Hydrochloric Acid → 4'-(chloromethyl)-[1,1'-Biphenyl]-2-carbonitrile

HRID 373237ノート

反応式

HRID 373237 の反応式
[C:1]1([C:7]2[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=2[C:9]#[N:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl:15][CH2:16]OC.C(OCC)(=O)C.Cl>[Ti](Cl)(Cl)(Cl)Cl.O>[Cl:15][CH2:16][C:4]1[CH:3]=[CH:2][C:1]([C:7]2[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=2[C:9]#[N:10])=[CH:6][CH:5]=1

参加物

7

反応物 4

HCID 313Hydrochloric AcidHCID 7864Chloromethyl Methyl Ether2 回HCID 8857Ethyl AcetateHCID 141162(1,1'-Biphenyl)-2-carbonitrile

生成物 1

HCID 217117564'-(chloromethyl)-[1,1'-Biphenyl]-2-carbonitrile収率 48.3%

試薬・触媒・溶媒 2

HCID 24193Titanium Tetrachloride触媒HCID 962Water溶媒

実験手順

To vigorously stirred 2-phenylbenzonitrile (68.1 g) under ice-cooling was added titanium tetrachloride (432 g) dropwise for 30 minutes. The precipitated crystals were pulverized and then chloromethyl-methyl ether (61 g) was added dropwise for 20 minutes with stirring under ice-cooling. After stirring at 60° C. for 2 hours, additional chloromethyl-methyl ether (15.3 g) was added and the mixture was stirred for an additional hour. To the reaction mixture was added ethyl acetate (200 ml) dropwise with stirring under ice-cooling. Then ice was added until hydrogen chloride gas development ceased and iced water (400 ml) was added before stirring for a while. The precipitated crystals were filtered and dried. The filtrate was extracted with ethyl acetate, washed with water, and concentrated to dryness in vacuo. The resulting residue was purified by column chromatography on silica gel to give crystals which were combined with the previously obtained crystal and recrystallized from methanol to yield pale yellow prisms (41.8 g, 48%).

後処理

  1. temperaturecooling
  2. stirringAfter stirring at 60° C. for 2 hours
  3. stirringthe mixture was stirred for an additional hour
  4. stirringwith stirring under ice-
  5. temperaturecooling
  6. stirringbefore stirring for a while
  7. filtrationThe precipitated crystals were filtered
  8. customdried
  9. extractionThe filtrate was extracted with ethyl acetate
  10. washwashed with water
  11. concentrationconcentrated to dryness in vacuo
  12. customThe resulting residue was purified by column chromatography on silica gel
  13. customto give crystals which
  14. customrecrystallized from methanol

出典と根拠

ORDレコード
ord-ee8d7b0f84bf405c9649bda763c5b915
出典データセット
uspto-grants-1992_11
特許番号
US05162326

反応ノート

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