1806
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
Gornostaev et al.
7.22 (d, 2 H, H(3´), H(5´), J = 7.7 Hz); 7.26 (d, 2 H, H(2´),
H(6´), J = 7.7 Hz); 7.72 (t, 1 H, H(8), J = 7.2 Hz); 7.77 (t, 1 H,
H(9), J = 7.2 Hz); 9.23 (br.d, 2 H, H(7), H(10), J = 7.2 Hz);
11.37 (s, 1 H, NH). Found (%): C, 70.73; H, 5.22; N, 8.76.
C27H24ClN3O2. Calculated (%): C, 70.82; H, 5.24; N, 9.19. MS
(EI, 70 eV), m/z (Irel (%)): 457 [M]+ (8.91), 423 [M – Cl + H]+
(100), 367 [M – CH2Cl – CH(Me)2 + 2 H]+ (10.11), 366
[M – CH2Cl – CH(Me)2 + H]+ (9.81).
3ꢀBenzylꢀ2ꢀchloromethylꢀ5ꢀ(4ꢀmethylphenyl)aminoꢀ3Hꢀanꢀ
thra[1,2ꢀd]imidazoleꢀ6,11ꢀdione (8b). The synthesis was carried
out analogously to that described above starting from 6b (1 g,
0.0023 mol). The yield of 8b was 0.66 g (62%), m.p. 219—220 °C.
1H NMR, δ: 2.32 (s, 3 H, PhMe); 5.21 (s, 2 H, CH2Cl); 5.21
(s, 2 H, CH2Ph); 6.93 (d, 2 H, H(3´), H(5´), J = 7.7 Hz); 7.12
(d, 2 H, H(2´), H(6´), J = 7.7 Hz); 7.19 (d, 2 H, oꢀPh, J = 7.2 Hz);
7.26 (s, 1 H, H (4)); 7.37 (m, 3 H, mꢀ, pꢀPh); 7.88 (m, 2 H, H(8),
H(9)); 8.13 (m, 1 H, H(7)); 8.22 (m, 1 H, H(10)); 11.25 (s, 1 H,
NH). Found (%): C, 73.30; H, 4.48; N, 8.55. C30H22ClN3O2.
Calculated (%): C, 73.24; H, 4.47; N, 8.54. MS (EI, 70 eV),
m/z (Irel (%)): 491 [M]+ (3.30), 456 [M – Cl]+ (5.21), 364
[M – Cl – H – PhCH2]+ (5.81), 91 [PhCH2]+ (100).
2ꢀChloroꢀ1ꢀchloroacetylaminoꢀ9,10ꢀanthraquinone (9a).
1ꢀAminoꢀ2ꢀchloroꢀ9,10ꢀanthraquinone (5.1 g, 0.02 mol) was reꢀ
fluxed in benzene (40 mL) with chloroacetyl chloride (5 mL) for
3 h. The precipitate that formed after cooling was filtered off,
washed with benzene and Et2O, and purified by recrystallization
from AcOH. The yield was 5.2 g (78%), m.p. 185—186 °C.
1H NMR (CDCl3), δ: 4.30 (s, 2 H, CH2Cl); 7.80 (m, 2 H, H(6),
H(7)); 7.86 (d, 1 H, H(3), J = 7.9 Hz); 8.21 (d, 1 H, H(4),
J = 7.9 Hz); 8.25 (m, 2 H, H(5), H(8)); 10.49 (s, 1 H, NH).
Found (%): C, 57.86; H, 2.78; N, 4.36. C16H9Cl2NO3. Calculatꢀ
ed (%): C, 57.49; H, 2.69; N, 4.19.
2ꢀBromoꢀ1ꢀchloroacetylaminoꢀ4ꢀ(4ꢀmethylphenyl)aminoꢀ
9,10ꢀanthraquinone (9b). 1ꢀAminoꢀ2ꢀbromoꢀ4ꢀ(4ꢀmethylphenyl)ꢀ
aminoꢀ9,10ꢀanthraquinone7 (6.1 g, 0.015 mol) was refluxed
in benzene (80 mL) with chloroacetyl chloride (6 mL) for 3 h.
The precipitate that formed after cooling was filtered off,
washed with benzene and Et2O, and purified by recrystallizaꢀ
tion from oꢀxylene. The yield was 6.2 g (86%), m.p. 198—199 °C.
1H NMR (CDCl3), δ: 2.49 (s, 3 H, PhMe); 4.25 (s, 2 H, CH2Cl);
7.17 (d, 2 H, H(3´), H(5´), J = 7.8 Hz); 7.24 (d, 2 H,
H(2´), H(6´), J = 7.8 Hz); 7.66 (s, 1 H, H(3)); 7.74 (t, 1 H,
H(6 or 7), J = 7.3 Hz); 7.78 (t, 1 H, H(6 or 7), J = 7.3 Hz); 8.18
(d, 1 H, H(5 or 8), J = 7.3 Hz); 8.25 (d, 1 H, H(5 or 8), J = 7.3 Hz);
10.04 (s, 1 H, NHCO); 11.47 (s, 1 H, NH). Found (%): C, 57.68;
H, 3.32; N, 6.08. C23H16BrClN2O3. Calculated (%): C, 57.08;
H, 3.31; N, 5.79.
Experimental
1
The H NMR spectra were recorded on a Bruker DRX inꢀ
strument (500 MHz) in DMSOꢀd6 with Me4Si as the internal
standard. The molecular weights of the reaction products were
confirmed by mass spectrometry on a Finnigan MAT 8200 inꢀ
strument. The UV spectra were measured on an Еvolution 300
instrument in toluene. The course of the reactions was moniꢀ
tored and the purity of the reaction products was checked by
TLC on Silufol UVꢀ254 plates with the use of a toluene—acetꢀ
one mixture (4 : 1) as the eluent. The melting points were meaꢀ
sured on a Boetius hotꢀstage apparatus.
1ꢀAminoꢀ2ꢀisobutylaminoꢀ4ꢀ(4ꢀmethylphenyl)aminoꢀ9,10ꢀ
anthraquinone (6a). Compound 5a (1 g, 0.0024 mol) was stirred
in a mixture of DMF (10 mL) and EtOH (10 mL) in the presence
of Pd/C (0.15 g). Then hydrazine hydrate (1 mL) was added
dropwise to the reaction mixture, and the mixture was refluxed for
1 h. The blueꢀviolet precipitate was filtered off hot, washed with
EtOH, and dried. The yield was 0.8 g (79%), m.p. 214—216 °C.
1H NMR, δ: 0.93 (d, 6 H, CH2CH(CH3)2, J = 6.6 Hz); 1.91
(m, 1 H, CH2CH(CH3)2); 2.32 (s, 3 H, PhMe); 2.89 (t, 2 H,
CH2CH(CH3)2, J = 6.0 Hz); 6.36 (s, 1 H, H(3)); 6.89 (t, 1 H,
NHBui, J = 6.0 Hz); 7.23 (s, 4 H, PhMe); 7.77 (t, 1 H, H(8),
J = 7.3 Hz); 7.79 (t, 1 H, H(7), J = 7.3 Hz); 8.26 (d, 2 H, H(6),
H(9), J = 7.3 Hz); 9.00 (br.s, 2 H, NH2); 13.01 (s, 1 H, NH).
Found (%): C, 75.01; H, 6.22; N, 10.46. C25H25N3O2. Calculatꢀ
ed (%): C, 75.19; H, 6.27; N, 10.53. UV (toluene), λmax/nm
(logε): 554 (4.07), 593 (4.07).
1ꢀAminoꢀ2ꢀbenzylaminoꢀ4ꢀ(4ꢀmethylphenyl)aminoꢀ9,10ꢀanꢀ
thraquinone (6b). The synthesis was carried out analogously to
that described above starting from 5b (0.25 g, 0.00058 mol). The
yield of product 6b was 0.2 g (81%), m.p. 241—243 °C. 1H NMR,
δ: 2.30 (s, 3 H, PhMe); 4.40 (d, 2 H, CH2Ph, J = 5.3 Hz); 6.28
(s, 1 H, H(3)); 6.82 (d, 2 H, H(3´), H(5´), J = 8.3 Hz); 7.07 (d, 2 H,
H(2´), H(6´), J = 8.3 Hz); 7.24 (d, 2 H, oꢀPh, J = 7.2 Hz); 7.32
(t, 1 H, pꢀPh, J = 7.2 Hz); 7.38 (t, 2 H, mꢀPh, J = 7.2 Hz); 7.57
(t, 1 H, NHBn, J = 5.3 Hz); 7.74 (t, 1 H, H(8), J = 7.3 Hz); 7.77
(t, 1 H, H(7), J = 7.3 Hz); 8.24 (d, 1 H, H(9), J = 7.3 Hz); 8.26
(d, 1 H, H(6), J = 7.3 Hz); 8.92 (s, 2 H, NH2); 12.93 (s, 1 H,
NH). Found (%): C, 77.55; H, 5.29; N, 9.6. C28H23N3O2. Calꢀ
culated (%): C, 77.59; H, 5.31; N, 9.69. UV (toluene), λmax/nm
(logε): 557 (4.11), 595 (4.11).
2ꢀBenzylaminoꢀ4ꢀ(4ꢀmethylphenyl)aminoꢀ1ꢀchloroacetylamiꢀ
noꢀ9,10ꢀanthraquinone (7b). Compound 6b (0.87 g, 0.002 mol)
was kept in anhydrous diethyl ether (30 mL) with chloroacetyl
chloride (0.34 g, 0.003 mol) for 30 min. The precipitate was
filtered off and washed with Et2O. The yield was 0.6 g (60%).
Unfortunately, attempts to isolate product 7b in the pure
form failed. Upon heating or chromatography, product 7b was
transformed into 8b. UV (toluene), λmax/nm: 535.
4ꢀBenzylꢀ3,4ꢀdihydronaphtho[2,3ꢀf]quinoxalineꢀ2,7,12ꢀ(1H)ꢀ
trione (11a). Compound 9a (0.67 g, 0.002 mol) was dissolved in
dioxane (10 mL). Then benzylamine (1 mL) was added. The
reaction mixture was refluxed for 1 h, water (5 mL) was added,
and the reaction mixture was cooled. The darkꢀcherry precipiꢀ
tate that formed was filtered off, washed with aqueous EtOH,
and recrystallized from ethyl cellosolve. The yield was 0.5 g
(71%), m.p. 201—202 °C. 1H NMR, δ: 4.24 (s, 2 H, H(3)); 4.71
(s, 2 H, CH2Ph); 7.12 (d, 1 H, H(5), J = 8.2 Hz); 7.30 (m, 1 H,
pꢀPh); 7.37 (m, 4 H, oꢀ, mꢀPh); 7.75 (d, 1 H, H(6), J = 8.2 Hz);
7.90 (m, 2 H, H(9), H(10)); 8.15 (m, 1 H, H(8)); 8.23 (m, 1 H,
H(11)); 11.89 (s, 1 H, NH). Found (%): C, 74.68; H, 4.35;
N, 7.40. C23H16N2O3. Calculated (%): C, 75.00; H, 4.35;
N, 7.60. MS (EI, 70 eV), m/z (Irel (%)): 368 [M]+ (33.03), 277
2ꢀChloromethylꢀ3ꢀisobutylꢀ5ꢀ(4ꢀmethylphenyl)aminoꢀ3Hꢀ
anthra[1,2ꢀd]imidazoleꢀ6,11ꢀdione (8a). Compound 6a (1 g,
0.0025 mol) was heated in benzene (15 mL). Then chloroacetyl
chloride (1 mL) was added dropwise. The reaction mixture was
refluxed for 3 h. The violet precipitate that formed after cooling
was filtered off, washed with benzene and Et2O, and purified by
recrystallization from toluene. The yield was 0.61 g (54%), m.p.
214—215 °C. 1H NMR (CDCl3), δ: 0.97 (d, 6 H, CH2CH(CH3)2,
J = 6.0 Hz); 2.45 (m, 1 H, CH2CH(CH3)2); 2.42 (s, 3 H, PhMe);
4.03 (d, 2 H, CH2CH(CH3)2, J = 7.2 Hz); 5.27 (s, 2 H, CH2Cl);