Synthesis of anthrathiopyrantriones by heterocyclization of alkynoyl derivatives of chloroanthraquinones

Article abstract of DOI:10.1007/s11172-005-0117-7

A procedure was developed for the synthesis of 2-substituted, including 2-alkenyl-substituted, 4H-anthra[1,2-b]thiopyran-4,7,12-triones and 4H-anthra[2,3-b]thiopyran-4,6,11-triones by cyclocondensation of vic-alkynoylchloroanthraquinones with Na₂

Full text of DOI:10.1007/s11172-005-0117-7

Russian Chemical Bulletin, International Edition, Vol. 53, No. 10, pp. 2303—2307, October, 2004
2303
Synthesis of anthrathiopyrantriones by heterocyclization
of alkynoyl derivatives of chloroanthraquinones
ꢀ
I. D. Ivanchikova and M. S. Shvartsberg
Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences,
3 ul. Institutskaya, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383 2) 34 2350. Eꢀmail: shvarts@ns.kinetics.nsc.ru
A procedure was developed for the synthesis of 2ꢀsubstituted, including 2ꢀalkenylꢀsubstiꢀ
tuted, 4Hꢀanthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀtriones and 4Hꢀanthra[2,3ꢀb]thiopyranꢀ4,6,11ꢀtriones
by cyclocondensation of vicꢀalkynoylchloroanthraquinones with Na2S.
Key words: vicꢀalkynoylchloroanthraquinones, synthesis, cyclocondensation, soꢀ
dium sulfide, 2ꢀsubstituted 4Hꢀanthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀtriones, 2ꢀsubstituted
4Hꢀanthra[2,3ꢀb]thiopyranꢀ4,6,11ꢀtriones.
The cyclic moiety of natural antitumor antibiotics of
the kidamycin group is alkynoyl the 4Hꢀanthra[1,2ꢀb]pyꢀ
ranꢀ4,7,12ꢀtrione system.1 A structural distinguishing feaꢀ
ture of these compounds is the presence of unsaturated or
other chemically labile substituents at position 2. The
introduction of such substituents presents considerable
synthetic difficulties. Earlier,2,3 we have demonstrated that
2ꢀalkenylꢀsubstituted anthrapyrantriones can be syntheꢀ
sized using acetylenic derivatives of anthraquinone as the
key intermediates and determined the synthesis condiꢀ
tions. In the present study, we developed a procedure for
the preparation of 2ꢀsubstituted, including 2ꢀalkenylꢀsubꢀ
stituted, 4Hꢀanthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀtriones within
the framework of the same soꢀcalled acetylenic approach.
The development of rational procedures for the synthesis
of sulfurꢀcontaining analogs of biologically active pyran
compounds is of importance, because the replacement of
the heteroatom in a cyclic pharmacophoric structure with
the S atom or the introduction of an Sꢀcontaining heteroꢀ
cycle often makes it possible to reduce the side effects of
pharmaceuticals with retention of their main activity or to
change the character of their biological activity.4—6
chloroquinones 2 would react with NaHS as a nucleoꢀ
phile under mild conditions, resulting in the thiopyroneꢀ
ring closure. The latter fact is of particular importance in
the synthesis of heterocycles containing chemically sensiꢀ
tive substituents.
Actually, we found that alkynoylchloroanthraquinoꢀ
nes 2 are readily subjected to heterocyclization to form
anthrathiopyrans 1 (Scheme 1). It appeared that Na2S
can successfully be used as a cyclizing agent instead of
NaHS, whose preparation requires a special proceꢀ
dure.8 The reaction proceeds rather rapidly in refluxing
95% EtOH in the presence of an excess of Na2S.
Scheme 1
2ꢀAlkynoylꢀ1ꢀmercaptoanthraquinones could seemꢀ
ingly serve as acetylenic precursors in the synthesis of
4Hꢀanthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀtriones 1. However,
these compounds are insufficiently stable and difficultly
accessible. Hence, we chose 2ꢀalkynoylꢀ1ꢀchloroanthraꢀ
quinones 2 as the key compounds. The Cl atom at posiꢀ
tion 1 of anthraquinone is labile and can readily be reꢀ
placed under the action of nucleophiles.7 In alkynoyl deꢀ
rivatives 2, this Cl atom is additionally activated by the
adjacent substituent. In addition, the triple bond in the
substituent is highly electrophilic and can also interact
with nucleophiles. Hence, we expected that alkynoylꢀ
2ꢀSubstituted anthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀtriones
1a—e were prepared in 68—82% yields (Table 1). The
possible competitive formation of the fiveꢀmembered hetꢀ
erocycle was not observed. Due to the mild conditions,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2205—2209, October, 2004.
1066ꢀ5285/04/5310ꢀ2303 © 2004 Springer Science+Business Media, Inc.

2304
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
Ivanchikova and Shvartsberg
Table 1. Yields, elemental analysis data, and physicochemical and spectroscopic characteristics of anthrathiopyrantriones 1a—e
and 4a,b
Comꢀ Yield M.p.*
Found
Calculated
Molecular
formula
1H NMR, δ (J/Hz)
(%)
S
poꢀ
(%)
/°С
und
С
Н
1a
1b
82
81
291—
292
75.20 3.43 8.60
74.98 3.28 8.70
С23Н12О3S
С23Н16О3S
7.30 (s, 1 H, H(3)); 7.50—7.60 (m, 3 H, 3 HPh); 7.75—7.90 (m,
4 H, 2 HPh, H(9), Н(10)); 8.25—8.40 (m, 2 H, H(8), Н(11));
8.50, 9.07 (both d, 1 H each, H(5), H(6), J = 8.3)
261—
263
74.30 4.53 8.40
74.17 4.33 8.61
1.60—1.90 (s, 4 H, C(4´)H2, C(5´)H2); 2.30—2.45 (m, 4 H,
C(3´)H2, C(6´)H2); 6.75—6.80 (m, 1 H, C(2´)H); 6.98 (s, 1 H,
H(3)); 7.80—7.90 (m, 2 H, H(9), Н(10)); 8.25—8.35 (m, 2 H,
H(8), Н(11)); 8.40, 8.94 (both d, 1 H each, H(5), H(6), J = 8.3)
1.75 (s, 6 H, Me); 2.35 (s, 1 H, OH); 7.20 (s, 1 H, H(3));
7.80—7.90 (m, 2 H, H(9), Н(10)); 8.25—8.35 (m, 2 H, H(8),
Н(11)); 8.45, 8.99 (both d, 1 H each, H(5), H(6), J = 8.3)
0.97 (t, 3 H, Me, J = 7.6); 1.45 (sext, 2 H, γꢀCH2, J = 7.6);
1.78 (q, 2 H, βꢀCH2, J = 7.6); 2.76 (t, 2 H, αꢀCH2, J = 7.6);
6.94 (s, 1 H, H(3)); 7.80—7.90 (m, 2 H, H(9), Н(10));
8.25—8.35 (m, 2 H, H(8), Н(11)); 8.44, 8.99 (both d, 1 H each,
H(5), H(6), J = 8.3)
1c
1d
78
80
261—
262
68.51 4.30 9.13
68.56 4.03 9.15
С20Н14О4S
С21Н16О3S
182—
183
72.50 4.73 9.05
72.39 4.63 9.20
1e
68
170—
171
72.85 4.32 9.13
72.81 4.07 9.26
С21Н14О3S
1.72, 1.92 (both br.d, 3 H each, MeCH=C, E isomer, Z isomer,
J = 7.0); 2.10 (br.s, 3 H, MeC=C); 5.80, 6.55 (both br.q, 1 H each,
CH=C, E isomer, Z isomer, J = 7.0); 6.87, 7.03 (both s, 1 H each,
H(3), E isomer, Z isomer); 7.80—7.90 (m, 2 H, H(9), Н(10));
8.25—8.40 (m, 2 H, H(8), Н(11)); 8.44, 8.99 (both d, 1 H each,
H(5), H(6), Z isomer, J = 8.3); 8.48, 9.05 (both d, 1 H each, H(5),
H(6), E isomer, J = 8.3)
4a
4b
94
75
338—
339
75.05 3.16 8.51
74.98 3.28 8.70
С23Н12О3S
С23Н16О3S
7.32 (s, 1 H, H(3)); 7.50—7.60 (m, 3 H, 3 HPh); 7.70—7.80 (m, 2 H,
2 HPh); 7.80—7.90 (m, 2 H, H(8), Н(9)); 8.35—8.45 (m, 2 H, H(7),
Н(10)); 8.61, 9.45 (both s, 1 H each, H(5), H(12))
1.60—1.90 (m, 4 H, C(4´)H2, C(5´)H2); 2.15—2.50 (m, 4 H,
C(3´)H2, C(6´)H2); 6.65—6.75 (m, 1 H, C(2´)H); 7.02 (s, 1 H,
H(3)); 7.80—7.90 (m, 2 H, H(8), Н(9)); 8.30—8.45 (m, 2 H, H(7),
Н(10)); 8.51, 9.37 (both s, 1 H each, H(5), H(12))
290—
291
73.68 4.32 8.08
74.17 4.33 8.61
* Benzene—hexane.
the reaction allows one to prepare anthrathiopyrans conꢀ
taining unsaturated substituents at position 2. The synꢀ
thesis of alkenylthiopyran 1e (a mixture of Z and E isoꢀ
mers) from labile vinylacetylenic ketone 2e, as well as the
preparation of cyclohexenylthiopyran 1b from ketone 2b,
demonstrates that the proposed method is applicable to
the synthesis of thio analogs of aglycones of anthrapyran
antibiotics.
and afforded linearly annelated anthra[2,3ꢀb]thiopyranꢀ
4,6,11ꢀtriones 4a,b (Scheme 2) in 94 and 75% yields,
respectively (see Table 1).
Scheme 2
The Cl atom in the anthraquinone moiety is characꢀ
terized by high nucleofugic lability regardless of its posiꢀ
tion.7 Hence, there is reason to hope that the new method
for the preparation of anthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀ
triones can be extended to the synthesis of compounds in
which the thiopyran ring is fused to the anthraquinone
moiety in another fashion. We subjected acetylenic keꢀ
tones 3a,b containing the Cl atom at position 2 to
cyclocondensation with Na2S. Cyclocondensation of these
ketones proceeded under the same conditions as those
used in the reactions of their positional isomers 2a,b

Synthesis of anthrathiopyrantriones
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
2305
Scheme 3
3.3 mmol) in anhydrous benzene (50 mL) under argon. The
reaction mixture was stirred at 20 °C for 20 min, diluted
with CHCl3 (300 mL), washed with water, and dried with
MgSO4. The solvent was removed in vacuo. Ketone 2a was
isolated by chromatography on SiO2 in toluene and crystalliꢀ
zation from a toluene—hexane mixture. The yield was 0.85 g
(Table 2).
1ꢀChloroꢀ2ꢀ[3ꢀ(1ꢀcyclohexenyl)ꢀ1ꢀoxopropynyl]anthraquiꢀ
none (2b). Acetylenic ketone 2b was prepared analogously
to ketone 2a from acid chloride 6 (1.50 g, 4.9 mmol)
and 1ꢀethynylcyclohexene (5b) (0.93 g, 8.8 mmol) in benꢀ
zene (70 mL) in the presence of Et3N (1.60 g, 15.7 mmol),
Pd(PPh3)2Cl2 (50 mg), and CuI (50 mg). The yield was 1.15 g
(see Table 2).
1ꢀChloroꢀ2ꢀ(4ꢀhydroxyꢀ4ꢀmethylꢀ1ꢀoxopentꢀ2ꢀynyl)anthraꢀ
quinone (2c) was prepared analogously to ketone 2a from acid
chloride 6 (0.37 g, 1.2 mmol) and 2ꢀmethylbutꢀ3ꢀynꢀ2ꢀol (5c)
(0.22 g, 2.6 mmol) in benzene (25 mL) in the presence of Et3N
(0.36 g, 3.6 mmol), Pd(PPh3)2Cl2 (15 mg), and CuI (15 mg).
The yield was 0.28 g (see Table 2).
Acetylenic ketones 2a—e and 3a,b, which are precurꢀ
sors of thiopyrans 1a—e and 4a,b, respectively, were synꢀ
thesized by acylation of terminal acetylenes 5 with
1ꢀchloroanthraquinoneꢀ2ꢀcarboxylic acid chloride (6) and
2ꢀchloroanthraquinoneꢀ3ꢀcarboxylic acid chloride (7), reꢀ
spectively, in benzene in the presence of Pd(PPh3)2Cl2,
CuI, and Et3N 9 at 20 °C for 10—20 min (Scheme 3).
Acid chlorides 6 and 7 were prepared by heating
anthraquinonecarboxylic acids 8 and 9 in SOCl2. After
removal of the reagent, acid chlorides 6 and 7 were used
without purification (see Scheme 3).
Therefore, cyclocondensation of vicꢀalkynoylchloroꢀ
anthraquinones with Na2S provides a rather general
method for the synthesis of 2ꢀsubstituted anthrathioꢀ
pyrantriones.
Experimental
1ꢀChloroꢀ2ꢀ(1ꢀoxoheptꢀ2ꢀynyl)anthraquinone (2d) was synꢀ
thesized analogously to ketone 2a by acylation of hexꢀ1ꢀyne (5d)
(0.18 g, 2.2 mmol) with acid chloride 6 (0.40 g, 1.3 mmol). The
yield was 0.30 g (see Table 2).
1
The H NMR spectra were recorded on a Bruker DPXꢀ200
instrument (200 MHz) in CDCl3 at 25 °C. The IR spectra were
measured on a URꢀ20 spectrometer in CHCl3. The course of the
reactions and purity of the compounds were monitored by TLC
on Silufol UV 254 plates.
1ꢀChloroanthraquinoneꢀ2ꢀcarboxylic acid chloride (6). A soꢀ
lution of 1ꢀchloroanthraquinoneꢀ2ꢀcarboxylic acid (8) (3.70 g,
1.3 mmol) in SOCl2 (13 mL) was refluxed for 4 h and an excess
of SOCl2 was removed under argon. The residue was washed
with hexane, brought to reflux in dry toluene (10—15 mL), and
cooled. The precipitate was filtered off and washed with hexane.
Acid chloride 6 was obtained in a yield of 3.35 g (85.0%) and
used without additional purification.
1ꢀChloroꢀ2ꢀ(4ꢀmethylꢀ1ꢀoxohexꢀ4ꢀenꢀ2ꢀynyl)anthraquinone
(2e). The reaction of acid chloride 6 (1.40 g, 4.6 mmol) with
3ꢀmethylpentꢀ3ꢀenꢀ1ꢀyne (5e) (0.74 g, 9.2 mmol) (a mixture of
Z and E isomers, the percentage of the Z isomer was ~70%) in
benzene (135 mL) in the presence of Et3N (1.30 g, 12.8 mmol),
Pd(PPh3)2Cl2 (65 mg), and CuI (65 mg) was carried out as
described for ketone 2a. The condensation time was 10 min. The
reaction mixture was filtered through a thin SiO2 layer under
pressure, concentrated in vacuo, and chromatographed on SiO2
in toluene. After crystallization from a hexane—diethyl ether
mixture, vinylacetylenic ketone 2e was isolated in a yield of
0.84 g (see Table 2).
1ꢀChloroꢀ2ꢀ(1ꢀoxoꢀ3ꢀphenylpropynyl)anthraquinone (2a).
Triethylamine (1.10 g, 11.0 mmol), Pd(PPh3)2Cl2 (40 mg), CuI
(40 mg), and phenylacetylene (5a) (0.56 g, 5.5 mmol) were
successively added to a solution of acid chloride 6 (1.00 g,
2ꢀChloroꢀ3ꢀ(1ꢀoxoꢀ3ꢀphenylpropynyl)anthraquinone (3a).
Condensation of acid chloride 7 (0.65 g, 2.1 mmol), which was

2306
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
Ivanchikova and Shvartsberg
Table 2. Yields, elemental analysis data, and physicochemical and spectroscopic characteristics of acetylenic ketones 2a—e and 3a,b
Comꢀ Yield M.p.*
Found
Calculated
Molecular
formula
1H NMR, δ (J/Hz)
IR,
ν/cm–1
(%)
Cl
poꢀ
(%)
/°С
und
С
Н
2a
2b
70
183—
183.5
74.48 3.14 9.65
74.50 2.99 9.56
С23Н11ClО3 7.35—7.55 (m, 3 H, 3 HPh); 7.60—7.70 (m, 2 H,
2 HPh); 7.75—7.90 (m, 2 H, H(6), Н(7));
1670, 1690
(С=О);
2205
(С≡С)
1670,
1690
(С=О);
2195
(С≡С)
1670, 1690
(С=О);
2225 (С≡С);
3400 br,
3610 (OH)
1670,
1690
(С=О);
2220
8.05 (d, 1 H, H(3), J = 7.9); 8.25—8.35 (m, 2 H,
H(5), Н(8)); 8.41 (d, 1 H, H(4), J = 7.9)
63
65
65
52
168—
169
73.80 4.19 9.61
73.70 4.03 9.46
С23Н15ClО3 1.45—1.75, 2.10—2.30 (both m, 4 H each, C(4´)H2,
C(5´)H2, C(3´)H2, C(6´)H2); 6.55—6.60 (m, 1 H,
C(2´)H); 7.75—7.90 (m, 2 H, H(6), Н(7)); 7.95 (d,
1 H, H(3), J = 8.0); 8.20—8.35 (m, 2 H, H(5),
Н(8)); 8.36 (d, 1 H, H(4), J = 8.0)
С20Н13ClО4 1.62 (s, 6 H, Me); 2.20 (br.s, 1 H, OH);
7.75—7.85 (m, 2 H, H(6), Н(7)); 7.94 (d, 1 H,
H(3), J = 8.0); 8.20—8.30 (m, 2 H, H(5), Н(8));
8.35 (d, 1 H, H(4), J = 8.0)
2c
2d
2e
145—
146.5
68.23 3.89 10.08
68.09 3.71 10.05
130—
130.5
71.68 4.22 10.19
71.90 4.31 10.11
С21Н15ClО3 0.92 (t, 3 H, Me, J = 7.2); 1.40—1.65 (m, 4 H,
βꢀCH2, γꢀCH2); 2.47 (t, 2 H, αꢀCH2, J = 7.0);
7.75—7.85 (m, 2 H, H(6), Н(7)); 7.94 (d, 1 H,
H(3), J = 8.0); 8.20—8.30 (m, 2 H, H(5), Н(8));
8.36 (d, 1 H, H(4), J = 8.0)
С21Н13ClО3 1.75, 1.87 (both d, 3 H each, MeCH=C, E isomer,
Z isomer, J = 7.0); 1.92, 1.95 (both br.s, 3 H each,
MeC=C, Z isomer, E isomer); 6.10—6.20,
(С≡С)
1670,
1690
(С=О);
2200
(С≡С)
177—
178.5
73.29 3.40 10.00
72.32 3.76 10.16
6.35—6.45 (both m, 1 H each, CH=C, Z isomer,
E isomer); 7.75—7.90 (m, 2 H, H(6), Н(7)); 7.95,
7.98 (both d, 1 H each, H(3), E isomer, Z isomer,
J = 8.0); 8.20—8.35 (m, 2 H, H(5), Н(8));
8.37, 8.38 (both d, 1 H each, H(4), E isomer,
Z isomer, J = 8.0)
3a
3b
76
232—
233
74.68 3.09 10.06
74.50 2.99 9.56
С23Н11ClО3 7.40—7.55 (m, 3 H, 3 HPh); 7.65—7.75 (m, 2 H,
2 HPh); 7.80—7.90, 8.30—8.40 (both m, 2 H each,
1670, 1690
(С=О);
H(6), Н(7), H(5), Н(8)); 8.40, 8.97 (both s, 1 H each, 2205
H(1), H(4))
С23Н15ClО3 1.55—1.70, 2.20—2.35 (both m, 4 H each, C(4´)H2,
C(5´)H2, C(3´)H2, C(6´)H2); 6.60—6.70 (m, 1 H,
C(2´)H); 7.80—7.90, 8.30—8.40 (both m, 2 H each,
(С≡С)
1680,
1690
(C=O);
49 149.5— 73.76 4.25 9.56
150.5 73.70 4.03 9.46
H(6), Н(7), H(5), Н(8)); 8.35, 8.85 (both s, 1 H each, 2230
H(1), H(4)) (C≡C)
* Benzene—hexane.
prepared from 2ꢀchloroanthraquinoneꢀ3ꢀcarboxylic acid (9)
analogously to acid chloride 6, with phenylacetylene (5a) (0.43 g,
4.2 mmol) was carried out under the conditions used in the
synthesis of ketone 2a in the presence of Et3N (0.72 g, 7.1 mmol),
Pd(PPh3)2Cl2 (20 mg), and CuI (20 mg) in benzene (40 mL).
The reaction mixture was diluted with hexane (60 mL) and
cooled. The precipitate that formed was filtered off, dissolved in
trichloroethylene (150 mL) with heating, and filtered through a
thin SiO2 layer under pressure. The solvent was distilled off
in vacuo and the residue was recrystallized from toluene. The
yield of ketone 3a was 0.60 g (see Table 2).
ride 7 (0.58 g, 1.9 mmol) and 1ꢀethynylcyclohexene (5b) (0.35 g,
3.3 mmol). The yield was 0.35 g (see Table 2).
2ꢀPhenylanthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀtrione (1a). Chloroꢀ
anthraquinone 2a (0.52 g, 1.4 mmol) was added to a suspension
of Na2S (0.50 g, 6.4 mmol) in 95% EtOH (90 mL) with heatꢀ
ing (~60 °C). The reaction mixture was refluxed with stirring
for 15 min, cooled, poured into water (500 mL), and extracted
with CHCl3 (3×100 mL). The chloroform solution was washed
with water and dried with MgSO4. The solvent was removed
in vacuo. The crude product was purified by chromatography
on SiO2 in CHCl3 and crystallization from a toluene—hexane
mixture. The yield of anthrathiopyrantrione 1a was 0.42 g (see
Table 1).
2ꢀChloroꢀ3ꢀ[3ꢀ(1ꢀcyclohexenyl)ꢀ1ꢀoxopropynyl]anthraquiꢀ
none (3b) was prepared analogously to ketone 3a from acid chloꢀ

Synthesis of anthrathiopyrantriones
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
2307
2ꢀ(1ꢀCyclohexenyl)anthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀtrione
(1b) was prepared analogously to compound 1a from ketone 2b
(0.40 g, 1.1 mmol) and Na2S (0.45 g, 5.8 mmol). The yield of
thiopyran 1b was 0.32 g (see Table 1).
2ꢀ(1ꢀHydroxyꢀ1ꢀmethylethyl)anthra[1,2ꢀb]thiopyranꢀ
4,7,12ꢀtrione (1c) was prepared analogously to compound 1a
from ketone 2c (0.40 g, 1.1 mmol) and Na2S (0.40 g, 5.1 mmol)
in 95% EtOH (60 mL). The yield of thiopyran 1c was 0.31 g (see
Table 1).
2ꢀButylanthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀtrione (1d). Condenꢀ
sation of ketone 2d (0.50 g, 1.4 mmol) with Na2S (0.50 g,
6.4 mmol) in 95% EtOH (80 mL) was carried out under the
conditions of synthesis of thiopyran 1a. The crude product was
chromatographed on SiO2 in toluene and crystallized from a
toluene—hexane mixture. The yield of anthrathiopyrantrione
1d was 0.40 g (see Table 1).
2ꢀ(1ꢀMethylpropꢀ1ꢀenyl)anthra[1,2ꢀb]thiopyranꢀ4,7,12ꢀ
trione (1e) was prepared from vinylacetylenic ketone 2e (a mixꢀ
ture of Z and E isomers) (0.40 g, 1.1 mmol) and Na2S (0.40 g,
5.1 mmol) analogously to thiopyran 1d. The yield was 0.27 g (see
Table 1).
2ꢀPhenylanthra[2,3ꢀb]thiopyranꢀ4,6,11ꢀtrione (4a) was preꢀ
pared from chloroanthraquinone 3a (0.30 g, 0.8 mmol) and
Na2S (0.45 g, 5.8 mmol) in 95% EtOH (80 mL) under the
conditions of synthesis of compound 1a. Compound 4a was
purified by crystallization from toluene. The yield was 0.28 g
(see Table 1).
2ꢀ(1ꢀCyclohexenyl)anthra[2,3ꢀb]thiopyranꢀ4,6,11ꢀtrione
(4b) was prepared from ketone 3b (0.20 g, 0.5 mmol) and Na2S
(0.30 g, 3.8 mmol) analogously to thiopyran 1a. The yield was
0.15 g (see Table 1).
References
1. F. M. Hauser and R. P. Rhee, J. Am. Chem. Soc., 1979,
101, 1628.
2. M. A. Mzhel´skaya, I. D. Ivanchikova, N. E. Polyakov, A. A.
Moroz, and M. S. Shvartsberg, Izv. Akad. Nauk, Ser. Khim.,
2004, 2686 [Russ. Chem. Bull., Int. Ed., 2004, 53, No. 12].
3. M. A. Mzhel´skaya, A. A. Moroz, and M. S. Shvartsberg, Izv.
Akad. Nauk SSSR, Ser. Khim., 1991, 1656 [Bull. Acad. Sci.
USSR, Div. Chem. Sci., 1991, 40, 1469 (Engl. Transl.)].
4. Y. Kita, M. Kirihara, J. Sekihachi, R. Okunaka, M. Sasho,
Sh. Mohri, T. Honda, Sh. Akai, Y. Tamura, and K. Shimooka,
Chem. Pharm. Bull., 1990, 38, 1836.
5. A. P. Krapcho, M. E. Petry, and M. P. Hacker, J. Med.
Chem., 1990, 33, 2651.
6. T. G. Tolstikova, V. F. Davydova, E. E. Shul´ts, G. F. Vafina,
G. M. Safarova, F. A. Zarudii, D. N. Lazareva, and G. A.
Tolstikov, Khim.ꢀfarm. Zh., 1990, 24, No. 7, 27 [Pharm.
Chem. J., 1990, 24 (Engl. Transl.)].
7. M. V. Gorelik, Khimiya antrakhinonov i ikh proizvodnykh
[Chemistry of Anthraquinones and Their Derivatives], Khimiya,
Moscow, 1983, 296 pp. (in Russian).
8. T. Sakamoto, Y. Kondo, R. Watanabe, and H. Yamanaka,
Chem. Pharm. Bull., 1986, 34, 2724.
9. A. S. Zanina, S. I. Shergina, I. E. Sokolov, and I. L.
Kotlyarevskii, Izv. Akad. Nauk SSSR, Ser. Khim., 1981, 1158
[Bull. Acad. Sci. USSR, Div. Chem. Sci., 1981, 30, 918 (Engl.
Transl.)].
Received June 15, 2004