Proton sponge → 3-Chloro-5-methoxybenzaldehyde

HRID 1735650Notes

Reaction equation

HRID 1735650 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([O:18][CH3:19])[C:9]=1OS(C(F)(F)F)(=O)=O)[CH:5]=[O:6].CN(C1C2C(N(C)C)=CC=CC=2C=CC=1)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].CC#N>[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([O:18][CH3:19])[CH:9]=1)[CH:5]=[O:6]

Participants

6

Reactant 2

HCID 88675Proton spongeHCID 183205273-Chloro-5-methoxy-4-trifluoromethanesulfonyloxy benzaldehyde

Product 1

HCID 219046333-Chloro-5-methoxybenzaldehydeYield 89%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
90 °C

Procedure

Triflate 5 (9 g, 28 mmol), palladium(II) acetate (120 mg, 0.5 mmol), 1,1'-bis(diphenyiphosphino)ferrocene (620 mg, 1 mmol) and hplc grade CH3CN (10 ml) were mixed well in a teflon-lined stainless steel bomb. After adding freshly made, pulverized proton sponge formate2 (7.84 g, 30 mmol), the bomb was sealed and heated at 90° C. for 4 h. The cooled reaction was then filtered to remove proton sponge crystals, partitioned between EtOAc and 3N HCl, washed once each with dilute brine and dilute NaHCO3, dried over Na2SO4, and evaporated. Silica gel chromatography (15% EtOAc/hexanes) yielded 4.25 g (88.5%) of chloromethoxybenzaldehyde 6, mp 45° C.

Workup

  1. additionAfter adding freshly
  2. customthe bomb was sealed
  3. customThe cooled reaction
  4. filtrationwas then filtered
  5. customto remove proton sponge crystals
  6. custompartitioned between EtOAc and 3N HCl
  7. washwashed once each with dilute brine and dilute NaHCO3
  8. dry with materialdried over Na2SO4
  9. customevaporated

Sources & evidence

ORD record
ord-7b7c833e4f1942e59e76e901666d6a60
Source dataset
uspto-grants-1996_07
Patent number
US05538847

Reaction notes

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