ethyl 2,2-dimethylpropanimidate;hydrochloride

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl pivalimidate hydrochloride (Example B3) (0.75 g, 4.5 mmol) was suspended in hexanes (11.3 mL) and DCM (11.3 mL) and cooled to 0° C. 2,4,6-Collidine (2.1 mL, 15.9 mmol) and ethyl chloroformate (0.98 g, 9.1 mmol) were sequentially added and the reaction mixture was allowed to warm to RT and stirred for 12 h. The solvent was removed in vacuo and the residue was slurried with EtOAc (50 mL). The solids were removed by filtration through a pad of diatomaceous earth. The filter cake was washed with EtOAc (3×10 mL) and the combined filtrates were concentrated in vacuo to afford ethyl N-ethoxycarbonylpivalimidate (0.81 g, 89%) as a yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 4.05 (q, J=7.1 Hz, 2H), 3.95 (q, J=7.0 Hz, 2H), 1.18 (t, J=7.1 Hz, 3H), 1.18 (t, 7.1 Hz, 3H), 1.15 (s, 9H). The solvent was removed in vacuo The solids were removed by filtration through a pad of diatomaceous earth The filter cake was washed with EtOAc (3×10 mL) the combined filtrates were concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Pivalonitrile (1.3 mL, 12.0 mmol) was dissolved in anhydrous ethanol (28 mL) under an atmosphere of Ar. The solution was cooled to 0° C., saturated with HCl gas, stirred for 6 h, allowed to warm to RT, and stirred for 54 h. The solvent was removed in vacuo to afford ethyl pivalimidate hydrochloride (2.0 g, 100%) as an off white solid. 1H NMR (400 MHz, DMSO-d6): δ 11.19 (br s, 1H), 4.42 (q, J=6.9 Hz, 2H), 1.33 (t, J=6.8 Hz, 3H), 1.24 (s, 9H). stirred for 54 h The solvent was removed in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl pivalimidate hydrochloride (Example B3) (0.75 g, 4.5 mmol) was suspended in hexanes (11.3 mL) and DCM (11.3 mL) and cooled to 0° C. 2,4,6-Collidine (2.1 mL, 15.9 mmol) and ethyl chloroformate (0.98 g, 9.1 mmol) were sequentially added and the reaction mixture was allowed to warm to RT and stirred for 12 h. The solvent was removed in vacuo and the residue was slurried with EtOAc (50 mL). The solids were removed by filtration through a pad of diatomaceous earth. The filter cake was washed with EtOAc (3×10 mL) and the combined filtrates were concentrated in vacuo to afford ethyl N-ethoxycarbonylpivalimidate (0.81 g, 89%) as a yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 4.05 (q, J=7.1 Hz, 2H), 3.95 (q, J=7.0 Hz, 2H), 1.18 (t, J=7.1 Hz, 3H), 1.18 (t, 7.1 Hz, 3H), 1.15 (s, 9H). The solvent was removed in vacuo The solids were removed by filtration through a pad of diatomaceous earth The filter cake was washed with EtOAc (3×10 mL) the combined filtrates were concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Pivalonitrile (1.3 mL, 12.0 mmol) was dissolved in anhydrous ethanol (28 mL) under an atmosphere of Ar. The solution was cooled to 0° C., saturated with HCl gas, stirred for 6 h, allowed to warm to RT, and stirred for 54 h. The solvent was removed in vacuo to afford ethyl pivalimidate hydrochloride (2.0 g, 100%) as an off white solid. 1H NMR (400 MHz, DMSO-d6): δ 11.19 (br s, 1H), 4.42 (q, J=6.9 Hz, 2H), 1.33 (t, J=6.8 Hz, 3H), 1.24 (s, 9H). stirred for 54 h The solvent was removed in vacuo