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

HRID 539364Notes

Reaction equation

HRID 539364 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-1b5b2b473e764b79a86c4c2ecbed8d2c
Source dataset
uspto-grants-2014_10
Patent number
US08865911B2

Reaction notes

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