Chloroform → 8-(beta-Chloroallyl)-7-butyroxy-4-methylcoumarin

HRID 1460127

反応式

HRID 1460127 の反応式
ClC(=C)CO[C:5]1[CH:14]=[C:13]2[C:8]([C:9](C)=[CH:10][C:11](=[O:15])[O:12]2)=[CH:7][CH:6]=1.[C:18]([O:23][C:24](=[O:28])[CH2:25][CH2:26][CH3:27])(=O)[CH2:19][CH2:20][CH3:21].C(Cl)(Cl)[Cl:30]>C(C1C=CC(C(C)C)=CC=1)(C)C>[Cl:30][C:6](=[CH2:7])[CH2:5][C:14]1[C:13]([O:12][C:11](=[O:15])[CH2:10][CH2:9][CH3:8])=[CH:21][CH:20]=[C:19]2[C:18]=1[O:23][C:24](=[O:28])[CH:25]=[C:26]2[CH3:27]

参加物

5

反応物 3

HCID 6212ChloroformHCID 7798Butyric anhydrideHCID 11215917-(beta-Chloroallyloxy)-4-methylcoumarin

生成物 1

HCID 234469868-(beta-Chloroallyl)-7-butyroxy-4-methylcoumarin

試薬・触媒・溶媒 1

HCID 74861,4-Diisopropylbenzene溶媒

実験手順

Rearrangement of CAMC was accomplished in high yield by refluxing the allyl ether from Step 2 (143.5 gm; 0.55 mole) in a mixture of p-diisopropylbenzene (Aldrich, 1000 ml) and butyric anhydride (96 ml, 92.8 gm; 0.59 mol, Aldrich) under argon for 18 hours. The cooled reaction mixture was diluted with chloroform, washed with water and then saturated sodium bicarbonate, dried (MgSO4) then evapaorated under pressure. Folloeing recrystallization from ethanol, 79.9 grams of mixed 6 and 8-(β-chloroallyl)-7-butyroxy-4-methylcoumarin (BCAMC,15) were obtained. HPLC analysis (Beckman; C18-ODS reverse phase column, isocratic elution with 60% CH3OH/40%H2O) showed the mixture to contain 85.7% of the desired 8-substituted isomer, of which a sample was purified by column chromatography (60-200 mesh silica gel, elution with CH2 Cl2). The structures of the two isomers were confined by NMR. NMR (CDCl3) d 7.56 (1H,d), 7.11 (1H,d), 6.26 (1 h,d), 5.05-5.19 (2H, m, 3.84 (2H, m), 2.55-2.62 (2H, m), 2.43 (3H, d), 1.78-1.82 (2H, m), 1.01-1.09 (3H,t).

後処理

  1. customin high yield
  2. customThe cooled reaction mixture
  3. washwashed with water
  4. dry with materialsaturated sodium bicarbonate, dried (MgSO4)
  5. customrecrystallization from ethanol, 79.9 grams
  6. additionof mixed 6

出典と根拠

ORDレコード
ord-e2d4e2f529ed4023b68aca6c903b2b33
出典データセット
uspto-grants-1998_12
特許番号
US05854967

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