-dimethyltetrahydropyran-4-yl)chroman-4-one2×

Product 1

HCID 67979341N-(6-Bromo-2-(2,2-dimethyltetrahydro-2H-pyran-4-yl)chroman-4-ylidene)-2-methylpropane-2-sulfinamideYield 95%

Reagents, catalysts & solvents 3

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

Titanium (IV) ethoxide (6.18 mL, 29.48 mmol) was added to a solution of 6-bromo-2-(2,2-dimethyltetrahydro-2H-pyran-4-yl)chroman-4-one (Intermediate 28, 4 g, 11.79 mmol) in dry THF (150 mL) under argon. The solution was stirred 5 min before addition of 2-methylpropane-2-sulfinamide (1.715 g, 14.15 mmol) was made in one portion. The reaction was refluxed over the weekend (˜70 h) with a heating bath temperature of 80° C. The reaction was cooled to r.t., and diluted with EtOAc (300 mL). Saturated NaHCO3 (150 mL) was added under vigorous stirring. After 5 min diatomaceous earth was added and the mixture was stirred for another 10 min. The slurry was filtered through diatomaceous earth (washed with EtOAc) and the filtrate was evaporated at reduced pressure. Purification by flash chromatography (EtOAc/heptane) on silica gel gave the title compound (4.93 g, 95% yield): MS (ES+) m/z 442 [M+H]+.

Workup

  1. temperatureThe reaction was cooled to r.t.
  2. additionAfter 5 min diatomaceous earth was added
  3. filtrationThe slurry was filtered through diatomaceous earth (washed with EtOAc)
  4. customthe filtrate was evaporated at reduced pressure
  5. customPurification by flash chromatography (EtOAc/heptane) on silica gel

Sources & evidence

ORD record
ord-4ea181aa7f1c43b7a9ae6dacc005be35
Source dataset
uspto-grants-2013_04
Patent number
US08415483B2

Reaction notes

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