Cesium carbonate → tert-butyl N-(4-fluoropyridin-2-yl)carbamate

HRID 706616

反応式

HRID 706616 の反応式
Cl[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][N:3]=1.[C:9](=[O:16])([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[NH2:10].C(=O)([O-])[O-].[Cs+].[Cs+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.O1CCCC1>[F:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([NH:10][C:9](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH:7]=1

参加物

7

反応物 3

HCID 10796Cesium carbonate2 回HCID 77922tert-Butyl carbamateHCID 27827922-Chloro-4-fluoropyridine

生成物 1

HCID 51354888tert-butyl N-(4-fluoropyridin-2-yl)carbamate収率 70.1%

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl触媒HCID 8028Tetrahydrofuran溶媒

実験手順

A flask was charged with 2-chloro-4-fluoropyridine (20 g, 152 mmol), tert-butyl carbamate (89 g, 760 mmol), tris(dibenzylideneacetone)dipalladium (1.39 g, 1.52 mmol), X-PHOS (1.48 g, 3.10 mmol), cesium carbonate (99 g, 588 mmol), and tetrahydrofuran (500 mL) under an atmosphere of dry nitrogen. This mixture was refluxed under nitrogen for 7 hours. An additional equivalent of cesium carbonate was added to drive reaction to completion. The mixture was cooled to ambient temperature and filtered through Celite, and the Celite was washed with ethyl acetate. The filtrate was partitioned between saturated sodium bicarbonate and ethyl acetate. The aqueous layer was washed with ethyl acetate twice. The combined organics were washed with brine and dried with sodium sulfate, concentrated under vacuum, and purified by column chromatography to give tert-butyl 4-fluoropyridin-2-ylcarbamate as a pale yellow solid (22.6 g).

後処理

  1. temperatureThis mixture was refluxed under nitrogen for 7 hours
  2. customreaction to completion
  3. filtrationfiltered through Celite
  4. washthe Celite was washed with ethyl acetate
  5. customThe filtrate was partitioned between saturated sodium bicarbonate and ethyl acetate
  6. washThe aqueous layer was washed with ethyl acetate twice
  7. washThe combined organics were washed with brine
  8. dry with materialdried with sodium sulfate
  9. concentrationconcentrated under vacuum
  10. custompurified by column chromatography

出典と根拠

ORDレコード
ord-e654febe1aab4a7ba5538020f8811df5
出典データセット
uspto-grants-2015_11
特許番号
US09174981B2

関連ノート

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