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

HRID 617698노트

반응식

HRID 617698 반응식
[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

참가 물질

7

반응물 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

생성물 1

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

시약·촉매·용매 2

HCID 6228Dimethylformamide촉매HCID 6344Dichloromethane용매

반응 조건

온도
0 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-adb458926fd74e01affac2a5d17300b9
출처 데이터셋
uspto-grants-1999_09
특허 번호
US05952266

반응 노트

불러오는 중…