Triphenylphosphine → 2-(Bromomethyl)pyridine-4-carbonitrile

HRID 14278ノート

反応式

HRID 14278 の反応式
[Br:1]Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:22]([C:24]1[CH:29]=[CH:28][N:27]=[C:26]([CH2:30]O)[CH:25]=1)#[N:23]>C(Cl)Cl>[C:22]([C:24]1[CH:29]=[CH:28][N:27]=[C:26]([CH2:30][Br:1])[CH:25]=1)#[N:23]

参加物

5

反応物 3

HCID 11776TriphenylphosphineHCID 24408BromineHCID 132925992-(Hydroxymethyl)pyridine-4-carbonitrile

生成物 1

HCID 210859452-(Bromomethyl)pyridine-4-carbonitrile収率 102.8%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

Bromine (1.07 mL, 20.8 mmol) was added slowly at 0° C. to a solution of triphenylphosphine (5.53 g, 21.1 mmol) in methylene chloride (97 mL). The solution was warmed to room temperature and a white precipitate was observed. 4-Cyano-2-hydroxymethylpyridine 36 (2.61 g, 19.5 mmol) in methylene chloride (20 mL) was added dropwise and the reaction mixture was stirred at room temperature overnight. The reaction mixture was partitioned between water and methylene chloride. The organic layer was washed with saturated sodium chloride, dried (sodium sulfate), filtered, and concentrated under reduced pressure to give a white solid. Purification by flash column chromatography (silica, 99:1 methylene chloride/methanol) gave 4-cyano-2-bromomethylpyridine (3.95 g), which was used immediately in the next step without further purification: 1H NMR (300 MHz, CDCl3) δ 8.76 (d, J=5.0 Hz, 1H), 7.7 (s, 1H), 7.46 (dd, J=5.0, 1.3 Hz, 1H), 4.58 (s, 2H).

後処理

  1. customThe reaction mixture was partitioned between water and methylene chloride
  2. washThe organic layer was washed with saturated sodium chloride
  3. dry with materialdried (sodium sulfate)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customto give a white solid
  7. customPurification by flash column chromatography (silica, 99:1 methylene chloride/methanol)

出典と根拠

ORDレコード
ord-3c8ba7a915c44de9829ac2e16c1ab776
出典データセット
uspto-grants-2010_06
特許番号
US07727997B2

反応ノート

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