Dibenzosuberone → 5-Methylene-10,11-dihydro-5H-dibenzo[a,d][7]annulene

HRID 2218680노트

반응식

HRID 2218680 반응식
[CH3:1][Mg]Br.[CH2:4]1[C:19]2[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=2)[C:12](=O)[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH2:5]1>C1COCC1>[CH2:1]=[C:12]1[C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][C:19]=2[CH2:4][CH2:5][C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:11]1=2

참가 물질

4

반응물 2

HCID 14589DibenzosuberoneHCID 178418573HCID 178418573, 화합물

생성물 1

HCID 46413975-Methylene-10,11-dihydro-5H-dibenzo[a,d][7]annulene수율 84.4%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

Add methylmagnesium bromide (3M solution in Et2O, 48.0 mL, 144 mmol) dropwise to a cooled (0° C.) solution of dibenzosuberone (20.0 g, 96.03 mmol) in THF (140 mL) under N2 (exothermic). Let solution warm up to room temperature and continue stirring for 2 h. Cool solution to 0° C. and quench with saturated aqueous NH4Cl (exothermic, emits gas). Extract into ethyl acetate, dry organics (MgSO4) and concentrate in-vacuo. Dissolve residue in 4N HCl/dioxane (40 mL) and stir at room temperature overnight. Concentrate and dilute with H2O. Extract into ethyl acetate, dry organics (MgSO4) and concentrate to a yellow oil. Purify crude product by loading onto a 30 g plug of silica gel and eluting with hexanes until eluent shows no UV activity. Combine and concentrate hexane washes to afford 16.72 g (84%) of the title compound as a white solid, mp 65.1° C. HPLC shows 98% purity.

후처리

  1. customCool solution to 0° C. and quench with saturated aqueous NH4Cl (exothermic, emits gas)
  2. extractionExtract into ethyl acetate, dry organics (MgSO4)
  3. concentrationconcentrate in-vacuo
  4. stirringDissolve residue in 4N HCl/dioxane (40 mL) and stir at room temperature overnight
  5. concentrationConcentrate
  6. additiondilute with H2O
  7. extractionExtract into ethyl acetate, dry organics (MgSO4)
  8. concentrationconcentrate to a yellow oil
  9. customPurify crude product
  10. washeluting with hexanes until eluent shows no UV activity
  11. concentrationCombine and concentrate hexane washes

출처 및 근거

ORD 기록
ord-293710443cfb44b4abe45b4ba9c21776
출처 데이터셋
uspto-grants-2008_08
특허 번호
US07411072B2

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