1,4-Dichlorobenzene → N-Benzhydrylidene-N'-(4-chlorophenyl)hydrazine

HRID 736283

反応式

HRID 736283 の反応式
Cl[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][CH:3]=1.[OH-].[Na+].[C:11](=[N:24][NH2:25])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1>C([O-])(=O)C.C([O-])(=O)C.[Pd+2].CC(O)(CC)C>[C:11](=[N:24][NH:25][C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][CH:3]=1)([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

参加物

6

反応物 3

HCID 46851,4-DichlorobenzeneHCID 14798Sodium HydroxideHCID 79304Diphenylmethylidenehydrazine

生成物 1

HCID 9948495N-Benzhydrylidene-N'-(4-chlorophenyl)hydrazine収率 85%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 64052-Methyl-2-butanol溶媒2 回

反応条件

温度
25 °C

実験手順

260 mL of 2-methyl-2-butanol are placed in a 500 mL round-bottomed flask, which is degassed with argon for 30 minutes. Once the degassing is complete, 60 mL of 2-methyl-2-butanol, palladium(II)diacetate (0.857 g, 1.27 mmol, 0.025 eq.) and the ligand MePHOS (0.928 g, 2.55 mmol, 0.05 eq.) are placed in a second dry round-bottomed flask under argon. The mixture is left stirring for 30 minutes at a temperature in the region of 25° C. Furthermore, 1,4-dichlorobenzene (7.49 g, 1 eq.) and sodium hydroxide powder (2.85 g, 1.4 eq.) are placed in the 500 mL round-bottomed flask. The catalyst is then transferred into the 500 mL round-bottomed flask, which is heated at a temperature in the region of 100° C. Finally, benzhydrylidenehydrazine (10 g, 50.9 mmol, 1 eq.) is added thereto. The resulting suspension is left stirring, and changes color quickly (dark red) until all of the halide has disappeared. The solvent is then evaporated to dryness and the residue is taken up in dichloromethane. The solid is filtered off through Celite® and then washed thoroughly with dichloromethane. The organic phase is washed with saturated ammonium chloride solution, dried over magnesium sulfate and then concentrated to dryness under vacuum. The residue is purified by chromatography on a column of silica gel, eluting at the start with an ethyl acetate/heptane mixture (10/90 by volume). N-Benzhydrylidene-N′-(4-chlorophenyl)hydrazine (85%) is thus obtained in the form of a yellow solid (Rf=0.35. EtOAc/Heptane 25/75 (v/v)).

後処理

  1. customwhich is degassed with argon for 30 minutes
  2. waitThe mixture is left
  3. temperatureis heated at a temperature in the region of 100° C
  4. waitThe resulting suspension is left
  5. stirringstirring
  6. customThe solvent is then evaporated to dryness
  7. filtrationThe solid is filtered off through Celite®
  8. washwashed thoroughly with dichloromethane
  9. washThe organic phase is washed with saturated ammonium chloride solution
  10. dry with materialdried over magnesium sulfate
  11. concentrationconcentrated to dryness under vacuum
  12. customThe residue is purified by chromatography on a column of silica gel
  13. washeluting at the start with an ethyl acetate/heptane mixture (10/90 by volume)

出典と根拠

ORDレコード
ord-f686179c2b9b4a178d98b500f0ce3cfc
出典データセット
uspto-grants-2009_09
特許番号
US07595320B2

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