(E)-3-(furan-3-yl)prop-2-enoyl chloride

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

Procedure: Free base of the titled compound was prepared from 4-methoxy-2-amino-N-(2-pyridyl)aniline and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A). The free base and oxalic acid were dissolved into ethyl acetate. Concentration and recrystallization from ethyl acetate/n-hexane yielded the titled compound. Concentration and recrystallization from ethyl acetate/n-hexane

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

Procedure: The titled compound was prepared from 4-fluoro-2-amino-N-(2-pyridyl)aniline and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A).

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

Procedure: Free base of the titled compound was prepared from 4-methyl-2-amino-N-(2-pyridyl)aniline and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A). The free base and oxalic acid were dissolved into ethyl acetate. Concentration and recrystallization from ethyl acetate/n-hexane yielded the titled compound. Concentration and recrystallization from ethyl acetate/n-hexane

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

Procedure: The procedure of Example 11 was repeated, except that 17-cyclopropylmethyl-4,5α-epoxy-14β-hydroxy-3-methoxy-6β-mercaptomorphinan(K. Kanematsu, T. Toshiyasu, M. Yoshida., Chem., Pharm. Bull., 38, 1141, (1990)) was used instead of 17-cyclopropylmethyl-4,5α-epoxy-3,14β-dihydroxy-6α-(N-methylamino)morphinan 4 and trans-3-(3-furyl)acryloyl chloride was used instead of 3,4-dichlorophenylacetyl chloride, thereby preparing 17-cyclopropylmethyl-4,5α-epoxy-14β-hydroxy-3-methoxy-6β-[trans-3-(3-furyl)acryloylthio]morphinan 169 (yield: 59%).

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

Procedure: Free base of the titled compound was prepared from 4-methoxy-2-amino-N-(2-pyridyl)aniline and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A). The free base and oxalic acid were dissolved into ethyl acetate. Concentration and recrystallization from ethyl acetate/n-hexane yielded the titled compound. Concentration and recrystallization from ethyl acetate/n-hexane

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

Procedure: The titled compound was prepared from 4-fluoro-2-amino-N-(2-pyridyl)aniline and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A).

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

Procedure: Free base of the titled compound was prepared from 4-methyl-2-amino-N-(2-pyridyl)aniline and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A). The free base and oxalic acid were dissolved into ethyl acetate. Concentration and recrystallization from ethyl acetate/n-hexane yielded the titled compound. Concentration and recrystallization from ethyl acetate/n-hexane

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

Procedure: Free base of the titled compound was prepared from 4-methoxy-2-amino-N-(2-pyridyl)aniline and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A). The free base and oxalic acid were dissolved into ethyl acetate. Concentration and recrystallization from ethyl acetate-hexane yielded the titled compound. MW: 407.39; mp: 196.0-198.0° C.; 1H-NMR (DMSO) δ: 8.75-8.73 (1H, m), 8.16 (1H, td, J=7.7, 1.8 Hz), 8.04 (1H, br.s), 7.76-7.58 (4H, m), 7.33 (1H, d, J=8.8 Hz), 7.23 (1H, d, J=2.2 Hz), 6.90-6.80 (3H, m), 3.82 (3H, s). Concentration and recrystallization from ethyl acetate-hexane

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

Procedure: Free base of the titled compound was prepared from 4-methyl-2-amino-N-(2-pyridyl)aniline and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A). The free base and oxalic acid were dissolved into ethyl acetate. Concentration and recrystallization from ethyl acetate-hexane yielded the titled compound. MW: 391.38; mp: 197.0-198.0° C.; 1H-NMR (DMSO) δ: 8.78-8.74 (1H, m), 8.16 (1H, td, J=7.7, 2.2 Hz), 8.05 (1H, br.s), 7.77 (1H, d, J=15.8 Hz), 7.70-7.67 (2H, m), 7.65-7.59 (1H, m), 7.51 (1H, br.s), 7.32 (1H, d, J=8.4 Hz), 7.10-7.06 (1H, m), 6.89 (1H, d, J=15.8 Hz), 6.81 (1H, br.s), 2.44 (3H, s). Concentration and recrystallization from ethyl acetate-hexane

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

Procedure: The titled compound was prepared from N-(4-pyridyl)-o-phenylenediamine and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(4-pyridyl)-2-styryl-1H-benzimidazole (Example 3). MW: 287.32; mp: 171.5-172.5° C.; 1H-NMR (DMSO) δ: 8.88 (2H, dd, J=4.6, 1.7 Hz), 8.07 (1H, br.s), 7.81 (1H, d, J=15.8 Hz), 7.74-7.65 (4H, m), 7.35-7.25 (3H, m), 6.89 (1H, br.s), 6.73 (1H, d, J=15.8 Hz).

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

Procedure: The titled compound was prepared from N-(2-pyridyl)-o-phenylenediamine and (E)-3-(3-furyl)acryloyl chloride (Shizuri, Y.; Ojika, M.; Yamada, K. Tetrahedron Lett., 1981, 22, 4291) according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A). MW: 287.32; mp: 162.5-164.0° C.; 1H-NMR (CDCl3) δ: 8.79-8.75 (1H, m), 7.99 (1H ddd, J=7.7, 7.7, 1.8 Hz), 7.87 (1H, d, J=15.8 Hz), 7.83-7.78 (1H, m), 7.64-7.62 (1H, m), 7.53-7.39 (4H, m), 7.37-7.22 (2H, m), 6.85 (1H, d, J=15.8 Hz), 6.55 (1H, d, J=1.8 Hz).

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

Procedure: Free base of the titled compound was prepared from 4-methoxy-2-amino-N-(2-pyridyl)aniline and (E)-3-(3-furyl)acryloyl chloride according to the preparation of (E)-1-(2-pyridyl)-2-styryl-1H-benzimidazole (Example 1, method A). The free base and oxalic acid were dissolved into ethyl acetate. Concentration and recrystallization from ethyl acetate-hexane yielded the titled compound. MW: 407.39; mp: 196.0-198.0° C.; 1H-NMR (DMSO) δ: 8.75-8.73 (1H, m), 8.16 (1H, td, J=7.7, 1.8 Hz), 8.04 (1H, br.s), 7.76-7.58 (4H, m), 7.33 (1H, d, J=8.8 Hz), 7.23 (1H, d, J=2.2 Hz), 6.90-6.80 (3H, m), 3.82 (3H, s). Concentration and recrystallization from ethyl acetate-hexane