Sodium hydride → 4-(Tetrahydropyran-4-ylidene)butanoic acid ethyl ester

HRID 1788386Notes

Reaction equation

HRID 1788386 reaction equation
[Br-].[CH2:2]([O:4][C:5]([CH2:7][CH2:8][CH2:9][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:6])[CH3:3].[H-].[Na+].[O:31]1[CH2:36][CH2:35][C:34](=O)[CH2:33][CH2:32]1>CN(C)C=O>[CH2:2]([O:4][C:5](=[O:6])[CH2:7][CH2:8][CH:9]=[C:34]1[CH2:35][CH2:36][O:31][CH2:32][CH2:33]1)[CH3:3]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 121599Tetrahydro-4H-pyran-4-oneHCID 2773643(3-(Ethoxycarbonyl)propyl)triphenylphosphonium Bromide

Product 1

HCID 576028974-(Tetrahydropyran-4-ylidene)butanoic acid ethyl esterYield 6.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of 11.2 g (24.5 mmol) of [3-(ethoxycarbonyl)propyl]triphenylphosphonium bromide in dimethylformamide (19 mL) was dropped into a cooled (10° C.) suspension of 1.13 g (28.2 mmol) of a 60% sodium hydride in dimethylformamide (2 mL) under an atmosphere of argon, and stirred for 40 minutes. Into this, 2.5 g (24.5 mmol) of tetrahydropyran-4-one was dropped. After dropping, stirring was continued for 1 hour at 10° C. and for 14 hours at room temperature. After the reaction was completed, the reaction mixture was poured into ice water and extracted with ether. The organic layer was washed with water (three times) and saturated brine successively, then dried over anhydrous magnesium sulfate and concentrated under a reduced pressure. The obtained residue was purified by medium pressure liquid column chromatography on silica gel (developing solvent: hexane:etyl acetate) to obtain 320 mg (yield 6.6%) of 4-(tetrahydropyran-4-ylidene)butanoic acid ethyl ester (IX-127) as colorless liquid. Its physical properties are shown below.

Workup

  1. temperaturea cooled
  2. stirringstirring
  3. waitwas continued for 1 hour at 10° C. and for 14 hours at room temperature
  4. extractionextracted with ether
  5. washThe organic layer was washed with water (three times) and saturated brine successively
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under a reduced pressure
  8. customThe obtained residue was purified by medium pressure liquid column chromatography on silica gel (developing solvent: hexane:etyl acetate)

Sources & evidence

ORD record
ord-2139e1c3124a41e38d8ac505bc3ba0c8
Source dataset
uspto-grants-2009_03
Patent number
US07511144B2

Reaction notes

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