Dimethyl Sulfoxide → Acetate

HRID 1160357Notes

Reaction equation

HRID 1160357 reaction equation
CS(C)=[O:3].[H-].[Na+].[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([CH2:14][C:15]#[N:16])=[CH:10][CH:9]=1.Br[CH2:18][CH2:19][O:20][CH2:21][CH2:22]Br>C(OCC)C>[C:21]([O-:3])(=[O:20])[CH3:22].[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2([C:15]#[N:16])[CH2:22][CH2:21][O:20][CH2:19][CH2:18]2)=[CH:10][CH:9]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 21521Bis(2-bromoethyl) etherHCID 24758Sodium hydrideHCID 2415824-Chlorobenzyl cyanide

Product 2

HCID 175AcetateHCID 219019604-(4-Chlorophenyl)tetrahydro-2H-pyran-4-carbonitrile

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
25 °C

Procedure

Into a round-bottom flask under argon fitted with an addition funnel and thermometer was added anhydrous dimethylsulfoxide (60 mL) and sodium hydride (1.17 g, 48.8 mmol, 95%). Then a solution of (4-chlorophenyl)acetonitrile (3.37 g, 22.2 mmol) and 2-bromoethyl ether (90%, 3.41 mL, 24.4 mmol) in diethyl ether (15 mL) was added slowly, while maintaining the reaction temperature at 20-30° C. The reaction mixture was maintained at room temperature for overnight. The reaction mixture was carefully quenched with water (50 mL) and then extracted with hexane (3×100 mL). The organic extracts were combined, washed with water (3×75 mL), brine (50 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated to give a pale yellow oil. The oil was purified by column chromatography on silica gel using hexane/ethyl:acetate (80:20) to give 4.7 g of 4-(4-chlorophenyl)tetrahydropyran-4-carbonitrile, as a colorless oil. 1H NMR (CDCl3, 300 MHz): δ 2.00-2.15 (m, 4H); 3.89 (dt, 2H, J1=12.6 Hz, J2=3 Hz); 4.05-4.11 (m, 2H); 7.37-7.45 (m, 4H); 13C NMR (CDCl3, 300 MHz): δ 36.66 (2C), 41.51, 64.98 (2C), 121.40, 127.03, 129.37, 134.31, 138.46.

Workup

  1. customInto a round-bottom flask under argon fitted with an addition funnel
  2. temperatureThe reaction mixture was maintained at room temperature for overnight
  3. customThe reaction mixture was carefully quenched with water (50 mL)
  4. extractionextracted with hexane (3×100 mL)
  5. washwashed with water (3×75 mL), brine (50 mL)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give a pale yellow oil
  10. customThe oil was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-c184288495474d86bae5a0802c3e801d
Source dataset
uspto-grants-2010_10
Patent number
US07816375B2

Reaction notes

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