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Abakumov et al.
mixture was heated for 10 min in a water bath at 80 °C. A yellow
compound 3 (0.27 g, 27%), m.p. 176 °C (with decomp.), precipꢀ
itated from the solution on cooling to room temperature.
Found (%): C, 72.83; H, 9.01. С30Н44N2О4. Calculated (%):
C, 72.58; H, 8.87. IR, ν/cm–1: 3550 (O—H); 1640 (C=N); 1125
(C—N); 1235 (C—O). 1Н NMR, δ: 1.41, 1.60 (both s, 18 Н
each, But); 5.77, 5.86 (both s, 2 Н each, ОН); 6.35 (s, 2 Н,
Н(5)); 8.13 (s, 2 Н, HC=N).
1,4ꢀBis(2,5ꢀdiꢀtertꢀbutylꢀ3,4ꢀdihydroxyphenyl)ꢀ2ꢀmethylꢀ
1,4ꢀdiazabutaꢀ1,3ꢀdiene (4). A solution of 40% methylglyoxal
(0.32 mL, 2.1 mmol) in methanol (25 mL) was poured to
a solution of compound 1 (1 g, 4.2 mmol) in methanol (50 mL).
The reaction mixture was heated for 1 h in a water bath at 80 °C,
and the color of the solution changed from light yellow to redꢀ
orange. Dark yellow crystals of compound 4 (0.68 g, 68%), m.p.
168 °C (with decomp.), precipitated from the solution on cooling
to room temperature. Found (%): C, 72.59; H, 9.14. С31Н46N2О4.
Calculated (%): C, 72.90; H, 9.02. IR, ν/cm–1: 1640 (C=N),
1125 (C—N), 1235 (C—O), 3550 (O—H). 1Н NMR, δ: 1.38,
1.41, 1.46, 1.62 (all s, 9 Н each, But); 2.12 (s, 3 Н, СН3); 5.25,
5.78, 5.86, 5.89 (all s, 1 Н each, ОН); 5.91, 6.40 (both s, 1 Н each,
НAr); 8.07 (s, 1 Н, HC=N).
1,4ꢀBis(2,5ꢀdiꢀtertꢀbutylꢀ3,4ꢀdihydroxyphenyl)ꢀ2,3ꢀdimethꢀ
ylꢀ1,4ꢀdiazabutaꢀ1,3ꢀdiene (5). A solution of diacetyl (0.15 g,
1.7 mmol) in methanol (30 mL) was poured to a solution of
compound 1 (0.83 g, 3.4 mmol) in methanol (50 mL). The reacꢀ
tion mixture was heated in a water bath for 40 h at 80 °C. Yellow
crystalline compound 5 precipitated from the solution during
the reaction. The yield was 0.56 g (67%), m.p. 185 °C (with
decomp.). Found (%): C, 73.00; H, 8.98. С32Н48N2О4. Calcuꢀ
lated (%): C, 73.28; H, 9.16. IR, ν/cm–1: 1620 (C=N), 1150
(C—N), 1205 (C—O), 3500 (O—H). 1Н NMR, δ: 1.39 (s, 18 Н,
But); 1.47 (s, 18 Н, But); 2.12 (s, 6 Н, СН3); 5.27 (s, 2 Н, НAr);
5.90 (s, 4 Н, ОН).
1ꢀ(2,6ꢀDiisopropylphenyl)ꢀ4ꢀ(2,5ꢀdiꢀtertꢀbutylcyclohexadiꢀ
eneꢀ1,5ꢀdionꢀ3,4ꢀyl)ꢀ2,3ꢀdimethylꢀ1,4ꢀdiazabutaꢀ1,3ꢀdiene (8).
The synthesis is analogous to the synthesis of compound 7. Red
crystals of compound 8 (0.12 g, 33%), which decompose at
117 °C, were isolated. Found (%): C, 77.81; H, 8.89. С30Н42N2О2.
Calculated (%): C, 77.92; H, 9.09. IR, ν/cm–1: 1640 (C=N);
1690 (C=O); 1125 (C—N). 1Н NMR, δ: 1.16 (d, 12 Н, СН(СН3)2,
J = 6.9 Hz); 1.27, 1.28 (both s, 9 Н each, But); 1.97, 2.32 (both s,
3 Н each, СН3); 2.61 (sept, 2 Н, СН(СН3)2, J = 6.9 Hz); 6.22
(s, 1 Н, Н(5)); 7.07—7.21 (m, 3 Н, Ar).
4,9ꢀDihydroxyꢀ2,5,7,10ꢀtetraꢀtertꢀbutylindolo[3,2ꢀb]indoleꢀ
3,8ꢀdione (9). Air was bubbled for 12 h through a methanolic
solution containing compound 3 (1.19 g, 2.4 mmol). The color
of the solution changed from light yellow to violet. The evaporaꢀ
tion of the solution gave 0.83 g (69.7%) of blueꢀviolet crystals of
compound 9, having no distinct melting temperature. Found (%):
С, 73.01; Н, 7.98. С30Н40N2O4. Calculated (%): С, 73.17;
Н, 8.13. IR, ν/cm–1: 3550 (O—H); 3290 (N—H); 1610 (C=O);
1585 (C=N). 1Н NMR, δ: 1.43, 1.47 (both s, 18 Н each, CH3);
7.33, 7.99 (both br.s, 2 Н each, ОH, NH). 13C NMR, DEPT
(200 МHz), δ: 30.7, 31.5 (C(CH3)3); 34.6, 36.5 (C(CH3)3);
107.5 (C); 118.3 (C); 121.3 (C); 143.2 (C); 144.8 (C); 154.6 (C);
180.2 (C=O).
3,9ꢀDihydroxyꢀ5bꢀmethylꢀ2,5,7,10ꢀtetraꢀtertꢀbutylꢀindoꢀ
lo[3,2ꢀb]indoleꢀ4,8ꢀdione (10). The synthesis was analogous to
that of compound 9. Dark blue crystals without distinct melting
temperature were obtained in a yield of 0.47 g (37%). Found (%):
С, 73.45; Н, 8.19. С31Н42N2O4. Calculated (%): С, 73.51;
Н, 8.30. IR, ν/cm–1: 3475—3190 (O—H, N—H); 1630 (C=O);
1570 (C=N). 1Н NMR, δ: 1.49, 1.50, 1.52, 1.63 (all s, 9 Н each,
CH3); 1.73 (s, 3 H, CH3); 5.93 (br.s, 1 Н, NH); 8.08, 8.89
(both br.s, 1 Н each, OH). 13C NMR, DEPT (200 MHz), δ:
30.6, 30.90, 30.94, 30.95 (C(CH3)3); 31.2 (CH3); 35.1, 35.8,
35.9, 37.0 (C(CH3)3); 74.4 (C(5b)); 114.3 (C), 117.8 (C),
117.9 (C), 125.4 (C), 139.0 (C), 145.7 (C), 147.8 (C), 150.0 (C),
162.0 (C), 172.7 (C); 172.8 (C); 179.0, 183.4 (C=O).
1ꢀ(2,6ꢀDiisopropylphenyl)ꢀ4ꢀ(2,5ꢀdiꢀtertꢀbutylꢀ3,4ꢀdihydrꢀ
oxyphenyl)ꢀ2,3ꢀdimethylꢀ1,4ꢀdiazabutaꢀ1,3ꢀdiene (6). A solution
of compound 2 (2.3 g, 9.4 mmol) in methanol (50 mL) was
poured to a solution of compound 1 (1.6 g, 6.7 mmol) in methaꢀ
nol (50 mL). The reaction mixture was heated for 8 h in a water
bath at 80 °C. Yellow crystals of compound 6, m.p. 117 °C,
precipitated on slow evaporation of the solution. The yield was
35.4%. Found (%): C, 77.97; H, 10.01. С30Н44N2О2. Calculatꢀ
ed (%): C, 77.58; H, 9.48. IR, ν/cm–1: 1640 (C=N), 1120, 1055,
This work was carried out in the framework of the
Federal Target Program "Scientific and Pedagogical Speꢀ
cialists of Innovative Russia for 2009—2013" (State Conꢀ
tract No. P839 of 25.05.2010) and was financially supꢀ
ported by the Russian Foundation for Basic Research
(Project No. 10ꢀ03ꢀ00788) and the Council on Grants
at the President of the Russian Federation (Program
for State Support of Leading Scientific Schools, Grant
NShꢀ7065.2010.3).
1
1025 (C—O, C—N); 3540, 3150 (O—H). Н NMR, δ: 1.16 (d,
12 Н, СН(СН3)2, J = 6.9 Hz); 1.41, 1.47 (both s, 9 Н each, But);
2.01, 2.18 (both s, 3 Н each, СН3); 2.70 (sept, 1 Н, СН(СН3)2,
J = 6.9 Hz); 5.24, 5.90 (both s, 1 Н each, ОН); 5.94 (s, 1 Н,
НAr(5)); 7.02—7.20 (m, 3 Н, Ar).
References
1,4ꢀBis(2,5ꢀdiꢀtertꢀbutylcyclohexadieneꢀ1,5ꢀdionꢀ3,4ꢀyl)ꢀ
2,3ꢀdimethylꢀ1,4ꢀdiazabutaꢀ1,3ꢀdiene (7). A solution of comꢀ
pound 5 (0.55 g, 1.05 mmol) in diethyl ether (40 mL) was oxiꢀ
dized with an excess of PbO2 in air. The reaction course
was monitored by TLC (Silufol UVꢀ254, hexane—ethyl aceꢀ
tate (100 : 1)). After the end of the reaction, lead oxides were
filtered off, and the solution was concentrated. Dark red crystals
of compound 7 (0.25 g, 25%) decomposing on heating above
100 °C were isolated on cooling. Found (%): С, 73.42;
Н, 8.65. С32Н44N2O4. Calculated (%): С, 73.81; Н, 8.52. IR,
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1
ν/cm–1: 1640 (C=N); 1690 (C=O); 1125 (C—N). Н NMR, δ:
1.24, 1.26 (both s, 18 Н each, But); 2.23 (s, 6 Н, СН3); 6.12
(s, 2 Н, НAr).