Ammonium Chloride → 4-((Trimethylsilyl)ethynyl)pyridin-2-amine

HRID 1023452ノート

反応式

HRID 1023452 の反応式
Cl[C:2]1[CH:7]=[C:6]([C:8]#[C:9][Si:10]([CH3:13])([CH3:12])[CH3:11])[CH:5]=[CH:4][N:3]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2)CCCCC1.[Li+].C[Si]([N-:44][Si](C)(C)C)(C)C.[NH4+].[Cl-]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O.C1COCC1>[CH3:11][Si:10]([C:9]#[C:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([NH2:44])[CH:7]=1)([CH3:13])[CH3:12]

参加物

8

反応物 4

HCID 25517Ammonium ChlorideHCID 2733832Lithium HexamethyldisilazideHCID 27342162-(Dicyclohexylphosphino)biphenylHCID 219853912-Chloro-4-(2-(trimethylsilyl)ethynyl)pyridine

生成物 1

HCID 210972634-((Trimethylsilyl)ethynyl)pyridin-2-amine収率 94.3%

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
60 °C

実験手順

2-Chloro-4-trimethylsilanylethynyl-pyridine (9.3 g, 44 mmol), tris(dibenzylideneacetone)dipalladium(0) (8.1 g, 8.9 mmol) and 2-(dicyclohexylphosphino)biphenyl (8.1 g, 23 mmol) are added into the de-gased dry THF (60 mL). Then 1.0 M LiHMDS (155 mL, 155 mmol) is added. The reaction mixture is heated at 60° C. for 16 hrs before it is cooled down to room temperature and saturated NH4Cl aqueous solution (100 mL) is added along with water (100 mL). The mixture is extracted with EtOAc (2×200 mL) and the organic layers are combined and concentrated to give the crude product. Purification by silica flash column chromatography using 33% EtOAc in hexanes affords 7.9 g of the desired product.

後処理

  1. temperatureis cooled down to room temperature
  2. extractionThe mixture is extracted with EtOAc (2×200 mL)
  3. concentrationconcentrated
  4. customto give the crude product
  5. customPurification by silica flash column chromatography

出典と根拠

ORDレコード
ord-12f80713b4914e53bcb3af4174cf1a70
出典データセット
uspto-grants-2014_05
特許番号
US08722709B2

反応ノート

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