Hydrochloric Acid → Monomethacylamideethylenediamine HCl

Participants

Reaction Conditions

Reaction Steps

A solution of ethylenediamine (15 mmol, 10.1 cm3) in water (150 cm3) at 0° C. was adjusted to pH 8.5 with 3N HCl. To this, was added a solution of methacryloyl chloride (16.5 mmol, 16.1 cm3) in chloroform (100 cm3), dropwise, over 2 h. After the addition was complete, the reaction mixture was stirred at 0° C. for a further 2 h. The organic and aqueous layers were then separated, and the aqueous layer extracted with chloroform (3×50 cm3). The aqueous layer was then collected and conc. in vacuo (freeze-dryer) to give a white solid. The residue was subjected to repeated fractional recrystallization from room temperature methanol, and the filtrate concentrated to give N-methacryloyl-ethylenediamine monohydrochloride as a clear, yellow oil (14.32 g, 58%). N-methacryloyl-ethylenediamine monohydrochloride (16 mmol, 20.0 g) was stirred in 2M NaOH (60 cm3) for 10 min. This solution was subsequently diluted to a volume of 160 cm3 with water, and stirred at 0° C. To this mixture was added a solution of acryloyl chloride (17.6 mmol, 14.3 cm3) in chloroform (300 cm3), dropwise, over 3 h. After the addition was complete, the reaction mixture was then stirred at 0° C. for a further 2 h. The organic and aqueous layers were separated, and the aqueous portion extracted with chloroform (3×100 cm3). The organic extracts were combined and concentrated to give the crude product as a white solid. Recrystallization from acetonitrile then gave N-acryloyl, N′-methacryloyl-ethylenediamine as colorless needles (10.70 g, 37%), m.p. 140-142/C. δH (400 MHz; CDCl3) 6.84 (1H, br s), NH; 6.74 (1H, br m), NH; 6.27 (1H, dd, J 16.9, 1.5 Hz), HC═CHaHb; 6.13 (1H, dd, J 17.0, 10.2), HC═CHaHb; 5.74 (1H, s), (H3C)C═CHcHd; 5.65 (1H, dd, J 10.3, 1.6 Hz), HC═CHaHb; 5.34 (1H, br m), (H3C)C═CHcHd; 3.49 (4H, m), 2×CH2; 1.95 (3H, s), CH3. δC (75.4 MHZ; CDCl3) 169.4, NHOC(H3C)C═CH2; 167.0, NHOCHC═CH2; 139.2, (H3C)C═CH2; 130.7, HC═CH2; 126.2, HC═CH2; 120.1, (H3C)C═CH2; 40.4, CH2CH2; 39.5, CH2CH2; 18.4, CH3. Found: M+. 182.1059.

Provenance & Evidence