Phenol → 850785-06-7

HRID 2221360Notes

Reaction equation

HRID 2221360 reaction equation
[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([OH:11])=[CH:7][CH:6]=1.C1(B(O)O)C=CC=CC=1.[CH3:22][C:23]([CH3:27])=[CH:24][CH:25]=O.C1(O)C=CC=CC=1>C(O)(=O)C.C1(C)C=CC=C(C)C=1>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:6]=[C:7]2[C:8](=[CH:9][CH:10]=1)[O:11][C:23]([CH3:27])([CH3:22])[CH:24]=[CH:25]2

Participants

7

Reactant 4

HCID 996PhenolHCID 610203-Methyl-2-butenalHCID 66827Phenylboronic AcidHCID 518900Benzeneacetic acid, 4-hydroxy-, methyl ester

Product 1

HCID 46918460850785-06-7Yield 43.2%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 7929M-XyleneSolvent

Procedure

175.6 g methyl-4-hydroxyphenylacetate and 128.9 g phenylboronic acid were added to 3.5 l m-xylene. 88.9 g 3-methylbut-2-enal, and 130 ml of glacial acetic acid were added to this mixture. The mixture was heated to 140° C. in a Dean-Stark apparatus under a nitrogen atmosphere until approximately 70% of the phenol had reacted (approximately 48-72 hours). Then the reaction mixture was allowed to cool to room temperature, the mixture was filtered, and the solvent was evaporated at reduced pressure. The remaining residue was dissolved in a 1:1 mixture of tetrahydrofuran (THF) and a 25%-strength aqueous ammonia solution (v/v) and stirred for 2 hours. The THF was largely evaporated off at reduced pressure and ethyl acetate was added. The organic phase was separated, washed in succession with an aqueous 1 N NaOH and a saturated aqueous common salt solution and finally dried over sodium sulfate. The solvent was largely evaporated at reduced pressure, and the remaining residue was chromatographed on silica gel (mobile phase: n-hexane/EA 15:1 to 10:1 v/v). Drying of the product fractions in an oil pump vacuum yielded 106 g methyl-(2,2-dimethyl-2H-chromen-6-yl)acetate as pale yellow oil, which was used without further characterization for the subsequent reaction.

Workup

  1. customhad reacted (approximately 48-72 hours)
  2. filtrationthe mixture was filtered
  3. customthe solvent was evaporated at reduced pressure
  4. dissolutionThe remaining residue was dissolved in a 1:1 mixture of tetrahydrofuran (THF)
  5. customThe THF was largely evaporated off at reduced pressure and ethyl acetate
  6. additionwas added
  7. customThe organic phase was separated
  8. washwashed in succession with an aqueous 1 N NaOH
  9. dry with materiala saturated aqueous common salt solution and finally dried over sodium sulfate
  10. customThe solvent was largely evaporated at reduced pressure
  11. customthe remaining residue was chromatographed on silica gel (mobile phase: n-hexane/EA 15:1 to 10:1 v/v)
  12. customDrying of the product fractions in an oil pump vacuum

Sources & evidence

ORD record
ord-035ccf04d8d64830b413300e0776b3bf
Source dataset
uspto-grants-2008_05
Patent number
US07368582B2

Reaction notes

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