Triethylamine → Ethyl 5-methyl-1H-pyrrolo[2,3-b]pyridine-2-carboxylate

HRID 1272107ノート

反応式

HRID 1272107 の反応式
[CH3:1][CH2:2][O:3][C:4]([C:6]1[N:15](C(OC(C)(C)C)=O)[C:9]2=[N:10][CH:11]=[C:12](O)[CH:13]=[C:8]2[CH:7]=1)=[O:5].[CH2:23](N(CC)CC)C.FC(F)(F)S(O)(=O)=O.C(=O)(O)[O-].[Na+].C[Al](C)C>ClCCl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O.C(OCC)(=O)C>[CH2:2]([O:3][C:4]([C:6]1[NH:15][C:9]2=[N:10][CH:11]=[C:12]([CH3:23])[CH:13]=[C:8]2[CH:7]=1)=[O:5])[CH3:1]

参加物

10

反応物 5

HCID 8471TriethylamineHCID 62406Trifluoromethanesulfonic acidHCID 516892Sodium BicarbonateHCID 16682925TrimethylaluminumHCID 684243571H-Pyrrolo[2,3-b]pyridine-1,2-dicarboxylic acid, 5-hydroxy-, 1-(1,1-dimethylethyl) 2-ethyl ester

生成物 1

HCID 45096886Ethyl 5-methyl-1H-pyrrolo[2,3-b]pyridine-2-carboxylate収率 64.5%

試薬・触媒・溶媒 4

HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A solution of 4.0 g (13.1 mmol) 5-hydroxy-pyrrolo[2,3-b]pyridine-1,2-dicarboxylic acid 1-tert-butyl ester 2-ethyl ester in 100 mL dichloromethane was cooled to 0° C. and 2.2 mL (1.6 g, 15.7 mmol) triethylamine and 2.6 mL (4.4 g, 15.7 mmol) trifluoromethanesulfonic acid were added. After 2 h at 0° C. the reaction was poured into 10% aqueous sodium bicarbonate solution and extracted with dichloromethane. The organic layer was washed with brine, dried over magnesium sulfate and evaporated. The residue was dissolved in 100 mL tetrahydrofuran and 0.75 g (0.65 mmol) tetrakis(triphenylphosphine)palladium (0) and 13.1 mL trimethylaluminium (2M solution in n-heptane) were added. The reaction mixture was heated to reflux for 2 h and after cooling to room temperature poured into ethyl acetate and water, filtered through speedex and extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, filtered and evaporated. The residue was purified by column chromatography over silica gel (0.030–0.063 mm) with ethyl acetate:n-hexane (1:1) as eluant to give the product as a light yellow solid (64.5%).

後処理

  1. extractionextracted with dichloromethane
  2. washThe organic layer was washed with brine
  3. dry with materialdried over magnesium sulfate
  4. customevaporated
  5. dissolutionThe residue was dissolved in 100 mL tetrahydrofuran
  6. temperatureThe reaction mixture was heated
  7. temperatureto reflux for 2 h
  8. filtrationfiltered through speedex
  9. extractionextracted with ethyl acetate
  10. washThe organic layer was washed with brine
  11. dry with materialdried over magnesium sulfate
  12. filtrationfiltered
  13. customevaporated
  14. customThe residue was purified by column chromatography over silica gel (0.030–0.063 mm) with ethyl acetate:n-hexane (1:1) as eluant

出典と根拠

ORDレコード
ord-46edc579ea544288805b7e43ae9a28a8
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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