Methanol → HCID 22617097, compound

HRID 843297Notes

Reaction equation

HRID 843297 reaction equation
[H-].[Na+].P(=O)([O-])O[C:5]([CH2:17][CH3:18])(CC)[C:6]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][CH:7]=1.[CH:21]1[C:31]2C=C[C:28]3[CH:32]=[CH:33][CH:34]=[CH:35][C:27]=3[C:26](=O)[C:25]=2[CH:24]=[CH:23][CH:22]=1.CO>CS(C)=O.[Cl-].[Na+].O>[N+:12]([C:9]1[CH:8]=[CH:7][C:6]([CH:5]=[C:17]2[C:18]3[CH:35]=[CH:34][CH:33]=[CH:32][C:28]=3[CH:27]=[CH:26][C:25]3[CH:31]=[CH:21][CH:22]=[CH:23][C:24]2=3)=[CH:11][CH:10]=1)([O-:14])=[O:13]

Participants

7

Reactant 4

HCID 887MethanolHCID 166795H-Dibenzo[a,d]cyclohepten-5-oneHCID 24758Sodium hydrideHCID 178447636HCID 178447636, compound

Product 1

HCID 22617097HCID 22617097, compoundYield 69.3%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
70 °C

Procedure

To 150 ml of dimethylsulfoxide, 3.60 g (about 90 mmol) of oily sodium hydride (about 60%) was added at room temperature. After the addition, the mixture was heated to the inner temperature of around 70° C. in an oil bath, and stirred under the same conditions for 1 hour. Thereafter, the reaction solution was cooled to room temperature, and then a solution of 25.1 g (92 mmol) of the diethyl-4-nitrobenzyl phosphonate and 10.0 g (48.6 mmol) of 5H-dibenzo[a,d]cyclohepten-5-one in 50 ml dimethyl sulfoxide was added dropwise thereto. After the addition was completed, the resulting mixture was stirred for 15 minutes at room temperature, and thereafter heated and stirred for 2 hours in an oil bath while keeping its internal temperature at 70 to 80° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and then poured in about 1 liter of saturated brine, followed by extraction with ethyl acetate. The organic layer was dried with anhydrous sodium sulfate, and the solvent was removed under reduced pressure. To the residue thus obtained was added methanol, and the precipitated crystals were collected by filtration. The crystals were then recrystallized using a methanol/acetone mixed solvent to obtain 10.94 g of 5-(4-nitrobenzylidene)-5H-dibenzo[a,d]cycloheptene. Yield: 69.3%; m.p.: 151.5 to 152.5° C.

Workup

  1. additionAfter the addition
  2. temperatureThereafter, the reaction solution was cooled to room temperature
  3. additionAfter the addition
  4. stirringthe resulting mixture was stirred for 15 minutes at room temperature
  5. temperatureheated
  6. stirringstirred for 2 hours in an oil bath
  7. customat 70 to 80° C
  8. temperaturethe reaction mixture was cooled to room temperature
  9. extractionfollowed by extraction with ethyl acetate
  10. dry with materialThe organic layer was dried with anhydrous sodium sulfate
  11. customthe solvent was removed under reduced pressure
  12. customTo the residue thus obtained
  13. filtrationthe precipitated crystals were collected by filtration
  14. customThe crystals were then recrystallized

Sources & evidence

ORD record
ord-033f65aa253947c8b814e64c7d548b45
Source dataset
uspto-grants-2002_04
Patent number
US06376695B1

Reaction notes

Loading…