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

HRID 2274577

Reaction equation

HRID 2274577 reaction equation
[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]

Participants

6

Reactant 4

HCID 8148DibutylamineHCID 9357Potassium Sodium TartrateHCID 604759HCID 604759, compoundHCID 16682925Trimethylaluminum

Product 1

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

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-7ff561779ea549daa6e5b98eaae88a0e
Source dataset
uspto-grants-2015_09
Patent number
US09126980B2

Linked notes

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