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 1272138노트

반응식

HRID 1272138 반응식
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]

참가 물질

6

반응물 5

HCID 311Citric AcidHCID 6228DimethylformamideHCID 8028TetrahydrofuranHCID 693563741H-Pyrrolo[2,3-b]pyridine-1,2-dicarboxylic acid, 5-(benzoyloxy)-, 1-(1,1-dimethylethyl) 2-ethyl ester2회HCID 178418306HCID 178418306, 화합물

생성물 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 ester수율 40.1%

실험 절차

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%).

후처리

  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

출처 및 근거

ORD 기록
ord-ce86f1dc4dd94653b2998c60ae82b374
출처 데이터셋
uspto-grants-2007_04
특허 번호
US07208494B2

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