Hydrogen Peroxide → Tert-butyl 2-methyl-6,7-bis(trifluoromethyl)spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4'-piperidine]-1'-carboxylate

HRID 1405365노트

반응식

HRID 1405365 반응식
[CH3:1][N:2]1[C:14]2([CH2:19][CH2:18][N:17]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:16][CH2:15]2)[C:6]2=[CH:7][CH:8]=[C:9]([C:10]([F:13])([F:12])[F:11])[N:5]2[CH2:4][CH2:3]1.[C:27](I)([F:30])([F:29])[F:28].OO>CS(C)=O>[CH3:1][N:2]1[C:14]2([CH2:19][CH2:18][N:17]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:16][CH2:15]2)[C:6]2=[CH:7][C:8]([C:27]([F:30])([F:29])[F:28])=[C:9]([C:10]([F:11])([F:13])[F:12])[N:5]2[CH2:4][CH2:3]1

참가 물질

5

반응물 3

HCID 784Hydrogen PeroxideHCID 16843TrifluoroiodomethaneHCID 68153221tert-Butyl 2'-methyl-6'-(trifluoromethyl)-3',4'-dihydro-2'H-spiro[piperidine-4,1'-pyrrolo[1,2-a]pyrazine]-1-carboxylate

생성물 1

HCID 86668522Tert-butyl 2-methyl-6,7-bis(trifluoromethyl)spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4'-piperidine]-1'-carboxylate

시약·촉매·용매 1

HCID 679Dimethyl Sulfoxide용매

실험 절차

Ferrous sulfate heptahydrate (803 μL of 1.00 M, 0.803 mmol) was added to a mixture of tert-butyl 2-methyl-6-(trifluoromethyl)spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4′-piperidine]-1′-carboxylate (1.00 g, 2.68 mmol) and DMSO (15 mL) at room temperature. The vessel was then charged with CF3I (gas) before H2O2 (304 μL of 30% w/v, 2.68 mmol) was added dropwise. The mixture was allowed to stir overnight at room temperature before it was partitioned between ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate (3×). The combined organics were washed with brine, dried over sodium sulfate, filtered and concentrated. The reside was purified by column chromatography (0-100% ethyl acetate/hexanes) to give tert-butyl 2-methyl-6,7-bis(trifluoromethyl)spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4′-piperidine]-1′-carboxylate. ESI-MS m/z calc. 441.2, found 442.5 (M+1)+; Retention time: 1.36 minutes (3 min run).

후처리

  1. additionwas added dropwise
  2. customwas partitioned between ethyl acetate and water
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with ethyl acetate (3×)
  5. washThe combined organics were washed with brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe reside was purified by column chromatography (0-100% ethyl acetate/hexanes)

출처 및 근거

ORD 기록
ord-b1d43d598cea4f2db41dc5bbbbb7e3cc
출처 데이터셋
uspto-grants-2014_12
특허 번호
US08916565B2

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