Synthesis of 9,10-anthracenedione diethyldithiocarbamates

Full text of DOI:10.1134/S1070363216120227

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 12, pp. 2699–2701. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © V.I. Zvarych, M.V. Stasevych, V.V. Lunin, M.V. Vovk, V.P. Novikov, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86,
No. 12, pp. 2067–2069.
LETTERS
TO THE EDITOR
Synthesis of 9,10-Anthracenedione Diethyldithiocarbamates
a
a
a
b
a
V. I. Zvarych , M. V. Stasevych , V. V. Lunin , M. V. Vovk , and V. P. Novikov *
a
Lviv Polytechnic National University, ul. S. Bandera 12, Lviv, 79013 Ukraine
*
e-mail: vnovikov@polynet.lviv.ua
b
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
Received September 29, 2016
Keywords: amino-9,10-anthracenediones, diazonium salts, diethyldithiocarbamates
DOI: 10.1134/S1070363216120227
Dithiocarbamates are valuable synthetic materials
widely used in agriculture as insecticides, herbicides,
pesticides, and fungicides [1], in the industry as
slimicides in water-cooled engines and paper
production [2], vulcanization accelerators [5], in
analytical chemistry for determining cations [3], in
polymer chemistry as agents for the controlled radical
polymerization of [4]. Some dithiocarbamates show
antitumor [6, 7], anti-HIV [8], antioxidant [9],
antibiotic [10], and anti-histamine [11] activity. Func-
tionalization of dithiocarbamates with biophoric frag-
ments was proved especially useful when creating
combinatorial libraries for rapid screening [12] and
drug design [13].
metal dithiocarbamates with aryl and diaryl diazonium
salts in the absence of any catalyst. Given the limited
number of such publications, it was worthwhile to
expand the synthetic potential of diazonium salts
derived from amino-9,10-anthracenediones for
obtaining new derivatives of dithiocarbamic acids.
At the beginning, 1-aminoanthracenediones 1–5
were converted to the corresponding diazonium sulfates
6
–10 by the method reported in [24]. Neutralization of
aqueous solutions with sodium carbonate followed by
treating with a 3-fold excess of sodium diethyldi-
thiocarbamate at 5–10°C led to the formation of S-
(
9,10-anthracen-1-yl)dithiocarbamates 11–15 with 59–
7
2% yield (Scheme 1).
9
,10-Anthracenedione derivatives are used as dyes,
Structure and composition of the obtained S-
pharmaceuticals, analytical reagents, indicators, phos-
phors, catalysts [14]. In recent years, they have been
widely studied as biologically active compounds with
antitumor, antiviral, antidiabetic, antibacterial, and
antifungal action [15]. Of special interest is the
creation of new 9,10-anthracenedione derivatives as
they can be promising objects for multi-purpose use.
anthracenyl dithiocarbamates 11–15 were unequi-
vocally confirmed by NMR spectroscopy and
1
elemental analysis data. In particular, the H NMR
spectra of 11–15 showed the signals of methyl and
methylene groups of diethylamino substituent in the
ranges of 1.16–1.37 and 3.84–3.96 ppm, respectively.
1
3
The C NMR spectra contained the signals of C=S
moiety of dithiocarbamate fragment at 191–192 ppm.
General method for the synthesis of dithio-
carbamates is reacting a primary or secondary amines
with carbon disulfide in the presence of alkali [16],
triethylamine [17] or without a base [18]. The
approach comprising the reaction of amines with
carbon disulfide and an alkyl halides/acrylates has
been reported in [19]. These methods allow obtaining
alkyl dithiocarbamates, but not aryl dithiocarbamates.
In general, S-aryl dithiocarbamates can be prepared
under metal-catalysis conditions [20], while in [21–23]
the synthesis has been performed by reacting alkali
General procedure for the synthesis of S-anthra-
cenyldithiocarbamates 11–15. A solution of 1.15 g
(6.72 mmol) of sodium diethyldithiocarbamate in
15 mL of water was added with stirring and cooling
(5–10°C) to a mixture of freshly prepared and
neutralized with 10% sodium carbonate solution
(pH = 7) diazonium salt 6–10 prepared from
2.24 mmol of the appropriate aminoanthracenedione
1–5 and 0.201 g (2.91 mmol) of sodium nitrite in
20 mL of concentrated sulfuric acid. The reaction
2
699

2
700
ZVARYCH et al.
Scheme 1.
N
N +
−
HSO
4
O
O
NH2
O
R1
R1
(
1) NaNO , H SO , H O
2 2 4 2
(
2) Na CO3
2
R2
R2
O
S
1−5
6−10
S
O
O
S
NEt2
R1
NaS
NEt
2
R2
1
1−15
1
2
1
2
1
2
1
2
R = R = H (1, 6, 11); R = H, R = NHMe (2, 7, 12); R = H, R = 4-HN-C
6
H
4
Me (3, 8, 13); R = Br, R = 4-HN-C
6
H
4
Me
1
2
(
6 4
4, 9, 14); R = Cl, R = 4-HN-C H Me (5, 10, 15).
mixture was stirred for 30 min. The resulting pre-
cipitate was filtered off, washed with water (2 × 40 mL),
and dried in air.
9,10-Dioxo-4-(p-tolylamino)-9,10-dihydroanthracen-
1-yldiethylcarbamodithioate (13). Yield 69%,
–
1
mp >110°С (decomp.). IR spectrum, ν, cm : 1674,
1
1
649 (С=О). Н NMR spectrum, δ, ppm: 1.17 t (3Н,
9,10-Dioxo-9,10-dihydroanthracen-1-yldiethylcar-
CH , J = 6.8 Hz), 1.37 t (3Н, CH , J = 7.2 Hz), 2.35 s
3
3
bamodithioate (11). Yield 90%, mp >100°С (decomp.).
–
1
1
(3Н, CH
3
), 3.86–3.95 m (4H, CH ), 7.37 m (2H,
2
IR spectrum, ν, cm : 1674, 1631 (С=О). Н NMR
CН ), 7.56–7.75 m (3H, CН ), 7.87–8.07 m (3H,
Ar
Ar
spectrum, δ, ppm: 1.21 t (3Н, СН , J = 6.8 Hz), 1.35 t
3
13
CН ), 8.21–8.29 m (2H, CН ), 13.07 s (1H, NH). С
Ar
Ar
(
3Н, CH , J = 7.2 Hz), 3.84–3.95 m (4H, CH ), 7.88–
3
2
1
3
NMR spectrum, δ
С
, ppm: 11.51 (СН ), 13.73 (СН ),
3 3
8
1
1
1
1
6
.24 m (7H, CНAr). С NMR spectrum, δ , ppm:
С
4
1
1
6
7.57 (CH ), 52.09 (CH ), 124.39, 126.71, 128.24,
2 2
1.68 (СН ), 13.76 (СН ), 48.97 (CH ), 49.61 (CH ),
3
3
2
2
29.86, 130.82, 133.97, 134.39, 135.21, 136.02 (CAr),
81.78, 182.45 (С=О), 191.63 (С=S). Found, %: C
7.65; H 5.09; N 6.134; S 14.12. C H N O S .
26.89, 127.29, 128.05, 132.44, 133.17, 133.87,
34.28, 134.67, 135.01, 135.19, 135.62, 141.55 (CAr),
82.46, 182.67 (С=О), 192.43 (С=S). Found, %: C
4.31; H 4.74; N 4.12; S 18.12. C H NO S .
2
6
24
2
2 2
Calculated, %: C 67.80; H 5.25; N 6.08; S 13.92.
1
9
17
2 2
Calculated, %: C 64.20; H 4.82; N 3.94; S 18.04.
-(Methylamino)-9,10-dioxo-9,10-dihydroanthracen-
-yldiethylcarbamodithioate (12). Yield 72%,
2
-Bromo-9,10-dioxo-4-(p-tolylamino)-9,10-dihyd-
4
roanthracen-1-yldiethylcarbamodithioate (14). Yield
67%, mp >110°С (decomp.). IR spectrum, ν, cm :
1681, 1637 (С=О). Н NMR spectrum, δ, ppm: 1.17 t
(3Н, CH , J = 6.8 Hz), 1.37 t (3Н, CH , J = 7.2 Hz),
–
1
1
–
1
1
mp >110°С (decomp.). IR spectrum, ν, cm : 1680,
1
1
645 (С=О). Н NMR spectrum, δ, ppm: 1.01 s (3Н,
3
3
CH ), 1.17 t (3Н, CH , J = 6.8 Hz), 1.37 t (3Н, CH ,
2.32 s (3Н, CH ), 3.85–3.96 m (4H, CH ), 7.26–7.41 m
3
3
3
3
2
J = 7.2 Hz), 3.85–3.96 m (4H, CH ), 7.90–8.26 m (6H,
(3H, CН ), 7.87–8.05 m (3H, CН ), 8.11–8.19 m
(3H, CН ), 11.27 s (1H, NH). С NMR spectrum, δ ,
Ar С
2
Ar Ar
1
3
13
CН ), 12.99 s (1H, NH). С NMR spectrum, δ , ppm:
Ar
С
1
1
1
1
1
1.67 (СН ), 13.92 (СН ), 48.37 (CH ), 49.87 (CH ),
ppm: 11.83 (СН ), 13.84 (СН ), 21.08 (СН ), 47.68
(CH ), 52.19 (CH ), 112.86, 114.09, 118.86, 124.89,
2 2
126.81, 127.19, 129.12, 130.95, 132.62, 134.12,
3
3
2
2
3 3 3
26.77, 126.95, 132.86, 133.67, 133.83, 134.38,
34.78, 136.08, 144.96 (Carоm), 182.05, 182.34 (С=О),
91.56 (С=S). Found, %: C 62.74; H 5.08; N 7.45; S
6.51. C H N O S . Calculated, %: C 62.47; H 5.24;
135.03, 135.53, 136.53, 145.27, 150.51 (C ), 182.21,
Ar
184.07 (С=О), 191.66 (С=S). Found, %: C 57.97; H
20
20
2
2 2
N 7.29; S 16.68.
4.27; Br 14.89; N 5.13; S 11.95. C26H23BrN O S .
2 2 2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 12 2016

SYNTHESIS OF 9,10-ANTHRACENEDIONE DIETHYLDITHIOCARBAMATES
2701
Calculated, %: C 57.88; H 4.30; Br 14.81; N 5.19; S
1.88.
Cheng, T.M., Lai, C.S., and Li, R.T., Bioorg. Med.
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9
,10-Dioxo-4-(p-tolylamino)-2-chloro-9,10-dihyd-
8
9
. AIDS Res. Hum. Retrov., 1993, vol. 9, p. 83. doi
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1
0.1089/aid.1993.9.83
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0.1002/0471725587.ch2
–
1
5
1
9%, mp >110°С (decomp.). IR specrtum, ν, cm :
1
681, 1637 (С=О). Н NMR spectrum, δ, ppm: 1.16 t
1
(
3Н, CH , J = 6.8 Hz), 1.38 t (3Н, CH , J = 7.2 Hz),
3
3
1
0. Nagano, R., Shibata, K., Naito, T., Fuse, A., Asano, K.,
Hashizume, T., and Nakagawa, S., Antimicrob. Agents
Chemother., 1997, vol. 41, p. 2278.
2
.32 s (3Н, CH ), 3.85–3.96 m (4H, CH ), 7.56–7.70 m
3 2
(
(
3H, CН ), 7.88–7.96 m (3H, CН ), 8.12–8.22 m
Ar Ar
1
3
3H, CН ), 12.14 s (1H, NH). С NMR spectrum, δ ,
Ar
С
11. Safak, C., Erdogan, H., Yesilada, A., Erol, K., and
ppm: 11.26 (СН ), 13.66 (СН ), 21.27 (СН ), 47.63
Cimgi, I., Arzneim. Forsch., 1992, vol. 42, p. 123.
3
3
3
(
CH ), 52.25 (CH ), 112.75, 116.76, 118.16, 124.87,
26.97, 130.88, 132.28, 134.59, 135.39, 135.89,
2 2
12. Warrass, R., Weismuller, K.H., and Jung, G., Tetra-
hedron Lett., 1998, vol. 39, p. 2715. doi 10.1016/S0040-
4039(98)00385-2
13. Li, Z., Bitha, P., Lang, Jr., S.A., and Lin, Y., Biol. Med.
Chem. Lett., 1997, vol. 7, p. 2909. doi 10.1016/S0960-
1
1
1
5
6
35.98, 141.09, 150.42 (C ), 182.07, 184.56 (С=О),
Ar
91.69 (С=S). Found, %: C 63.36; H 4.84; Cl 7.10; N
.649; S 12.87. C H ClN O S . Calculated, %: C
2
6
23
2
2 2
8
94X(97)10111-1
3.08; H 4.68; Cl 7.16; N 5.66; S 11.88.
1
4. Fain, V.Ya., 9,10-Antrakhinony i ikh primenenie (9,10-
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1
13
Н and С NMR spectra were registered on a
Varian Mercury-400 spectrometer in the solutions of
DMSO-d (399.96 and 100.61 MHz, respectively),
internal reference TMS. IR spectra (KBr) were
recorded on a Specord M-80 spectrometer. Purity of
compounds obtained was monitored by TLC method
6
1
1
5. Arai, S., Kato, S., and Hida, M.B., Chem. Soc. Japan,
1
985, vol. 58, p. 1458.
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(
Silufol UV-254 plates, benzene–acetonitrile, 6 : 1).
1
7. Guerin, D., Carlier, R., and Lorcy, D., J. Org. Chem.,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 12 2016