Sodium Hydroxide → HCID 53825216, compound

HRID 1735855Notes

Reaction equation

HRID 1735855 reaction equation
[H-].[Na+].[CH3:3][O:4][C:5]([CH2:7]P(OC)(OC)=O)=[O:6].[H][H].[CH2:16]([C:19]1([CH:34]=O)[C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][C:24]=2[CH2:23][CH2:22][C:21]2[CH:30]=[CH:31][CH:32]=[CH:33][C:20]1=2)[CH:17]=[CH2:18].[OH-].[Na+]>CCCCCC.C1COCC1.CN(C=O)C>[CH2:16]([C:19]1([CH:34]=[CH:7][C:5]([O:4][CH3:3])=[O:6])[C:20]2[CH:33]=[CH:32][CH:31]=[CH:30][C:21]=2[CH2:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][C:25]1=2)[CH:17]=[CH2:18]

Participants

9

Reactant 5

HCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 80029Trimethyl phosphonoacetateHCID 19079053HCID 19079053, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 53825216HCID 53825216, compoundYield 66.2%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolvent2×HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

Washed sodium hydride (1.72 g of 60 weight % in oil, 0.0429 mol) two times with hexane under a nitrogen atmosphere. Added 100 mL of dry THF, and cooled to 0° C. Added trimethyl phosphonoacetate (7.81 g, 6.9 mL, 0.0429 mol) dissolved in 15 mL of dry THF dropwise via addition funnel. Hydrogen evolution was observed. Added 50 mL of dry DMF, and stirred at room temperature for 30 mins. Added 10,11-dihydro-5-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-5-carboxaldehyde (7.50 g, 0.0286 mol) dissolved in 25 mL of dry DMF dropwise via addition funnel. Stirred at room temperature for 45 mins then heated at 75° C. for 16 hours. Cooled to room temperature, and added 0.5N NaOH. Extracted with ethyl acetate. Washed combined organic extracts with 0.5N HCl and saturated NaCl, dried with MgSO4, filtered, and evaporated. Purified crude product by flash chromatography on silica gel eluting with 2% ethyl acetate-hexane, 5% ethyl acetate-hexane, then 10% ethyl acetate-hexane. Combined appropriate fractions, and evaporated to give 6.03 g (66% yield) of methyl 3-[10,11-dihydro-5-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-5-yl]-propenoate as a colorless oil.

Workup

  1. stirringStirred at room temperature for 45 mins
  2. temperaturethen heated at 75° C. for 16 hours
  3. temperatureCooled to room temperature
  4. extractionExtracted with ethyl acetate
  5. washWashed
  6. dry with materialdried with MgSO4
  7. filtrationfiltered
  8. customevaporated
  9. customPurified crude product by flash chromatography on silica gel eluting with 2% ethyl acetate-hexane, 5% ethyl acetate-hexane
  10. customevaporated

Sources & evidence

ORD record
ord-ced92946a4534df9b538406df6a2522a
Source dataset
uspto-grants-1996_07
Patent number
US05538986

Reaction notes

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