Trimethylsilylacetylene → 4-Chloro-5-nitro-3-((trimethylsilyl)ethynyl)pyridin-2-amine

HRID 1969796노트

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HRID 1969796 반응식
[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=[C:4]([NH2:11])[C:3]=1I.[CH3:13][Si:14]([C:17]#[CH:18])([CH3:16])[CH3:15]>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=[C:4]([NH2:11])[C:3]=1[C:18]#[C:17][Si:14]([CH3:16])([CH3:15])[CH3:13]

참가 물질

6

반응물 2

HCID 66111TrimethylsilylacetyleneHCID 585571744-Chloro-3-iodo-5-nitropyridin-2-amine

생성물 1

HCID 585574594-Chloro-5-nitro-3-((trimethylsilyl)ethynyl)pyridin-2-amine수율 16.1%

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매HCID 8028Tetrahydrofuran용매

반응 조건

온도
60 °C

실험 절차

To a solution of 4-chloro-3-iodo-5-nitropyridin-2-amine (5.30 g, 17.7 mmol) in THF (90 mL) was added TEA (15.0 mL, 108 mmol). The reaction mixture was degassed and purged with nitrogen 3 times. Bis(triphenylphosphine)-palladium(II) dichloride (0.62 g, 0.88 mmol, Strem), copper(I) iodide (0.17 g, 0.89 mmol), and trimethylsilylacetylene (5.4 mL, 39 mmol) were added to the reaction mixture, degassed, and purged 3 times with nitrogen. The reaction was heated at about 60° C. for about 16 h. The reaction mixture was cooled to ambient temperature. The reaction mixture was filtered and washed with THF (200 mL). The filtrate was concd under reduced pressure. DCM (100 mL) was added to the residue and the precipitate that formed was filtered and collected to give 4-chloro-5-nitro-3-((trimethylsilyl)ethynyl)pyridin-2-amine (0.77 g). The remaining filtrate was concd under reduced pressure and the crude material was purified by flash chromatography on silica gel eluting with a gradient of 0-100% EtOAc in DCM. The purified material was combined with the 0.77 g of precipitate to afford 4-chloro-5-nitro-3-((trimethylsilyl)ethynyl)pyridin-2-amine (2.22 g, 47%) as a yellow solid: LC/MS (Table 1, Method c) Rt=1.62 min; MS m/z 268 (M−H)−.

후처리

  1. customThe reaction mixture was degassed
  2. custompurged with nitrogen 3 times
  3. customdegassed
  4. custompurged 3 times with nitrogen
  5. temperatureThe reaction mixture was cooled to ambient temperature
  6. filtrationThe reaction mixture was filtered
  7. washwashed with THF (200 mL)
  8. additionDCM (100 mL) was added to the residue
  9. customthe precipitate that formed
  10. filtrationwas filtered
  11. customcollected

출처 및 근거

ORD 기록
ord-49c4769411c44ee796cd9100cecb92cd
출처 데이터셋
uspto-grants-2013_04
특허 번호
US08426411B2

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