New Compounds
475
Methyl 2-Azido-3-(5-methyl-2-furyl)propenoate (I)
A solution of 5-methyl-2-furancarbaldehyde (2.2 g, 0.02 mol) and methyl azidoacetate (9.2 g,
0.08 mol) was added at 0 °C during 30 min to sodium metal (1.84 g, 0.08 mol) in methanol (60 ml).
Stirring was continued for additional 60 min at temperature not exceeding 5 °C, the reaction mixture
was then cooled to 0 °C, a solution of ammonium chloride (4.4 g, 0.08 mol) in water (10 ml) was
added and poured in ice water. The separated precipitate was filtered off and crystallized. Yield
2.57 g (62%); m. p. 30 – 32 °C (methanol). For C9H9N3O3 (207.2) calculated: 52.17% C, 4.4% H,
20.28% N; found: 52.26% C, 4.40% H, 20.44% N. IR spectrum: 2 118 (N3), 1 707 (C=O). UV spec-
trum: 343 (3.40). 1H NMR spectrum (CDCl3): 7.00 d, 1 H (H-3, J3,4 = 3.2); 6.81 s, 1 H (H-6);
6.12 bd, 1 H (H-4); 3.86 s, 3 H (OCH3); 2.33 bs, 3 H (CH3). Using the same method the compounds
II – IV were prepared:
Methyl 2-azido-3-(4,5-dimethyl-2-furyl)propenoate (II): Yield 66%; m. p. 51 – 55 °C (methanol).
For C10H11N3O3 (221.2) calculated: 54.29% C, 5.01% H, 19.00% N; found: 53.99% C, 4.96% H,
19.02% N. IR spectrum: 2 124 (N3), 1 713 (C=O). UV spectrum: 352 (3.45). 1H NMR spectrum
(CDCl3): 6.92 s, 1 H (H-3); 6.78 s, 1 H (H-6); 3.86 s, 3 H (OCH3); 2.24 bs, 3 H (C5-CH3); 1.97 bs,
3 H (C4-CH3). 13C NMR spectrum (CDCl3): 163.9 (CO), 150.5 (C-5), 146.8 (C-2), 120.6 (C-7),
119.3 (C-3), 117.9 (C-4), 114.3 (C-6), 52.6 (O-CH3), 11.6 (C5-CH3), 9.8 (C4-CH3), 3J(CO, H-6) =
5.0 Hz.
Methyl 2-azido-3-[5-(4-chloro-2-methylphenoxy)-2-furyl]propenoate (III): Yield 54%; m. p.
47 – 49 °C (methanol). For C15H12ClN3O4 (333.7) calculated: 53.99% C, 3.68% H, 12.59% N;
found: 53.82% C, 3.41% H, 12.68% N. IR spectrum: 2 126 (N3), 1 711 (C=O). UV spectrum: 350
1
(3.45). H NMR spectrum (CDCl3): 7.04 d, 1 H (H-3, J3,4 = 3.5); 6.72 s, 1 H (H-6); 6.80 – 7.28 m,
3 H (H arom.); 5.46 d, 1 H (H-4); 3.86 s, 3 H (OCH3); 2.27 s, 3 H (CH3).
Methyl 2-azido-3-(2-benzo[b]furyl)propenoate (IV): Yield 68%; m. p. 107 – 110 °C (methanol).
For C12H9N3O3 (243.2) calculated: 59.26% C, 3.73% H, 17.28% N; found: 59.16% C, 3.68% H,
17.16% N. IR spectrum: 2 116 (N3), 1 715 (C=O). UV spectrum: 347 (3.61). 1H NMR spectrum
(CDCl3): 7.45 s, 1 H (H-3); 6.94 s, 1 H (H-6); 7.10 – 7.60 m, 4 H (H arom.); 3.91 s, 3 H (OCH3).
Collect. Czech. Chem. Commun. (Vol. 59) (1994)