Methylparaben → HCID 60778955, compound

HRID 239898Notes

Reaction equation

HRID 239898 reaction equation
[O:1]1[CH2:5][CH2:4][CH:3]([CH2:6][OH:7])[CH2:2]1.O[C:9]1[CH:18]=[CH:17][C:12]([C:13]([O:15]C)=[O:14])=[CH:11][CH:10]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[OH-].[Na+]>O1CCCC1.C1(C)C=CC=CC=1.CO>[O:1]1[CH2:5][CH2:4][CH:3]([CH2:6][O:7][C:9]2[CH:18]=[CH:17][C:12]([C:13]([OH:15])=[O:14])=[CH:11][CH:10]=2)[CH2:2]1

Participants

9

Reactant 5

HCID 7456MethylparabenHCID 11776TriphenylphosphineHCID 14798Sodium HydroxideHCID 139980Tetrahydro-3-furanmethanolHCID 220568ethyl N-ethoxycarbonyliminocarbamate

Product 1

HCID 60778955HCID 60778955, compoundYield 48.3%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of tetrahydrofuran-3-ylmethanol (21.89 g), methyl 4-hydroxybenzoate (33.5 g) and triphenylphosphine (64.5 g) in tetrahydrofuran (400 mL) was slowly added dropwise a solution (120 mL, 40% toluene solution) of diethyl azodicarboxylate in toluene at 0° C., and the mixture was stirred at room temperature for 2 hr. The reaction solution was concentrated, and triphenylphosphine oxide was precipitated from ethyl acetate-hexane. The mixture was filtered through a glass filter to remove triphenylphosphine oxide, and the filtrate was concentrated. The residue was purified by silica gel column chromatography [eluent; hexane:ethyl acetate=90:10 (volume ratio)→hexane:ethyl acetate=40:10] to give a colorless oil. The obtained colorless oil was dissolved in tetrahydrofuran (200 mL) and methanol (100 mL), 8N aqueous sodium hydroxide solution (100 mL) was added, and the mixture was stirred with heating at 80° C. for 2 hr. The reaction solution was concentrated, cooled to 0° C., and neutralized with 6N hydrochloric acid, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give the title compound (23 g, yield 48%) as colorless crystals.

Workup

  1. concentrationThe reaction solution was concentrated
  2. customtriphenylphosphine oxide was precipitated from ethyl acetate-hexane
  3. filtrationThe mixture was filtered through a glass
  4. filtrationfilter
  5. customto remove triphenylphosphine oxide
  6. concentrationthe filtrate was concentrated
  7. customThe residue was purified by silica gel column chromatography [eluent; hexane:ethyl acetate=90:10 (volume ratio)→hexane:ethyl acetate=40:10]
  8. customto give a colorless oil
  9. stirringthe mixture was stirred
  10. temperaturewith heating at 80° C. for 2 hr
  11. concentrationThe reaction solution was concentrated
  12. temperaturecooled to 0° C.
  13. extractionthe mixture was extracted with ethyl acetate
  14. washThe organic layer was washed with saturated brine
  15. dry with materialdried over anhydrous magnesium sulfate
  16. customthe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-9147293bb1d24009b2d982c750c21583
Source dataset
uspto-grants-2014_02
Patent number
US08642770B2

Reaction notes

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