4-Fluorobenzaldehyde → HCID 85746095, compound

HRID 1456595Notes

Reaction equation

HRID 1456595 reaction equation
[F:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][CH:3]=1.[Cl-].[F:11][C:12]1[CH:13]=[CH:14][C:15]([O:38][CH2:39][O:40][CH3:41])=[C:16]([CH:37]=1)[CH2:17][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:11][C:12]1[CH:13]=[CH:14][C:15]([O:38][CH2:39][O:40][CH3:41])=[C:16]([CH2:17][CH2:6][C:5]2[CH:8]=[CH:9][C:2]([F:1])=[CH:3][CH:4]=2)[CH:37]=1

Participants

8

Reactant 3

HCID 680234-FluorobenzaldehydeHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 22441842HCID 22441842, compound

Product 1

HCID 85746095HCID 85746095, compoundYield 87%

Reagents, catalysts & solvents 4

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

Conditions

Temperature
60 °C

Procedure

950 mg of 4-fluorobenzaldehyde, 3860 mg of 5-fluoro-2-methoxymethoxybenzyltriphenylphosphonium chloride (prepared as described in Preparation 8) and 1.26 ml of DBU were allowed to react together in 60 ml of acetonitrile, subsequently treated, and purified by silica gel column chromatography, using a 9:1 by volume mixture of hexane and ethyl acetate as the eluent, in the same manner as described in Preparation 2, to give 2030 mg of an oily substance. 1980 mg of this oily substance were dissolved in 12 ml of a 1:2 by volume mixture of benzene and ethanol, and then 155 mg of tris-(triphenylphosphine)rhodium(I) chloride were added to the resulting solution. The mixture was then stirred under a hydrogen atmosphere at atmospheric pressure and at 60° C. for 20 hours. At the end of this time, the reaction solution was filtered with diatomaceous earth. The filtrate was concentrated by evaporation under reduced pressure, and purified by silica gel column chromatography, using a 9:1 by volume mixture of hexane and ethyl acetate as the eluent, to give 1816 mg (yield 87%) of the title compound as an oily 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 2030 mg of an oily substance
  6. filtrationAt the end of this time, the reaction solution was filtered with diatomaceous earth
  7. concentrationThe filtrate was concentrated by evaporation under reduced pressure
  8. custompurified by silica gel column chromatography
  9. additionby volume mixture of hexane and ethyl acetate as the eluent

Sources & evidence

ORD record
ord-049ed91ca1fd42699b1e1f22b84ac13c
Source dataset
uspto-grants-1998_12
Patent number
US05843983

Reaction notes

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