Sodium hydride → (2-Hydroxy-5-carbomethoxy-benzoyl)-(2-methoxy-5-methyl-benzoyl)-methane

HRID 236701

반응식

HRID 236701 반응식
[C:1]([C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][C:13]=1[OH:14])[C:7]([O:9][CH3:10])=[O:8])(=[O:3])[CH3:2].[CH3:15][O:16][C:17]1[CH:26]=[CH:25][C:24]([CH3:27])=[CH:23][C:18]=1[C:19](OC)=[O:20].[H-].[Na+]>O1CCOCC1>[OH:14][C:13]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][C:4]=1[C:1]([CH2:2][C:19](=[O:20])[C:18]1[CH:23]=[C:24]([CH3:27])[CH:25]=[CH:26][C:17]=1[O:16][CH3:15])=[O:3]

참가 물질

5

반응물 3

HCID 24758Sodium hydrideHCID 10241396Methyl 2-methoxy-5-methylbenzoateHCID 12332833Methyl 3-acetyl-4-hydroxybenzoate

생성물 1

HCID 21315745(2-Hydroxy-5-carbomethoxy-benzoyl)-(2-methoxy-5-methyl-benzoyl)-methane수율 74.7%

시약·촉매·용매 1

HCID 312751,4-Dioxane용매2회

반응 조건

온도
80 °C

실험 절차

A solution of methyl 3-acetyl-4-hydroxy-benzoate (6 g) and methyl 2-methoxy-5-methyl-benzoate (12 g) in dioxane (40 ml) was slowly added under stirring at room temperature to a suspension of sodium hydride 50% (4.5 g) in dioxane (40 ml). The mixture was kept under stirring for 3 hours at 80° C., cooled, then diluted with petroleum ether (100 ml), and filtered. The collected precipitate was dissolved in water, acidified with acetic acid and extracted with ethyl-acetate. The organic phase was washed with potassium carbonate 5% and water, then evaporated to dryness and crystallized from ethanol to give (2-hydroxy-5-carbomethoxy-benzoyl)-(2-methoxy-5-methyl-benzoyl)-methane (7.9 g; m.p.=145°-147° C.), which was then refluxed for 15 minutes with 99% formic acid (28 ml). After cooling and dilution in water and filtration, the collected precipitate was crystallized from acetone to obtain 6-carbomethoxy-2'-methoxy-5'-methyl-flavone (6 g), m.p.=154°-156° C., which was hydrolyzed with a 1% solution of potassium hydroxide (100 ml) in 95% ethanol at reflux temperature for 30 minutes. The mixture was cooled, acidified with 23% HCl to pH=3, and the precipitate was filtered, washed with ethanol 95% and water so obtaining, after crystallization from ethanol, 6-carboxy-2'-methoxy-5'-methyl-flavone (5.3 g), m.p.=246°-247° C.

후처리

  1. temperaturecooled
  2. filtrationfiltered
  3. dissolutionThe collected precipitate was dissolved in water
  4. extractionextracted with ethyl-acetate
  5. washThe organic phase was washed with potassium carbonate 5% and water
  6. customevaporated to dryness
  7. customcrystallized from ethanol

출처 및 근거

ORD 기록
ord-6d382ec765ae4fe99e09d0dd5da7a70c
출처 데이터셋
uspto-grants-1979_06
특허 번호
US04157334

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