Triethylamine → 3-oxo-1-cyclohexen-1-yl 2,3-dihydrospiro[4H-1-benzothiopyran-4,2'-[1,3]dioxolane]-6-carboxylate 1,1-dioxide

HRID 617698ノート

反応式

HRID 617698 の反応式
[O:1]1[CH2:5][CH2:4][O:3][C:2]21[C:10]1[CH:11]=[C:12]([C:15]([OH:17])=[O:16])[CH:13]=[CH:14][C:9]=1[S:8](=[O:19])(=[O:18])[CH2:7][CH2:6]2.C(Cl)(=O)C(Cl)=O.[C:26]1(=O)[CH2:31][CH2:30][CH2:29][C:28](=[O:32])[CH2:27]1.C(N(CC)CC)C>CN(C)C=O.C(Cl)Cl>[O:1]1[CH2:5][CH2:4][O:3][C:2]21[C:10]1[CH:11]=[C:12]([C:15]([O:17][C:26]3[CH2:31][CH2:30][CH2:29][C:28](=[O:32])[CH:27]=3)=[O:16])[CH:13]=[CH:14][C:9]=1[S:8](=[O:19])(=[O:18])[CH2:7][CH2:6]2

参加物

7

反応物 4

HCID 8471TriethylamineHCID 104341,3-CyclohexanedioneHCID 65578Oxalyl chlorideHCID 675608462,3-dihydrospiro[4H-1-benzothiopyran-4,2'-[1,3]dioxolane]-6-carboxylic acid 1,1-dioxide

生成物 1

HCID 218490223-oxo-1-cyclohexen-1-yl 2,3-dihydrospiro[4H-1-benzothiopyran-4,2'-[1,3]dioxolane]-6-carboxylate 1,1-dioxide収率 82.7%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

2.0 g (7.0 mmol) of the title compound of Step E, 1.2 mL (0.014 mol) of oxalyl chloride (purchase from Janssen), and 2 drops of N,N-dimethylformamide were added to 50 mL of methylene chloride. The mixture was refluxed under nitrogen for 2 h, and was then evaporated to dryness. 50 mL of methylene chloride was added to the residue and the resulting mixture was evaporated to dryness. Another 50 mL of methylene chloride was added to the residue, and the solution was cooled to about 0° C. 0.86 g (7.7 mmol) of 1,3-cyclohexanedione (purchased from Aldrich Chemical Company) was added followed by 2.7 mL (0.0196 mol) of triethylamine, and the mixture was stirred overnight while warming to room temperature. The mixture was evaporated to dryness, the residue was stirred in 100 mL of water and filtered. The crude product was washed with hexane to yield 2.19 g of the title compound of Step F as a solid melting at 185-186° C. 1H NMR (CDCl3): δ2.2 (m,2H), 2.5 (t,2H), 2.7 (t,4H), 3.7 (m,2H), 4.2 (m,2H), 4.3 (m,2H), 6.0 (s,1H), 8.0-8.25 (3H).

後処理

  1. temperatureThe mixture was refluxed under nitrogen for 2 h
  2. customwas then evaporated to dryness
  3. addition50 mL of methylene chloride was added to the residue
  4. customthe resulting mixture was evaporated to dryness
  5. additionAnother 50 mL of methylene chloride was added to the residue
  6. temperaturewhile warming to room temperature
  7. customThe mixture was evaporated to dryness
  8. stirringthe residue was stirred in 100 mL of water
  9. filtrationfiltered
  10. washThe crude product was washed with hexane

出典と根拠

ORDレコード
ord-adb458926fd74e01affac2a5d17300b9
出典データセット
uspto-grants-1999_09
特許番号
US05952266

反応ノート

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