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

HRID 1460254

反応式

HRID 1460254 の反応式
[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]

参加物

6

反応物 4

HCID 1245Vanillylmandelic AcidHCID 7498Benzyl Bromide3 回HCID 8471Triethylamine3 回HCID 21584569Ethylacetate acetone

生成物 1

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

試薬・触媒・溶媒 1

HCID 180Acetone溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-cc0b6c02281245d692fa52254ca4f063
出典データセット
uspto-grants-1991_12
特許番号
US05070087

関連ノート

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