hydroxylamine-O-sulfonic acid → (3-Methyl-4-nitrophenyl)methanesulfonamide

HRID 907461노트

반응식

HRID 907461 반응식
[CH3:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[N+:10]([O-:12])=[O:11])[CH2:5]Br.COC(=O)CC[S:18]([O-:21])(=O)=[O:19].[Na+].[NH2:24]OS(O)(=O)=O.CC([O-])=O.[Na+]>CS(C)=O.CCOC(C)=O.O.CCOC(C)=O.CCCCCC>[CH3:1][C:2]1[CH:3]=[C:4]([CH2:5][S:18]([NH2:24])(=[O:21])=[O:19])[CH:7]=[CH:8][C:9]=1[N+:10]([O-:12])=[O:11]

참가 물질

9

반응물 4

HCID 76284hydroxylamine-O-sulfonic acidHCID 517045Sodium AcetateHCID 44459783-Methyl-4-nitrobenzyl bromideHCID 57659405Sodium 3-methoxy-3-oxopropane-1-sulfonate

생성물 1

HCID 44245339(3-Methyl-4-nitrophenyl)methanesulfonamide

시약·촉매·용매 4

HCID 679Dimethyl Sulfoxide용매HCID 962Water용매HCID 8857Ethyl Acetate용매HCID 21226206Ethyl acetate hexane용매

실험 절차

3-Methyl-4-nitrobenzyl bromide (60 g, 261 mmol) was added portionwise to a suspension of sodium 3-methoxy-3-oxopropane-1-sulfonate 13 (50 g, 1.1 equiv) in DMSO (400 ml) at r.t. (with occasional ice bath cooling to keep the temperature below 28 C) and this mixture was stirred at r.t. for 3 h (TLC (EtOAc/hexane 50%) indicated complete consumption of the starting material to cleanly form a new spot). MeOH (400 ml) was then added and the mixture was cooled down to −10 C. MeONa (62 ml of a 25% solution in MeOH) was added dropwise at −9 C and the reaction was warmed slowly to 0 C (where complete disappearance of the intermediate was seen by TLC). Finally, this mixture was poured portionwise into an aqueous solution containing hydroxylamine-O-sulfonic acid (118 g, 4 equiv) and NaOAc (107 g, 5 equiv) at 0 C (very exothermic reaction). The reaction was warmed very slowly to r.t. and was stirred at that temperature o.n. More water (1 L) and EtOAc (1 L) were added to dissolve the precipitate. The product was extracted into EtOAc, washed with brine and dried over Na2SO4. Evaporation of solvents gave a gummy solid, which was triturated in toluene (300 ml) for an hour to yield 49.35 g (82%) of pure 14 as a white solid.

후처리

  1. temperaturecooling
  2. customconsumption of the starting material to cleanly form a new spot)
  3. additionMeOH (400 ml) was then added
  4. temperaturethe mixture was cooled down to −10 C
  5. additionMeONa (62 ml of a 25% solution in MeOH) was added dropwise at −9 C
  6. temperaturethe reaction was warmed slowly to 0 C (where complete disappearance of the intermediate
  7. additionFinally, this mixture was poured portionwise into an aqueous solution
  8. customvery exothermic reaction)
  9. dissolutionto dissolve the precipitate
  10. extractionThe product was extracted into EtOAc
  11. washwashed with brine
  12. dry with materialdried over Na2SO4
  13. customEvaporation of solvents
  14. customgave a gummy solid, which
  15. customwas triturated in toluene (300 ml) for an hour

출처 및 근거

ORD 기록
ord-d4a768b5e7d04fc294fad619db4f4a67
출처 데이터셋
uspto-grants-2011_09
특허 번호
US08013159B2

반응 노트

불러오는 중…