Hydrochloric Acid → 6-(4-Hydroxy-3-methoxyphenyl)hex-5-ene-2,4-dione

HRID 247888Notes

Reaction equation

HRID 247888 reaction equation
[C:1]([CH2:4][C:5](=[O:7])[CH3:6])(=[O:3])[CH3:2].[OH:8][C:9]1[CH:16]=[CH:15][C:12]([CH:13]=O)=[CH:11][C:10]=1[O:17][CH3:18].B(OCCCC)(OCCCC)OCCCC.C(N)CCC.Cl>C(OCC)(=O)C.C(OCC)(=O)C.C(Cl)(Cl)Cl.O>[OH:8][C:9]1[CH:16]=[CH:15][C:12]([CH:13]=[CH:6][C:5](=[O:7])[CH2:4][C:1](=[O:3])[CH3:2])=[CH:11][C:10]=1[O:17][CH3:18]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 1183VanillinHCID 8007ButylamineHCID 12712Tributyl borateHCID 31261Acetylacetone

Product 1

HCID 543188196-(4-Hydroxy-3-methoxyphenyl)hex-5-ene-2,4-dioneYield 40%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 21584013Chloroform ethylacetateSolvent

Procedure

Boric anhydride (16.32 g, 237.2 mmoles) and acetylacetone are stirred at room temperature under nitrogen for 12 hours. 4-Hydroxy-3-methoxybenzaldehyde (18.06 g, 118.8 mmoles) and tributyl borate (364 g, 3.16 moles) are combined with the acetyl acetone/boric anhydride complex in 100 ml of ethyl acetate. The reaction is stirred at room temperature for one hour, at which time n-butylamine (4.34 g, 59.4 mmoles) is added in 4 equal portions over 8 hours. The reaction is allowed to stir for 12 hours. 300 ml of water containing 20 ml of concentrated hydrochloric acid is added to the reaction and stirred for 2 hours. The solid which forms is removed by filtration through celite, and the layers of filtrate are separated. The ethyl acetate layer is washed with 2×100 ml of saturated sodium bicarbonate, followed by 100 ml of brine. Drying over magnesium sulfate followed by evaporation of the solvent gives a red solid. Chromatography in 5% ethyl acetate/chloroform gives 11.06 g (40%) of a yellow solid. mp=146°-147° C. Analysis for C13H14O4 requires C-66.65, H-6.04. Found C-66.88, H-6.18.

Workup

  1. additionis added in 4 equal portions over 8 hours
  2. stirringstirred for 2 hours
  3. customThe solid which forms is removed by filtration through celite
  4. customthe layers of filtrate are separated
  5. washThe ethyl acetate layer is washed with 2×100 ml of saturated sodium bicarbonate
  6. dry with materialDrying over magnesium sulfate
  7. customfollowed by evaporation of the solvent
  8. customgives a red solid

Sources & evidence

ORD record
ord-eb3f08036b974523a25ef1e9c466c6e1
Source dataset
uspto-grants-1993_05
Patent number
US05208251

Reaction notes

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