Silane, (chloromethyl)trimethyl- → HCID 9836619, compound

HRID 2292986Notes

Reaction equation

HRID 2292986 reaction equation
C([Li])CCC.[F:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]2[CH2:17][CH2:16][CH2:15][C:14]=2[C:18]2[CH:23]=[CH:22][C:21]([S:24](C)(=[O:26])=[O:25])=[CH:20][CH:19]=2)=[CH:9][CH:8]=1.ClC[Si](C)(C)C.[F-].C([N+:39](CCCC)(CCCC)CCCC)CCC.CC([O-])=O.[Na+].NOS(O)(=O)=O>C(OCC)(=O)C.O.O1CCCC1>[F:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]2[CH2:17][CH2:16][CH2:15][C:14]=2[C:18]2[CH:23]=[CH:22][C:21]([S:24]([NH2:39])(=[O:26])=[O:25])=[CH:20][CH:19]=2)=[CH:9][CH:8]=1

Participants

10

Reactant 6

HCID 75361Silane, (chloromethyl)trimethyl-HCID 76284hydroxylamine-O-sulfonic acidHCID 443373SC-57666HCID 517045Sodium AcetateHCID 2724141Tetrabutylammonium FluorideHCID 178418339Butyllithium

Product 1

HCID 9836619HCID 9836619, compoundYield 84%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

n-Butyllithium (0.54 mL, 1.34 mmol, 2.49M) was added dropwise via syringe to 1-[2-(4-fluorophenyl)cyclopenten-1-yl]-4-(methylsulfonyl)benzene (prepared as described in U.S. Pat. No. 5,344,991) (0.352 g, 1.11 mmol) and dry tetrahydrofuran (THF) (3.5 mL) cooled in an ice-bath. The resulting orange solution was stirred for 1 hour in the ice-bath and (chloromethyl)trimethylsilane (235 μL, 1.68 mmol) was added in one portion via syringe. The ice-bath was removed and the reaction mixture was stirred for 6 hours at room temperature. Tetrabutylammonium fluoride (6.0 mL, 6.00 mmol, 1M in THF) was added in one portion via syringe, and the resulting mixture was heated to reflux for 45 minutes, then cooled to room temperature. To the reaction mixture was added sequentially NaOAc (0.501 g, 6.11 mmol), water (15.0 mL), and H2NOSO3H (0.712 g, 6.30 mmol) and the reaction was stirred overnight at room temperature. The reaction mixture was diluted with ethyl acetate (20.0 mL), the layers were separated, and the organic layer was washed with saturated NaHCO3 (2×10 mL), water (10.0 mL), and brine (10.0 mL) then dried over MgSO4. The solution was filtered, the solvents removed under reduced pressure, the crude product was purified by silica gel chromatography to afford 0.294 g (84%) of product as a white solid.

Workup

  1. customprepared
  2. additionwas added in one portion via syringe
  3. customThe ice-bath was removed
  4. temperaturethe resulting mixture was heated
  5. temperatureto reflux for 45 minutes
  6. temperaturecooled to room temperature
  7. stirringthe reaction was stirred overnight at room temperature
  8. customthe layers were separated
  9. washthe organic layer was washed with saturated NaHCO3 (2×10 mL), water (10.0 mL), and brine (10.0 mL)
  10. dry with materialthen dried over MgSO4
  11. filtrationThe solution was filtered
  12. customthe solvents removed under reduced pressure
  13. customthe crude product was purified by silica gel chromatography

Sources & evidence

ORD record
ord-5ee61bc912f14965a7a62d7a16945e02
Source dataset
uspto-grants-1997_11
Patent number
US05684195

Reaction notes

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