Methylparaben → HCID 60778955, compound

HRID 390373Notes

Reaction equation

HRID 390373 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 of diethyl azodicarboxylate in toluene (120 mL, 40% toluene solution) at 0° C., and the mixture was stirred at room temperature for 2 hr. The reaction solution was concentrated, triphenylphosphine oxide was precipitated from ethyl acetate-hexane and removed by filtration with a glass filter, and the mother liquor was concentrated. The residue was purified by silica gel column chromatography [developing solvent; hexane:ethyl acetate=90:10 (volume ratio)-*hexane:ethyl acetate=40:10 (volume ratio)] 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 at 80° C. for 2 hr with heating. The reaction solution was concentrated, cooled to 0° C., neutralized with 6N hydrochloric acid, and 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. customremoved by filtration with a glass
  4. filtrationfilter
  5. concentrationthe mother liquor was concentrated
  6. customThe residue was purified by silica gel column chromatography [
  7. customhexane:ethyl acetate=90:10 (volume ratio)-*hexane:ethyl acetate=40:10 (volume ratio)] to give a colorless oil
  8. stirringthe mixture was stirred at 80° C. for 2 hr
  9. temperaturewith heating
  10. concentrationThe reaction solution was concentrated
  11. temperaturecooled to 0° C.
  12. extractionextracted with ethyl acetate
  13. washThe organic layer was washed with saturated brine
  14. dry with materialdried over anhydrous magnesium sulfate
  15. customthe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-b0dc01a8a09344759effe9472df36e17
Source dataset
uspto-grants-2013_02
Patent number
US08383647B2

Reaction notes

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