Methacryloyl chloride → N'-methacryloyl-ethylenediamine

Temperatur

0 °C

The intermediate N-t-BOC, N-methyl-ethylenediamine monohydrochloride prepared in example 5 (10 mmol, 2.1 g) was stirred with 2M NaOH (11 cm3) at room temperature for 10 min. The solution was then cooled to 0° C., and to this, was added a solution of methacryloyl chloride (11 mmol, 1.1 cm3) in chloroform (30 cm3), dropwise. 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) afforded N-t-BOC, N-methyl, N′-methacryloyl-ethylenediamine (Rf 0.51) as a yellow oil (1.63 g, 67%). δH (400 MHz; CDCl3) 6.94 (1H, br s), HNOC(H3C)C═CHaHb; 5.74 (1H, br m), (H3C)C═CHaHb; 5.30 (1H, br m), (H3C)C═CHaHb; 3.43 (4H, br m). 2×CH2; 2.87 (3H, s), N(CH3); 1.93 (3H, br m), CH3; 1.44 (9H, s), C(CH3)3. δC (75.4 MHz; CDCl3) 168.52, NHOC(H3C)C═CH2; 157.33, NHCO2C(CH3)3; 139.36, (H3C)C═CH2; 119.81, (H3C)C═CH2; 80.85 C(CH3)3; 47.32, CH2N(CH3)OC(H3C)C═CH2; 39.32, CH2NHCO2C(CH3)3; 34.68, N(CH3); 28.33, C(CH3)3; 18.47, CH3. Found: (MH+) 243.17178.

1. additionAfter the addition
2. customThe organic and aqueous phases were then separated
3. extractionthe aqueous phase extracted with chloroform
4. dry with materialdried (MgSO4)
5. filtrationfiltered and conc. in vacuo
6. customto give the crude product
7. customRemoval of the alumina and concentration of the filtrate
8. customthen gave a pale yellow oil
9. customPurification
10. washby flash chromatography (silica gel, diethyl ether:hexane:methanol elution)

ORD-Eintrag

ord-c3c4610c6630434cb2476fcd08de0d6e

Quelldatensatz

uspto-grants-2004_11

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06818718B2