Dimethylformamide → 3-Chloro-5-hydroxypicolinonitrile

HRID 221798ノート

反応式

HRID 221798 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]([O:9]C(=O)C)[CH:5]=[N:6][C:7]=1Cl.[CH3:13][N:14](C=O)C>CC(OC)(C)C.O.[Ar].[Zn].[C-]#N.[C-]#N.[Zn+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].Cl[Pd]Cl>[Cl:1][C:2]1[C:7]([C:13]#[N:14])=[N:6][CH:5]=[C:4]([OH:9])[CH:3]=1

参加物

8

反応物 2

HCID 6228DimethylformamideHCID 145952225,6-Dichloropyridin-3-yl acetate

生成物 1

HCID 666654733-Chloro-5-hydroxypicolinonitrile

試薬・触媒・溶媒 5

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 85978949argon Zn触媒HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 962Water溶媒HCID 15413tert-Butyl methyl ether溶媒

反応条件

温度
150 °C

実験手順

To a solution of acetic acid 5,6-dichloro-pyridin-3-yl ester (CA 110861-18-2, Synthesis, 1990, 499) (4.88 g, 23.6 mmol) in anhydrous DMF (45 ml) was added after degasing with argon Zn-dust (70 mg, 1.07 mmol), Zn(CN)2 (1.28 g, 10.9 mmol) and DPPF PdCl2 (966 mg, 1.18 mmol) and the reaction mixture was heated for 6 h at 130° C. and 18 h at 150° C. The reaction mixture was diluted with TBME and H2O, filtered over Celite, and the product was extracted with TBME. Combined extracts were washed with water and brine, dried over MgSO4, filtered and concentrated. The title compound was obtained as a beige solid after crystallization from EtOAc-hexane: TLC(CH2Cl2-MeOH 19:1): Rf=0.22;

後処理

  1. filtrationfiltered over Celite
  2. extractionthe product was extracted with TBME
  3. washCombined extracts were washed with water and brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated

出典と根拠

ORDレコード
ord-73c6c07de58346f880298eee000aa0f6
出典データセット
uspto-grants-2012_06
特許番号
US08207164B2

反応ノート

読み込み中…