Ammonium Chloride → (5-Bromo-2-chlorophenyl)-(1-phenylpyrazol-4-yl)methanol

HRID 221147

反応式

HRID 221147 の反応式
[C:1]1([N:7]2[CH:11]=[C:10](Br)[CH:9]=[N:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([Li])CCC.[Br:18][C:19]1[CH:20]=[CH:21][C:22]([Cl:27])=[C:23]([CH:26]=1)[CH:24]=[O:25].[Cl-].[NH4+]>C(OCC)C.O1CCCC1>[Br:18][C:19]1[CH:20]=[CH:21][C:22]([Cl:27])=[C:23]([CH:24]([C:10]2[CH:9]=[N:8][N:7]([C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)[CH:11]=2)[OH:25])[CH:26]=1

参加物

7

反応物 4

HCID 25517Ammonium ChlorideHCID 7868114-Bromo-1-phenyl-1H-pyrazoleHCID 106089255-Bromo-2-chlorobenzaldehydeHCID 178418339Butyllithium

生成物 1

HCID 46930334(5-Bromo-2-chlorophenyl)-(1-phenylpyrazol-4-yl)methanol

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒2 回HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of 1-phenyl-4-bromopyrazole (see M. A. Khan, et al., Can. J. Chem., (1963) 41 1540) (2.23 g) in diethyl ether (30 ml) wad cooled to −78° C. under argon atmosphere, and added dropwise thereto was n-butyl lithium (1.59 M hexane solution, 6.9 ml). The mixture was stirred at −20° C. to −10° C. for 5 hours, and added dropwise thereto at the same temperature was a solution of 5-bromo-2-chlorobenzaldehyde (2.19 g) obtained in Reference Example 16-(1) in diethyl ether (30 ml). The mixture was stirred at the same temperature for 30 minutes, and added thereto was tetrahydrofuran (30 ml), and the mixture was stirred at 0° C. for further 30 minutes. A saturated aqueous ammonium chloride solution was added thereto, and the mixture was extracted with ethyl acetate. The extract was washed with brine and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate=83:17-80:20) to give 5-bromo-2-chlorophenyl-1-phenyl-4-pyrazolylmethanol (831 mg) as yellow oil. APCI-Mass m/Z 363/365 (M+H). (2) The above 5-bromo-2-chlorophenyl-1-phenyl-4-pyrazolylmethanol was treated in a manner similar to Reference Example 120-(2) to give the desired 5-bromo-2-chloro-1-(1-phenyl-4-pyrazolylmethyl)benzene as colorless powder. APCI-Mass m/Z 347/349 (M+H).

後処理

  1. additionadded dropwise
  2. additionadded dropwise
  3. stirringThe mixture was stirred at the same temperature for 30 minutes
  4. additionadded
  5. stirringthe mixture was stirred at 0° C. for further 30 minutes
  6. extractionthe mixture was extracted with ethyl acetate
  7. washThe extract was washed with brine
  8. dry with materialdried over sodium sulfate
  9. customThe solvent was evaporated under reduced pressure
  10. customthe residue was purified by silica gel column chromatography (hexane:ethyl acetate=83:17-80:20)

出典と根拠

ORDレコード
ord-5ca73fb93f14468f820a5ac5b130836f
出典データセット
uspto-grants-2012_06
特許番号
US08202984B2

関連ノート

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