Hydrochloric Acid → (1R*,5S*)-3-(4-bromo-2-ethylphenyl)-1-methyl-8-oxabicyclo[3.2.1]octane-2,4-dione

HRID 341653

반응식

HRID 341653 반응식
[CH3:1][C@@:2]12[O:9][C@@H:6]([CH2:7][CH2:8]1)[C:5](=[O:10])[CH2:4][C:3]2=[O:11].C(Cl)(Cl)Cl.C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.[Br:28][C:29]1[CH:34]=[CH:33][C:32]([Pb+3])=[C:31]([CH2:36][CH3:37])[CH:30]=1.Cl>CN(C)C1C=CN=CC=1.C1(C)C=CC=CC=1>[Br:28][C:29]1[CH:34]=[CH:33][C:32]([CH:4]2[C:5](=[O:10])[C@H:6]3[O:9][C@:2]([CH3:1])([CH2:8][CH2:7]3)[C:3]2=[O:11])=[C:31]([CH2:36][CH3:37])[CH:30]=1

참가 물질

7

반응물 4

HCID 313Hydrochloric AcidHCID 6212ChloroformHCID 67533518(1R*,5S*)-1-methyl-8-oxabicyclo[3.2.1]octane-2,4-dioneHCID 178476529HCID 178476529, 화합물

생성물 1

HCID 68735332(1R*,5S*)-3-(4-bromo-2-ethylphenyl)-1-methyl-8-oxabicyclo[3.2.1]octane-2,4-dione수율 45.7%

시약·촉매·용매 2

HCID 142844-(Dimethylamino)pyridine촉매HCID 1140Toluene용매

반응 조건

온도
80 °C

실험 절차

(1R*,5S*)-1-Methyl-8-oxabicyclo[3.2.1]octane-2,4-dione (6 g, 38.96 mmol) and 4-dimethylaminopyridine (23.76 g, 194.75 mmol) are added to a mixture of chloroform (120 ml) and toluene (30 ml). The reaction mixture is flushed with nitrogen for 15 minutes at ambient temperature. 4-Bromo-2-ethylphenyllead triacetate (24.3 g, 42.85 mmol) is added in one portion and the reaction mixture is stirred and heated to 80° C. (pre-heated oil bath) under an atmosphere of nitrogen for 1 hour. The reaction mixture is cooled to room temperature, acidified to pH 1 with 2N aqueous hydrochloric acid, filtered through a plug of diatomaceous earth and the two phases separated. The aqueous phase is extracted with dichloromethane (2×50 ml), the organic phases are combined, washed with water, and dried over anhydrous sodium sulfate. The mixture is filtered, and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give (1R*,5S*)-3-(4-bromo-2-ethylphenyl)-1-methyl-8-oxabicyclo[3.2.1]octane-2,4-dione as a white solid (6 g).

후처리

  1. customThe reaction mixture is flushed with nitrogen for 15 minutes at ambient temperature
  2. temperature(pre-heated oil bath) under an atmosphere of nitrogen for 1 hour
  3. temperatureThe reaction mixture is cooled to room temperature
  4. filtrationfiltered through a plug of diatomaceous earth
  5. customthe two phases separated
  6. extractionThe aqueous phase is extracted with dichloromethane (2×50 ml)
  7. washwashed with water
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationThe mixture is filtered
  10. customthe filtrate is evaporated under reduced pressure
  11. customThe residue is purified by column chromatography on silica gel

출처 및 근거

ORD 기록
ord-8d88638a538c48268e8671cb769ec0df
출처 데이터셋
uspto-grants-2014_11
특허 번호
US08895761B2

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