Diisopropylethylamine → (2E)-2-cyclopentyloxyimino-2-(3,4-dichlorophenyl)-N-(1-methylpyrazol-3-yl)acetamide

HRID 600972Notes

Reaction equation

HRID 600972 reaction equation
[CH:1]1([O:6]/[N:7]=[C:8](\[C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[C:14]([Cl:19])[CH:13]=2)/[C:9]([OH:11])=O)[CH2:5][CH2:4][CH2:3][CH2:2]1.C(N(CC)C(C)C)(C)C.[CH3:29][N:30]1[CH:34]=[CH:33][C:32]([NH2:35])=[N:31]1>C(Cl)Cl.C(Cl)(Cl)Cl>[CH:1]1([O:6]/[N:7]=[C:8](\[C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[C:14]([Cl:19])[CH:13]=2)/[C:9]([NH:35][C:32]2[CH:33]=[CH:34][N:30]([CH3:29])[N:31]=2)=[O:11])[CH2:2][CH2:3][CH2:4][CH2:5]1

Participants

6

Reactant 3

HCID 81531DiisopropylethylamineHCID 1372541-Methyl-3-aminopyrazoleHCID 87416813(2E)-2-cyclopentyloxyimino-2-(3,4-dichlorophenyl)acetic acid

Product 1

HCID 59745105(2E)-2-cyclopentyloxyimino-2-(3,4-dichlorophenyl)-N-(1-methylpyrazol-3-yl)acetamideYield 82%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

(E)-Cyclopentyloxyimino-(3,4-dichloro-phenyl)-acetic acid (100 mg, 0.33 mmol) was dissolved in methylene chloride (1.6 mL). N,N-diisopropylethylamine (173 μL, 0.99 mmol) and 1-methyl-1H-pyrazol-3-ylamine (32 μL, 0.33 mmol) were added and the reaction mixture was cooled to 0° C. O-(7-Azabenzotriazole-1-yl)-N,N,N′N′-tetramethyluronium hexafluorophosphate (126 mg, 0.33 mmol) was added and the reaction mixture was allowed to warm to 25° C. After stirring 16 h, the reaction mixture was diluted with chloroform (2 mL) and washed with saturated aqueous sodium bicarbonate solution (1.5 mL). The aqueous phase was extracted with chloroform (1.5 mL) and the combined organic phases were filtered through sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography (Merck silica gel 60, 40-63 μm; 40% ethyl acetate/hexanes) to afford (E)-2-cyclopentyloxyimino-2-(3,4-dichloro-phenyl)-N-(1-methyl-1H-pyrazol-3-yl)-acetamide (103 mg, 82%) as a white solid after lyophilization from aqueous dioxane: LC-MS (ESI) m/e calcd for C17H18Cl2N4O2 [M+] 380.08, found 381 [M+H+]; H1-NMR (400 MHz, CDCl3) □ ppm 1.64 (m, 4 H, 2×CH2), 1.85 (m, 4 H, 2×CH2), 3.83 (s, 3 H, NCH3), 4.84 (m, 1 H, OCH), 6.70 (d, J=2.3 Hz, 1 H, Ar), 7.26 (d, J=2.3 Hz, 1 H, Ar), 7.33 (dd, Jo=8.3, Jm=1.9 Hz, 1 H, Ar), 7.47 (d, Jo=8.3 Hz, 1 H, Ar), 7.61 (d, Jm=1.9 Hz, 1 H, Ar), 9.15 (s, 1 H, NH).

Workup

  1. temperatureto warm to 25° C
  2. washwashed with saturated aqueous sodium bicarbonate solution (1.5 mL)
  3. extractionThe aqueous phase was extracted with chloroform (1.5 mL)
  4. filtrationthe combined organic phases were filtered through sodium sulfate
  5. customevaporated in vacuo
  6. customThe residue was purified by flash column chromatography (Merck silica gel 60, 40-63 μm; 40% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-e3d9c3098abf4241a86ba13945ac7a73
Source dataset
uspto-grants-2011_03
Patent number
US07902248B2

Reaction notes

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