Potassium Sodium Tartrate → 1-Oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbaldehyde

HRID 77361노트

반응식

HRID 77361 반응식
[O:1]=[C:2]1[NH:7][C:6]([C:8]2[CH:13]=[CH:12][C:11]([C:14]([F:17])([F:16])[F:15])=[CH:10][CH:9]=2)=[CH:5][N:4]2[C:18]([C:21]#N)=[CH:19][CH:20]=[C:3]12.[H-].C([Al+]CC(C)C)C(C)C.[C@H](O)(C([O-])=O)[C@@H](O)C([O-])=[O:36].[Na+].[K+]>C(Cl)Cl>[O:1]=[C:2]1[NH:7][C:6]([C:8]2[CH:13]=[CH:12][C:11]([C:14]([F:15])([F:17])[F:16])=[CH:10][CH:9]=2)=[CH:5][N:4]2[C:18]([CH:21]=[O:36])=[CH:19][CH:20]=[C:3]12

참가 물질

5

반응물 3

HCID 9357Potassium Sodium TartrateHCID 21225700Diisobutylaluminumhydride2회HCID 727149431-Oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbonitrile

생성물 1

HCID 867066601-Oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbaldehyde수율 40%

시약·촉매·용매 1

HCID 6344Dichloromethane용매3회

반응 조건

온도
-75 °C

실험 절차

A mixture of 1-oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbonitrile (Example 2) (55 mg, 0.18 mmol) in methylene chloride (1 mL) cooled −75° C. was treated dropwise with 1M diisobutylaluminum hydride in methylene chloride (275 μL, 0.27 mmol). The reaction was stirred at −75° C. for 1.5 h. At this time, the reaction was treated with additional 1M diisobutylaluminum hydride in methylene chloride (0.1 mL, 0.1 mmol) and allowed to stir at −75° C. for an additional 1 h. At this time, the reaction was treated with a solution of Rochelle's salt, and the mixture was allowed to warm up to room temperature where it stirred overnight. At this time, the resulting suspension was absorbed onto silica gel. Flash chromatography (4 g silica column, 0-50% ethyl acetate/hexanes) afforded 1-oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbaldehyde (22 mg, 40%) as light yellow solid. 1H NMR (acetone-d6) δ ppm 10.02 (s, 1H), 8.11 (d, J=1.5 Hz, 1H), 8.03 (d, J=8.0 Hz, 2H), 7.89 (d, J=8.5 Hz, 2H), 7.85 (s, 1H), 7.42 (s, 1H). LC-MS calcd. for C15H10F3N2O2 [(M+H)+] 307, obsd. 306.8.

후처리

  1. stirringto stir at −75° C. for an additional 1 h
  2. temperatureto warm up to room temperature where it
  3. stirringstirred overnight
  4. customAt this time, the resulting suspension was absorbed onto silica gel

출처 및 근거

ORD 기록
ord-7a36bf40573e4080b19c075ef0998172
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08841299B2

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