Formic Acid → 2,6-Dimethyl-4-hydroxybenzaldehyde

HRID 1369939Notes

Reaction equation

HRID 1369939 reaction equation
C([O:4][C:5]1[CH:12]=[C:11]([CH3:13])[C:8]([CH:9]=[O:10])=[C:7]([CH3:14])[CH:6]=1)C=C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(O)=O>C(OCC)(=O)C.CC(O)=O.CC(O)=O.[Pd]>[CH3:13][C:11]1[CH:12]=[C:5]([OH:4])[CH:6]=[C:7]([CH3:14])[C:8]=1[CH:9]=[O:10]

Participants

6

Reactant 3

HCID 284Formic AcidHCID 11776TriphenylphosphineHCID 185158104-Allyloxy-2,6-dimethyl-benzaldehyde

Product 1

HCID 5910722,6-Dimethyl-4-hydroxybenzaldehydeYield 51%

Reagents, catalysts & solvents 2

HCID 4144353Palladium (II) acetateCatalystHCID 8857Ethyl AcetateSolvent

Procedure

4-Allyloxy-2,6-dimethyl-benzaldehyde, 9.67 g (50.9 mmole), 1.14 g (5.09 mmole) of palladium II acetate, and 8.00 g (30.5 mmole) of triphenylphosphine was mixed in a flask. Formic acid, 2.11 ml (56 mmole), was added and the mixture was swirled in a 80° oil bath. Within 15 seconds the reaction exothermed and turned very dark. The gum was dissolved in ethyl acetate, washed once in sodium bicarbonate, once in water, and once in brine then chromatographed on 350 ml silica, using 20%, then 40% ethyl acetate/hexane. Fractions were bulked and crystallize from methylene chloride/hexane to give 3.90 g (51%) of subtitled product which was used without further purification.

Workup

  1. customwas swirled in a 80°
  2. washwashed once in sodium bicarbonate, once in water
  3. customonce in brine then chromatographed on 350 ml silica
  4. customcrystallize from methylene chloride/hexane

Sources & evidence

ORD record
ord-5f30db222810494a9caccf2f5a4d3b3f
Source dataset
uspto-grants-2003_06
Patent number
US06579871B2

Reaction notes

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