Carbon Dioxide → (4-t-Butylphenylthio)nitromethane

HRID 465495

반응식

HRID 465495 반응식
C([Li])CCC.CCCCCC.[N+]([O-])(OCCC)=O.[Li][Li].[C:21]([C:25]1[CH:30]=[CH:29][C:28]([S:31][CH:32]([N+:36]([O-:38])=[O:37])C(O)=O)=[CH:27][CH:26]=1)([CH3:24])([CH3:23])[CH3:22].Cl.C(=O)=O>O1CCCC1.O>[C:21]([C:25]1[CH:30]=[CH:29][C:28]([S:31][CH2:32][N+:36]([O-:38])=[O:37])=[CH:27][CH:26]=1)([CH3:24])([CH3:22])[CH3:23]

참가 물질

10

반응물 7

HCID 280Carbon DioxideHCID 313Hydrochloric AcidHCID 8058HexaneHCID 12307n-PROPYL NITRATEHCID 139759Lithium, mol. (Li2)HCID 571165772-(4-t-Butylphenylthio) 2-nitroacetic acidHCID 178418339Butyllithium

생성물 1

HCID 14404080(4-t-Butylphenylthio)nitromethane

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매

반응 조건

온도
-40 °C

실험 절차

A 1.6 M solution of butyllithium in hexane (51.25 ml, 82 mmol) was added dropwise to a stirred solution of B (9.07 g, 40.5 mmol) in anhydrous tetrahydrofuran (150 ml) maintained a -40° C. under an atmosphere of argon. When the addition was complete, the mixture was stirred for 1 hour at -5° C. Propyl nitrate (12.92 g, 123 mmol) was added dropwise to the stirred mixture at -5° C., which was then stirred for a further 2 hours, maintaining the temperature below 0° C. throughout. The mixture [containing the dilithium salt of 2-(4-t-butylphenylthio) 2-nitroacetic acid]was acidified to pH 2 by addition of 2M hydrochloric acid. The mixture was allowed to stand for 30 minutes at ambient temperature after which time evolution of carbon dioxide [obtained from decarboxylation of 2-(4-t-butylphenylthio) 2-nitroacetic acid] had ceased. Water (300 ml) was then added and the mixture was extracted with ethyl acetate. The combined extracts were washed successively with an aqueous solution of sodium hydrogen carbonate, water and brine, and then dried (MgSO4) and the solvent removed by evaporation. The residual oil was purified by chromatography on silica, eluting with (3:20 v/v) ethyl acetate/hexane, to give (4-t-butylphenylthio)nitromethane (A) as an orange oil (4.76 g), NMR spectrum (200 MHz, d6DMSO): 1.27 (s, 9H), 6.02 (s, 2H), 7.42 (s, 4H).

후처리

  1. additionWhen the addition
  2. stirringwhich was then stirred for a further 2 hours
  3. temperaturemaintaining the temperature below 0° C. throughout
  4. waitto stand for 30 minutes at ambient temperature
  5. extractionthe mixture was extracted with ethyl acetate
  6. washThe combined extracts were washed successively with an aqueous solution of sodium hydrogen carbonate, water and brine
  7. dry with materialdried (MgSO4)
  8. customthe solvent removed by evaporation
  9. customThe residual oil was purified by chromatography on silica
  10. washeluting with (3:20 v/v) ethyl acetate/hexane

출처 및 근거

ORD 기록
ord-63c8fe9c12904d528ba594dd3066acac
출처 데이터셋
uspto-grants-1992_10
특허 번호
US05153227

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