Proton sponge → 3-Chloro-5-methoxybenzaldehyde

HRID 376945Notes

Reaction equation

HRID 376945 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>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

5

Reactant 2

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

Product 1

HCID 219046333-Chloro-5-methoxybenzaldehydeYield 88.5%

Reagents, catalysts & solvents 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
90 °C

Procedure

Triflate 5 (9 g, 28 mmol) pallidum(II) acetate (120 mg, 0.5 mmol), 1,1'-bis(diphenylphosphino)ferrocene (620 mg, 1 mmol) and hplc grad 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 3 N 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 3 N HCl
  7. washwashed once each with dilute brine and dilute NaHCO3
  8. dry with materialdried over Na2SO4
  9. customevaporated

Sources & evidence

ORD record
ord-4a65a14407854fd98b1081394b0130a1
Source dataset
uspto-grants-2000_02
Patent number
US06022964

Reaction notes

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