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

HRID 1969796ノート

反応式

HRID 1969796 の反応式
[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]

参加物

6

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
60 °C

実験手順

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)−.

後処理

  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

出典と根拠

ORDレコード
ord-49c4769411c44ee796cd9100cecb92cd
出典データセット
uspto-grants-2013_04
特許番号
US08426411B2

反応ノート

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