Hydrochloric Acid → Monomethacylamideethylenediamine HCl

N-t-BOC, N′-methyl, N′-methacryloyl-ethylenediamine (2.5 mmol, 0.61 g) was stirred in a solution of 3M HCl in ethyl acetate (2.5 cm3) at room temperature for 30 min. The solution was then conc. in vacuo to give the intermediate N-methyl, N′-methacryloyl-ethylenediamine monohydrochloride as a clear yellow oil. This intermediate (2.5 mmol) was then stirred at room temperature in 2M NaOH (3 cm3) for 10 min. The reaction mixture was cooled to 0° C. and to this, was then added a solution of acryloyl chloride (2.8 mmol, 0.23 cm3) in chloroform (7 cm3), dropwise, over 30 min. After the addition was complete, the reaction mixture was stirred at 0° C. for a further 1 h. The organic and aqueous phases were then separated, and the aqueous phase extracted with chloroform. The organic extracts were combined, dried (MgSO4), filtered and conc. in vacuo, to give the crude product. The crude product was stirred at room temperature over a slurry of basic alumina in chloroform for 18 hr. Removal of the alumina and concentration of the filtrate then gave a pale yellow oil. Purification by flash chromatography (silica gel, diethyl ether:hexane:methanol elution) then gave the crosslinker N-methyl, N-acryloyl, N′-methacryloyl-ethylenediamine as a pale yellow oil (0.26 g, 53%). δH (300 MHz; CDCl3) 7.01 (1H, br s), NH; 6.50 (1H, dd, J 16.8, 10.4 Hz), HC═CHaHb; 6.22 (1H, dd, J 12.4, 2.0), HC═CHaHb; 5.66 (br m), (H3C)C═CHcHd; 5.61 (1H, d, J 10.5 Hz), HC═CHaHb; 5.23 (br m) (H3C)C═CHcHd; 3.57 (2H, br m), CH2; 3.43 (2H, br m), CH2; 3.00, (3H, br m) N(CH3);1.85 (3H, br m), CH3. δC (75.4 MHz; CDCl3, 50° C.) 166.10, NHOC(H3C)C═CH2; 165.04, NOCHC═CH2; 140.40, (H3C)C═CH2; 130.92, HC═CH2; 126.01, HC═CH2; 118.50, (H3C)C═CH2; 44.83, CH2CH2; 35.47, CH2CH2; 34.12, N(CH3); 18.50, CH3. Found: M+. 196.26.

ORD record

ord-0b6bfd29d3cd4f4da37ab173952f9f2d

Source dataset

uspto-grants-2004_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06818718B2