Synthesis of S,S-dialkyl-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl) sulfoximides and specificities of their base-catalyzed intramolecular heterocyclizations into naphtho[1,2,3-cd]-indol-6(2H)-ones

Article abstract of DOI:10.1134/S1070428013010132

Heating of 6H-anthra[1,9-cd][1,2]oxazol-6-ones with dialkyl sulfoxides in sulfolane gave S,S-dialkyl-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)sulfoximides which underwent cyclization to naphtho-[1,2,3-cd]indol-6(2H)-one derivatives on heating in boiling tetrahydrofuran in the presence of sodium methoxide. p-Toluenesulfinic acid was isolated as by-product in the cyclization of S-methyl-S-(4-methylphenyl)-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl) sulfoximide. The heterocyclizations of S,S-dipropyl- and S,S-dibutyl-N-(9,10- dioxo-9,10-dihydroanthracen-1-yl)sulfoximides to 1-ethyl- and 1-propylnaphtho[1,2,3-cd]-indol-6(2H)-ones were accompanied by formation of the corresponding 1-[1-hydroxyethyl(propyl)]naphtho-[1,2,3-cd]indol-6(2H)-ones.

Full text of DOI:10.1134/S1070428013010132

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 1, pp. 70–77. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © O.I. Kargina, L.M. Gornostaev, A.A. Nefedov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 1,
pp. 79–85.
Synthesis of S,S-Dialkyl-N-(9,10-dioxo-9,10-dihydroanthracen-
1-yl)sulfoximides and Specificities of Their Base-Catalyzed
Intramolecular Heterocyclizations into Naphtho[1,2,3-cd]-
indol-6(2H)-ones
O. I. Karginaa, L. M. Gornostaeva, and A. A. Nefedovb
a Astaf’ev Krasnoyarsk State Pedagogical University, ul. A. Lebedevoi 89, Krasnoyarsk, 660049 Russia
e-mail: gornostaev@kspu.ru
b Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
Received July 10, 2012
Abstract—Heating of 6H-anthra[1,9-cd][1,2]oxazol-6-ones with dialkyl sulfoxides in sulfolane gave S,S-di-
alkyl-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)sulfoximides which underwent cyclization to naphtho-
[1,2,3-cd]indol-6(2H)-one derivatives on heating in boiling tetrahydrofuran in the presence of sodium
methoxide. p-Toluenesulfinic acid was isolated as by-product in the cyclization of S-methyl-S-(4-methyl-
phenyl)-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)sulfoximide. The heterocyclizations of S,S-dipropyl- and
S,S-dibutyl-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)sulfoximides to 1-ethyl- and 1-propylnaphtho[1,2,3-cd]-
indol-6(2H)-ones were accompanied by formation of the corresponding 1-[1-hydroxyethyl(propyl)]naphtho-
[1,2,3-cd]indol-6(2H)-ones.
DOI: 10.1134/S1070428013010132
We previously [1] described the cyclization of
S,S-dimethyl-N-(9,10-dioxo-9,10-dihydroanthracen-1-
yl)sulfoximide (IIa) and S-methyl-S-phenyl sulfox-
imides IIi and IIj to naphtho[1,2,3-cd]indol-6(2H)-
ones (pyrrolanthrones) IVa and IVb. Taking into
account prospects in using pyrrolanthrones as lumino-
phores and sensitizers [2], in the present work we
synthesized various S,S-dialkyl-N-(9,10-dioxo-9,10-di-
hydroanthracen-1-yl)sulfoximides II and examined
their heterocyclization into naphtho[1,2,3-cd]indol-
6(2H)-ones IV.
We found that reactions of anthra[1,9-cd][1,2]-
oxazol-6-ones Ia–Ig with various dialkyl sulfoxides,
apart from targeted S,S-dialkyl-N-(9,10-dioxo-9,10-
dihydroanthracen-1-yl)sulfoximides IIa–IIn, gave the
corresponding 1-aminoanthraquinones IIIa–IIIg as by-
Scheme 1.
O
S
R1
R2
R3
O
N
O
NH2
O
N
R3
R3
O
S
+
+
R1
R2
O
R4
O
R4
O
R4
Ia–Ig
IIa–IIn
IIIa–IIIg
I, III, R3 = H, R4 = H (a), Cl (b), MeO (c), 4-MeC6H4O (d), 4-t-BuC6H4O (e), O2N (f); R3 = Cl, R4 = H (g); II, R1 = R2 = Me, R3 = H,
R4 = H (a), Cl (b), MeO (c), 4-MeC6H4O (d), 4-t-BuC6H4O (e), O2N (f); R1 = R2 = Me, R3 = Cl, R4 = H (g); R1 = Me, R2 =
4-MeC6H4, R3 = R4 = H (h); R1 = Me, R2 = Ph, R3 = H, R4 = H (i), Cl (j); R1 = R2 = Et, R3 = H, R4 = H (k), Cl (l); R1 = R2 = Pr, R3 =
R4 = H (m); R1 = R2 = Bu, R3 = R4 = H (n).
70

SYNTHESIS OF S,S-DIALKYL-N-(9,10-DIOXO-9,10-DIHYDROANTHRACEN-1-YL)...
71
Scheme 2.
O
Me
S
O
O
N
Me
NH
IIb
+
O
N
O
IIo
O
S
Me
Me
O
O
N
N
NH
N
MeONa, THF
IIf
+
N
H
O
IIp
IVj
Scheme 3.
R1
NH
R2
MeONa, THF
IIa–IIe, IIg, IIh, IIk, IIl, IIo
O
IVa–IVi
R3
IV, R1 = R2 = H, R3 = H (a), Cl (b), MeO (c), 4-MeC6H4O (d), 4-t-BuC6H4O (e), morpholin-4-yl (f); R1 = R3 = H, R2 = Cl (g);
R1 = Me, R2 = H, R3 = H (h), Cl (i).
products (Scheme 1). When the reaction was carried
out in sulfolane and the reaction mixture was then
treated with nitrosylsulfuric acid we succeeded in
separating compounds III as water-soluble diazotiza-
tion products.
The chlorine atom and nitro group in sulfoximides
IIb and IIf, respectively, are highly reactive toward
nucleophiles. By reacting these compounds with mor-
pholine and pyrrolidine we obtained sulfoximides IIo
and IIp, respectively; in the latter case, nucleophilic
replacement of the nitro group in IIf was accompanied
by cyclization with formation of compound IVj
(Scheme 2). Heterocyclizations of sulfoximides IIa–
IIe, IIg, IIh, IIk, IIl, and IIo were carried out in THF
in the presence of sodium methoxide (Scheme 3).
cyclization follows a path shown in Scheme 4. Facile
elimination of p-toluenesulfinic acid fragment from
intermediate A is likely to be favored by electron-
acceptor effect of the carbonyl group on the hetero-
cyclic fragment. Thiazine A was not detected, presum-
ably due to its high reactivity. Known [3, 4] fused and
monocyclic thiazines are stable under analogous
conditions.
The cyclization of compounds IIm and IIn in THF
in the presence of sodium methoxide resulted in the
formation of mixtures of pyrrolanthrones VIa and VIb
with 1-(1-hydroxyethyl)- and 1-(1-hydroxypropyl)-
naphtho[1,2,3-cd]indol-6(2H)-ones VIIa and VIIb
(Scheme 5). The ratio VI–VII was 3:1 regardless of
whether the reaction was carried out under argon or on
exposure to air. In addition, by special experiments we
found that prolonged heating of compounds VIa and
VIb under the cyclization conditions (MeONa, THF)
In the cyclization of IIh we isolated p-toluenesul-
finic acid sodium salt V together with heterocycliza-
tion product IVa. The formation of V suggests that the
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KARGINA et al.
72
Scheme 4.
Me
Me
Me
OH
S
OH
S
O
O
O
N
S
··
N
N
MeONa
–H2O
IIh
O
O
O
A
O
S
NH
ONa
+
Me
O
IVa
V
Scheme 5.
OH
R
O
R
R
S
R
N
NH
NH
MeONa, THF
IIm, IIn
+
O
O
O
B
VIa, VIb
VIIa, VIIb
R = Me (a), Et (b).
was not accompanied by their hydroxylation at the
α-methylene group. Taking into account that the trans-
formation of IIm and IIn into VI and VII is fairly fast
(20–30 min) and that the presence of oxygen does not
affect the product ratio, compounds VII are likely to
be formed via intramolecular oxidation of intermediate
B. In this case, the cyclization of IIm and IIn should
produce the corresponding alkanesulfenic acid as by-
product. In fact, dibutyl disulfide was detected in the
reaction mixture by GC–MS in addition to compounds
VIb and VIIb in the cyclization of S,S-dibutyl-
sulfoximide IIn (see Experimental). Obviously, dibutyl
disulfide results from thermal disproportionation of
butanesulfenic acid [5].
solvent and tetramethylsilane as internal reference. The
mass spectra were obtained on a Finnigan MAT 8200
instrument, and the high-resolution mass spectra were
recorded on a Thermo Scientific DFC mass spectrom-
eter with direct sample admission into the ion source
(70 eV, ion source temperature 270°C). Gas chromato-
graphic–mass spectrometric analysis was performed on
an HP G1800A instrument (electron impact, 70 eV;
injector temperature 300°C, ion source temperature
280°C; HP5-MS column, 30000×0.25 mm, film thick-
ness 0.25 μm; oven temperature programming from 50
to 300°C at a rate of 10 deg/min; carrier gas helium,
flow rate 1 ml/min; sample volume 1 μl, 1–3% solu-
tion). The GC–MS data were processed using Chem-
station software and Wiley W8N08.L database. The
progress of reactions and the purity of products were
monitored by TLC on Silufol plates (eluent acetone–
toluene, 1:4). The melting points were determined on
a Boetius hot stage.
EXPERIMENTAL
1
The H NMR spectra were recorded on a Bruker
DRX spectrometer at 500 MHz using DMSO-d6 as
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SYNTHESIS OF S,S-DIALKYL-N-(9,10-DIOXO-9,10-DIHYDROANTHRACEN-1-YL)...
73
Compounds IIb, IIc, and IIf were synthesized
according to the procedure described in [6], and their
physical constants were consistent with published data.
SMe), 7.85 d (1H, 3-H, J = 8.0 Hz), 7.93 d (1H, 4-H,
J = 8.0 Hz), 7.87 br.t (1H, 6-H or 7-H, J = 7.0 Hz),
7.91 br.t (1H, 7-H or 6-H, J = 7.0 Hz), 8.12 br.d (2H,
5-H, 8-H, J = 7.0 Hz). Mass spectrum, m/z (Irel, %):
335 (16) [M + 2]+, 334 (7) [M + 1]+, 333 (44) [M]+,
255 (100), 164 (76), 63 (32). Found, %: C 57.74;
H 3.43; N 4.38; S 9.65. C16H12ClNO3S. Calculated, %:
C 57.57; H 3.59; N 4.19; S 9.59.
S,S-Dimethyl-N-[4-(4-methylphenoxy)-9,10-di-
oxo-9,10-dihydroanthracen-1-yl]sulfoximide (IId).
A mixture of 1.65 g (5.05 mmol) of compound Id and
15 ml of DMSO was heated for 1 h at 160°C. The
mixture was cooled to 40°C, and 3 ml of water was
added dropwise. A solid separated, the mixture was
heated until it became homogeneous and cooled, and
the yellow crystals were filtered off, washed with
aqueous alcohol and alcohol, and recrystallized from
80% aqueous alcohol. Yield 1.60 g (78%), mp 168°C.
1H NMR spectrum, δ, ppm: 2.35 s (3H, MeC6H4),
3.29 s (6H, SMe), 6.84 d (2H, 2′-H, 6′-H, J = 8.0 Hz),
7.14 d (2H, 3′-H, 5′-H, J = 8.0 Hz), 7.23 d (1H, 3-H,
J = 8.5 Hz), 7.52 d (1H, 2-H, J = 8.5 Hz), 7.79 br.t
(1H, 6-H or 7-H, J = 8.0 Hz), 7.83 br.t (1H, 7-H or
6-H, J = 8.0 Hz), 7.96 br.d (1H, 5-H or 8-H, J =
8.0 Hz), 8.04 br.d (1H, 8-H or 5-H, J = 8.0 Hz). Mass
spectrum, m/z (Irel, %): 405 (13) [M]+, 327 (34), 164
(22), 91 (86), 65 (100). Found, %: C 67.81; H 4.69;
N 3.72; S 7.57. C23H19NO4S. Calculated, %: C 68.15;
H 4.69; N 3.46; S 7.90.
N-(9,10-Dioxo-9,10-dihydroanthracen-1-yl)-
S-methyl-S-(4-methylphenyl)sulfoximide (IIh).
A mixture of 2.21 g (10 mmol) of compound Ia and
5.00 g (32.45 mmol) of methyl 4-methylphenyl sulf-
oxide in 15 ml of sulfolane was heated for 1.5 h at
130°C. The mixture was cooled to 18–20°C, 10 ml of
acetic acid was added, and nitrosylsulfuric acid (0.5 g
of NaNO2 and 6 ml of H2SO4) was then added. The
mixture was poured onto 250 g of ice, and the yellow
precipitate was filtered off, washed with water and
aqueous alcohol, and recrystallized from alcohol. Yield
1
2.50 g (66%), mp 170–171°C. H NMR spectrum, δ,
ppm: 2.38 s (3H, MeC6H4), 3.41 s (3H, SMe), 7.46 d
(2H, 3′-H, 5′-H, J = 8.0 Hz), 7.51 br.d (1H, 2-H, J =
7.5 Hz), 7.57 t (1H, 3-H, J = 7.5 Hz), 7.75 br.d (1H,
4-H, J = 7.5 Hz), 7.86 br.t (1H, 6-H or 7-H, J =
7.5 Hz), 7.92 br.t (1H, 7-H or 6-H, J = 7.5 Hz), 8.06 d
(2H, 2′-H, 6′-H, J = 8.0 Hz), 8.15 br.d (1H, 5-H or 8-H,
J = 7.5 Hz), 8.20 br.d (1H, 8-H or 5-H, J = 7.5 Hz).
Mass spectrum, m/z (Irel, %): 375 (11) [M]+, 221 (28),
164 (23), 139 (100), 91 (47). Found, %: C 70.01;
H 4.54; N 3.73; S 8.06. C22H17NO3S. Calculated, %:
C 70.40; H 4.53; N 3.73; S 8.53.
N-[4-(4-tert-Butylphenoxy)-9,10-dioxo-9,10-
dihydroanthracen-1-yl]-S,S-dimethylsulfoximide
(IIe). A mixture of 1.00 g (2.71 mmol) of compound Ie
and 15 ml of DMSO was heated for 2.5 h at 150°C.
The mixture was cooled to 18–20°C and poured onto
150 g of ice. The yellow precipitate was filtered off,
washed with water and aqueous alcohol, and recrystal-
lized from heptane. Yield 1.00 g (83%), mp 162°C.
1H NMR spectrum, δ, ppm: 1.25 s (9H, t-Bu), 3.23 s
(6H, SMe), 6.85 d (2H, 2′-H, 6′-H, J = 8.0 Hz), 7.25 d
(1H, 3-H, J = 8.0 Hz), 7.34 d (2H, 3′-H, 5′-H, J =
8.0 Hz), 7.53 d (1H, 2-H, J = 8.0 Hz), 7.79 br.t (1H,
6-H or 7-H, J 8.0 Hz), 7.82 br.t (1H, 7-H or 6-H, J =
8.0 Hz), 7.96 br.d (1H, 5-H or 8-H, J = 8.0 Hz),
8.04 br.d (1H, 8-H or 5-H, J = 8.0 Hz). Mass spectrum,
m/z (Irel, %): 447 (29) [M]+, 354 (100), 164 (25), 115
(48), 91 (69). Found, %: C 69.89; H 5.52; N 3.33;
S 7.50. C26H25NO4S. Calculated, %: C 69.79; H 5.59;
N 3.13; S 7.16.
Compounds IIk–IIn were synthesized in a simi-
lar way.
N-(9,10-Dioxo-9,10-dihydroanthracen-1-yl)-
S,S-diethylsulfoximide (IIk) was synthesized from
2.21 g (10 mmol) of compound Ia and 4.80 g
(45.28 mmol) of diethyl sulfoxide in 15 ml of sul-
folane. The mixture was heated for 3 h at 130°C, and
the product was recrystallized from heptane. Yield
2.20 g (67%), yellow crystals, mp 119–121°C. 1H NMR
spectrum, δ, ppm: 1.36 t (6H, Me, J = 7.0 Hz), 3.34–
3.46 m (4H, CH2), 7.60–7.63 m (2H, 2-H, 4-H), 7.76 t
(1H, 3-H, J = 4.5 Hz), 7.83 t (1H, 6-H or 7-H, J =
7.0 Hz), 7.88 t (1H, 7-H or 6-H, J = 7.0 Hz), 8.11–
8.15 m (2H, 5-H, 8-H). Mass spectrum, m/z (Irel, %):
327 (21) [M]+, 270 (100), 164 (21), 78 (34). Found, %:
C 66.09; H 5.07; N 4.16; S 9.72. C18H17NO3S. Cal-
culated, %: C 66.05; H 5.19; N 4.28; S 9.76.
N-(2-Chloro-9,10-dioxo-9,10-dihydroanthracen-
1-yl)-S,S-dimethylsulfoximide (IIg) was synthesized
in a similar way from 2.55 g (10 mmol) of Ig and
40 ml of DMSO. The mixture was heated for 2 h at
140–145°C, and the product was recrystallized from
toluene. Yield 2.50 g (84%), yellow crystals,
N-(4-Chloro-9,10-dioxo-9,10-dihydroanthracen-
1-yl)-S,S-diethylsulfoximide (IIl) was synthesized
1
mp 232°C. H NMR spectrum, δ, ppm: 3.32 s (6H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013

KARGINA et al.
74
from 1.30 g (5.08 mmol) of compound Ib and 2.40 g
(22.64 mmol) of diethyl sulfoxide in 10 ml of sul-
folane. The mixture was stirred for 2 h at 130°C, and
the product was recrystallized from heptane. Yield
1.30 g (70%), yellow crystals, mp 128–129°C.
1H NMR spectrum, δ, ppm: 1.35 t (6H, Me, J =
7.0 Hz), 3.36–3.46 m (4H, CH2), 7.56 d (1H, 2-H, J =
9.0 Hz), 7.62 d (1H, 3-H, J = 9.0 Hz), 7.80–7.87 m
(2H, 6-H, 7-H), 8.03 t (2H, 5-H, 8-H, J = 8.0 Hz).
Mass spectrum, m/z (Irel, %): 363 (4) [M + 2]+, 362 (1)
[M + 1]+, 361 (17) [M]+, 304 (100), 255 (36), 164 (43),
78 (34). Found, %: C 59.82; H 4.27; N 4.02; S 8.78.
C18H16ClNO3S. Calculated, %: C 59.75; H 4.43;
N 3.87; S 8.85.
A mixture of 1.00 g (2.99 mmol) of compound IIb and
15 ml (172.24 mmol) of morpholine was heated for 3 h
under reflux. After cooling, the dark red precipitate
was filtered off, washed with water, and recrystallized
from alcohol. Yield 0.75 g (68%), mp 134°C. 1H NMR
spectrum, δ, ppm: 3.09 br.t (4H, CH2N, J = 4.5 Hz),
3.32 s (6H, Me), 3.83 br.t (4H, CH2O, J = 4.5 Hz),
7.41 d (1H, 3-H, J = 9.0 Hz), 7.45 d (1H, 2-H, J =
9.0 Hz), 7.77–7.80 m (2H, 6-H, 7-H), 7.97–7.99 m
(1H, 5-H or 8-H), 8.06–8.08 m (1H, 8-H or 5-H). Mass
spectrum, m/z (Irel, %): 384 (7) [M]+, 263 (28), 221
(42), 164 (54), 63 (100). Found, %: C 62.22; H 5.52;
N 7.13; S 8.24. C20H20N2O4S. Calculated, %: C 62.50;
H 5.21; N 7.29; S 8.33.
N-(9,10-Dioxo-9,10-dihydroanthracen-1-yl)-
S,S-dipropylsulfoximide (IIm) was synthesized from
2.21 g (10 mmol) of compound Ia and 4.00 g
(29.85 mmol) of dipropyl sulfoxide in 20 ml of sul-
folane. The mixture was heated for 3.5 h at 130°C, and
the product was recrystallized from heptane. Yield
1.97 g (68%), yellow crystals, mp 102–103°C.
1H NMR spectrum, δ, ppm: 0.90 t (6H, Me, J =
7.0 Hz), 1.78–1.93 m (4H, CH2), 3.30–3.44 m (4H,
CH2), 7.72–7.76 m (2H, 2-H, 4-H), 7.73 t (1H, 3-H,
J = 4.0 Hz), 7.82 t (1H, 6-H or 7-H, J = 7.0 Hz), 7.88 t
(1H, 7-H or 6-H, J = 7.0 Hz), 8.10 d (1H, 5-H or 8-H,
J = 7.0 Hz), 8.12 d (1H, 8-H or 5-H, J = 7.0 Hz). Mass
spectrum, m/z (Irel, %): 355 (4) [M]+, 270 (81), 164
(16), 43 (100). Found, %: C 67.65; H 5.95; N 3.96;
S 8.87. C20H21NO3S. Calculated, %: C 67.60; H 5.91;
N 3.94; S 9.01.
Transformation of sulfoximide IIh in THF in the
presence of sodium methoxide. A 10% solution of
sodium methoxide, 5 ml, was added to 1.88 g
(5.01 mmol) of compound IIh in 30 ml of THF, and
the mixture was heated for 20 min under reflux. The
mixture was cooled to 18–20°C, 30 ml of 2% aqueous
HCl was added dropwise until pH 7, and the precip-
itate of naphtho[1,2,3-cd]indol-6(2H)-one (IVa) was
filtered off and washed with water. Yield 1.00 g (91%),
yellow crystals, mp 251–252°C. The filtrate was evap-
orated under reduced pressure almost to dryness, the
residue was treated with 50 ml of a 9% solution of
sodium hydroxide at 60–70°C, the mixture was filtered
while hot, and the filtrate was concentrated to a vol-
ume of 10 ml under reduced pressure. After cooling,
the colorless crystals of sodium p-toluenesulfinate (V)
were filtered off. Yield 0.80 g (76%), mp >300°C.
1H NMR spectrum, δ, ppm: 2.30 s (3H, Me), 7.10 d
(2H, 3-H, 5-H, J = 8.0 Hz), 7.35 d (2H, 2-H, 6-H,
J = 8.0 Hz).
S,S-Dibutyl-N-(9,10-dioxo-9,10-dihydroanthra-
cen-1-yl)sulfoximide (IIn) was synthesized from
2.21 g (10 mmol) of compound Ib and 4.00 g
(24.69 mmol) of dibutyl sulfoxide in 20 ml of sul-
folane. The mixture was heated for 3 h at 140°C, and
the product was recrystallized from heptane. Yield
Transformation of sulfoximide IIn in THF in the
presence of sodium methoxide. A 10% solution of
sodium methoxide, 1 ml, was added to 0.10 g
(0.26 mmol) of compound IIn in 7 ml of THF, and the
mixture was heated for 30 min under reflux. The
mixture was then cooled to 18–20°C and evaporated to
dryness under reduced pressure. The dark red residue
was analyzed by high-resolution mass spectrometry to
identify compounds VIb and VIIb and dibutyl disul-
fide; the mass spectrum of the latter was identical to
the reference spectrum. Mass spectrum, m/z (Irel, %):
178 (48) [M]+, 122 (40), 57 (100).
1
2.60 g (68%), yellow crystals, mp 78–79°C. H NMR
spectrum, δ, ppm: 0.88 t (6H, Me, J = 7.0 Hz), 1.37–
1.44 m (4H, CH2), 1.74–1.88 m (4H, CH2), 3.35–
3.44 m (4H, CH2), 7.60–7.63 m (2H, 2-H, 4-H), 7.75 t
(1H, 3-H, J = 5.0 Hz), 7.83 t (1H, 6-H or 7-H, J =
7.0 Hz), 7.88 t (1H, 7-H or 6-H, J = 7.0 Hz), 8.12 d
(2H, 5-H, 8-H, J = 8.0 Hz). Mass spectrum, m/z
(Irel, %): 383 (2) [M]+, 270 (100), 164 (7), 41 (51).
Found, %: C 68.73; H 6.53; N 3.92; S 8.24.
C22H25NO3S. Calculated, %: C 68.93; H 6.53; N 3.65;
S 8.35.
5-Chloronaphtho[1,2,3-cd]indol-6(2H)-one
(IVb). A 10% solution of sodium methoxide, 5 ml, was
added to 0.50 g (1.49 mmol) of compound IIb in 10 ml
of THF, and the mixture was heated for 10 min under
S,S-Dimethyl-N-[4-(morpholin-4-yl)-9,10-dioxo-
9,10-dihydroanthracen-1-yl]sulfoximide (IIo).
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SYNTHESIS OF S,S-DIALKYL-N-(9,10-DIOXO-9,10-DIHYDROANTHRACEN-1-YL)...
75
reflux. The mixture was then cooled to 40°C, 2 ml of
acetic acid was added, and 5 ml of water was added
dropwise. The yellow crystals were filtered off,
washed with water, and recrystallized from alcohol.
(1.12 mmol) of compound IIe using 2 ml of 10% so-
dium methoxide and 10 ml of THF. The mixture was
heated for 1 h under reflux, and the product was
recrystallized from toluene. Yield 0.35 g (85%), yellow
1
1
Yield 0.36 g (94%), mp 312–314°C. H NMR spec-
crystals, mp >320°C. H NMR spectrum, δ, ppm:
trum, δ, ppm: 7.44 t (1H, 8-H or 9-H, J = 7.5 Hz),
7.48 d (1H, 3-H, J = 7.5 Hz), 7.72 t (1H, 9-H or 8-H,
J = 7.0 Hz), 7.85 d (1H, 4-H, J = 8.0 Hz), 8.13 d (1H,
10-H, J = 8.0 Hz), 8.30 d (1H, 7-H, J = 8.0 Hz), 8.52 d
(1H, 1-H, J = 3.0 Hz), 12.20 br.s (1H, NH). Mass
spectrum, m/z (Irel, %): 255 (31) [M + 2]+, 254 (16)
[M + 1]+, 253 (100) [M]+, 163 (44), 81 (18). Found, %:
C 71.04; H 3.21; N 5.42. C15H8ClNO. Calculated, %:
C 71.01; H 3.16; N 5.52.
1.40 s (9H, t-Bu), 6.85 d (2H, 2′-H, 6′-H, J = 8.0 Hz),
7.02 d (1H, 4-H, J = 8.0 Hz), 7.33 d (2H, 3′-H, 5′-H,
J = 8.0 Hz), 7.39 t (1H, 8-H or 9-H, J = 8.0 Hz), 7.68 t
(1H, 9-H or 8-H, J = 8.0 Hz), 7.86 d (1H, 3-H, J =
8.0 Hz), 8.11 d (1H, 10-H, J = 8.0 Hz), 8.21 d (1H,
7-H, J = 8.0 Hz), 8.40 s (1H, 1-H), 12.01 s (1H, NH).
Mass spectrum, m/z (Irel, %): 367 (32) [M]+, 352 (100),
163 (15). Found, %: C 81.84; H 5.82; N 3.85.
C25H21NO2. Calculated, %: C 81.74; H 5.72; N 3.81.
Compounds IVc–IVi were synthesized in a simi-
lar way.
5-(Morpholin-4-yl)naphtho[1,2,3-cd]indol-6(2H)-
one (IVf) was synthesized from 0.57 g (1.48 mmol) of
compound IIo using 2 ml of 10% sodium methoxide
and 10 ml of THF. The mixture was heated for 1 h
under reflux, and the product was recrystallized from
alcohol. Yield 0.39 g (86%), yellow crystals,
5-Methoxynaphtho[1,2,3-cd]indol-6(2H)-one
(IVc) was synthesized from 0.329 g (1 mmol) of com-
pound IIc using 5 ml of 10% sodium methoxide and
15 ml of THF. The mixture was heated for 1.5 h under
reflux, and the product was recrystallized from 80%
aqueous alcohol. Yield 0.21 g (84%), yellow crystals,
1
mp 155°C. H NMR spectrum, δ, ppm: 3.18 br.t (4H,
CH2N, J = 4.5 Hz), 3.89 br.t (4H, CH2O, J = 4.5 Hz),
7.09 d (1H, 4-H, J = 8.0 Hz), 7.38 t (1H, 8-H or 9-H,
J = 8.0 Hz), 7.65 t (1H, 9-H or 8-H, J = 8.0 Hz), 7.81 d
(1H, 3-H, J = 8.0 Hz), 8.10 d (1H, 10-H, J = 8.0 Hz),
8.33 d (1H, 7-H, J = 8.0 Hz), 8.39 d (1H, 1-H, J =
2.5 Hz), 11.90 br.s (1H, NH). Mass spectrum, m/z
(Irel, %): 304 (12) [M]+, 219 (70), 164 (49), 44 (100).
Found, %: C 74.68; H 5.46; N 8.49. C19H16N2O2. Cal-
culated, %: C 75.00; H 5.26; N 9.21.
1
mp 281–282°C. H NMR spectrum, δ, ppm: 3.95 s
(3H, OMe), 7.14 d (1H, 4-H, J = 8.0 Hz), 7.38 t (1H,
8-H or 9-H, J = 8.0 Hz), 7.65 t (1H, 9-H or 8-H, J =
8.0 Hz), 7.84 d (1H, 3-H, J = 8.0 Hz), 8.09 d (1H,
10-H, J = 8.0 Hz), 8.29 d (1H, 7-H, J = 8.0 Hz), 8.40 d
(1H, 1-H, J = 2.5 Hz), 11.90 br.s (1H, NH). Mass
spectrum, m/z (Irel, %): 249 (73) [M]+, 220 (100), 164
(51), 96 (35). Found, %: C 76.92; H 4.26; N 5.69.
C16H11NO2. Calculated, %: C 77.12; H 4.42; N 5.62.
3-Chloronaphtho[1,2,3-cd]indol-6(2H)-one (IVg)
was synthesized from 0.50 g (1.49 mmol) of com-
pound IIg using 2 ml of 10% sodium methoxide and
10 ml of THF. The mixture was heated for 20 min
under reflux, and the product was recrystallized from
80% aqueous acetic acid. Yield 0.33 g (86%), yellow
5-(4-Methylphenoxy)naphtho[1,2,3-cd]indol-
6(2H)-one (IVd) was synthesized from 0.405 g
(1 mmol) of compound IId using 3 ml of 10% sodium
methoxide and 7 ml of THF. The mixture was heated
for 1.5 h under reflux, and the product was recrystal-
lized from toluene. Yield 0.32 g (98%), yellow crys-
tals, mp 283–284°C. 1H NMR spectrum, δ, ppm: 2.25 s
(3H, Me), 6.83 d (2H, 2′-H, 6′-H, J = 8.0 Hz), 6.99 d
(1H, 4-H, J = 8.0 Hz), 7.13 d (2H, 3′-H, 5′-H, J =
8.0 Hz), 7.38 t (1H, 8-H or 9-H, J = 7.5 Hz), 7.68 t
(1H, 9-H or 8-H, J = 7.5 Hz), 7.86 d (1H, 3-H, J =
8.0 Hz), 8.12 d (1H, 10-H, J = 7.5 Hz), 8.21 d (1H,
7-H, J = 7.5 Hz), 8.48 d (1H, 1-H, J = 2.5 Hz),
12.01 br.s (1H, NH). Mass spectrum, m/z (Irel, %): 325
(91) [M]+, 308 (80), 163 (68), 65 (100). Found, %:
C 80.82; H 4.64; N 4.50. C22H15NO2. Calculated, %:
C 81.23; H 4.62; N 4.31.
1
crystals, mp 317–318°C. H NMR spectrum, δ, ppm:
7.45 t (1H, 8-H or 9-H, J = 8.0 Hz), 7.56 d (1H, 4-H,
J = 8.0 Hz), 7.74 t (1H, 9-H or 8-H, J = 8.0 Hz), 7.93 d
(1H, 5-H, J = 8.0 Hz), 8.16 d (1H, 10-H, J = 8.0 Hz),
8.29 d (1H, 7-H, J = 8.0 Hz), 8.52 d (1H, 1-H, J =
2.5 Hz), 12.50 br.s (1H, NH). Mass spectrum, m/z
(Irel, %): 255 (43) [M + 2]+, 254 (23) [M + 1]+, 253
(100) [M]+, 163 (34), 95 (24). Found, %: C 70.73;
H 3.22; N 5.32. C15H8ClNO. Calculated, %: C 71.01;
H 3.16; N 5.52.
1-Methylnaphtho[1,2,3-cd]indol-6(2H)-one (IVh)
was synthesized from 0.82 g (2.50 mmol) of com-
pound IIk using 2 ml of 10% sodium methoxide and
8 ml of THF. The mixture was heated for 30 min under
5-(4-tert-Butylphenoxy)naphtho[1,2,3-cd]indol-
6(2H)-one (IVe) was synthesized from 0.50 g
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KARGINA et al.
76
reflux, and the product was recrystallized from 80%
aqueous alcohol. Yield 0.22 g (84%), yellow crystals,
mp 296–298°C. H NMR spectrum, δ, ppm: 2.90 s
compound IIm, 15 ml of THF, and 5 ml of 10% so-
dium methoxide was heated for 20 min under reflux.
The mixture was cooled to 18–20°C and poured onto
100 g of ice, and the precipitate was filtered off,
washed with water, dried, and subjected to column
chromatography on silica gel using benzene as eluent.
1
(3H, Me), 7.40 t (1H, 4-H, J = 7.0 Hz), 7.45 t (1H, 8-H
or 9-H, J = 7.0 Hz), 7.72 t (1H, 9-H or 8-H, J =
7.0 Hz), 7.76 d (1H, 3-H, J = 7.0 Hz), 7.92 d (1H, 5-H,
J = 7.0 Hz), 8.03 d (1H, 10-H, J = 7.0 Hz), 8.37 d (1H,
7-H, J = 7.0 Hz), 11.90 s (1H, NH). Mass spectrum,
m/z (Irel, %): 233 (100) [M]+, 204 (14), 163 (5), 63
(13). Found, %: C 82.62; H 4.45; N 5.95. C16H11NO.
Calculated, %: C 82.40; H 4.72; N 6.01.
Compound VIa. Yield 0.32 g (66%), yellow crys-
tals, mp 224°C. 1H NMR spectrum, δ, ppm: 1.44 t (3H,
Me, J = 7.5 Hz), 3.30 q (2H, CH2, J = 7.5 Hz), 7.42 t
(1H, 4-H, J = 7.5 Hz), 7.46 t (1H, 8-H or 9-H, J =
7.5 Hz), 7.74 t (1H, 9-H or 8-H, J = 7.5 Hz), 7.78 d
(1H, 3-H, J = 7.5 Hz), 7.93 d (1H, 5-H, J = 7.5 Hz),
8.03 d (1H, 10-H, J = 7.5 Hz), 8.38 d (1H, 7-H, J =
7.5 Hz). Found: m/z 247.0994 [M]+. C17H13NO. Calcu-
lated: M 247.0991.
5-Chloro-1-methylnaphtho[1,2,3-cd]indol-6(2H)-
one (IVi) was synthesized from 0.73 g (2.02 mmol) of
compound IIl using 2 ml of 10% sodium methoxide
and 7 ml of THF. The mixture was heated for 1 h under
reflux, and the product was recrystallized from 80%
aqueous alcohol. Yield 0.46 g (79%), yellow crystals,
Compound VIIa. Yield 0.10 g (25%), yellow crys-
1
tals, mp 278°C. H NMR spectrum, δ, ppm: 1.62 d
1
mp 345°C. H NMR spectrum, δ, ppm: 2.90 s (3H,
(3H, Me, J = 7.0 Hz), 5.61–5.66 m (1H, CH), 6.00 s
(1H, OH), 7.41 t (1H, 4-H, J = 7.0 Hz), 7.47 t (1H, 8-H
or 9-H, J = 7.0 Hz), 7.72 t (1H, 9-H or 8-H, J =
7.0 Hz), 7.79 d (1H, 3-H, J = 7.0 Hz), 7.94 d (1H, 5-H,
J = 7.0 Hz), 8.08 d (1H, 10-H, J = 7.0 Hz), 8.37 d
(1H, 7-H, J = 7.0 Hz). Found: m/z 263.0945 [M]+.
C17H13NO2. Calculated: M 263.0941.
Me), 7.37 d (1H, 4-H, J = 8.0 Hz), 7.42 t (1H, 8-H or
9-H, J = 8.0 Hz), 7.70 d (1H, 3-H, J = 8.0 Hz), 7.72 t
(1H, 9-H or 8-H, J = 8.0 Hz), 7.99 d (1H, 10-H, J =
8.0 Hz), 8.34 d (1H, 7-H, J = 8.0 Hz), 12.10 s (1H,
NH). Mass spectrum, m/z (Irel, %): 269 (31) [M + 2]+,
268 (29) [M + 1]+, 267 (100) [M]+, 203 (22), 163 (8),
88 (23). Found, %: C 71.25; H 3.78; N 5.09.
C16H10ClNO. Calculated, %: C 71.77; H 3.74; N 5.23.
1-Propylnaphtho[1,2,3-cd]indol-6-(2H)-one
(VIb) and 1-(1-hydroxypropyl)naphtho[1,2,3-cd]in-
dol-6(2H)-one (VIIb) were synthesized in a similar
way from 0.77 g (2.01 mmol) of compound IIn using
5 ml of 10% sodium methoxide and 15 ml of THF. The
mixture was heated for 30 min under reflux, and the
products were isolated by column chromatography on
silica gel using benzene as eluent.
5-(Pyrrolidin-1-yl)naphtho[1,2,3-cd]indol-6(2H)-
one (IVj). A mixture of 0.30 g (0.87 mmol) of com-
pound IIf and 5 ml (60.00 mmol) of pyrrolidine was
heated for 1 h at 45°C. The mixture was cooled to 18–
20°C, 7 ml of THF and 2 ml of a 10% solution of
sodium methoxide were added, the mixture was heated
for 15 min under reflux and cooled again to 18–20°C,
1 ml of acetic acid was added, and 3 ml of water was
added dropwise. After cooling, the precipitate was
filtered off, washed with water, and recrystallized from
80% aqueous 2-ethoxyethanol. Yield 0.22 g (88%),
Compound VIb. Yield 0.38 g (73%), yellow crys-
tals, mp 205°C. 1H NMR spectrum, δ, ppm: 1.05 t (3H,
CH3, J = 7.0 Hz), 1.84–1.82 m (2H, CH2CH3), 3.25 t
(2H, 1-CH2, J = 7.0 Hz), 7.41 t (1H, 4-H, J = 7.5 Hz),
7.46 t (1H, 8-H or 9-H, J = 7.5 Hz), 7.74 t (1H, 9-H or
8-H, J = 7.5 Hz ), 7.77 d (1H, 3-H, J = 7.5 Hz), 7.93 d
(1H, 5-H, J = 7.5 Hz), 8.03 d (1H, 10-H, J = 7.5 Hz),
8.37 d (1H, 7-H, J = 7.5 Hz), 11.90 s (1H, NH).
Found: m/z 261.1148 [M]+. C18H15NO. Calculated:
M 261.1148.
1
yellow crystals, mp 243–244°C. H NMR spectrum, δ,
ppm: 1.90 br.s (4H, CH2), 3.40 br.s (4H, CH2N), 6.95 d
(1H, 4-H, J = 8.0 Hz), 7.36 t (1H, 8-H or 9-H, J =
8.0 Hz), 7.61 t (1H, 9-H or 8-H, J = 8.0 Hz), 7.71 d
(1H, 3-H, J = 8.0 Hz), 8.07 d (1H, 10-H, J = 8.0 Hz),
8.23 d (1H, 1-H, J = 2.5 Hz), 8.26 d (1H, 7-H, J =
8.0 Hz), 11.80 br.s (1H, NH). Mass spectrum, m/z
(Irel, %): 288 (46) [M]+, 245 (39), 219 (100), 164 (51).
Found, %: C 79.02; H 5.67; N 9.73. C19H16N2O. Cal-
culated, %: C 79.16; H 5.55; N 9.72.
Compound VIIb. Yield 0.12 g (23%), yellow crys-
tals, mp 255°C. 1H NMR spectrum, δ, ppm: 1.00 t (3H,
CH3, J = 7.0 Hz), 1.90–1.97 m (2H, CH2CH3), 5.39–
5.45 m (1H, CHOH), 6.09 d (1H, OH, J = 4.0 Hz),
7.41 t (1H, 4-H, J = 7.5 Hz), 7.47 t (1H, 8-H or 9-H,
J = 7.5 Hz), 7.73 t (1H, 9-H or 8-H, J = 7.5 Hz), 7.79 d
(1H, 3-H, J = 7.5 Hz), 7.94 d (1H, 5-H, J = 7.5 Hz),
8.09 d (1H, 10-H, J = 7.5 Hz), 8.37 d (1H, 7-H, J =
1-Ethylnaphtho[1,2,3-cd]indol-6-(2H)-one (VIa)
and 1-(1-hydroxyethyl)naphtho[1,2,3-cd]indol-
6(2H)-one (VIIa). A mixture of 0.71 g (2 mmol) of
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SYNTHESIS OF S,S-DIALKYL-N-(9,10-DIOXO-9,10-DIHYDROANTHRACEN-1-YL)...
77
7.5 Hz), 11.90 s (1H, NH). Found: m/z 277.1094 [M]+.
C18H15NO2. Calculated: M 277.1097.
2. Takahashi, H. and Iiizumi, Y., JPN Patent Appl. Publ.
no. 2000-200683, 2000; Chem. Abstr., 2000, vol. 133,
no. 12220t.
This study was performed under financial support
by the Astaf’ev Krasnoyarsk State Pedagogical
University (project no. 01-12-1/NP).
3. Haramata, M., Tetrahedron Lett., 1988, vol. 29, p. 5229.
4. Ikeda, M., Tsubouchi, H., Tsunekawa, M., Kondo, H., and
Tamura, Y., Heterocycles, 1983, vol. 20, p. 2185.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013