Sodium Carbonate → (R)-4,6-Dimethyl-3,4-dihydro-1H-2,4a,5-triaza-fluorene-2-carboxylic Acid Tert-butyl Ester

HRID 11915

반응식

HRID 11915 반응식
[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C:10](=[CH:11][C:12]3[C:17]2=[N:16][C:15](Br)=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:23](=O)([O-])[O-].[Na+].[Na+].CB1OB(C)OB(C)O1.[OH-].[Na+]>COCCOC.C1COCC1.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>[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C:10](=[CH:11][C:12]3[C:17]2=[N:16][C:15]([CH3:23])=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

참가 물질

8

반응물 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 574072TrimethylboroxineHCID 86590112(4R)-6-bromo-4-methyl-3,4-dihydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

생성물 1

HCID 69357516(R)-4,6-Dimethyl-3,4-dihydro-1H-2,4a,5-triaza-fluorene-2-carboxylic Acid Tert-butyl Ester수율 71.1%

시약·촉매·용매 3

HCID 178418397HCID 178418397, 화합물촉매HCID 8028Tetrahydrofuran용매HCID 80711,2-Dimethoxyethane용매

실험 절차

To a solution of 0.20 g (0.55 mmol) (R)-6-bromo-4-methyl-3,4-dihydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester (Example 5, intermediate a) in 10 ml 1,2-dimethoxyethane was added 63 mg (55 μmol) tetrakis(triphenylphosphine)palladium. After 30 min, 5 ml saturated aqueous sodium carbonate solution and 0.09 ml (0.65 mmol) of a 1M trimethylboroxine solution in THF were added and the resulting suspension was heated to reflux for 5 h. The reaction mixture was cooled to room temperature, poured into 20 ml 1M aqueous sodium hydroxide solution and extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and evaporated. The residue was purified by flash column chromatography on silica gel (0.032–0.063 mm) with ethyl acetate:n-hexane (1:1) as eluant to yield the desired product as a yellow solid (71.1%).

후처리

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

출처 및 근거

ORD 기록
ord-45ca063676444665b7e575b5a775cc21
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07098337B2

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