Dimethylformamide → 1,3-Bis(2-hydroxyethoxy)-10,11-dihydrodibenz[b,f]oxepin

HRID 567874Notes

Reaction equation

HRID 567874 reaction equation
CN(C)[CH:3]=[O:4].[C:6](=[O:9])([O-])[O-].[K+].[K+].Br[CH2:13][C:14](OC)=[O:15].[C:18]1([OH:34])[C:28]2[CH2:27][CH2:26][C:25]3[CH:29]=[CH:30][CH:31]=[CH:32][C:24]=3[O:23][C:22]=2[CH:21]=[C:20](O)[CH:19]=1>CCCCCC>[OH:15][CH2:14][CH2:13][O:34][C:18]1[C:28]2[CH2:27][CH2:26][C:25]3[CH:29]=[CH:30][CH:31]=[CH:32][C:24]=3[O:23][C:22]=2[CH:21]=[C:20]([O:9][CH2:6][CH2:3][OH:4])[CH:19]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 60984Methyl bromoacetateHCID 1551249510,11-Dihydrodibenz[b,f]oxepin-1,3-diol

Product 1

HCID 183800041,3-Bis(2-hydroxyethoxy)-10,11-dihydrodibenz[b,f]oxepinYield 58%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

N,N-Dimethylformamide (0.6 ml), potassium carbonate (90 mg) and methyl bromoacetate (51 μl) were added to 50 mg of the Compound 12 recovered in the Production Example 12, and the resulting mixture was stirred at room temperature for 2 hours. The reaction solution was partitioned between ethyl acetate and dilute hydrochloric acid, and the resulting ethyl acetate layer was washed in water and then in an aqueous saturated sodium chloride solution and dried over anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. To the residue was added anhydrous diethyl ether of 0.5 ml, for stirring at 0° C. Then, LiAlH4 (20 mg) was added to the resulting mixture, followed by stirring at room temperature for 2 hours. To the resulting mixture were added trace amounts of ethyl acetate and an aqueous saturated sodium chloride solution, followed by filtration and evaporation of the solvent under reduced pressure. The residue was purified by silica gel column chromatography (elution solvent; ethyl acetate:hexane=1:2), followed by recrystallization in ethyl acetate and hexane, to recover the entitled Compound 56 (40 mg; yield of 58%) as colorless needles, represented by the following formula. The melting point of the Compound 56 was 111.5-113.5° C.

Workup

  1. customrecovered in the Production Example 12
  2. customThe reaction solution was partitioned between ethyl acetate and dilute hydrochloric acid
  3. washthe resulting ethyl acetate layer was washed in water
  4. dry with materialin an aqueous saturated sodium chloride solution and dried over anhydrous magnesium sulfate
  5. distillationby distilling off the solvent under reduced pressure
  6. additionTo the residue was added anhydrous diethyl ether of 0.5 ml
  7. stirringfor stirring at 0° C
  8. additionThen, LiAlH4 (20 mg) was added to the resulting mixture
  9. stirringby stirring at room temperature for 2 hours
  10. additionTo the resulting mixture were added trace amounts of ethyl acetate
  11. filtrationan aqueous saturated sodium chloride solution, followed by filtration and evaporation of the solvent under reduced pressure
  12. customThe residue was purified by silica gel column chromatography (elution solvent; ethyl acetate:hexane=1:2)
  13. customfollowed by recrystallization in ethyl acetate

Sources & evidence

ORD record
ord-5284bb0592b8444da7187b3b5437dfaa
Source dataset
uspto-grants-2001_01
Patent number
US06180659B2

Reaction notes

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