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

HRID 221147

반응식

HRID 221147 반응식
[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

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 3283Diethyl Ether용매2회HCID 8028Tetrahydrofuran용매

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-5ca73fb93f14468f820a5ac5b130836f
출처 데이터셋
uspto-grants-2012_06
특허 번호
US08202984B2

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