Potassium tert-butoxide → 1H-Pyrrole-3-carbonitrile, 4-(4-chlorophenyl)-5-(trifluoromethyl)-

HRID 1030784

反応式

HRID 1030784 の反応式
CC(C)([O-])C.[K+].[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([CH2:14][C:15](=[N:20]O)[C:16]([F:19])([F:18])[F:17])=[CH:10][CH:9]=1.Cl[CH:23]=[CH:24][C:25]#[N:26]>O1CCCC1.C(Cl)Cl>[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2[C:24]([C:25]#[N:26])=[CH:23][NH:20][C:15]=2[C:16]([F:19])([F:18])[F:17])=[CH:10][CH:9]=1

参加物

6

反応物 3

HCID 23665647Potassium tert-butoxideHCID 53439748beta-ChloroacrylonitrileHCID 85405208HCID 85405208、化合物

生成物 1

HCID 118217011H-Pyrrole-3-carbonitrile, 4-(4-chlorophenyl)-5-(trifluoromethyl)-

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

Potassium-t-butoxide (2.46 g, 0.022 mol) is added in portions to a solution of 3-(p-chlorophenyl)-1,1,1-trifluoro-2-propanone oxime, (E)-, or (Z)-(4.75 g, 0.02 mol) in tetrahydrofuran (20 mL) at such a rate that the temperature if maintained at 25°-30° C. (ice-water bath). The resulting solution is stirred for 15 minutes and then added dropwise to a solution of β-chloroacrylonitrile (1.75 g, 0.02 mol) in tetrahydrofuran (15 mL) at 15°-10° C. over 1/2 hour. The ice bath is removed and the reaction mixture is stirred for 1 hour, diluted with water, made acidic with a small amount of dilute HCl and extracted with ether. The combined ether extracts are washed with water and brine and dried (Na2SO4). Concentration in vacuo gives an oil which is dissolved in methylene chloride and filtered through a bed of flash column silica gel (30 mL size) and washed with an ethyl acetate/methylene chloride mixture (1:1). The filtrate is evaporated and the residual semi-solid is crystallized from methylene chloride/hexanes to give the title product as a yellow solid (2.10 g): mp 162.5°-164.0° C. IR (Nujol) 3200, 2250 cm-1, 1H NMR (DMSO-d6) δ7.42, 7.56 (AB, JAB =8.3 Hz, ArH), 8.03 (s, 1H, 2H); 19F NMR δ-51.2; 13C NMR δ94.2 (C-3), 115.0 (CN), 116.6 (q, 2JCF =38.3 Hz, C-5), 120.6 (q, 1JCF =268.7 Hz, CF3), 127.0 (q, 3JCF =3.5 Hz, C-4), 128.6 (C-2') 129.1 (C-1'), 129.7 (C-2), 130.8 (C-3'), 133.4 (C-4').

後処理

  1. customThe ice bath is removed
  2. stirringthe reaction mixture is stirred for 1 hour
  3. additiondiluted with water
  4. extractionextracted with ether
  5. washThe combined ether extracts are washed with water and brine
  6. dry with materialdried (Na2SO4)
  7. concentrationConcentration in vacuo
  8. customgives an oil which
  9. filtrationfiltered through a bed of flash column silica gel (30 mL size)
  10. washwashed with an ethyl acetate/methylene chloride mixture (1:1)
  11. customThe filtrate is evaporated
  12. customthe residual semi-solid is crystallized from methylene chloride/hexanes

出典と根拠

ORDレコード
ord-52a6139fe5294b749e0bbaf6550724e8
出典データセット
uspto-grants-1992_04
特許番号
US05106985

関連ノート

読み込み中…