Hydrochloric Acid → HCID 67119193、化合物

HRID 2076590ノート

反応式

HRID 2076590 の反応式
Cl([O-])=O.[Na+].O.P([O-])(O)(O)=O.[Na+].C([O:15][C:16]1[C:17]([CH:45]=[O:46])=[C:18]([CH:38]=[CH:39][C:40]=1[C:41]([F:44])([F:43])[F:42])[CH2:19][O:20][C:21]1[CH:26]=[CH:25][C:24]([C:27]2[CH:32]=[CH:31][C:30]([CH2:33][C:34]([O:36][CH3:37])=[O:35])=[CH:29][CH:28]=2)=[CH:23][CH:22]=1)C=C.CC(=CC)C.S([O-])([O-])(=O)=S.[Na+].[Na+].Cl.[C:60]([O:64]C(OC(C)(C)C)N(C)C)([CH3:63])([CH3:62])[CH3:61].N1CCCC1>C(O)(C)(C)C.C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O.O1CCOCC1>[OH:15][C:16]1[C:40]([C:41]([F:42])([F:44])[F:43])=[CH:39][CH:38]=[C:18]([CH2:19][O:20][C:21]2[CH:22]=[CH:23][C:24]([C:27]3[CH:32]=[CH:31][C:30]([CH2:33][C:34]([O:36][CH3:37])=[O:35])=[CH:29][CH:28]=3)=[CH:25][CH:26]=2)[C:17]=1[C:45]([O:64][C:60]([CH3:63])([CH3:62])[CH3:61])=[O:46]

参加物

14

反応物 8

HCID 313Hydrochloric AcidHCID 105532-Methyl-2-buteneHCID 24477Sodium ThiosulfateHCID 31268PyrrolidineHCID 516949Sodium Phosphate, Monobasic, MonohydrateHCID 5477121,1-bis(1,1-dimethylethoxy)-N,N,N-trimethylamineHCID 23668197Sodium ChloriteHCID 86617396HCID 86617396、化合物

生成物 1

HCID 67119193HCID 67119193、化合物収率 59.2%

試薬・触媒・溶媒 5

HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 6386tert-Butanol溶媒HCID 312751,4-Dioxane溶媒

実験手順

After an aqueous solution (7.5 ml) of sodium chlorite (1.28 g, 14.2 mmol) and sodium dihydrogenphosphate monohydrate (1.28 g, 9.28 mmol) was added dropwise to a solution of methyl (4′-([3-(allyloxy)-2-formyl-4-(trifluoromethyl)benzyl]oxy)-1,1′-biphenyl-4-yl)acetate (1.71 g, 3.53 mmol) obtained in Example (6-8) in a mixture of tert-butyl alcohol (15 ml), 1,4-dioxane (3.5 ml) and 2-methyl-2-butene (4.5 ml), the mixture was stirred at room temperature for 4 hours. After a 5% aqueous sodium thiosulfate solution was added to the reaction mixture, the mixture was poured into 0.5N hydrochloric acid and extracted with ethyl acetate (twice). The organic layer was successively washed with water and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. The solvent was removed under reduced pressure to give a residue. After the obtained residue was dissolved in toluene (12 ml), N,N-dimethylformamide di-tert-butyl acetal (3.39 ml, 14.1 mmol) was added thereto and the mixture was heated under reflux for 4 hours. After the reaction mixture was poured into water and the mixture was extracted with ethyl acetate (three times), the organic layer was successively washed with water (twice) and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. Pyrrolidine (0.500 ml, 5.99 mmol) and tetrakis(triphenylphosphine)palladium (81.6 mg, 70.6 mmol) were added to a solution of the residue obtained by removing the solvent under reduced pressure in a mixture of 1,4-dioxane-water (30:1, 12 ml), and the mixture was stirred at room temperature for 4 hours. After water was poured into the reaction mixture and the mixture was extracted with ethyl acetate, the organic layer was successively washed with water and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. The mixture was purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=98/2-85/15) to give the title compound as a pale yellow powder (1.08 g, yield: 59%).

後処理

  1. extractionextracted with ethyl acetate (twice)
  2. washThe organic layer was successively washed with water
  3. dry with materiala saturated aqueous NaCl solution and dried with anhydrous sodium sulfate
  4. customThe solvent was removed under reduced pressure
  5. customto give a residue
  6. temperaturethe mixture was heated
  7. temperatureunder reflux for 4 hours
  8. extractionthe mixture was extracted with ethyl acetate (three times)
  9. washthe organic layer was successively washed with water (twice) and a saturated aqueous NaCl solution
  10. dry with materialdried with anhydrous sodium sulfate
  11. customobtained
  12. customby removing the solvent under reduced pressure
  13. additionin a mixture of 1,4-dioxane-water (30:1, 12 ml)
  14. stirringthe mixture was stirred at room temperature for 4 hours
  15. additionAfter water was poured into the reaction mixture
  16. extractionthe mixture was extracted with ethyl acetate
  17. washthe organic layer was successively washed with water
  18. dry with materiala saturated aqueous NaCl solution and dried with anhydrous sodium sulfate
  19. customThe mixture was purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=98/2-85/15)

出典と根拠

ORDレコード
ord-6e1b329a31a74692acf0bc37c7033266
出典データセット
uspto-grants-2011_04
特許番号
US07923573B2

反応ノート

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