Hydrochloric Acid → 5-chloro-1-cyclohexyl-1H-pyrazole-4-carboxylic acid ethyl ester

HRID 12879

반응식

HRID 12879 반응식
N(OC(C)(C)C)=O.[CH2:8]([O:10][C:11]([C:13]1[CH:14]=[N:15][N:16]([CH:19]2[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]2)[C:17]=1N)=[O:12])[CH3:9].[ClH:25]>C(#N)C.[Cu]Cl>[CH2:8]([O:10][C:11]([C:13]1[CH:14]=[N:15][N:16]([CH:19]2[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]2)[C:17]=1[Cl:25])=[O:12])[CH3:9]

참가 물질

6

반응물 3

HCID 313Hydrochloric AcidHCID 10906Tert-Butyl nitriteHCID 351028ethyl 5-amino-1-cyclohexyl-1H-pyrazole-4-carboxylate

생성물 1

HCID 670209265-chloro-1-cyclohexyl-1H-pyrazole-4-carboxylic acid ethyl ester수율 42%

시약·촉매·용매 2

HCID 62652Cuprous chloride촉매HCID 6342Acetonitrile용매2회

실험 절차

Copper(I) chloride (2.500 g, 25.25 mmol) was suspended in 7.0 mL cold (ice/acetone bath) anhydrous acetonitrile. t-Butyl nitrite (5.75 mL, 90%, 43.56 mmol) was added, followed by a suspension of 5-amino-1-cyclohexyl-1H-pyrazole-4-carboxylic acid ethyl ester (4.408 g, 18.58 mmol) in 27.0 mL acetonitrile. The mixture was stirred at room temperature for 45 minutes and then at 70° C. for 1.25 hour. The mixture was cooled to room temperature, slowly added to 6N HCl (17.5 mL) and then extracted with methylene chloride. The organic phase was washed sequentially with water and brine. The aqueous phases were back extracted with a second portion of methylene chloride. The two organic phases were combined, dried over sodium sulfate and concentrated in vacuo. The crude residue was chromatographed by flash chromatography eluting with a gradient of 10-50% ethyl acetate/hexanes to give 5-chloro-1-cyclohexyl-1H-pyrazole-4-carboxylic acid ethyl ester (1.98 g; 42%). Mass spectrum: m/z: 257.3 (M+H).

후처리

  1. waitat 70° C. for 1.25 hour
  2. temperatureThe mixture was cooled to room temperature
  3. extractionextracted with methylene chloride
  4. washThe organic phase was washed sequentially with water and brine
  5. extractionThe aqueous phases were back extracted with a second portion of methylene chloride
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe crude residue was chromatographed by flash chromatography
  9. washeluting with a gradient of 10-50% ethyl acetate/hexanes

출처 및 근거

ORD 기록
ord-b3919ed3436a4960839e99ad25df6759
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07728029B2

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