Dibutylamine → N,N-dibutyl-4-chloro-5-methyl-1H-pyrazole-3-carboxamide

HRID 2274600

반응식

HRID 2274600 반응식
[CH2:1]([NH:5][CH2:6][CH2:7][CH2:8][CH3:9])[CH2:2][CH2:3][CH3:4].C[Al](C)C.C(O[C:17]([C:19]1[C:23]([Cl:24])=[C:22]([CH3:25])[NH:21][N:20]=1)=[O:18])C.[C@H](O)(C([O-])=O)[C@@H](O)C([O-])=O.[Na+].[K+]>ClCCl>[CH2:1]([N:5]([CH2:6][CH2:7][CH2:8][CH3:9])[C:17]([C:19]1[C:23]([Cl:24])=[C:22]([CH3:25])[NH:21][N:20]=1)=[O:18])[CH2:2][CH2:3][CH3:4]

참가 물질

6

반응물 4

HCID 8148DibutylamineHCID 9357Potassium Sodium TartrateHCID 604759ethyl 4-chloro-5-methyl-1H-pyrazole-3-carboxylateHCID 16682925Trimethylaluminum

생성물 1

HCID 71062189N,N-dibutyl-4-chloro-5-methyl-1H-pyrazole-3-carboxamide수율 69.2%

시약·촉매·용매 1

HCID 6344Dichloromethane용매2회

실험 절차

To a stirred solution of dibutylamine (13 mL, 76 mmol) in dichloromethane (250 mL) under nitrogen atmosphere was added trimethylaluminium (38 mL, 2M in toluene, 76 mmol). The mixture was stirred at ambient temperature for 30 minutes. (4-Chloro-5-methyl-1H-pyrazole-3-carboxylic acid ethyl ester (4.8 g, 25 mmol) in dichloromethane (30 mL) was added dropwise to the mixture. The reaction was stirred for 12 hours under a nitrogen atmosphere. The mixture was poured into saturated Rochelle salt solution slowly and stirred at ambient temperature for 2 hours. The organic layer was collected. The aqueous layer was extracted with dichloromethane and combined with the organic layer. The organic phase was brine-washed, dried over sodium sulfate, filtered, concentrated down, and dried. The residue was purified by eluting through a silica gel column with a 0 to 100% ethyl acetate/heptane gradient to afford the title compound (4.7 g, 68% yield) as a clear oil. MS (ESI) [m/e, (M+H)+]=272.4. 1H NMR (400 MHz, chloroform-d) δ ppm 3.50 (t, J=7.5 Hz, 2H), 3.37 (t, J=7.5 Hz, 2H), 2.28 (s, 3H), 1.64 (quin, J=7.5 Hz, 2H), 1.44-1.55 (m, 2H), 1.30-1.43 (m, 2H), 1.10-1.22 (m, 2H), 0.97 (t, J=8.0 Hz, 3H), 0.82 (t, J=7.3 Hz, 3H).

후처리

  1. stirringThe reaction was stirred for 12 hours under a nitrogen atmosphere
  2. stirringstirred at ambient temperature for 2 hours
  3. customThe organic layer was collected
  4. extractionThe aqueous layer was extracted with dichloromethane
  5. washwashed
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated down
  9. customdried
  10. customThe residue was purified
  11. washby eluting through a silica gel column with a 0 to 100% ethyl acetate/heptane gradient

출처 및 근거

ORD 기록
ord-5a4e4dbc904f4dc08a053bfe39172cc0
출처 데이터셋
uspto-grants-2015_09
특허 번호
US09126979B2

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