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Tetrahydrofuran → 1-Benzoyloxy-3-hydroxymethyl-2-methylenecyclobutane

HRID 5958
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HRID 5958 반응식
[C:1]([O:9][CH:10]1[CH2:13][CH:12]([CH2:14][OH:15])[CH:11]1[CH2:16]Br)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.C1COCC1>C(Cl)Cl>[C:1]([O:9][CH:10]1[CH2:13][CH:12]([CH2:14][OH:15])[C:11]1=[CH2:16])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
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참가 물질

5

반응물 3

HCID 8028TetrahydrofuranHCID 2724141Tetrabutylammonium FluorideHCID 197942491-Benzoyloxy-2-bromomethyl-3-hydroxymethylcyclobutane

생성물 1

HCID 197943161-Benzoyloxy-3-hydroxymethyl-2-methylenecyclobutane수율 85%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

1-Benzoyloxy-2-bromomethyl-3-hydroxymethylcyclobutane (2.5 g, 8.36 mmol) from Step F and tetra-n-butylammonium fluoride ((8.1 g, 25 mmol) were combined in 200 mL of freshly distilled THF and the reaction mixture was stirred at ambient temperature, under a nitrogen atmosphere, overnight. The volume of the reaction mixture was then reduced to 25 mL and this was dissolved in 250 mL of methylene chloride. The methylene chloride solution was washed with 150 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue (4.9 g) was dissolved in ~5 mL of methylene chloride and purified on a 2.5×35 cm silica gel column eluted @ 5 psi with a step-wise (4×200 mL steps) of methanol in methylene chloride from 0% to 3% methanol to give 1.54 g (85% yield) of the title compound as a syrup; 1H NMR (CDCl3) δ 2.38 (m, 2H), 3.22 (m, 1H), 3.69-3.85 (m, 2H), 5.13 (t, 1H), 5.32 (t, 1H), 5.79 (M, 1H), 7.45 (m, 2H), 7.58 (m, 1H), 8.08 (m, 2H); MS DCI-NH3M/Z: 219 (M+H)+, 236 (M+NH4)+.

후처리

  1. washThe methylene chloride solution was washed with 150 mL of water
  2. dry with materialdried over anhydrous magnesium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. dissolutionThe residue (4.9 g) was dissolved in ~5 mL of methylene chloride
  6. custompurified on a 2.5×35 cm silica gel column
  7. washeluted @ 5 psi with a step-wise (4×200 mL steps) of methanol in methylene chloride from 0% to 3% methanol

출처 및 근거

ORD 기록
ord-3d62ca5f75db401fa27c51497eb470a9
출처 데이터셋
uspto-grants-1993_09
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05246931

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