Diisopropylamine → HCID 18675576, compound

Participants

Reaction Conditions

Reaction Steps

To a stirring solution of diisopropylamine (3.72 mL, 28.35 mmol) in anhydrous THF (75 mL) at −78° C. was added 11.4 mL of a 2.5M solution of n-butyllithium in hexanes. The solution was allowed to warm to 0° C., then cooled back down to −78° C. A solution of 1-cyano-2-ethylbutane (3 g, 27 mmol) in anhydrous THF (15 mL) was added to the cooled solution. After stirring for 10 min., ethyl formate (2.7 mL, 32.4 mmol) was added and the resulting reaction mixture was stirred at −78° C. for 1 h, then allowed to slowly warm to room temperature over 3 h. The reaction mixture was then partitioned between Et2O and water. The organic layer was washed with water and the aqueous layers were combined and acidified with 1N HCl. The resulting acidic aqueous mixture was extracted with Et2O. The organic layer was washed with brine, dried over Na2SO4, filtered and evaporated in vacuo to yield a colorless oil. This residue was dissolved in ethanol (15 mL) and to the resulting solution was added water (10 mL), thiosemicarbazide (2.71 g, 29.7 mmol), and acetic acid (5.5 mL). The resulting mixture was stirred under reflux for 3 hr., then cooled and diluted with water (25 mL). The off-white precipitate which formed was collected by vacuum filtration to yield 4.7 g of the 5-amino-1-thiocarbamoylpyrazole. 1H NMR (300 mHz, CDCl3): δ7.2 (bs, 1H), 7.17 (d, 1H, J=4.4 Hz), 6.37 (bs, 1H), 3.65 (t, 1H, J=4.4, 4.8 Hz), 1.71 (m, 1H), 1.53 (m, 4H), 0.97 (m, 6H). Spectrum corresponds to imine tautomer. 1H NMR (300 mHz, dmso-d6): δ8.3 (bs, 1H), 7.4 (bs, 1H), 7.36 (d, 1H, J=4.8 Hz), 3.93 (t, 1H, J=5.13, 4.8 Hz), 1.76 (m, 1H), 1.4 (m, 4H), 0.89 (m, 6H). Spectrum corresponds to imine tautomer.

Provenance & Evidence