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Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
Amitina et al.
the residue was treated with ether to give an additional crop of
the condensation product.
C16H13BrN2O3. Calculated (%): C, 53.20; H, 3.63; Br, 22.12;
N, 7.76. UV (EtOH, saturated solution (the concentration not
measured)), λmax/nm: 260. IR (KBr), ν/cm–1: 1677 (C=O).
1H NMR ((CD3)2CO), δ: 4.14 (dd, 1 H, H(4), J = 18.4 Hz, J =
1.5 Hz); 4.25—4.38 (br.s, 1 H, H(4)); 5.86 (br.s, 1 H, H(6));
7.41—7.46, 7.69—7.75, 8.07—8.12 (all m, 9 H, Ar); 8.25
(br.s, 1 H, OH).
6ꢀAcetylꢀ5ꢀhydroxyꢀ3ꢀphenylꢀ5,6ꢀdihydroꢀ4Hꢀ1,2,5ꢀoxaꢀ
diazine (3a). Yield 50%, m.p. 136 °C (decomp., from MeOH).
Found (%): C, 59.79; H, 5.43; N, 12.66. C11H12N2O3. Calꢀ
culated (%): C, 59.99; H, 5.49; N, 12.72. UV (EtOH),
λ
max/nm (logε): 244 (4.00). IR (KBr), ν/cm–1: 1732 (C=O).
1H NMR (DMSOꢀd6), δ: 2.27 (s, 3 H, Ac); 3.94 (d, 1 H, H(4),
J = 17.6 Hz); 4.27 (br.s, 1 H, H(4)); 5.07 (s, 1 H, H(6));
7.40—7.50, 7.60—7.70 (both m, 5 H, Ar); 9.00 (br.s, 1 H, OH).
6ꢀAcetylꢀ5ꢀhydroxyꢀ4ꢀmethylꢀ3ꢀphenylꢀ5,6ꢀdihydroꢀ4Hꢀ
1,2,5ꢀoxadiazine (3b). Yield 55%, m.p. 145 °C (decomp., from
MeOH). Found (%): C, 61.89; H, 6.19; N, 12.08. C12H14N2O3.
Calculated (%): C, 61.52; H, 6.02; N, 11.96. UV (EtOH),
6ꢀ(4ꢀChlorobenzoyl)ꢀ5ꢀhydroxyꢀ3ꢀphenylꢀ5,6ꢀdihydroꢀ4Hꢀ
1,2,5ꢀoxadiazine (6c). Yield 68%, m.p. 144 °C (decomp., from
MeOH). Found (%): C, 60.30; H, 4.10; Cl, 10.95; N, 8.77.
C16H13ClN2O3. Calculated (%): C, 60.67; H, 4.14; Cl, 11.19;
N, 8.84. UV (EtOH, saturated solution (the concentration not
measured)), λmax/nm: 256. IR (KBr), ν/cm–1: 1698 (C=O).
1H NMR ((CD3)2CO), δ: 4.14 (dd, 1 H, H(4), J = 18.4 Hz, J =
1.5 Hz); 4.24—4.39 (br.s, 1 H, H(4)); 5.87 (br.s, 1 H, H(6));
7.41—7.46, 7.55—7.59, 7.69—7.73, 8.15—8.19 (all m, 9 H, Ar);
8.29 (br.s, 1 H, OH).
λ
max/nm (logε): 242 (3.99). IR (KBr), ν/cm–1: 1736 (C=O).
1H NMR (CDCl3), δ: 1.35 (d, 3 H, C(4)Me, J = 7.2 Hz); 2.45
(s, 3 H, Ac); 4.20 (dq, 1 H, H(4), J = 1.6 Hz, J = 7.2 Hz); 4.85
(d, 1 H, H(6), J = 1.6 Hz); 5.97 (s, 1 H, OH); 7.37—7.44,
7.54—7.60 (both m, 5 H, Ar).
5ꢀHydroxyꢀ6ꢀ(4ꢀmethoxybenzoyl)ꢀ3ꢀphenylꢀ5,6ꢀdihydroꢀ
4Hꢀ1,2,5ꢀoxadiazine (6d). Yield 58%, m.p. 134 °C (decomp.,
from MeOH). Found (%): C, 65.38; H, 5.13; N, 9.01.
C17H16N2O4. Calculated (%): C, 65.37; H, 5.16; N, 8.97.
UV (EtOH), λmax/nm (logε): 221 (4.29), 280 (4.28). IR (KBr),
6ꢀAcetylꢀ3ꢀ(4ꢀchlorophenyl)ꢀ5ꢀhydroxyꢀ4ꢀmethylꢀ5,6ꢀdiꢀ
hydroꢀ4Hꢀ1,2,5ꢀoxadiazine (3c). Yield 41%, m.p. 142 °C
(decomp., from AcOEt). Found (%): C, 53.67; H, 4.87;
Cl, 12.96; N, 10.25. C12H13ClN2O3. Calculated (%): C, 53.64;
H, 4.88; Cl, 13.20; N, 10.43. UV (EtOH), λmax/nm (logε): 250
(4.04). IR (KBr), ν/cm–1: 1734 (C=O). 1H NMR ((CD3)2CO),
δ: 1.36 (d, 3 H, C(4)Me, J = 7.2 Hz); 2.30 (s, 3 H, Ac); 4.23 (dq,
1 H, H(4), J = 2.0 Hz, J = 7.2 Hz); 5.03 (d, 1 H, H(6), J =
2.0 Hz); 7.44—7.48, 7.67—7.71 (both m, 4 H, Ar); 8.10
(s, 1 H, OH).
1
ν/cm–1: 1661 (C=O). H NMR ((CD3)2CO), δ: 3.90 (s, 3 H,
OMe); 4.12 (d, 1 H, H(4), J = 18.5 Hz); 4.18—4.35 (br.s, 1 H,
H(4)); 5.86 (s, 1 H, H(6)); 7.02—7.06, 7.41—7.45, 7.69—7.73,
8.13—8.17 (all m, 9 H, Ar); 8.15—8.30 (br.s, 1 H, OH).
6ꢀBenzoylꢀ5ꢀhydroxyꢀ4ꢀmethylꢀ3ꢀphenylꢀ5,6ꢀdihydroꢀ4Hꢀ
1,2,5ꢀoxadiazine (6e). Yield 56.5%, m.p. 139 °C (decomp., from
MeOH). Found (%): C, 69.20; H, 5.46; N, 9.48. C17H16N2O3.
Calculated (%): C, 68.90; H, 5.44; N, 9.45. UV (EtOH),
2ꢀAcetylꢀ1ꢀhydroxyꢀ1,9,10,10aꢀtetrahydroꢀ2Hꢀ3ꢀoxaꢀ1,4ꢀ
diazaphenanthrene (3d). Yield 61%, m.p. 164 °C (decomp., from
MeOH). Found (%): C, 63.15; H, 5.68; N, 11.37. C13H14N2O3.
Calculated (%): C, 63.40; H, 5.73; N, 11.38. UV (EtOH),
λ
max/nm (logε): 248 (4.31). IR (KBr), ν/cm–1: 1703 (C=O).
1H NMR ((CD3)2CO), δ: 1.51 (d, 3 H, C(4)Me, J = 7.6 Hz);
4.32 (dq, 1 H, H(4), J = 1.6 Hz, J = 7.6 Hz); 6.01 (d, 1 H, H(6),
J = 1.6 Hz); 7.42—7.46, 7.49—7.55, 7.61—7.66, 7.67—7.71,
8.11—8.15 (all m, 10 H, Ar); 7.99 (s, 1 H, OH).
λ
max/nm (logε): 257 (4.04), 287 sh (3.69), 298 (3.55). IR (KBr),
ν/cm–1: 1732 (C=O). H NMR (DMSOꢀd6), δ: 1.75—1.90 (m,
1 H, H(10)); 2.26 (s, 3 H, Ac); 2.92 (m, 2 H, H(9)); 3.90 (br.s,
1 H, H(10a)); 4.80—5.30 (br.s, 1 H, H(2)); 7.20—7.37 (m, 3 H,
Ar); 7.86 (m, 1 H, Ar); 8.73 (br.s, 1 H, OH) (the signal for one
of the H(10) protons coincides with the signal for the protons of
the acetyl group).
1
6ꢀ(4ꢀBromobenzoyl)ꢀ5ꢀhydroxyꢀ4ꢀmethylꢀ3ꢀphenylꢀ5,6ꢀdiꢀ
hydroꢀ4Hꢀ1,2,5ꢀoxadiazine (6f). Yield 76%, m.p. 162 °C
(decomp., from MeOH). Found (%): C, 54.41; H, 4.02;
Br, 21.30; N, 7.20. C17H15BrN2O3. Calculated (%): C, 54.42;
H, 4.03; Br, 21.30; N, 7.47. UV (EtOH, saturated solution),
Condensation of 1,2ꢀhydroxylamino oximes 1a—c with arylꢀ
glyoxals 5 (general procedure). Arylglyoxal 5 (2.0 mmol) was
added to a warm solution of hydroxylamino oxime 1a—c
(2.0 mmol) in MeOH (5—8 mL). Then trifluoroacetic acid
(0.3 mL) was added and the mixture was kept for two days. The
precipitate of condensation products 6a—j that formed was filꢀ
tered off, washed with MeOH, and dried. The filtrate was conꢀ
centrated and the residue was treated with ether to give an addiꢀ
tional crop of the condensation product.
6ꢀBenzoylꢀ5ꢀhydroxyꢀ3ꢀphenylꢀ5,6ꢀdihydroꢀ4Hꢀ1,2,5ꢀoxaꢀ
diazine (6a). Yield 62%, m.p. 120—121 °C (decomp., from
MeOH). Found (%): C, 68.06; H, 5.03; N, 9.91. C16H14N2O3.
Calculated (%): C, 68.07; H, 5.00; N, 9.92. UV (EtOH),
λ
max/nm: 260. IR (KBr), ν/cm–1: 1701 (C=O). 1H NMR
(DMSOꢀd6), δ: 1.39 (d, 3 H, C(4)Me, J = 7.2 Hz); 4.13 (q, 1 H,
H(4), J = 7.2 Hz); 6.09 (s, 1 H, H(6)); 7.40—7.49, 7.55—7.65,
7.70—7.80, 7.89—7.98 (all m, 9 H, Ar); 8.89 (s, 1 H, OH).
13C NMR (DMSOꢀd6), δ: 19.18 (4ꢀMe); 55.80 (C(4)); 84.77
(C(6)); 126.27 (d); 128.15 (s); 129.35, 130.44, 131.60, 132.05
(all d); 134.08, 134.32 (both s); 158,65 (C=N); 191.26 (C=O).
6ꢀ(4ꢀChlorobenzoyl)ꢀ5ꢀhydroxyꢀ4ꢀmethylꢀ3ꢀphenylꢀ5,6ꢀdiꢀ
hydroꢀ4Hꢀ1,2,5ꢀoxadiazine (6g). Yield 54%, m.p. 148 °C
(decomp., from MeOH). Found (%): C, 61.63; H, 4.51;
Cl, 10.85; N, 8.49. C17H15ClN2O3. Calculated (%): C, 61.73;
H, 4.57; Cl, 10.72; N, 8.47. UV (EtOH), λmax/nm (logε): 256
(4.04). IR (KBr), ν/cm–1: 1702 (C=O). 1H NMR ((CD3)2CO),
δ: 1.51 (d, 3 H, C(4)Me, J = 7.2 Hz); 4.32 (dq, 1 H, H(4), J =
1.6 Hz, J = 7.2 Hz); 5.88 (d, 1 H, H(6), J = 1.6 Hz); 7.42—7.49,
7.54—7.61, 7.66—7.72, 8.12—8.17 (all m, 9 H, Ar); 8.05
(br.s, 1 H, OH).
λ
max/nm (logε): 250 (3.97). IR (KBr), ν/cm–1: 1700 (C=O).
1H NMR ((CD3)2CO), δ: 4.11 (dd, 1 H, H(4), J = 18.4 Hz, J =
1.2 Hz); 4.22—4.39 (br.s, 1 H, H(4)); 5.95 (dd, 1 H, H(6), J =
1.2 Hz, J = 1.2 Hz); 7.40—7.74, 8.12—8.18 (both m, 10 H, Ar);
8.35 (br.s, 1 H, OH).
6ꢀBenzoylꢀ3ꢀ(4ꢀchlorophenyl)ꢀ5ꢀhydroxyꢀ4ꢀmethylꢀ5,6ꢀdiꢀ
hydroꢀ4Hꢀ1,2,5ꢀoxadiazine (6h). Yield 61%, m.p. 149 °C
(decomp., from MeOH). Found (%): C, 61.42; H, 4.83;
Cl, 10.47; N, 8.50. C17H15ClN2O3. Calculated (%): C, 61.73;
6ꢀ(4ꢀBromobenzoyl)ꢀ5ꢀhydroxyꢀ3ꢀphenylꢀ5,6ꢀdihydroꢀ4Hꢀ
1,2,5ꢀoxadiazine (6b). Yield 76%, m.p. 146 °C (decomp., from
MeOH). Found (%): C, 53.19; H, 3.60; Br, 22.19; N, 7.53.