Benzaldehyde → HCID 22106947, compound

HRID 1456592Notes

Reaction equation

HRID 1456592 reaction equation
[CH:1](=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl-].[F:10][C:11]1[CH:12]=[CH:13][C:14]([O:37]COC)=[C:15]([CH:36]=1)[CH2:16][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1CCN2C(=NCCC2)CC1>C(#N)C.C1C=CC=CC=1.C(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]>[F:10][C:11]1[CH:12]=[CH:13][C:14]([OH:37])=[C:15]([CH2:16][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH:36]=1

Participants

8

Reactant 3

HCID 240BenzaldehydeHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 22441842HCID 22441842, compound

Product 1

HCID 22106947HCID 22106947, compoundYield 79%

Reagents, catalysts & solvents 4

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)CatalystHCID 241BenzeneSolventHCID 702EthanolSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

0.91 g of benzaldehyde, 4.00 g of 5-fluoro-2-methoxymethoxybenzyl-triphenylphosphonium chloride (prepared as described in Preparation 8) and 1.28 ml of DBU were allowed to react together in 40 ml of acetonitrile, 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 2.04 g of an oily substance. 2.03 g of this oily substance were dissolved in 12 ml of a 1:2 by volume mixture of benzene and ethanol, and then 0.30 g of tris-(triphenylphosphine)rhodium(I) chloride were added to the resulting solution. The resulting mixture was stirred under a hydrogen atmosphere at atmospheric pressure and at 60° C. for 8 hours. At the end of this time, the reaction solution was filtered with a Celite (trade mark) filter aid. The filtrate was concentrated by evaporation under reduced pressure, and purified by silica gel column chromatography, using a 10:1 by volume mixture of hexane and ethyl acetate as the eluent. The purified substance was then dissolved in 10 ml of ethyl acetate, and then 10 ml of a 4N solution of hydrogen chloride in ethyl acetate were added to the resulting solution, with ice-cooling. The resulting mixture was allowed to stand at room temperature for 2 hours, after which it 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 1.45 g (yield 79%) of the title compound as a solid substance.

Workup

  1. additionsubsequently 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 2.04 g of an oily substance
  6. filtrationAt the end of this time, the reaction solution was filtered with a Celite (trade mark)
  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. dissolutionThe purified substance was then dissolved in 10 ml of ethyl acetate
  12. addition10 ml of a 4N solution of hydrogen chloride in ethyl acetate were added to the resulting solution, with ice-
  13. temperaturecooling
  14. waitto stand at room temperature for 2 hours
  15. concentrationafter which it was concentrated by evaporation under reduced pressure
  16. custompurified by silica gel column chromatography
  17. additionby volume mixture of hexane and ethyl acetate as the eluent

Sources & evidence

ORD record
ord-6a080c2a2a1a4a35aa36c907b5b4f5ec
Source dataset
uspto-grants-1998_12
Patent number
US05843983

Reaction notes

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