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

HRID 77361ノート

反応式

HRID 77361 の反応式
[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

参加物

5

反応物 3

HCID 9357Potassium Sodium TartrateHCID 21225700Diisobutylaluminumhydride2 回HCID 727149431-Oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbonitrile

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒3 回

反応条件

温度
-75 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-7a36bf40573e4080b19c075ef0998172
出典データセット
uspto-grants-2014_09
特許番号
US08841299B2

反応ノート

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