Sodium borohydride → Diethyl 4-(4-chloro-2-aminobenzoyl)-1H-pyrazole-3,5-dicarboxylate

HRID 428412

반응식

HRID 428412 반응식
[BH4-].[Na+].[Cl:3][C:4]1[CH:26]=[CH:25][C:7]([C:8]([C:10]2[C:11]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[N:12][NH:13][C:14]=2[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[O:9])=[C:6]([N+:27]([O-])=O)[CH:5]=1>O.Cl.C([O-])(=O)C.[Ni+2].C([O-])(=O)C>[Cl:3][C:4]1[CH:26]=[CH:25][C:7]([C:8]([C:10]2[C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[N:13][NH:12][C:11]=2[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[O:9])=[C:6]([NH2:27])[CH:5]=1

참가 물질

6

반응물 2

HCID 4311764Sodium borohydrideHCID 18358912diethyl 4-(4-chloro-2-nitrobenzoyl)-1H-pyrazole-3,5-dicarboxylate

생성물 1

HCID 18358868Diethyl 4-(4-chloro-2-aminobenzoyl)-1H-pyrazole-3,5-dicarboxylate수율 96.5%

시약·촉매·용매 3

HCID 9756Nickel Acetate촉매HCID 313Hydrochloric Acid용매HCID 962Water용매2회

반응 조건

온도
8 °C

실험 절차

Alternatively, the title compound can be prepared as follows: A mixture of nickel acetate (444 g, 1.78 moles) and water (6.6 L) was cooled to 8° C. with stirring under nitrogen; then a solution of sodium borohydride (271 g, 7.16 moles) in water (3.55 L) was added dropwise over 1.5 hours maintaining the reaction temperature between 8° C. and 12° C. The reaction mixture was then stirred for 1.5 hours at 8-12° C. The reaction mixture was filtered through a coarse scintered glass filter funnel, keeping the black filter cake wet (Caution: this black powder may be pyrophoric if allowed to dry.). The filter cake was washed first with water (6×2 L), then with ethanol (2×2 L) and finally with methanol (1 L). The methanol wet filter cake (Ni2B, pyrophoric) was transferred to a 22 L flask with methanol (8 L) . A solution of diethyl 4-(4-chloro-2-nitrobenzoyl)-1H-pyrazole-3,5-dicarboxylate (111.0 g, 0.28 mole) in hydrochloric acid (2.52 L) was added. The reaction mixture was heated to 64° C. and was kept at 64° C. for 6 hours; then was allowed to cool to room temperature and was filtered through CELITE™. The CELITE™ layer was washed with methanol (2×2 L). The filtrate and wash liquors were combined and the methanol was distilled off under water aspirator vacuum. Water (1 L) was added to the reaction and the mixture was filtered. The filter cake was washed with water (2×500 m L) and dried under vacuum at 40° C. to give the title compound as a yellowish solid (98.81 g, 96%).

후처리

  1. temperaturemaintaining the reaction temperature between 8° C. and 12° C
  2. stirringThe reaction mixture was then stirred for 1.5 hours at 8-12° C
  3. filtrationThe reaction mixture was filtered through a coarse scintered glass
  4. filtrationfilter funnel
  5. customto dry
  6. washThe filter cake was washed first with water (6×2 L)
  7. customThe methanol wet filter cake (Ni2B, pyrophoric) was transferred to a 22 L flask with methanol (8 L)
  8. temperatureThe reaction mixture was heated to 64° C.
  9. temperatureto cool to room temperature
  10. filtrationwas filtered through CELITE™
  11. washThe CELITE™ layer was washed with methanol (2×2 L)
  12. washThe filtrate and wash liquors
  13. distillationthe methanol was distilled off under water
  14. additionWater (1 L) was added to the reaction
  15. filtrationthe mixture was filtered
  16. washThe filter cake was washed with water (2×500 m L)
  17. customdried under vacuum at 40° C.

출처 및 근거

ORD 기록
ord-f9a79d5b41384789b77865164d9ec1c0
출처 데이터셋
uspto-grants-2001_11
특허 번호
US06313290B1

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