Vanillylmandelic Acid → 4-Hydroxy-3-methoxymandelic acid (phenylmethyl) ester

HRID 1460254

반응식

HRID 1460254 반응식
[OH:1][C:2]1[CH:12]=[CH:11][C:5]([CH:6]([OH:10])[C:7]([OH:9])=[O:8])=[CH:4][C:3]=1[O:13][CH3:14].C(N(CC)CC)C.[CH2:22](Br)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.CC(C)=O.C(OCC)(=O)C>CC(C)=O>[OH:1][C:2]1[CH:12]=[CH:11][C:5]([CH:6]([OH:10])[C:7]([O:9][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[O:8])=[CH:4][C:3]=1[O:13][CH3:14]

참가 물질

6

반응물 4

HCID 1245Vanillylmandelic AcidHCID 7498Benzyl Bromide3회HCID 8471Triethylamine3회HCID 21584569Ethylacetate acetone

생성물 1

HCID 150203674-Hydroxy-3-methoxymandelic acid (phenylmethyl) ester수율 277.5%

시약·촉매·용매 1

HCID 180Acetone용매

실험 절차

To a mixture of 4.371 g (0.022 mole) of 4-hydroxy-3-methoxymandelic acid, 11 ml of triethylamine in 100 ml of acetone was added 3.13 ml (0.0265 mole) of benzyl bromide. The reaction mixture was stirred (magnetic stirring) and heated at reflux (oil bath) under a nitrogen atmosphere. After 5 minutes of heating the reaction mixture became cloudy. Thin layer chromatography (TLC) (silica gel, acetone/ethyl acetate 95:5) showed 50% of the starting material remaining after 5 hours. Additional triethylamine (2 ml) and benzyl bromide (1.5 ml) were added, and the mixture was heated at reflux for 4 hours. TLC still showed starting material present. Additional reagents were added (1.5 ml benzyl bromide and 2 ml triethylamine) and heating was continued for 14 hours. The triethylamine hydrobromide was removed by filtration, and the filter cake was washed with acetone (3×10 ml). The filtrate and washings were evaporated to give 17.6 g of a semi-solid residue. The residue was triturated with water (30 ml), and the product extracted with methylene chloride (4×15 ml) and dried (sodium sulfate). Evaporation of the solvent yielded 4.99 g of a light-brown oil which was triturated with hexanes (20 ml) to crystallize the product. The cream-colored solid was separated and washed with hexanes (3×10 ml) to give 3.351 g (53% yield) of the product. Estimated purity by TLC was 98% (hexanes/acetone 5:1).

후처리

  1. stirring(magnetic stirring)
  2. temperatureheated
  3. temperatureat reflux (oil bath) under a nitrogen atmosphere
  4. temperatureAfter 5 minutes of heating the reaction mixture
  5. temperaturethe mixture was heated
  6. temperatureat reflux for 4 hours
  7. temperatureheating
  8. waitwas continued for 14 hours
  9. customThe triethylamine hydrobromide was removed by filtration
  10. washthe filter cake was washed with acetone (3×10 ml)
  11. customThe filtrate and washings were evaporated

출처 및 근거

ORD 기록
ord-cc0b6c02281245d692fa52254ca4f063
출처 데이터셋
uspto-grants-1991_12
특허 번호
US05070087

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