Sodium hydride → HCID 66740127, compound

HRID 1035686Notes

Reaction equation

HRID 1035686 reaction equation
C([C:3]([CH2:14][CH3:15])(P(=O)=O)[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])C.[H-].[Na+].O=C1C[CH2:23][CH:22]([C:25]2[CH:35]=[CH:34][C:28]([C:29]([O:31][CH2:32][CH3:33])=[O:30])=[CH:27][CH:26]=2)[CH2:21][CH2:20]1>CN(C)C=O>[C:7]([O:6][C:4]([CH:3]=[C:14]1[CH2:15][CH2:23][CH:22]([C:25]2[CH:26]=[CH:27][C:28]([C:29]([O:31][CH2:32][CH3:33])=[O:30])=[CH:34][CH:35]=2)[CH2:21][CH2:20]1)=[O:5])([CH3:8])([CH3:9])[CH3:10]

Participants

5

Reactant 3

HCID 24758Sodium hydride2×HCID 22633634Ethyl 4-(4-oxocyclohexyl)benzoateHCID 86662109HCID 86662109, compound

Product 1

HCID 66740127HCID 66740127, compoundYield 72.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
4 °C

Procedure

5.63 g of tert-butyl diethylphosphoacetate (20.3 mmol, 1 eq.) are placed in 20 mL of dimethylformamide with stirring. The solution is cooled to a temperature of 4° C. by placing it in an ice bath, and 0.536 g of sodium hydride (22.33 mmol, 1.1 eq.) is then added portionwise. After 30 minutes, 5 g of ethyl 4-(4-oxo-cyclohexyl)benzoate (20.3 mmol, 1 eq.) are added and the ice bath is removed. After stirring for 1 hour, the flask is placed in an ice bath to cool the reaction medium to a temperature of 4° C., and 0.049 g of sodium hydride (2.04 mmol, 0.1 eq.) is added. The ice bath is removed and, after 30 minutes, the mixture is poured into 200 mL of 1N potassium hydrogen sulfate and extracted with 300 mL of ethyl ether. The organic phase is washed 4 times with brine. The organic phase is dried over sodium sulfate and evaporated. The residue is chromatographed on silica gel, eluting with a gradient of methanol in dichloromethane ranging from 0% to 5%. 5.04 g of ethyl 4-(4-tert-butoxycarbonylmethylenecyclohexyl)benzoate are obtained.

Workup

  1. customthe ice bath is removed
  2. stirringAfter stirring for 1 hour
  3. customthe flask is placed in an ice bath
  4. additionis added
  5. customThe ice bath is removed and, after 30 minutes
  6. additionthe mixture is poured into 200 mL of 1N potassium hydrogen sulfate
  7. extractionextracted with 300 mL of ethyl ether
  8. washThe organic phase is washed 4 times with brine
  9. dry with materialThe organic phase is dried over sodium sulfate
  10. customevaporated
  11. customThe residue is chromatographed on silica gel
  12. washeluting with a gradient of methanol in dichloromethane ranging from 0% to 5%

Sources & evidence

ORD record
ord-5683200e5e6f41d3b5fc30a99ca35f00
Source dataset
uspto-grants-2013_10
Patent number
US08546391B2

Reaction notes

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