Phenyl Vinyl Sulfide → Dimethyl 3-(phenylthio)cyclobutane-1,2-dicarboxylate

HRID 5972

반응식

HRID 5972 반응식
[C:1]([O:9][CH3:10])(=[O:8])/[CH:2]=[CH:3]/[C:4]([O:6][CH3:7])=[O:5].[Cl-].[Cl-].C([Al+2])C.[CH:16]([S:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[CH2:17]>ClCCCl.CCCCCC>[C:19]1([S:18][CH:16]2[CH2:17][CH:3]([C:4]([O:6][CH3:7])=[O:5])[CH:2]2[C:1]([O:9][CH3:10])=[O:8])[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

참가 물질

6

반응물 3

HCID 74572Phenyl Vinyl SulfideHCID 637568Dimethyl FumarateHCID 16686341Ethyl aluminium dichloride

생성물 1

HCID 19794294Dimethyl 3-(phenylthio)cyclobutane-1,2-dicarboxylate

시약·촉매·용매 2

HCID 111,2-Dichloroethane용매2회HCID 8058Hexane용매

실험 절차

To a solution of 1.06 g (7.34 mmol) of dimethyl fumarate in 20 mL of dry 1,2-dichloroethane under nitrogen atmosphere, was added with stirring, 7.34 mmol of a 1.0 M solution of ethylaluminum dichloride in hexane. The resultant yellow solution was heated to reflux and a solution of 1.0 g (7.34 mmol) of phenyl vinyl sulfide in 4 mL of dry 1,2-dichloroethane was added dropwise, via syringe, over a period of 20 minutes. The reaction mixture was allowed to stir at reflux for 3 h. After cooling to ambient temperature, the reaction was quenched carefully with 100 mL of 1.0 N hydrochloric acid solution and the reaction mixture was extracted with 3×50 mL of ethyl acetate. The organic extract was washed with 2×50 mL of water and 50 mL of brine, dried over anhydrous magnesium sulfate, filtered and concentrated to a viscous orange oil. The oil (1.56 g) was chromatographed on silica gel (25 g) eluted with 300 mL of 3% ethyl acetate in 1,2-dichloroethane. The resultant yellow oil was purified by bulb-to-bulb distillation to give the title compound as a yellow oil; b.p 120° C. (0.05 mm Hg); EI-MS, m/e (relative intensity): 280 (M+, 18), 136 (100), 91 (13); 1H NMR (CDCl3) δ2.20 (q, 1H), 2.61 (m, 1H), 3.22 (q, 1H), 3.34 (t, 1H), 3.66 (s, 3H), 3.67 (s, 3H), 3.87 (m, 1H), 7.30 (m, 5H).

후처리

  1. temperatureThe resultant yellow solution was heated
  2. temperatureto reflux
  3. stirringto stir
  4. temperatureat reflux for 3 h
  5. customthe reaction was quenched carefully with 100 mL of 1.0 N hydrochloric acid solution
  6. extractionthe reaction mixture was extracted with 3×50 mL of ethyl acetate
  7. extractionThe organic extract
  8. washwas washed with 2×50 mL of water and 50 mL of brine
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated to a viscous orange oil
  12. customThe oil (1.56 g) was chromatographed on silica gel (25 g)
  13. washeluted with 300 mL of 3% ethyl acetate in 1,2-dichloroethane
  14. distillationThe resultant yellow oil was purified by bulb-to-bulb distillation

출처 및 근거

ORD 기록
ord-219ddea43bb2403b9dc232f4a67c5dcb
출처 데이터셋
uspto-grants-1993_09
특허 번호
US05246931

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