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Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
Lesiv et al.
(DMSOꢀd6) Zꢀ2d: 1.70 (s, 3 H, H3C(1)); 3.24 (s, 6 H, H3C(7));
5.12 (s, 2 H, H2C(3)); 6.98 (d, 2 H, HC(4), J = 7.3 Hz); 8.21 (d,
2 H, HC(5), J = 7.3 Hz); 11.33 (s, 1 H, OH). 13C NMR
(DMSOꢀd6) Zꢀ2d: 15.1 (C(1)); 39.9 (C(7)); 51.3 (C(3)); 106.9
(C(5)); 139.2 (C(4)); 150.9 (C(2)); 155.9 (C(6)); E/Z = 40 : 1.
3ꢀ(2ꢀHydroxyiminoꢀ1ꢀmethylethyl)ꢀ1ꢀmethylꢀ3Hꢀimidazoꢀ
lium chloride (2e). M.p. 47—62 °C (MeOH), Rf, EtOH = 0.76.
Found (%): C, 44.89; H, 6.00;
4 H each, H2C(3), H2C(4)); 3.18 (s, 6 H, H3C(10)); 3.61 (s,
3 H, H3C(1)); 5.18 (s, 2 H, H2C(6)); 7.04 (d, 2 H, HC(8), J =
7.3 Hz); 8.30 (d, 2 H, HC(8), J = 7.3 Hz); 11.30 (s, 1 H, OH).
13C NMR (DMSOꢀd6) Eꢀ2g: 21.9 (C(4)); 28.8 (C(3)); 40.8
(C(10)); 53.4 (C(1)); 58.8 (C(1)); 107.3 (C(8)); 142.9 (C(7);
152.9 (C(5)); 155.9 (C(9)); 172.5 (C(2)).
1ꢀMethylꢀ3ꢀ(2ꢀethoxycarbonylꢀ2ꢀhydroxyiminoethyl)ꢀ3Hꢀ
imidazolium chloride (2h). M.p. > 350 °C (MeOH). Found (%):
C, 43.70; H, 5.75; N, 16.64; Cl, l4.56. C9H14N3O3Cl (247.68).
Calculated (%): C, 43.64; H, 5.70;
N, 22.65. C7H12N3OCl (189.64).
Calculated (%): C, 44.33; H, 6.38;
N, 22.16.
N, 16.97; Cl, 14.31.
1H NMR (DMSOꢀd6) Eꢀ2e:
1H NMR (DMSOꢀd6) Eꢀ2h:
1.66 (d, 3 H, H3C(3), J = 6.6 Hz);
1.24 (t, 3 H, H3C(1), J = 7.3 Hz);
3.91 (s, 3 H, H3C(7)); 5.40 (m,
3.91 (s, 3 H, H3C(9)); 4.23 (q,
1 H, HC(2)); 7.54 (d, 1 H, HC(1), J = 5.2 Hz); 7.81, 7.93
(both s, 2 H each, HC(4), HC(5)); 9.55 (s, 1 H, HC(6)); 11.4
(br.s, 1 H, OH). 13C NMR (DMSOꢀd6) Eꢀ2e: 18.3 (C(3)); 35.8
(C(7)); 54.6 (C(2)); 121.2, 123.7 (C(4), C(5)); 136.2 (C(6));
147.2 (C(1)). 1H NMR (DMSOꢀd6) Zꢀ2e: 1.66 (d, 3 H, H3C(3),
J = 6.6 Hz); 3.91 (s, 3 H, H3C(7)); 5.72 (m, 1 H, HC(2)); 7.20
(d, 1 H, HC(1), J = 5.9 Hz); 7.81, 7.96 (both s, 2 H each,
HC(4), HC(5)); 9.58 (s, 1 H, HC(6)); 11.90 (s, 1 H, OH).
13C NMR (DMSOꢀd6) Zꢀ2e: 17.9 (C(3)); 35.8 (C(7)); 50.0
(C(2)); 121.0, 123.8 (C(4), C(5)); 136.4 (C(6)); 146.8 (C(1));
E/Z = 3 : 1.
2 H, H2C(2), J = 7.3 Hz); 5.33 (s,
2 H, H2C(5)); 7.68, 7.82 (both s,
2 H each, HC(6), HC(7)); 9.50 (s,
1 H, HC(8)); 12.68 (s, 1 H, OH).
13C NMR (DMSOꢀd6) Eꢀ2h: 14.4
(C(1)); 35.8 (C(5)); 36.3 (C(9)); 62.0 (C(2)); 123.5, 124.1 (C(6)
and C(7)); 137.7 (C(6)); 143.7 (C(4)); 161.0 (C(3)). 1H NMR
(DMSOꢀd6) Zꢀ2h: 1.24 (t, 3 H, H3C(1), J = 7.3 Hz); 3.91 (s,
3 H, H3C(9)); 4.23 (q, 2 H, H2C(2), J = 7.3 Hz); 5.20 (s, 2 H,
H2C(5)); 7.68, 7.82 (both s, 2 H each, HC(6), HC(7)); 9.33 (s,
1 H, HC(8)); 13.79 (s, 1 H, OH). 13C NMR (DMSOꢀd6) Zꢀ2h:
14.4 (C(1)); 36.3 (C(7)); 41.5 (C(5)); 62.0 (C(2)); 123.3,
124.1 (C(6), C(7)); 137.7 (C(6)); 144.3 (C(4)); 163.0 (C(3));
E/Z = 30 : 1.
(2ꢀHydroxyiminopropyl)trimethylammonium chloride (2i).
Trimethylchlorosilane 4а (0.70 mL, 5.5 mmol) and then BENA
2b (1.17 g, 5 mmol) were added to a solution of anhydrous
trimethylamine 3c (1.48 g, 25 mmol) in acetonitrile (2 mL)
at 0 °C. The mixture was kept for 0.5 h at 0 °C, and the temperaꢀ
ture was raised to 20 °C. After 1 h, the mixture was concentrated
at 0.1 Torr (20 °C) and MeOH (10 mL)
3ꢀ[2ꢀHydroxyiminoꢀ4ꢀ(methoxycarbonyl)butyl]ꢀ1ꢀmethylꢀ
3Hꢀimidazolium chloride (2f). M.p. 220—221 °C (MeOH).
Found (%): C, 45.67; H, 6.30; N, 16.35; Cl, 13.90.
C10H16N3O3Cl (261.71). Calcuꢀ
lated (%): C, 45.89; H, 6.16;
N, 16.06; Cl, 13.55.
1H NMR (DMSOꢀd6) Eꢀ2f:
2.41, 2.55 (both t, 4 H each,
H2C(3), H2C(4), J = 8.0 Hz); 3.52
(s, 3 H, H3C(1)); 3.87 (s, 3 H,
H3C(10)); 5.11 (s, 2 H, H2C(6));
was added. After 24 h, the mixture was
7.77, 7.87 (both s, 2 H each,
concentrated at 0.01 Torr and kept for 3 h
HC(7), HC(8)); 9.48 (s, 1 H,
at the same pressure, and the residue was
HC(9)); 11.61 (s,
1
H, OH).
washed with a large amount of ether. Salt
2i was obtained in a yield of 0.6 g (72%),
13C NMR (DMSOꢀd6) Eꢀ2f: 21.7
(C(4)); 28.8 (C(3)); 35.9 (C(10)); 50.5 (C(6)); 51.5 (C(1));
123.1, 123.4 (C(7), C(8)); 137.4 (C(9)); 151.9 (C(5)); 172.4
(C(2)). 1H NMR (DMSOꢀd6) Zꢀ2f: 2.47, 2.55 (both t, 4 H each,
H2C(3), H2C(4), J = 8.0 Hz); 3.58 (s, 3 H, H3C(1)); 3.91 (s,
3 H, H3C(10)); 5.19 (s, 2 H, H2C(6)); 7.75, 7.81 (both s, 2 H
each, HC(7), HC(8)); 9.48 (s, 1 H, HC(9)); 11.40 (s, 1 H, OH).
13C NMR (DMSOꢀd6) Zꢀ2f: 26.5 (C(4)); 29.2 (C(3)); 34.9
(C(10)); 44.9 (C(6)); 51.3 (C(1)); 123.0, 123.6 (C(7), C(8));
137.5 (C(9)); 150.0 (C(5)); 172.4 (C(2)); E/Z = 1 : 5.
1ꢀ(2ꢀHydroxyiminoꢀ4ꢀ
m.p. 230—235 °C (MeOH). Found (%): C, 43.35; H, 9.23;
N, 17.06; Cl, 21.68. C6H15N2OCl (166.65). Calculated (%):
C, 43.24; H, 9.07; N, 16.81; Cl, 21.27.
1H NMR (DMSOꢀd6): 1.88 (s, 3 H, H3C(1)); 3.12 (s, 9 H,
H3C(4)); 4.22 (s, 2 H, H2C(3)); 11.85 (s, 1 H, OH). 13C NMR
(DMSOꢀd6): 15.8 (C(1)); 52.4 (C(4)); 67.5 (C(3)); 147.3 (C(2)).
1,3ꢀBis(2ꢀhydroxyiminopropyl)ꢀ3Hꢀimidazolium chloride (2j).
Trimethylchlorosilane 4а (0.70 mL, 5.5 mmol) was added to a
solution of azole 3d (0.70 g, 5 mmol) in СH2Cl2 (2.5 mL) at
20 °С and then BENA 2b (2.33 g, 10 mmol) was added over
30 min. After 24 h, volaꢀ
methoxycarbonylbutyl)ꢀ4ꢀdiꢀ
methylaminopyridinium chloꢀ
tile components were disꢀ
ride (2g). M.p. 270—275 °C
tilled off at 0.1 Torr
(MeOH).
Found
(%):
(20 °C) and MeOH
C, 52.01; H, 6.78; N, 13.50;
Cl, 12.17. C13H20N3O3Cl
(301.77). Calculated (%):
C, 51.74; H, 6.68; N, 13.92;
Cl, 11.75.
1H NMR (DMSOꢀd6)
Eꢀ2g: 2.43, 2.62 (both m,
(10 mL) was added to the
residue. After 24 h, the
precipitated crystals of 2j
were filtered off, the filꢀ
trate was concentrated in vacuo, and the residue was recrystalꢀ
lized from MeOH. White crystals of 2j were obtained in a yield
of 1.03 g (83%). M.p. 265—270 °C (MeOH). Found (%):