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

HRID 1274467Notes

Reaction equation

HRID 1274467 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 800 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. washwashed once in sodium bicarbonate, once in water
  2. customonce in brine then chromatographed on 350 ml silica
  3. customcrystallize from methylene chloride/hexane

Sources & evidence

ORD record
ord-67346c36cace4126b89e57eb71f58709
Source dataset
uspto-grants-2000_12
Patent number
US06156748

Reaction notes

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