Water → HCID 86706695, compound

HRID 1468083Notes

Reaction equation

HRID 1468083 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:16][CH2:15][CH:14]([O:17][CH3:18])[CH2:13][CH2:12]3)[C:8]2=O)=[CH:4][C:3]=1[CH3:19].[CH3:20][C:21]([S:24]([NH2:26])=[O:25])([CH3:23])[CH3:22].O>CCOC(C)=O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:10]=[C:9]2[C:5](=[CH:4][C:3]=1[CH3:19])[CH2:6][C:7]1([CH2:16][CH2:15][CH:14]([O:17][CH3:18])[CH2:13][CH2:12]1)[C:8]2=[N:26][S:24]([C:21]([CH3:23])([CH3:22])[CH3:20])=[O:25]

Participants

6

Reactant 3

HCID 962WaterHCID 3382465Tert-Butanesulfinamide2×HCID 86706691HCID 86706691, compound2×

Product 1

HCID 86706695HCID 86706695, compoundYield 45%

Reagents, catalysts & solvents 2

HCID 76524Titanium tetraethoxideCatalyst2×HCID 8857Ethyl AcetateSolvent

Procedure

6′-Bromo-4-methoxy-5′-methylspiro[cyclohexane-1,2′-inden]-1′(3′H)-one (Intermediate 4, 1.38 g, 4.27 mmol) and 2-methylpropane-2-sulfinamide (0.931 g, 7.68 mmol) were dissolved in 2-Me THF (8 mL). Titanium(IV) ethoxide (1.78 mL, 8.53 mmol) was added and the resulting mixture was heated to reflux overnight. 2-Methylpropane-2-sulfinamide (0.259 g, 2.13 mmol) and titanium(IV) ethoxide (0.624 mL, 2.99 mmol) were added and heating was continued. After a total of 4 days, the reaction was allowed to cool to r.t. and diluted with EtOAc (25 mL). Water (12 mL) was added dropwise under vigorous stirring and after stirring for another 10 min, the mixture was allowed to stand without stirring for 1.5 h. The solids were filtered off and the solvent was evaporated. The residue was purified by flash chromatography using a gradient of 0-30% EtOAc in heptane as eluent to afford 812 mg (45% yield) of the title compound: 1H NMR (500 MHz, DMSO-d6) δ ppm 1.23 (m, 9 H), 1.31 (m, 2 H), 1.58 (m, 4 H), 1.90 (m, 1 H), 2.02 (m, 1 H), 2.42 (s, 3 H), 2.98 (m, 2 H), 3.18 (m, 1 H), 3.25 (m, 3 H), 7.51 (m, 1 H), 8.53 (m, 1 H); MS (ES+) m/z 426, 428 [M+H]+.

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureto reflux overnight
  3. temperatureheating
  4. customAfter a total of 4 days
  5. stirringafter stirring for another 10 min
  6. stirringwithout stirring for 1.5 h
  7. filtrationThe solids were filtered off
  8. customthe solvent was evaporated
  9. customThe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-0e7643ac4b19481e9639ba17dfc5617a
Source dataset
uspto-grants-2015_04
Patent number
US09000183B2

Reaction notes

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