Benzaldehyde → HCID 22106913, compound

HRID 1456602Notes

Reaction equation

HRID 1456602 reaction equation
[CH:1](=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl-].[Cl:10][C:11]1[CH:36]=[CH:35][C:14]([CH2:15][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=[C:13]([O:37]C)[CH:12]=1.C1CCN2C(=NCCC2)CC1.Cl>C(#N)C.C(O)C.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Rh]>[Cl:10][C:11]1[CH:36]=[CH:35][C:14]([CH2:15][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[C:13]([OH:37])[CH:12]=1

Participants

9

Reactant 4

HCID 240BenzaldehydeHCID 313Hydrochloric AcidHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 88345694HCID 88345694, compound

Product 1

HCID 22106913HCID 22106913, compound

Reagents, catalysts & solvents 4

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)CatalystHCID 702EthanolSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
50 °C

Procedure

1.10 g of benzaldehyde, 6.02g of 4-chloro-2-methoxybenzyltriphenyl-phosphonium chloride and 1.85 ml of DBU were allowed to react together in 20 ml of acetonitrile and were subsequently treated and purified by silica gel column chromatography, using a 10: 1 by volume mixture of hexane and ethyl acetate as the eluent, in the same manner as described in Preparation 2, to give 2.85 g of an oily substance. This oily substance was dissolved in 50 ml of ethanol, and 0.40 g of tris(triphenylphosphine)rhodium(I) chloride was added to the resulting solution. The resulting mixture was then stirred under a hydrogen atmosphere at atmospheric pressure and at 50° C. for 14 hours. At the end of this time, the reaction solution was filtered using a Celite (trade mark) filter aid. The filtrate was concentrated by evaporation under reduced pressure, and purified by silica gel column chromatography, using a 5:1 by volume mixture of hexane and ethyl acetate as the eluent, to give an intermediate compound. This intermediate compound was dissolved in 10 ml of ethyl acetate, and 10 ml of a 4N solution of hydrogen chloride in ethyl acetate were added to the resulting solution, whilst ice-cooling. The reaction mixture was then allowed to stand at room temperature for 1 hour. At the end of this time, the solvent was removed by evaporation under reduced pressure. The residue was purified by silica gel column chromatography, using a 5:1 by volume mixture of hexane and ethyl acetate as the eluent, to give 2.40 g (a quantitative yield) of the title compound as a colorless oily substance.

Workup

  1. additionwere subsequently treated
  2. custompurified by silica gel column chromatography
  3. additionby volume mixture of hexane and ethyl acetate as the eluent
  4. customin the same manner as described in Preparation 2
  5. customto give 2.85 g of an oily substance
  6. filtrationAt the end of this time, the reaction solution was filtered
  7. filtrationfilter aid
  8. concentrationThe filtrate was concentrated by evaporation under reduced pressure
  9. custompurified by silica gel column chromatography
  10. additionby volume mixture of hexane and ethyl acetate as the eluent
  11. customto give an intermediate compound
  12. temperaturecooling
  13. waitto stand at room temperature for 1 hour
  14. customAt the end of this time, the solvent was removed by evaporation under reduced pressure
  15. customThe residue was purified by silica gel column chromatography
  16. additionby volume mixture of hexane and ethyl acetate as the eluent

Sources & evidence

ORD record
ord-f0307efb1c56469eb6b1814f0f8296f3
Source dataset
uspto-grants-1998_12
Patent number
US05843983

Reaction notes

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