N-bromobutanimide → Tert-butyl 6-bromo-2-methyl-spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4'-piperidine]-1'-carboxylate

HRID 1405350노트

반응식

HRID 1405350 반응식
[CH3:1][N:2]1[C:10]2([CH2:15][CH2:14][N:13]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:12][CH2:11]2)[C:6]2=[CH:7][CH:8]=[CH:9][N:5]2[CH2:4][CH2:3]1.[Br:23]N1C(=O)CCC1=O>C(Cl)Cl.[O-]S([O-])(=S)=O.[Na+].[Na+]>[Br:23][C:9]1[N:5]2[CH2:4][CH2:3][N:2]([CH3:1])[C:10]3([CH2:11][CH2:12][N:13]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:14][CH2:15]3)[C:6]2=[CH:7][CH:8]=1

참가 물질

5

반응물 2

HCID 67184N-bromobutanimide2회HCID 68153652tert-Butyl 2'-methyl-3',4'-dihydro-2'H-spiro[piperidine-4,1'-pyrrolo[1,2-a]pyrazine]-1-carboxylate

생성물 1

HCID 68153511Tert-butyl 6-bromo-2-methyl-spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4'-piperidine]-1'-carboxylate

시약·촉매·용매 2

HCID 6344Dichloromethane용매HCID 24477Sodium Thiosulfate용매

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온도
0 °C

실험 절차

To tert-butyl 2-methylspiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4′-piperidine]-1′-carboxylate (10 g, 32.74 mmol) in methylene chloride (73.5 mL) at 0° C. was added N-bromosuccinimide (5.53 g, 31.10 mmol) portionwise. The reaction was stirred at 0° C. After 30 minutes, additional N-bromosuccinimide (291.4 mg, 1.64 mmol) was added and the reaction was stirred for 1 hour. The reaction was diluted with 0.5 M Na2S2O3 (135 mL) and the aqueous phase was removed. The organic layer was washed with brine (135 mL). The organic layer was dried over sodium sulfate, filtered and the solvent was evaporated under reduced pressure to yield tert-butyl 6-bromo-2-methyl-spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4′-piperidine]-1′-carboxylate as a red viscous liquid that was used in the next step without further purification. 1H NMR (400 MHz, DMSO) δ 6.09 (d, J=3.7 Hz, 1H), 5.99 (d, J=3.7 Hz, 1H), 3.78-3.65 (m, 4H), 3.27 (t, J=6.0 Hz, 2H), 3.17-2.92 (m, 2H), 2.21 (s, 3H), 2.03-1.93 (m, 2H), 1.65-1.53 (m, 2H), 1.40 (s, 9H). ESI-MS m/z calc. 383.1, found 386.0 (M+1)+; Retention time: 1.13 minutes (3 minute run).

후처리

  1. stirringthe reaction was stirred for 1 hour
  2. customthe aqueous phase was removed
  3. washThe organic layer was washed with brine (135 mL)
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. filtrationfiltered
  6. customthe solvent was evaporated under reduced pressure

출처 및 근거

ORD 기록
ord-2062b0b1012d42a095eae00c371b6d13
출처 데이터셋
uspto-grants-2014_12
특허 번호
US08916565B2

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