Lithium Hydroxide → HCID 59718740, compound

HRID 1925617Notes

Reaction equation

HRID 1925617 reaction equation
[CH3:1][CH2:2][CH2:3][C:4](=O)[CH2:5][CH2:6][CH3:7].[CH2:9]([NH2:13])[CH2:10][CH2:11][CH3:12].C[O:15][CH:16]=[C:17]([C:22]([O:24]C)=[O:23])[C:18](OC)=O.[OH-].[Li+]>Cl.C1COCC1.O>[CH2:9]([N:13]1[C:4]([CH2:5][CH2:6][CH3:7])=[C:3]([CH2:2][CH3:1])[CH:18]=[C:17]([C:22]([OH:24])=[O:23])[C:16]1=[O:15])[CH2:10][CH2:11][CH3:12]

Participants

8

Reactant 4

HCID 3939Lithium HydroxideHCID 8007ButylamineHCID 312464-HeptanoneHCID 90770Dimethyl methoxymethylenemalonate

Product 1

HCID 59718740HCID 59718740, compound

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidCatalystHCID 962WaterSolvent3×HCID 8028TetrahydrofuranSolvent

Procedure

Under the nitrogen gas atmosphere, a solution of 4-heptanone (5.0 mM, 35.75 mmol), n-butylamine (4.25 mL, 4.29 mmol), and three drops of concentrated hydrochloric acid was stirred for 18.5 hours at room temperature. After that, water was added and the mixture was extracted with ethyl acetate. After the organic layer had been washed with water and then dried with anhydrous sodium sulfate, the solvent was removed by distillation under reduced pressure. The obtained oily matter was dissolved in 2-methoxyethyl ether (40 mL), and heated and stirred with dimethyl methoxymethylenemalonate (5.66 g, 32.5 mmol) at 120° C. for 3 hours. After the solvent had been removed by distillation under reduced pressure, the residue was refined with silica gel (100 g) column chromatography (ethyl acetate-hexane of 1:1 in mixing ratio and then that of 2:1), and a ark reddish-brown oily substance was obtained. The substance was dissolved in THF (20 mL) without purification, and a 1M lithium hydroxide aqueous solution (15.18 mL) and water (4.82 mL) were added, and then the mixture was stirred for 2 hours at room temperature. After that, the mixture was diluted with water and washed with diethyl ether. After 2M hydrochloric acid had been added to the water layer to acidify it, the water layer was extracted with ethyl acetate. The organic layer was washed with water and then dried with anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure and a pale yellow solid (AA03, 1.68 g, 18%) was obtained.

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washAfter the organic layer had been washed with water
  3. dry with materialdried with anhydrous sodium sulfate
  4. customthe solvent was removed by distillation under reduced pressure
  5. dissolutionThe obtained oily matter was dissolved in 2-methoxyethyl ether (40 mL)
  6. temperatureheated
  7. customAfter the solvent had been removed by distillation under reduced pressure
  8. additionin mixing ratio
  9. customthat of 2:1), and a ark reddish-brown oily substance was obtained
  10. washwashed with diethyl ether
  11. additionAfter 2M hydrochloric acid had been added to the water layer
  12. extractionthe water layer was extracted with ethyl acetate
  13. washThe organic layer was washed with water
  14. dry with materialdried with anhydrous sodium sulfate
  15. customThe solvent was removed by distillation under reduced pressure
  16. customa pale yellow solid (AA03, 1.68 g, 18%) was obtained

Sources & evidence

ORD record
ord-26a133d3b50945e1acdefa4274e3e8f0
Source dataset
uspto-grants-2012_05
Patent number
US08178681B2

Reaction notes

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