Hydrochloric Acid → 2,2,2-Trichloroethyl 1-isopropyl-3-(thiophen-2-yl)-1h-pyrazol-5-ylcarbamate

HRID 1930339Notes

Reaction equation

[CH:1]([N:4]1[C:8](C(O)=O)=[CH:7][C:6]([C:12]2[S:13][CH:14]=[CH:15][CH:16]=2)=[N:5]1)([CH3:3])[CH3:2].C([N:19]([CH2:22]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:31])C=CC=CC=1.[CH:41](Cl)([OH:45])[CH:42]([Cl:44])[Cl:43].[ClH:47]>O1CCOCC1>[CH:1]([N:4]1[C:8]([NH:19][C:22](=[O:31])[O:45][CH2:41][C:42]([Cl:44])([Cl:43])[Cl:47])=[CH:7][C:6]([C:12]2[S:13][CH:14]=[CH:15][CH:16]=2)=[N:5]1)([CH3:2])[CH3:3]

Participants

Conditions

Temperature: 90 °C

Procedure

To a solution of 1-isopropyl-3-(thiophen-2-yl)-1H-pyrazole-5-carboxylic acid (0.68 g, 2.9 mmol) in dioxane (10 mL) was added with triethylamine (0.44 g, 4.3 mmol), diphenylphosphorylazide (0.95 g, 3.5 mmol) and trichloroethanol (0.86 g, 5.8 mmol) and the mixture was heated to 90° C. for 4 h. The mixture was poured into 3 M HCl (40 mL) solution and the product was extracted with EtOAc (2×40 mL). The combined organics were washed with brine, dried (Na2SO4) and concentrated in vacuo. Purification by silica gel chromatography provided 2,2,2-trichloroethyl 1-isopropyl-3-(thiophen-2-yl)-1H-pyrazol-5-ylcarbamate (0.88 g, 80% yield) as a white solid. 1H NMR (400 MHz, Acetone-d6): δ 7.36-7.34 (m, 3H), 7.07 (dd, J=5.6 Hz, 4.0 Hz, 1H), 6.52 (s, 1H), 5.83 (t, J=7.2 Hz, 3H), 4.95 (s, 2H), 4.66-4.62 (m, 1H), 1.45 (d, J=6.8 Hz, 6H); MS (ESI) m/z: 382.0 (M+H+).

Workup

extractionthe product was extracted with EtOAc (2×40 mL)
washThe combined organics were washed with brine
dry with materialdried (Na2SO4)
concentrationconcentrated in vacuo
customPurification by silica gel chromatography

Sources & evidence

ORD record: ord-c0c9cca43ad8428dbf78179843149592
Source dataset: uspto-grants-2012_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08188113B2

Reaction notes

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