Citric Acid → (4R,9aR)-6-Formyl-4-methyl-3,4,9,9a-tetrahydro-1 H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

HRID 1272138ノート

反応式

HRID 1272138 の反応式
CCO[C:4]([C:6]1[N:23]([C:24](OC(C)(C)C)=O)[C:9]2=[N:10][CH:11]=[C:12](OC(=O)C3C=CC=CC=3)[CH:13]=[C:8]2[CH:7]=1)=O.[C:31]([Li])(C)(C)C.[CH3:36][N:37](C)[CH:38]=[O:39].C(O)(=O)[CH2:42][C:43]([CH2:48]C(O)=O)([C:45](O)=O)[OH:44].[O:54]1CCC[CH2:55]1>>[C:43]([O:44][C:38]([N:37]1[CH2:36][C@@H:24]([CH3:31])[N:23]2[C@H:6]([CH2:7][C:8]3[C:9]2=[N:10][C:11]([CH:55]=[O:54])=[CH:12][CH:13]=3)[CH2:4]1)=[O:39])([CH3:42])([CH3:45])[CH3:48]

参加物

6

反応物 5

HCID 311Citric AcidHCID 6228DimethylformamideHCID 8028TetrahydrofuranHCID 693563741H-Pyrrolo[2,3-b]pyridine-1,2-dicarboxylic acid, 5-(benzoyloxy)-, 1-(1,1-dimethylethyl) 2-ethyl ester2 回HCID 178418306HCID 178418306、化合物

生成物 1

HCID 86596361(4R,9aR)-6-Formyl-4-methyl-3,4,9,9a-tetrahydro-1 H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester収率 40.1%

実験手順

A solution of 2.0 g (5.43 mmol) (4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester (example 5, intermediate c) in 15 mL tetrahydrofuran was cooled to −75 deg C. and treated with 4.40 mL (0.65 mmol) tert-butyllithium (1.5 M solution in n-pentane). After 30 min., 0.60 mL (0.63 g, 8.15 mmol) N,N-dimethylformamide was added dropwise. After 2.5 h the reaction mixture was poured on 10% aqueous citric acid solution and extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and evaporated. The remaining residue was purified by flash column chromatography on silica gel (0.032–0.063 mm) with ethyl acetate:n-hexane (1:3) as eluant to give the desired compound as a yellow oil (40.1%).

後処理

  1. extractionextracted three times with ethyl acetate
  2. washThe combined organic layers were washed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customThe remaining residue was purified by flash column chromatography on silica gel (0.032–0.063 mm) with ethyl acetate:n-hexane (1:3) as eluant

出典と根拠

ORDレコード
ord-ce86f1dc4dd94653b2998c60ae82b374
出典データセット
uspto-grants-2007_04
特許番号
US07208494B2

反応ノート

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