p-Toluenesulfonic acid → HCID 19434123, compound

HRID 1736003Notes

Reaction equation

HRID 1736003 reaction equation
[CH2:1]([O:3][C:4](=[O:21])[CH2:5][N:6]([S:8]([C:11]1[S:12][CH:13]=[CH:14][C:15]=1[CH:16]1OCCO1)(=O)=O)[CH3:7])[CH3:2].C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)(O)[O-].[Na+].C1CN2C(=NCCC2)C1>CC(C)=O.C(OCC)(=O)C.O>[CH3:7][N:6]1[C:5]([C:4]([O:3][CH2:1][CH3:2])=[O:21])=[CH:16][C:15]2[CH:14]=[CH:13][S:12][C:11]=2[S:8]1

Participants

8

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 763491,5-Diazabicyclo(4.3.0)non-5-eneHCID 516892Sodium BicarbonateHCID 19434100HCID 19434100, compound

Product 1

HCID 19434123HCID 19434123, compoundYield 79.6%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolvent2×HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of the product from Step A (8.80 g, 26.3 mmol) and 4-toluenesulfonic acid (1.0 g) in acetone (250 mL) was stirred overnight at ambient temperature. Water (0.5 mL) was added and this mixture was stirred for 4 h followed by addition of a saturated aqueous solution of sodium bicarbonate (50 mL) and evaporation of the acetone. The aqueous mixture was extracted with ethyl acetate (2×200 mL) and the combined extracts were dried (MgSO4) and evaporated to give crude aldehyde which was dissolved in ethyl acetate (150 mL). DBN (0.5 g) was added and the mixture heated at reflux temperature for 2 h, cooled and washed with a saturated aqueous solution of sodium bicarbonate (50 mL). The ethyl acetate solution was dried (MgSO4) and evaporated to a residue which was purified by column chromatography (silica, 30 to 50% ethyl acetate/hexane) to give the desired product as a white solid (5.05 g, 70%).

Workup

  1. stirringthis mixture was stirred for 4 h
  2. extractionThe aqueous mixture was extracted with ethyl acetate (2×200 mL)
  3. dry with materialthe combined extracts were dried (MgSO4)
  4. customevaporated
  5. customto give crude aldehyde which
  6. temperaturethe mixture heated
  7. temperatureat reflux temperature for 2 h
  8. temperaturecooled
  9. washwashed with a saturated aqueous solution of sodium bicarbonate (50 mL)
  10. dry with materialThe ethyl acetate solution was dried (MgSO4)
  11. customevaporated to a residue which
  12. customwas purified by column chromatography (silica, 30 to 50% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-4ed206a7930c4c24a3980052ed06a118
Source dataset
uspto-grants-1996_07
Patent number
US05538966

Reaction notes

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