Ethanol → HCID 22033768, compound

HRID 1791979Notes

Reaction equation

HRID 1791979 reaction equation
[C:1]1([CH:6]=O)([CH:4]=[O:5])[CH2:3][CH2:2]1.[CH2:8]([OH:10])[CH3:9].C([O-])([O-])O[CH2:13][CH3:14].C(=O)(O)[O-].[Na+].[CH2:22]([NH2:29])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.[C-:30]#[N:31].[K+].S(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(OCC)(=O)C.CCCCCC.O>[CH2:22]([NH:29][CH:6]([C:1]1([CH:4]([O:5][CH2:13][CH3:14])[O:10][CH2:8][CH3:9])[CH2:2][CH2:3]1)[C:30]#[N:31])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

13

Reactant 7

HCID 702EthanolHCID 7504BenzylamineHCID 9032Potassium CyanideHCID 516892Sodium Bicarbonate2×HCID 220337631,1-CyclopropanedicarboxaldehydeHCID 23665763Sodium BisulfiteHCID 53630039Ethylorthoformate

Product 1

HCID 22033768HCID 22033768, compoundYield 712%

Reagents, catalysts & solvents 5

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

In toluene (30 ml) was dissolved 1,1-cyclopropane dicarboaldehyde (2.94 g, 30 mmol). Under ice cooling and stirring, a solution of p-toluenesulfonate monohydrate (5.7 mg, 0.03 mmol) in ethanol (138 mg, 3.0 mmol), and then, ethyl orthoformate (4.67 g, 31.5 mmol) were added. The resulting mixture was stirred at the external temperature of 40° C. for 1 hour. After addition of a saturated aqueous solution (3 ml) of sodium bicarbonate to the reaction mixture, benzyl amine (3.54 g, 33 mmol) was added under ice cooling and stirring. At the same temperature, the mixture was stirred for 30 minutes. To the reaction mixture were added successively potassium cyanide (2.15 g, 33 mmol) and sodium bisulfite (4.69 g, 45 mmol), and then water (30 ml). The resulting mixture was stirred at room temperature for 13 hours. A saturated aqueous solution of sodium bicarbonate was added, followed by extraction with ethyl acetate. The organic layer was washed successively with water and saturated saline, dried over anhydrous sodium sulfate, filtered, and then evaporated under reduced pressure. The pale yellow oil thus obtained was subjected to chromatography on a silica gel column (silica gel; 150 g, hexane:ethyl acetate=10:1.) to give a colorless oil as the title compound (6.16 g, 71.2%).

Workup

  1. stirringThe resulting mixture was stirred at the external temperature of 40° C. for 1 hour
  2. additionwas added under ice cooling
  3. stirringstirring
  4. stirringAt the same temperature, the mixture was stirred for 30 minutes
  5. stirringThe resulting mixture was stirred at room temperature for 13 hours
  6. extractionfollowed by extraction with ethyl acetate
  7. washThe organic layer was washed successively with water and saturated saline
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. customevaporated under reduced pressure
  11. customThe pale yellow oil thus obtained

Sources & evidence

ORD record
ord-1d4978a87be3401ca1a50f6435b78c9c
Source dataset
uspto-grants-2006_07
Patent number
US07074837B2

Reaction notes

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