Sodium hydride → 1-(2-Benzoyl-4-nitrophenyl)-3,5-pyrazole dicarboxylic acid dimethyl ester

HRID 66229

반응식

HRID 66229 반응식
[H-].[Na+].[CH3:3][O:4][C:5]([C:7]1[CH:11]=[C:10]([C:12]([O:14][CH3:15])=[O:13])[NH:9][N:8]=1)=[O:6].[H][H].F[C:19]1[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][C:20]=1[C:21]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:22]>[Cl-].[Na+].O.CN(C=O)C>[CH3:15][O:14][C:12]([C:10]1[CH:11]=[C:7]([C:5]([O:4][CH3:3])=[O:6])[N:8]([C:19]2[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][C:20]=2[C:21](=[O:22])[C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)[N:9]=1)=[O:13]

참가 물질

7

반응물 4

HCID 24758Sodium hydrideHCID 14844913,5-dimethyl 1H-pyrazole-3,5-dicarboxylateHCID 12377535(2-Fluoro-5-nitrophenyl)(phenyl)methanoneHCID 178418361HCID 178418361, 화합물

생성물 1

HCID 123778731-(2-Benzoyl-4-nitrophenyl)-3,5-pyrazole dicarboxylic acid dimethyl ester

시약·촉매·용매 2

HCID 6228Dimethylformamide용매2회HCID 57417360Sodium chloride; water용매

실험 절차

To a slurry of 5.3 g. (110 mmol) of 50% NaH in mineral oil in 425 ml. of dry DMF, stirred at 3° under argon, was added portionwise over a 20 minute time period, 20.26 g. (110 mmol) of 3,5-pyrazole dicarboxylic acid dimethyl ester*, maintaining a temperature of 5°-8°. When the vigorous hydrogen evolution had stopped, the ice bath was removed and the reaction allowed to warm to room temperature while stirring for 20 minutes. A solution of 24.5 g. (110 mmol) of 2-fluoro-5-nitrobenzophenone, in 100 ml. of dry DMF was added dropwise over 40 minutes and when addition was complete, the reaction was heated at 65° for 1.5 hr. After cooling, the mixture was poured over a mixture of ice and brine and extracted well with a 1:1 EtOAc:ether mixture. The combined extracts were washed with brine, dried over MgSO4 and concentrated. The crude mixture was chromatographed on silica gel using as an eluent benzene mixed with 0-100% EtOAc. The residue remaining after the solvents were evaporated was recrystallized from EtOAc/hexane to give the final product. The analytical sample was prepared by an additional recrystallization from EtOAc/hexane and was obtained as off-white needles: mp 150°-152°.

후처리

  1. additionwas added portionwise over a 20 minute time period, 20.26 g
  2. customthe ice bath was removed
  3. additionwhen addition
  4. temperaturethe reaction was heated at 65° for 1.5 hr
  5. temperatureAfter cooling
  6. extractionextracted well with a 1:1 EtOAc
  7. washThe combined extracts were washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated
  10. customThe crude mixture was chromatographed on silica gel using as an eluent benzene
  11. additionmixed with 0-100% EtOAc
  12. customwere evaporated
  13. customwas recrystallized from EtOAc/hexane

출처 및 근거

ORD 기록
ord-9bc63c263f784bf5bdf57b366e4d56bf
출처 데이터셋
uspto-grants-1978_12
특허 번호
US04130716

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