Synthesis of 4-alkyl-3,4-dihydronaphtho[2,3-f]quinoxaline-2,7,12-(1H)- triones and 3-alkyl-5-arylamino-2-chloromethyl-3H-anthra[1,2-d]imidazole-6,11- diones based on reactions of 1-amino-9,10-anthraquinones with chloroacetyl chloride

Article abstract of DOI:10.1007/s11172-010-0316-8

A method was developed for the synthesis of 4-alkyl-3,4-dihydronaphtho[2,3- f]quinoxaline-2,7,12-(1H)-triones starting from 1-chloroacetylamino-2-halo-9,10- anthraquinones and primary and secondary amines. The reactions of 1-amino-2-alkylamino-9,10-anthraquinones with chloroacetyl chloride afforded 3-alkyl-5-arylamino-2-chloromethyl-3H-anthra[1,2-d]-imidazole-6,11-diones. The reaction products contain chloroalkyl groups, which can undergo further modifications.

Full text of DOI:10.1007/s11172-010-0316-8

Russian Chemical Bulletin, International Edition, Vol. 59, No. 9, pp. 1803—1807, September, 2010
1803
Synthesis of 4ꢀalkylꢀ3,4ꢀdihydronaphtho[2,3ꢀf]quinoxalineꢀ
2,7,12ꢀ(1H)ꢀtriones and 3ꢀalkylꢀ5ꢀarylaminoꢀ2ꢀchloromethylꢀ
3Hꢀanthra[1,2ꢀd]imidazoleꢀ6,11ꢀdiones based on reactions
of 1ꢀaminoꢀ9,10ꢀanthraquinones with chloroacetyl chloride
L. M. Gornostaev,a M. S. Sokolova,a T. I. Lavrikova,a O. I. Kargina,a G. A. Stashina,b and S. I. Firgangb
aV. P. Astaf´ev Krasnoyarsk State Pedagogical University,
89 ul. A. Lebedevoi, 660049 Krasnoyarsk, Russian Federation.
Eꢀmail: gornostaev@kspu.ru
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Eꢀmail: galina_stashina@chemicalꢀblock.com
A method was developed for the synthesis of 4ꢀalkylꢀ3,4ꢀdihydronaphtho[2,3ꢀf]quinoxalineꢀ
2,7,12ꢀ(1H)ꢀtriones starting from 1ꢀchloroacetylaminoꢀ2ꢀhaloꢀ9,10ꢀanthraquinones and priꢀ
mary and secondary amines. The reactions of 1ꢀaminoꢀ2ꢀalkylaminoꢀ9,10ꢀanthraquinones
with chloroacetyl chloride afforded 3ꢀalkylꢀ5ꢀarylaminoꢀ2ꢀchloromethylꢀ3Hꢀanthra[1,2ꢀd]ꢀ
imidazoleꢀ6,11ꢀdiones. The reaction products contain chloroalkyl groups, which can undergo
further modifications.
Key words: anthraquinones, heterocycles, 1,2ꢀheterocyclization, imidazoles, quinoid hetꢀ
erocycles, quinoxalines.
The fact that amino derivatives of 1ꢀchloroacetylꢀ
aminoꢀ9,10ꢀanthraquinones easily undergo 1,9ꢀheteroꢀ
cyclization is attributed to the high CHꢀacidity of the
methylene group. The 1,2ꢀheterocyclization of 1ꢀchloroꢀ
acetylaminoꢀ9,10ꢀanthraquinone derivatives is almost unꢀ
It is known that 1ꢀchloroacetylaminoꢀ9,10ꢀanthraꢀ
quinone 1 is a convenient precursor for the synthesis of
1ꢀaminoꢀ3Hꢀnaphtho[1,2,3ꢀde]quinolineꢀ2,7ꢀdiones (2a,b),1,2
which hold promise for the practical application as luminoꢀ
phores3 (Scheme 1).
Scheme 1
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1755—1759, September, 2010.
1066ꢀ5285/10/5909ꢀ1803 © 2010 Springer Science+Business Media, Inc.

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Gornostaev et al.
Scheme 2
R = Bui (a), CH2Ph (b)
known. Only the reaction of 1,2ꢀdiaminoꢀ9,10ꢀanthraꢀ
quinone with chloroacetyl chloride giving 2ꢀchloromethꢀ
ylꢀ2,3,6,11ꢀtetrahydroꢀ1Hꢀanthra[1,2ꢀd]imidazoleꢀ6,11ꢀ
dione in low yield was described, and this reaction product
was used for the synthesis of potent biologically active
compounds.4
We studied the heterocyclization of 1ꢀaminoꢀ9,10ꢀanꢀ
thraquinone derivatives containing the alkylamino group
or the halogen atom in position 2.
The successive amination of 3,5ꢀdibromoꢀ6Hꢀ
[1,9ꢀcd]isoxazolꢀ6ꢀone (3) reactive toward nucleophiles5
(Scheme 2) gave amines 6a,b.
Amines 6a,b were transformed into 3ꢀalkylꢀ2ꢀchloromꢀ
ethylꢀ5ꢀ(4ꢀmethylphenyl)aminoꢀ3Hꢀanthra[1,2ꢀd]imidꢀ
azoleꢀ6,11ꢀdiones 8a,b upon heating in benzene with
chloroacetyl chloride (Scheme 3).
(4ꢀmethylphenyl)aminoꢀ9,10ꢀanthraquinone (6b) (λmax =
= 595 nm) with chloroacetyl chloride initially gives a prodꢀ
uct with an absorption maximum at 535 nm followed
by the formation of final imidazole 8b (λmax = 550 nm).
The hypsochromic shift (~60 nm) observed upon acylaꢀ
tion of the starting compound 6b indicates that it is
the primary amino group that is involved in the reaction.
The acylation of product 6b at the benzylamino group
would not disturb the 1ꢀaminoꢀ4ꢀarylaminoꢀ9,10ꢀanꢀ
thraquinone chromophoric system and would lead to
the bathochromic shift of the longꢀwavelength absorpꢀ
tion maximum.6 According to the UV spectroscopic data,
2ꢀbenzylaminoꢀ1ꢀchloroacetylaminoꢀ4ꢀ(4ꢀmethylphenꢀ
yl)aminoꢀ9,10ꢀanthraquinone (7b) was formed as the
intermediate in the course of the reaction of amine 6b
with chloroacetyl chloride in diethyl ether. We failed
to isolate this intermediate in the pure form. On heatꢀ
ing under reflux in ethyl cellosolve, compound 7b was
also transformed into imidazole 8b. Consequently, the forꢀ
Redꢀviolet products were detected by TLC in the course
of the reaction 6→8. The spectrophotometric study conꢀ
firmed that the reaction of 1ꢀaminoꢀ2ꢀbenzylaminoꢀ4ꢀ
Scheme 3
R = Bui (a), CH2Ph (b)

Synthesis of imidazoles and quinoxalines
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
1805
Scheme 4
9: X = Cl, Y = H (a); X = Br, Y = 4ꢀMe—C6H4NH
11: R = CH2Ph, Y = H (a); R = Bui, Y = H (b); R = CH2Ph, Y = 4ꢀMe—C6H4NH (c)
mation of imidazoles 8 from amines occurs according to
Scheme 3.
uct was transformed into the corresponding quinoxaline
even upon heating under reflux in ethyl cellosolve for
a short time. Apparently, the formation of compounds
13a,b occurs according to Scheme 5.
The reactions giving compounds 12 and their cyclizaꢀ
tion products, viz., 4ꢀ(ωꢀchloroalkyl)ꢀ3,4ꢀdihydronaphꢀ
tho[2,3ꢀf]quinoxalineꢀ2,7,12ꢀ(1H)ꢀtriones (13), can be
performed as the oneꢀpot synthesis, as we showed by the
transformation 9a→12b→13b.
The reaction products, 3ꢀalkylꢀ5ꢀarylaminoꢀ2ꢀchloꢀ
romethylꢀ3Hꢀanthra[1,2ꢀd]imidazoleꢀ6,11ꢀdiones (8a,b)
and 4ꢀ(ωꢀchloroalkyl)ꢀ3,4ꢀdihydronaphtho[2,3ꢀf]quinꢀ
oxalineꢀ2,7,12ꢀ(1H)ꢀtriones (13a,b), contain the chloroꢀ
alkyl group and may be of interest for the synthesis of
biologically active compounds.
We found that the reaction of 1ꢀchloroacetylaminoꢀ2ꢀ
haloꢀ9,10ꢀanthraquinones with amines (Scheme 4) gives
alternative cyclization products of amides 7, viz., 4ꢀalkylꢀ
3,4ꢀdihydronaphtho[2,3ꢀf]quinoxalineꢀ2,7,12ꢀ(1H)ꢀtriꢀ
ones (11a—c).
This pathway of the heterocyclization apparently inꢀ
volves the initial nucleophilic substitution of the exocyclic
chlorine atom in substrates 9a,b followed by the closure of
the quinoxaline ring in intermediates 10.
This reaction pathway is confirmed by the fact that we
isolated product 12a as a result of the replacement of the
exocyclic chlorine atom in the reaction of chloroacetyꢀ
laminoanthraquinone 9a with morpholine, and this prodꢀ
Scheme 5
12: X = O (a), CH2 (b)

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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);

Synthesis of imidazoles and quinoxalines
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
1807
[M – PhCH2]+ (10.71), 249 [M – PhCH2NCH2]+ (16.72),
91 [PhCH2]+ (100).
J = 5.3 Hz); 3.72 (m, 4 H, NCH2CH2O); 3.77 (t, 2 H, CH2Cl,
J = 5.3 Hz); 4.29 (s, 2 H, H(3)); 7.16 (d, 1 H, H(5), J = 8.8 Hz);
7.78 (d, 1 H, H(6), J = 8.8 Hz); 7.88 (m, 2 H, H(9), H(10));
8.12 (d, 1 H, H(8), J = 7.3 Hz); 8.17 (d, 1 H, H(11), J = 7.3 Hz);
11.85 (s, 1 H, NH). Found (%): C, 62.05; H, 4.57; N, 7.39.
C20H17ClN2O4. Calculated (%): C, 62.42; H, 4.42; N, 7.28.
MS (EI, 70 eV), m/z (Irel (%)): 384 [M]+ (20.92), 291 [M –
– CH2OCH2CH2 – Cl]+ (81.08), 264 [M – CH2OCH2CH2 –
– Cl – CO + H]+ (21.42), 263 [M – CH2OCH2CH2 – Cl –
– CO]+ (100).
4ꢀ(5ꢀChloropentyl)ꢀ3,4ꢀdihydronaphtho[2,3ꢀf]quinoxalineꢀ
2,7,12ꢀ(1H)ꢀtrione (13b). A solution of compound 9a (0.38 g,
0.001 mol) in dioxane (5 mL) containing piperidine (1 mL) was
refluxed for 1 h. After completion of the reaction, the cold mixꢀ
ture was poured onto ice. The precipitate that formed was filꢀ
tered, washed with aqueous EtOH and Et2O, and recrystallized
from ethyl cellosolve. The yield was 0.28 g (73%), m.p. 199—201 °C.
1H NMR, δ: 1.48 (m, 2 H, CH2(3´)); 1.64 (m, 2 H, CH2(2´));
1.79 (m, 2 H, CH2(4´)); 3.40 (t, 2 H, CH2(1´), J = 7.6 Hz); 3.66
(t, 2 H, CH2(5´)); 7.10 (d, 1 H, H(5), J = 8.6 Hz); 7.81 (d, 1 H,
H(6), J = 8.6 Hz); 7.88 (m, 2 H, H(9), H(10)); 8.13 (d, 1 H,
H(8), J = 7.3 Hz); 8.18 (d, 1 H, H(11), J = 7.3 Hz); 11.85 (s, 1 H,
NH). Found (%): C, 65.88; H, 4.97; N, 7.32. C21H19ClN2O3.
Calculated (%): C, 65.64; H, 4.88; N, 7.30. MS (EI, 70 eV), m/z
(Irel (%)): 382 [M]+ (36.84), 346 [M – Cl – H]+ (7.11), 291
[M – CH2CH2CH2CH2 – Cl]+ (68.97), 264 [M – CH2CH2ꢀ
CH2CH2 – Cl – CO + H]+ (22.32), 263 [M – CH2CH2CH2CH2 –
– Cl – CO]+ (100).
4ꢀIsobutylꢀ3,4ꢀdihydronaphtho[2,3ꢀf]quinoxalineꢀ2,7,12ꢀ
(1H)ꢀtrione (11b). The synthesis was carried out analogously to
that described above starting from 9a (0.65 g, 0.002 mol)
and isobutylamine (1 mL). The yield was 0.58 g (89%), m.p.
214—215 °C. 1H NMR, δ: 0.95 (d, 6 H, CH2CH(CH3)2, J = 6.6 Hz);
2.10 (m, 1 H, CH2CH(CH3)2); 3.24 (d, 2 H, CH2CH(CH3)2,
J = 7.5 Hz); 4.21 (s, 2 H, H(3)); 7.16 (d, 1 H, H(5), J = 8.7 Hz);
7.80 (d, 1 H, H(6), J = 8.7 Hz); 7.87 (t, 1 H, H(9), J = 7.3 Hz);
7.90 (t, 1 H, H(10), J = 7.3 Hz); 8.13 (d, 1 H, H(8), J = 7.3 Hz);
8.19 (d, 1 H, H(11), J = 7.3 Hz); 11.89 (s, 1 H, NH). Found (%):
C, 71.09; H, 5.41; N, 8.50. C20H18N2O3. Calculated (%):
C, 71.86; H, 5.39; N, 8.38. MS (EI, 70 eV), m/z (Irel (%)):
334 [M]+ (22.82), 291 [M – CH(Me)2]+ (100), 264 [M –
– CH(Me)2 – CO + H]+ (45.65), 263 [M – CH(Me)2 – CO]+
(80.18).
4ꢀBenzylꢀ6ꢀ(4ꢀmethylphenyl)aminoꢀ3,4ꢀdihydronaphtho[2,3ꢀf]ꢀ
quinoxalineꢀ2,7,12ꢀ(1H)ꢀtrione (11c). The synthesis was carried
out analogously to that described above starting from 9b (0.9 g,
0.002 mol) and benzylamine (1 mL) at 60—80 °C for 1 h. The
blue precipitate that formed was filtered off, washed with aqueꢀ
ous EtOH, and purified by recrystallization from butanꢀ1ꢀol.
The yield was 0.6 g (75%), m.p. 205—206 °C. 1H NMR, δ: 2.30
(s, 3 H, PhMe); 4.40 (s, 2 H, H(3)); 4.51 (s, 2 H, CH2Ph); 6.37
(s, 1 H, H(5)); 6.81 (d, 2 H, H(3´), H(5´), J = 8.3 Hz); 7.05
(d, 2 H, H(2´), H(6´), J = 8.3 Hz); 7.21 (d, 2 H, oꢀPh); 7.35
(m, 3 H, mꢀ, pꢀPh); 7.81 (t, 1 H, H(9), J = 7.3 Hz); 7.89 (t, 1 H,
H(10), J = 7.3 Hz); 8.21 (br.d, 2 H, H(8), H(11), J = 7.3 Hz);
12.12 (s, 1 H, NHCO); 12.51 (s, 1 H, NH). Found (%): C, 76.61;
H, 4.91; N, 8.68. C30H23N3O3. Calculated (%): C, 76.11;
H, 4.86; N, 8.88. MS (EI, 70 eV), m/z (Irel (%)): 473 [M]+
(77.88), 381 [M – PhCH2 – H]+ (26.03), 354 [M – PhCH2 –
– CO]+ (32.13), 91 [PhCH2]+ (100).
References
1. M. V. Kazankov, G. I. Putsa, L. L. Mukhina, Khim. Geterotsikl.
Soedin., 1972, 1651 [Chem. Heterocycl. Compd. (Engl. Transl.),
1972].
2ꢀChloroꢀ1ꢀmorpholinoacetylaminoꢀ9,10ꢀanthraquinone (12a).
Compound 9a (0.5 g, 0.0015 mol) in dioxane (6 mL) containing
morpholine (1 mL) was kept at 20—25 °C for 1 h. After compleꢀ
tion of the reaction, the mixture was poured onto ice and filꢀ
tered. The precipitate that formed was washed with water and
aqueous EtOH and purified by recrystallization from toluene.
The yield was 0.35 g (61%), m.p. 161—163 °C. 1H NMR
(CDCl3), δ: 2.77 (t, 4 H, NCH2, J = 3.9 Hz); 3.28 (s, 2 H,
COCH2N); 3.96 (t, 4 H, OCH2, J = 4.6 Hz); 7.80 (m, 2 H, H(7),
H(8)); 7.85 (d, 1 H, H(3), J = 8.4 Hz); 8.20 (m, 2 H, H(4),
H(6)); 8.26 (m, 1 H, H(9)); 10.75 (s, 1 H, NH). Found (%):
C, 62.42; H, 4.42; N, 7.33. C20H17ClN2O4. Calculated (%):
C, 62.42; H, 4.42; N, 7.28. MS (EI, 70 eV), m/z (Irel (%)): 384 [M]+
(0.50), 356 [M – CO]+ (0.50), 257 [M – C4H8NOCH2CO +
+ H]+ (6.91), 164 [M – C4H8NOCH2 – 3 CO – Cl – H]+
(21.02), 100 [C4H8NOCH2]+ (100).
2. M. S. Sokolova, T. I. Lavrikova, L. M. Gornostaev, Zh. Org.
Khim., 2007, 43, 627 [Russ. J. Org. Chem. (Engl. Transl.),
2007, 43].
3. B. M. Krasovitskii, D. G. Pereyaslova, Yu. M. Vinetskaya,
M. V. Kazankov, Zh. Prikl. Khim, 1969, 42, 956 [J. Appl.
Chem. USSR (Engl. Transl.), 1969, 42].
4. P. Chang, C. Chen, J. Heterocycl. Chem., 1996, 33, 367.
5. O. N. Yunosova, R. V. Mitrokhin, T. I. Lavrikova, L. M.
Gornostaev, Izv. Vuzov, Ser. Khim. i Khimich. Tekh. [Proceedꢀ
ings of Institutes: Chemistry and Chemical Technology], 2004,
47, No. 8, 124 (in Russian).
6. V. Ya. Fain, Elektronnye spektry pogloshcheniya i stroenie
9,10ꢀantrakhinonov 2. Dizameshchennye 9,10ꢀantrakhinony
[Electronic Absorption Spectra and Structures of 9,10ꢀAnthraꢀ
quinones. 2. Disubstituted 9,10ꢀAnthraquinones], Kompania
Spuntnik+, Moscow, 2003, p. 288 (in Russian).
7. T. Tokumitsu, M. Okamoto, T. Hayashi, J. Chem. Soc., 1964,
67, 201.
4ꢀ(5ꢀChloroꢀ3ꢀoxapentyl)ꢀ3,4ꢀdihydronaphtho[2,3ꢀf]quinꢀ
oxalineꢀ2,7,12ꢀ(1H)ꢀtrione (13a). A solution of compound 12a
(0.38 g, 0.001 mmol) in ethyl cellosolve was refluxed for 5 min.
The resulting darkꢀcherry precipitate was filtered off, washed
with aqueous EtOH and Et2O, and recrystallized from butanꢀ1ꢀol.
Received December 9, 2009;
in revised form March 16, 2010
1
The yield was 0.26 g (68%). H NMR, δ: 3.64 (t, 2 H, OCH2,