ether (4 × 50 ml), and the extracts were washed with water (3 × 50 ml) and dried over potassium carbonate. After
evaporating the ether we obtained 1.6 g of a black-red resinous mass, from which by column chromatography
(basic Al2O3, eluant diethyl ether) we isolated 0.31 g of a fraction containing compound 7 as the main
component (purity ~30%, 1H NMR). Yield ~3%. 1H NMR spectrum (CDCl3), δ, ppm (J, Hz); 7.06 (2H, d, 3J4,5
=
3
3
3
3
2.9, H-5); 6.42 (2H, dd, JB,X = 15.8, JA,X = 9.08, HX); 6.16 (2H, d, J4,5 = 2.9, H-4); 4.91 (2H, d, JB,X = 15.8,
HB); 4.44 (2H, d, 3JAX = 9.08, HA); 1.89 (6H, s, CH3).
1,8-Divinyl-4,5-dihydropyrrolo[3,2-g]indole (9), 8-Methyl-1-vinyl-4,5-dihydro-1H-pyrrolo[3,2-h]-
quinoline (10), and 1-Vinyl-1,4,5,6-tetrahydro-7H-indol-7-one (11). From the dioxime 8 (2 g, 14 mmol) in
the presence of KOH·0.5H2O (0.91 g, 14 mmol) by analogy with compound 7 we obtained 2.26 g of a black
resinous mass, from which by column chromatography (basic aluminum oxide, eluant diethyl ether) we isolated
0.2, 0.17, 0.19, and 0.37 g of fractions containing the dipyrrole 9 (purity ~40%, yield ~3%), 2-pyridylpyrrole 10
(purity ~30%, yield ~2%), and 2-acylpyrrole 11 (purity ~40%, yield ~3%) derivatives of pyrrole and the
cyclohexanedione 12 (purity ~60%, yield ~14%) respectively as the main components.
1
1,8-Divinyl-4,5-dihydropyrrolo[3,2-g]indole (9). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.96
(2H, dd, 3JB,X = 15.6, 3JA,X = 8.8, HX); 5.12 (2H, dd, 2JB,X = 15.6, 2JA,B = 1.1, HB); 6.83 (2H, d, 3J2,3 = 3J6,7 = 2.9,
H-2,7); 6.19 (2H, d, 3J2,3 = 3J6,7 = 2.9, H-3,6); 4.71 (2H, d, 3JA,X = 8.8, HA); 2.58 (4H, s, CH2).
1
8-Methyl-1-vinyl-4,5-dihydropyrrolo[3,2-h]quinoline (10). H NMR spectrum (CDCl3), δ, ppm
3
3
3
(J, Hz): 8.62 (1H, dd, JB,X = 16.4, JA,X = 8.8, HX); 7.29 (1H, d, J6,7 = 7.6, H-6); 7.13 (1H, d, 3J2,3 = 2.7, H-2);
3
3
3
6.76 (1H, d, J6,7 = 7.6, H-7); 6.10 (1H, d, J2,3 = 2.7, H-3); 5.11 (1H, d, JB,X = 16,4. HB); 4.68 (1H, d,
3JA,X = 8.8, HA); 2.84 (2H, t, 3J4,5 = 7.3, H-5); 2.69 (2H, t, 3J4,5 = 7.3, H-4); 2.48 (3H, s, 3J2,3 = 2.7, CH3).
1-Vinyl-1,4,5,6-tetrahydro-7H-indol-7-one (11). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.99 (1H,
dd, 3JB,X = 16.0, 3JA,X = 8.8, HX); 7.23 (1H, d, 3J2,3 = 2.8, H-2); 6.07 (1H, d, 3J2,3 = 2.8, H-3); 5.11 (1H, d, 3JB,X
=
16.0, HB); 4.73 (1H, d, 3JA,X = 8.8, HA); 2.71 (2H, t, 3J4,5 = 6.1, H-4), 2.46 (2H, t, 3JB,X = 6.1, H-6); 2.03 (2H, m,
H-5).
O-Vinyl-α-benzil Dioxime (14) and O,O'-Divinyl-α-benzil Dioxime (15). A. A mixture of lithium
hydroxide (0.8 g, 33 mmol), cesium fluoride (5.06 g, 33 mmol), and methanol (10 ml) was stirred for 10 min,
α-benzil dioxime 13 (4 g, 17 mmol) was added, the mixture was stirred for a further 10 min, and DMSO (10 ml)
was added. The methanol was distilled from the obtained mixture under vacuum (~30 mm Hg) with gentle heat
(~50°C) until the DMSO began to distil. To the residue, which contained cesium benzildioximate, we added
90 ml of DMSO. The whole mass was transferred to a half-liter autoclave, saturated with acetylene at room
temperature (initial pressure 14 atm), heated to 80°C over 30 min, and kept at this temperature for 5 min
(residual pressure 6 atm). After the addition of water (150 ml) the reaction mixture unloaded from the autoclave
was neutralized with solid CO2 and extracted with ether (4 × 50 ml). The extracts were washed with water
(3 × 50 ml) and dried over potassium carbonate. From the viscous liquid (3.71 g) obtained after removal of the
succinic ester we isolated by column chromatography (basic aluminum oxide, eluant diethyl ether, methanol)
2.39. g of the monovinyl oxime 14 and 0.85 g of the divinyl benzil dioxime 15. The yields were 54 and 18%
respectively.
B. A mixture of α-benzil dioxime 13 (4 g, 17 mmol) and KOH·0.5H2O (2.16 g, 33 mmol) in DMSO
(100 ml) in a half-liter revolving autoclave was saturated with acetylene at room temperature (initial pressure
14 atm, residual pressure 5 atm). See method A for the further treatment. From 3.2 g of amber liquid we isolated
2.27 g of monovinylbenzil dioxime 14 and 0.61 g of divinylbenzil dioxime 15. The yields were 50 and 12%
respectively.
O-Vinyl-α-benzil Dioxime (14). mp 124-126°C (methanol). IR spectrum, ν, cm-1: 3251 (s), 3062 (w),
2924 (w), 2893 (w), 1638 (s), 1603 (w), 1572 (w), 1494 (m), 1446 (m), 1379 (w), 1334 (w), 1309 (w), 1260 (m),
1167 (s), 1142 (s), 1080 (m), 1031 (w), 987 (s), 949 (w), 937 (s), 917 (w), 866 (m), 841 (m), 752 (m), 688 (s),
1
611 (m), 550 (w). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 8.10 (1H, br. s, OH); 7.69 (2H, m, o-H-2); 7.59
39