Dimethylformamide → 2-Chloro-6-(4-chloro-benzylamino)-pyridine-3-carbaldehyde

HRID 1256787노트

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HRID 1256787 반응식
Br[C:2]1[CH:3]=[CH:4][C:5]([NH:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)=[N:6][C:7]=1[Cl:8].C([Mg]Cl)(C)C.C([Li])(C)(C)C.CN(C)[CH:30]=[O:31]>O1CCCC1.O>[Cl:8][C:7]1[C:2]([CH:30]=[O:31])=[CH:3][CH:4]=[C:5]([NH:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)[N:6]=1

참가 물질

7

반응물 4

HCID 6228DimethylformamideHCID 57619309(5-Bromo-6-chloro-pyridin-2-yl)-(4-chloro-benzyl)-amineHCID 178418306HCID 178418306, 화합물HCID 178418918HCID 178418918, 화합물

생성물 1

HCID 576192992-Chloro-6-(4-chloro-benzylamino)-pyridine-3-carbaldehyde

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매

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온도
-78 °C

실험 절차

To (5-bromo-6-chloro-pyridin-2-yl)-(4-chloro-benzyl)-amine (539, 2.60 g, 7.83 mmol) in tetrahydrofuran (60.0 mL) under an atmosphere of nitrogen at −78° C., isopropylmagnesium chloride (2.00 M in tetrahydrofuran, 4.20 mL) was added over 10 minutes. The reaction was stirred at −78° C. for 20 minutes, then allowed to warm to room temperature for 10 minutes. The reaction was cooled to −78° C. tert-Butyllithium (1.70 M in hexane, 10.2 mL) was added to the reaction over 10 minutes. After 40 minutes, N,N-dimethylformamide (1.80 mL, 0.0232 mol) was added to the reaction. The reaction was stirred at −78° C. for 40 minutes, then allowed to warm to room temperature for another 30 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, concentrated and purified by silica gel column chromatography eluting with 35% to 100% ethyl acetate in hexane to give a light yellow solid (540, 1.0 g, 45.4%). MS (ESI) [M−H+]−=279.0.

후처리

  1. temperatureto warm to room temperature for 10 minutes
  2. additionwas added to the reaction over 10 minutes
  3. waitAfter 40 minutes
  4. stirringThe reaction was stirred at −78° C. for 40 minutes
  5. temperatureto warm to room temperature for another 30 minutes
  6. extractionextracted with ethyl acetate
  7. washThe organic layer was washed with brine
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated
  10. custompurified by silica gel column chromatography
  11. washeluting with 35% to 100% ethyl acetate in hexane
  12. customto give a light yellow solid (540, 1.0 g, 45.4%)

출처 및 근거

ORD 기록
ord-c0c7c49a36d44640b6d97f7600018812
출처 데이터셋
uspto-grants-2013_06
특허 번호
US08461169B2

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