tert-Butyl Dimethylphosphonoacetate → HCID 131736285, compound

HRID 1053549Notes

Reaction equation

HRID 1053549 reaction equation
CC(C)([O-])C.[K+].COP([CH2:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])(OC)=O.[CH2:21]([C:23]1[CH2:24][C@H:25]2[C@@H:28]([CH:29]=1)[C:27](=O)[CH2:26]2)[CH3:22]>O1CCCC1.CC(C)([O-])C.[K+].C(OC(=O)CP(OC)(OC)=O)(C)(C)C>[CH2:21]([C:23]1[CH2:29][C@H:28]2[C@@H:25]([CH:24]=1)[C:26](=[CH:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:27]2)[CH3:22]

Participants

7

Reactant 3

HCID 4564495tert-Butyl DimethylphosphonoacetateHCID 23665647Potassium tert-butoxideHCID 71582576HCID 71582576, compound

Product 1

HCID 131736285HCID 131736285, compoundYield 134.2%

Reagents, catalysts & solvents 3

HCID 4564495tert-Butyl DimethylphosphonoacetateCatalystHCID 23665647Potassium tert-butoxideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
5 °C

Procedure

Potassium t-butoxide (8.66 g) was dissolved in tetrahydrofuran (50 mL) under a nitrogen atmosphere, and the solution was then cooled to approximately 5° C. Tert-butyl (dimethoxyphosphoryl)acetate (17.30 g) was added thereto at 15° C. or lower, and the mixture was stirred at 5 to 15° C. for 1 hour. (1R,5S)-3-Ethylbicyclo[3.2.0]hept-3-en-6-one (10.00 g) and tetrahydrofuran (25 mL) were further added thereto, and the mixture was stirred at 5 to 15° C. for 1.5 hours. Potassium t-butoxide (0.90 g) and tert-butyl(dimethoxyphosphoryl)acetate (1.73 g) were further added thereto, and the mixture was stirred for approximately 1 hour. Then, the reaction mixture was separated into aqueous and organic layers by the addition of toluene (85 mL) and water (40 mL). The organic layer was washed twice with water (20 mL) and then concentrated under reduced pressure to obtain tert-butyl [(1R,5S)-3-ethylbicyclo[3.2.0]hept-3-en-6-ylidene]acetate (23.09 g) as a yellow oil.

Workup

  1. stirringthe mixture was stirred at 5 to 15° C. for 1.5 hours
  2. stirringthe mixture was stirred for approximately 1 hour
  3. customThen, the reaction mixture was separated into aqueous and organic layers
  4. additionby the addition of toluene (85 mL) and water (40 mL)
  5. washThe organic layer was washed twice with water (20 mL)
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-7c386574e7a9482faa7bc59c4ac68082
Source dataset
uspto-grants-2016_07
Patent number
US09394235B2

Reaction notes

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