Nitrobenzene → 5,7-Dihydroxy-8-propionyl-4-propyl-2H-chromen-2-one

HRID 342809ノート

反応式

HRID 342809 の反応式
[OH:1][C:2]1[CH:11]=[C:10]([OH:12])[CH:9]=[C:8]2[C:3]=1[C:4]([CH2:14][CH2:15][CH3:16])=[CH:5][C:6](=[O:13])[O:7]2.[Cl-].[Al+3].[Cl-].[Cl-].[N+](C1C=CC=CC=1)([O-])=O.[C:30](Cl)(=[O:33])[CH2:31][CH3:32]>C(=S)=S.C(OCC)(=O)C.CCCCCC>[OH:1][C:2]1[CH:11]=[C:10]([OH:12])[C:9]([C:30](=[O:33])[CH2:31][CH3:32])=[C:8]2[C:3]=1[C:4]([CH2:14][CH2:15][CH3:16])=[CH:5][C:6](=[O:13])[O:7]2

参加物

7

反応物 4

HCID 7416NitrobenzeneHCID 62324Propionyl chloride2 回HCID 53912605,7-Dihydroxy-4-propylcoumarinHCID 6451240Aluminum(III) Chloride

生成物 1

HCID 54948785,7-Dihydroxy-8-propionyl-4-propyl-2H-chromen-2-one

試薬・触媒・溶媒 2

HCID 6348Carbon Disulfide溶媒2 回HCID 21226206Ethyl acetate hexane溶媒

反応条件

温度
0 °C

実験手順

A three-neck flask (500 mL) equipped with an efficient methanical stirrer, thermometer and addition funnel was charged with 5,7-dihydroxy-4-propylcoumarin, 2, (25.0 g, 0.113 mol), aluminum chloride (62.1 g; 0.466 mol), and nitrobenzene (150 mL) and the mixture was stirred until a solution was obtained, which was cooled to 0° C. in an ice bath. A solution of propionyl chloride (15.2 g; 0.165 mol) in carbon disulfide (50 mL) was added dropwise at such a rate that the reaction temperature was maintained at 8°-10° C. Addition was completed over a period of 1 hour with vigorous stirring. The reaction was monitored by TLC using a mobile phase of 50% ethyl acetate/hexane. After three hours, an additional portion of propionyl chloride (2.10 g; 0.0227 mol) in carbon disulfide (10 mL) was added. Immediately after the TLC analysis indicated the total consumption of starting material, the reaction mixture was poured onto ice, and allowed to stand overnight. The nitrobenzene was removed by steam distillation, and the remaining solution was extracted several times with ethyl acetate. The extracts were combined and dried over Na2SO4. The crude product obtained by evaporation in vacuo was purified by chromatography on a silica gel column eluting with 50% ether/hexane to provide the desired propionylated coumarin 3, mp (corr) 244°-246° C. 1H-NMR (DMSO-d6) δ 0.96 (3H, t, J=7.3 Hz, CH3); 1.10 (3H, t, J=7.2 Hz, CH3); 1.60 (2H, m, CH2); 2.88 (2H, t, J=7.7 Hz, CH2); 3.04 (2H, q, J=7.2 Hz, CH2); 5.95 (1H, s, H3); 6.31 (1H, s, H6); 11.07 (1H, s, OH); 11.50 (1H, s, OH); MS (EI): 277 (6.6, M+1); 276 (9.0, M+); 247 (100, M--C2H5); IR (KBr): 3239 (s and broad, OH); 1693 (s, C=O), 1625 and 1593 (s) cm-1 ; Anal. calcd. for C15H16O5 : C, 65.21; H, 5.84; Found: c, 64.92; H, 5.83. The isomer assignment was made by analogy to precedent.15

後処理

  1. customA three-neck flask (500 mL) equipped with an efficient methanical stirrer
  2. additionthermometer and addition funnel
  3. customwas obtained
  4. temperaturewas maintained at 8°-10° C
  5. additionAddition
  6. waitAfter three hours
  7. customthe total consumption of starting material
  8. additionthe reaction mixture was poured onto ice
  9. waitto stand overnight
  10. customThe nitrobenzene was removed by steam distillation
  11. extractionthe remaining solution was extracted several times with ethyl acetate
  12. dry with materialdried over Na2SO4
  13. customThe crude product obtained by evaporation in vacuo
  14. customwas purified by chromatography on a silica gel column
  15. washeluting with 50% ether/hexane

出典と根拠

ORDレコード
ord-f826bc23f3994f9fbb9566435486dfff
出典データセット
uspto-grants-1999_01
特許番号
US05859050

反応ノート

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