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Russ.Chem.Bull., Int.Ed., Vol. 55, No. 6, June, 2006
Amitina et al.
λ
max/nm (logε): 259 (4.28), 315 sh (3.71). IR (KBr), ν/cm–1
:
(4.25). IR (KBr), ν/cm–1: 1692 (C=O). 1H NMR (DMSOꢀd6),
δ: 1.14 (d, 3 H, C(4)Me, J = 7.0 Hz); 1.66 (s, 3 H, C(6)Me);
4.10 (q, 1 H, H(4), J = 7.0 Hz); 7.37 (s, 5 H, Ar); 7.76 and 8.19
(both d, 2 H each, Ar, J = 6.8 Hz); 8.94 (s, 1 H, OH).
1
1668 (C=O). H NMR (DMSOꢀd6), δ: 2.08 (s, 3 H, αꢀMe);
2.40 (s, 3 H, Me); 5.35 (s, 2 H, CH2); 7.30—7.80 (m, 8 H, Ar);
11.77 (s, 1 H, OH).
Nꢀ[αꢀ(4ꢀEthoxybenzoyl)ethylidene]ꢀNꢀ[2ꢀ(Z )ꢀhydroxyꢀ
iminoꢀ2ꢀphenylethyl]amine Nꢀoxide (6eA). The yield was 83%,
m.p. 160 °C (decomp., from MeOH). Found (%): C, 67.28;
H, 5.85; N, 8.31. C19H20N2O4. Calculated (%): C, 67.04;
H, 5.92; N, 8.23. UV (EtOH), λmax/nm (logε): 231 (4.37), 293
Condensation product 6i. The yield was 50%, m.p. 148 °C
(decomp., from AcOEt). Found (%): C, 62.76; H, 4.98;
Cl, 10.47; N, 8.16. C18H17ClN2O3. Calculated (%): C, 62.70;
H, 4.97; Cl, 10.28; N, 8.12. UV (EtOH), λmax/nm (logε):
248 (4.35), 295 sh (3.72). IR (KBr), ν/cm–1: 1673 (C=O).
Nꢀ(αꢀBenzoylethylidene)ꢀNꢀ[2ꢀ(4ꢀchlorophenylethyl)ꢀ2ꢀ(Z )ꢀ
hydroxyiminoꢀ1ꢀmethyl]amine Nꢀoxide (6iA) (37%), 1H NMR
(CDCl3), δ: 1.58 (d, 3 H, Me, J = 7.2 Hz); 2.29 (s, 3 H, αꢀMe);
5.95 (q, 1 H, CH, J = 7.2 Hz); 7.15—7.70 (m, 9 H, Ar); 9.73
(br.s, 1 H, OH). 6ꢀBenzoylꢀ3ꢀ(4ꢀchlorophenyl)ꢀ5ꢀhydroxyꢀ4,6ꢀ
dimethylꢀ5,6ꢀdihydroꢀ4Hꢀ1,2,5ꢀoxadiazine (6iB) (63%), the maꢀ
jor diastereomer (70%), 1H NMR (CDCl3), δ: 1.36 (d, 3 H,
C(4)Me); 1.94 (s, 3 H, C(6)Me); 4.36 (q, 1 H, H(4), J = 6.8 Hz);
6.19 (s, 1 H, OH); 7.15—7.70 (m, 7 H, Ar); 8.31 (m, 2 H, Ar).
1
(4.35). IR (KBr), ν/cm–1: 1650 (C=O). H NMR (DMSOꢀd6),
δ: 1.36 (t, 3 H, Me, J = 7.0 Hz); 2.09 (s, 3 H, αꢀMe); 4.14 (q,
2 H, CH2, J = 7.0 Hz); 5.27 (s, 2 H, CH2); 7.07 (d, 2 H, Ar, J =
8.8 Hz); 7.30—7.40 and 7.60—7.80 (both m, 5 H, Ar); 7.70 (d,
2 H, Ar, J = 8.8 Hz); 11.71 (s, 1 H, OH).
Nꢀ[αꢀ(4ꢀPentyloxybenzoyl)ethylidene]ꢀNꢀ[2ꢀ(Z )ꢀhydroxyꢀ
iminoꢀ2ꢀphenylethyl]amine Nꢀoxide (6fA). The yield was 60%,
m.p. 142 °C (decomp., from MeOH). Found (%): C, 69.06;
H, 6.73; N, 7.28. C22H26N2O4. Calculated (%): C, 69.09;
H, 6.85; N, 7.32. UV (EtOH), λmax/nm (logε): 230 (4.22), 293
1
The minor diastereomer (30%), H NMR (CDCl3), δ: 1.26 (d,
1
(4.22). IR (KBr), ν/cm–1: 1656 (C=O). H NMR (DMSOꢀd6),
3 H, C(4)Me, J = 7.2 Hz); 1.72 (s, 3 H, C(6)Me); 4.18 (q, 1 H,
H(4), J = 7.2 Hz); 5.75 (s, 1 H, OH); 7.15—7.70 (m, 7 H, Ar);
8.31 (m, 2 H, Ar).
δ: 0.91 (t, 3 H, Me, J = 7.0 Hz); 1.37 (m, 4 H, CH2CH2); 1.73
(m, 2 H, CH2); 2.08 (s, 3 H, αꢀMe); 4.08 (t, 2 H, OCH2, J =
7.0 Hz); 5.25 (s, 2 H, CH2); 7.07 (d, 2 H, Ar, J = 8.8 Hz);
7.30—7.40 and 7.60—7.70 (both m, 5 H, Ar); 7.69 (d, 2 H, Ar,
J = 8.8 Hz); 11.70 (s, 1 H, OH).
Nꢀ(αꢀBenzoylethylidene)ꢀNꢀ[2ꢀ(Z )ꢀhydroxyiminoꢀ1ꢀisoproꢀ
pylꢀ2ꢀphenylethyl]amine Nꢀoxide (6jA). The yield was 71%, m.p.
176 °C (decomp., from MeOH). Found (%): C, 71.10; H, 6.53;
N, 8.41. C20H22N2O3. Calculated (%): C, 70.98; H, 6.55;
N, 8.28. UV (EtOH), λmax/nm (logε): 246 (4.38), 285 sh (3.72).
IR (KBr), ν/cm–1: 1672 (C=O). 1H NMR (DMSOꢀd6), δ: 0.73
and 1.03 (both d, 3 H each, Me, J = 6.4 Hz); 2.35 (s, 3 H,
αꢀMe); 5.60 (d, 1 H, CH, J = 11.0 Hz); 7.30—7.80 (m, 10 H,
Ar); 12.36 (s, 1 H, OH); the signal of CHMe2 overlaps with the
signal of the solvent.
Condensation of 1,2ꢀhydroxylamino oximes 1b,c with 1ꢀarylꢀ
propaneꢀ1,2ꢀdiones 5 (general procedure). A suspension of the
Z isomer of 1,2ꢀhydroxylamino oximes (7 mmol) and the correꢀ
sponding 1ꢀarylpropaneꢀ1,2ꢀdione 5 (7 mmol) in MeOH (20 mL)
was heated until complete dissolution was achieved and then
refluxed for 6 h. The solvent was evaporated, the residue was
chromatographed on a silica gel column (CHCl3—MeOBut, 1 : 1,
as the eluent), and the condensation product was isolated.
Condensation product 6g. The yield was 39%, m.p. 142 °C
(decomp., from AcOEt). Found (%): C, 69.34; H, 5.83; N, 9.00.
C18H18N2O3. Calculated (%): C, 69.66; H, 5.85; N, 9.03.
UV (EtOH), λmax/nm (logε): 247 (4.25), 283 sh (3.65). IR (KBr),
ν/cm–1: 1662, 1685 (C=O). Nꢀ(αꢀBenzoylethylidene)ꢀNꢀ[2ꢀ(Z )ꢀ
hydroxyiminoꢀ1ꢀmethylꢀ2ꢀphenylethyl]amine Nꢀoxide (6gA)
(40%), 1H NMR (DMSOꢀd6), δ: 1.45 (d, 3 H, Me, J = 7.5 Hz);
2.09 (s, 3 H, αꢀMe); 6.21 (q, 1 H, CH, J = 6.8 Hz); 7.30—7.70
(m, 10 H, Ar); 11.67 (s, 1 H, OH). 6ꢀBenzoylꢀ5ꢀhydroxyꢀ
4,6ꢀdimethylꢀ3ꢀphenylꢀ5,6ꢀdihydroꢀ4Hꢀ1,2,5ꢀoxadiazine (6gB)
Condensation product 6k. The yield was 78%, m.p. 176 °C
(decomp., from MeOH). Found (%): C, 71.47; H, 6.74; N, 8.05.
C
21H24N2O3. Calculated (%): C, 71.57; H, 6.86; N, 7.95.
UV (EtOH), λmax/nm (logε): 260 (4.19), 304 sh (3.79). IR (KBr),
ν/cm–1: 1663 (C=O). Nꢀ[2ꢀ(Z )ꢀHydroxyiminoꢀ1ꢀisopropylꢀ2ꢀ
phenylethyl]ꢀNꢀ[αꢀ(4ꢀmethylbenzoyl)ethylidene]amine Nꢀoxide
1
(6kA) (100%), H NMR (DMSOꢀd6), δ: 0.63 and 0.99 (both d,
3 H each, Me, J = 6.6 Hz); 2.13 (s, 3 H, αꢀMe); 2.40 (s, 3 H,
C(4)Me); 5.96 (d, 1 H, CH, J = 11.0 Hz); 7.30—7.40 (m, 5 H,
Ar); 7.60—7.85 (m, 4 H, Ar); 11.61 (s, 1 H, OH); the signal of
CHMe2 overlaps with the signal of the solvent. Nitrone 6kA
1
1
(60%), H NMR (DMSOꢀd6), δ: 1.15 (d, 3 H, C(4)Me, J =
(20%), H NMR (CDCl3), δ: 0.78 and 1.09 (both d, 3 H each,
6.8 Hz); 1.67 (s, 3 H, C(6)Me); 4.09 (q, 1 H, H(4), J = 6.8 Hz);
Me, J = 6.8 Hz); 2.28 (s, 3 H, αꢀMe); 2.37 (s, 3 H, C(4)Me);
2.92 (m, 1 H, CH); 5.68 (d, 1 H, CH, J = 11.0 Hz); 7.10—7.70
(m, 9 H, Ar). 5ꢀHydroxyꢀ4ꢀisopropylꢀ6ꢀmethylꢀ6ꢀ(4ꢀmethylꢀ
benzoyl)ꢀ3ꢀphenylꢀ5,6ꢀdihydroꢀ4Hꢀ1,2,5ꢀoxadiazine (6kB)
7.30—7.70 (m, 8 H, Ar); 8.28 (d, 2 H, Ar, J = 7.2 Hz); 8.87 (s,
1
1 H, OH). Nitrone 6gA (27%), H NMR (CDCl3), δ: 1.60 (d,
3 H, Me, J = 7.0 Hz); 2.30 (s, 3 H, αꢀMe); 5.95 (q, 1 H, CH, J =
1
6.8 Hz); 7.10—7.80 (m, 10 H, Ar); 9.95 (br.s, 1 H, OH). The
(80%), the major diastereomer (94%), H NMR (CDCl3), δ:
1
major isomer of oxadiazine 6gB (48%), H NMR (CDCl3), δ:
0.79 and 1.15 (both d, 3 H each, Me, J = 6.8 Hz); 1.95 (s, 3 H,
C(6)Me); 2.34 (s, 3 H, Me); 4.43 (d, 1 H, H(4), J = 2.5 Hz);
6.87 (s, 1 H, OH); 7.10—7.70 (m, 7 H, Ar); 8.19 (d, 2 H, Ar, J =
1.36 (d, 3 H, C(4)Me); 1.94 (s, 3 H, C(6)Me); 4.42 (q, 1 H,
H(4), J = 7.0 Hz); 6.31 (s, 1 H, OH); 7.10—7.50 (m, 8 H, Ar);
8.25—8.35 (m, 2 H, Ar). The minor isomer of oxadiazine 6gB
1
8.4 Hz). The minor diastereomer (6%), H NMR (CDCl3), δ:
1
(25%), H NMR (CDCl3), δ: 1.27 (d, 3 H, C(4)Me); 1.73 (s,
3.99 (d, 1 H, H(4), J = 2.6 Hz); 5.58 (s, 1 H, OH); other signals
3 H, C(6)Me); 4.20 (q, 1 H, H(4), J = 7.0 Hz); 5.88 (s, 1 H,
overlap with more intense signals.
OH); 7.10—7.50 (m, 8 H, Ar); 8.25—8.35 (m, 2 H, Ar).
Nꢀ[αꢀ(4ꢀFluorobenzoyl)ethylidene]ꢀNꢀ[2ꢀ(Z )ꢀhydroxyiminoꢀ
1ꢀisopropylꢀ2ꢀphenylethyl]amine Nꢀoxide (6lA). The yield was
80%, m.p. 174 °C (decomp., from MeOH). Found (%): C, 67.25;
H, 5.89; F, 5.34; N, 7.86. C20H21FN2O3. Calculated (%): C,
67.40; H, 5.94; F, 5.33; N, 7.86. UV (EtOH), λmax/nm (logε):
249 (4.26), 292 sh (3.61). IR (KBr), ν/cm–1: 1666 (C=O).
6ꢀ(4ꢀBromobenzoyl)ꢀ5ꢀhydroxyꢀ4,6ꢀdimethylꢀ3ꢀphenylꢀ5,6ꢀ
dihydroꢀ4Hꢀ1,2,5ꢀoxadiazine (6hB). The yield was 72%, m.p.
168 °C (decomp., from MeOH). Found (%): C, 55.50; H, 4.45;
Br, 20.75; N, 7.11. C18H17BrN2O3. Calculated (%): C, 55.54;
H, 4.40; Br, 20.53; N, 7.20. UV (EtOH), λmax/nm (logε): 259