Acetic Acid → (2-Hydroxy-5-carbomethoxy-benzoyl)-nicotinoylmethane

HRID 26220

反応式

HRID 26220 の反応式
[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].[C:15](OC)(=[O:22])[C:16]1[CH:21]=[CH:20][CH:19]=[N:18][CH:17]=1.[H-].[Na+].C(O)(=O)C>O1CCOCC1.O>[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:15](=[O:22])[C:16]1[CH:21]=[CH:20][CH:19]=[N:18][CH:17]=1)=[O:3]

参加物

7

反応物 4

HCID 176Acetic AcidHCID 7151Methyl NicotinateHCID 24758Sodium hydrideHCID 12332833Methyl 3-acetyl-4-hydroxybenzoate

生成物 1

HCID 21325074(2-Hydroxy-5-carbomethoxy-benzoyl)-nicotinoylmethane収率 69.8%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 312751,4-Dioxane溶媒2 回

実験手順

A solution consisting of methyl 3-acetyl-4-hydroxy-benzoate (16 g) and methyl nicotinate (23 g) in dioxane (100 ml) was slowly added at room temperature under stirring to a suspension of sodium hydride 50% (12 g) in dioxane (60 ml). The solution was kept for 6 hours at 80° C., then cooled, diluted with petroleum ether (200 ml), and filtered. The product obtained was dissolved in water and treated with acetic acid; the precipitate obtained was washed with water and crystallised with methylene chloride/methanol to give (2-hydroxy-5-carbomethoxy-benzoyl)-nicotinoylmethane (17.2 g; m.p. 200°-202° C.) which was then treated with ethanol (300 ml) containing concentrated hydrochloric acid 1% at reflux temperature for 2 hours. After concentration under vacuum, dilution with water, neutralisation with sodium acetate, the precipitate was filtered. The raw 6-carbomethoxy-2-(3'-pyridyl)-chromone (15.1 g) was hydrolysed with the stoichiometric quantity of potassium hydroxide 1% in ethanol 95% at reflux temperature for an hour. After cooling, dilution with water (600 ml), neutralisation with acetic acid, the precipitate was collected, to obtain, after crystallisation from dimethylformamide, 6-carboxy-2-(3'-pyridyl)-chromone (9.8 g; m.p.> 350° C.); I.R. (KBr): νC=O (carboxy) 1680 cm-1, νC=O (chromone) 1630 cm-1, 1610 cm-1, γC-H (meta-substituted pyridine) 770 cm-1, 696 cm-1.

後処理

  1. additionwas slowly added at room temperature
  2. temperaturecooled
  3. filtrationfiltered
  4. customThe product obtained
  5. customthe precipitate obtained
  6. washwas washed with water
  7. customcrystallised with methylene chloride/methanol

出典と根拠

ORDレコード
ord-4cb6fec64ce24f8c8181d866f9fc9825
出典データセット
uspto-grants-1979_04
特許番号
US04148900

関連ノート

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