Dimethyl Sulfide → trans-6-pentafluoroethyl-2,2-bisfluoromethyl-3,4-dihydro-4-(3-oxo-cyclopent-1-enyloxy)-2H-1-benzopyran-3-ol

HRID 363457

反応式

HRID 363457 の反応式
[C:1]1(=[O:7])[CH2:5][CH2:4][C:3](=[O:6])[CH2:2]1.[H-].[Na+].CSC.[O:13]1[CH:19]2[CH:14]1[C:15]([CH2:33][F:34])([CH2:31][F:32])[O:16][C:17]1[CH:23]=[CH:22][C:21]([C:24]([F:30])([F:29])[C:25]([F:28])([F:27])[F:26])=[CH:20][C:18]=12.S(=O)(=O)(O)O>O1CCCC1.[Cu]Br.O>[F:30][C:24]([F:29])([C:21]1[CH:22]=[CH:23][C:17]2[O:16][C:15]([CH2:33][F:34])([CH2:31][F:32])[C@@H:14]([OH:13])[C@H:19]([O:6][C:3]3[CH2:4][CH2:5][C:1](=[O:7])[CH:2]=3)[C:18]=2[CH:20]=1)[C:25]([F:28])([F:27])[F:26]

参加物

9

反応物 5

HCID 1068Dimethyl SulfideHCID 1118Sulfuric AcidHCID 24758Sodium hydrideHCID 774661,3-CyclopentanedioneHCID 158717923,4-epoxy-6-pentafluoroethyl-2,2-bisfluoromethyl-3,4-dihydro-2H-1-benzopyran

生成物 1

HCID 86750614trans-6-pentafluoroethyl-2,2-bisfluoromethyl-3,4-dihydro-4-(3-oxo-cyclopent-1-enyloxy)-2H-1-benzopyran-3-ol収率 3.4%

試薬・触媒・溶媒 3

HCID 24593copper(I) bromide触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-20 °C

実験手順

In 40 ml of tetrahydrofuran was dissolved 0.36 g of cyclopentan-1,3-dione and 0.13 g of sodium hydride (60%) was added thereto under nitrogen stream with cooling at -20° C. After the mixture was stirred at room temperature for 15 minutes, 0.72 g of a complex of copper (I) bromide and dimethyl sulfide was added. To the reaction mixture was added 0.92 g of 3,4-epoxy-6-pentafluoroethyl-2,2-bisfluoromethyl-3,4-dihydro-2H-1-benzopyran dissolved in 10 ml of tetrahydrofuran. The mixture was stirred for 6 days. To the mixture were added water and a small amount of concentrated sulfuric acid. The mixture was extracted with methylene chloride and the organic layer was washed with water and dried. The solvent was distilled off and the resultant residue was purified using silica gel column chromatography (developing solution, MeOH:CH2Cl2 =1:99) and another silica gel column chromatography (developing solution, AcOEt:hexane=1:1) to obtain 0.04 g of trans-6-pentafluoroethyl-2,2-bisfluoromethyl-3,4-dihydro-4-(3-oxo-cyclopent-1-enyloxy)-2H-1-benzopyran-3-ol represented by the following formula having a melting point of 165°-167° C.

後処理

  1. additionwas added
  2. stirringThe mixture was stirred for 6 days
  3. extractionThe mixture was extracted with methylene chloride
  4. washthe organic layer was washed with water
  5. customdried
  6. distillationThe solvent was distilled off
  7. customthe resultant residue was purified

出典と根拠

ORDレコード
ord-1fbfe959989745e5821f9fc33ddeecac
出典データセット
uspto-grants-1999_02
特許番号
US05874446

関連ノート

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