Sodium hydride → HCID 54200668, compound

HRID 1275959Notes

Reaction equation

HRID 1275959 reaction equation
[CH3:1][CH2:2][O:3][C:4]([CH:6](P(OCC)(OCC)=O)[CH3:7])=[O:5].[H-].[Na+].[CH3:18][C:19]1([CH3:29])[C:23]([CH3:24])=[CH:22][CH2:21][CH:20]1[CH2:25][C:26](=O)[CH3:27].CC1C(C)(C)C(CC=O)CC=1>C1COCC1>[CH2:2]([O:3][C:4](=[O:5])[C:6]([CH3:7])=[C:26]([CH3:27])[CH2:25][CH:20]1[CH2:21][CH:22]=[C:23]([CH3:24])[C:19]1([CH3:29])[CH3:18])[CH3:1]

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 984973-Cyclopentene-1-acetaldehyde, 2,2,3-trimethyl-HCID 107155Triethyl 2-phosphonopropionateHCID 13975758HCID 13975758, compound

Product 1

HCID 54200668HCID 54200668, compoundYield 28.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

47.6 g (0.20 mol) of triethyl 2-phosphonopropionate was added dropwise under nitrogen to a cooled and stirred suspension of 4.8 g (0.20 mol) of sodium hydride in 300 ml of THF and stirring continued for 30 min. at room temperature. After addition of 30 g (0.18 mol) of 1-(2,2,3-trimethylcyclopent-3-enyl)propan-2-one, prepared from campholenic aldehyde as known per se, and 46 hours of more stirring, the reaction mixture was poured into 400 ml of ice-cold 1N hydrochloric acid and extracted with 2×300 ml of MTBE. The extract was washed with 5×350 ml of brine, dried (MgSO4) and concentrated in vacuo. The distillation at 90-97° C./0.065-0.075 Torr yielded 13 g of the product which was further purified by flash chromatography on silica gel (eluent: hexane/MTBE 15:1) to give 6.4 g (14% yield) of2,3-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)but-2-enoic acid ethyl ester.

Workup

  1. temperaturea cooled
  2. stirringstirring
  3. customas known per se, and 46 hours
  4. stirringof more stirring
  5. extractionextracted with 2×300 ml of MTBE
  6. washThe extract was washed with 5×350 ml of brine
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. distillationThe distillation at 90-97° C./0.065-0.075 Torr

Sources & evidence

ORD record
ord-da555067d31342cb8c5bccfba1883610
Source dataset
uspto-grants-2000_12
Patent number
US06162954

Reaction notes

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