1-Chloro-2-iodo-4-nitrobenzene → 2-(2-Chloro-5-nitrophenyl)pyridine

HRID 632984노트

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HRID 632984 반응식
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1I.[Br-].[N:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[Zn+]>CC(N(C)C)=O.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.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][N:13]=1

참가 물질

6

반응물 2

HCID 3127141-Chloro-2-iodo-4-nitrobenzeneHCID 178418723HCID 178418723, 화합물

생성물 1

HCID 401519232-(2-Chloro-5-nitrophenyl)pyridine수율 60%

시약·촉매·용매 3

HCID 11776Triphenylphosphine촉매HCID 178418397HCID 178418397, 화합물촉매HCID 31374Dimethylacetamide용매

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온도
60 °C

실험 절차

The 2-chloro-5-nitro-iodobenzene (5 g, 17.6 mmol) was dissolved in 5 mL DMA in an oven dried flask and a 0.5M solution of 2-pyridylzincbromide (53 mL, 26.5 mmol, 0.5 M in THF) was added. The solution was degassed with N2 for ½ hr., the PPh3 (0.185 g, 0.7 mmol) and Pd(PPh3)4 (0.825 g, 0.7 mmol) were added, rinsed in with several mLs THF and the solution was degassed for a further 10 min before heating to 60° C. under N2. The reaction was complete by TLC in ˜8 h, cooled to RT, and poured into a 1:1 mixture of EtOAc/2.5N NaOH (500 mL). This solution was stirred for 10 min, passed through a course fritted filter containing celite to remove the solid, and then extracted. The organics were washed with brine and concentrated to a brown solid. The combined aqueous layers were backextracted with Et2O (1×200 mL). This was used to suspend the crude product, which was extracted with 1N HCl (1×200 mL, 3×100 mL). The combined aqueous extracts were cooled to 0° C., diluted with EtOAc (250 mL), and made basic with 10N NaOH (100 mL). This solution was separated, the aqueous layer extracted with EtOAc, and the combined organics were dried over Na2SO4 and charcoal with stirring. This solution was filtered through celite and concentrated to yield pure 4-chloro-3-(pyridin-2-yl)nitrobenzene (2.47 g, 10.5 mmol, 60% yield) which was used in the next reaction without further purification.

후처리

  1. customdried flask
  2. customThe solution was degassed with N2 for ½ hr
  3. washrinsed in with several mLs THF
  4. customthe solution was degassed for a further 10 min
  5. temperaturecooled to RT
  6. additionpoured into a 1:1 mixture of EtOAc/2.5N NaOH (500 mL)
  7. additioncontaining celite
  8. customto remove the solid
  9. extractionextracted
  10. washThe organics were washed with brine
  11. concentrationconcentrated to a brown solid
  12. extractionwas extracted with 1N HCl (1×200 mL, 3×100 mL)
  13. temperatureThe combined aqueous extracts were cooled to 0° C.
  14. additiondiluted with EtOAc (250 mL)
  15. customThis solution was separated
  16. extractionthe aqueous layer extracted with EtOAc
  17. dry with materialthe combined organics were dried over Na2SO4 and charcoal
  18. stirringwith stirring
  19. filtrationThis solution was filtered through celite and
  20. concentrationconcentrated

출처 및 근거

ORD 기록
ord-d940bbae67aa4db4bf0a49f1d20b8bb5
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09321761B2

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