4,6-Bis(1,2,3-thiadiazol-4-yl)-1,3-benzenediol as a source of furo[3′,2′:4,5]benzo[b]furan-2,6-dithiolate

Full text of DOI:10.1007/s11178-005-0081-6

Russian Journal of Organic Chemistry, Vol. 40, No. 11, 2004, pp. 1691 -1693. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11,
2004, pp. 1737-1739.
Original Russian Text Copyright Ó 2004 by Petrov, Androsov, Lyakhovetskii.
SHORT
COMMUNICATIONS
4,6-Bis(1,2,3-thiadiazol-4-yl)-1,3-benzenediol as a Source
of Furo[3',2':4,5]benzo[b]furan-2,6-dithiolate
M.L. Petrov, D.A.Androsov, andYu.I. Lyakhovetskii
St. Petersburg State Technological Institute, St. Petersburg, 190013 Russia
e-mail: mlpetrov@tu.spb.ru
Received February 19, 2004
Compounds containing furo[3',2':4,5]benzo[b]-furan
heterocyclic structure were found in some algae (so-called
cyperaquinone [1]). As a rule these heterocycles can be
synthesized from resorcinol [2] and have been first men-
tioned in the literature in 1932 [3]. We recently developed
a new preparation procedure for 2-benzofuranchalco-
genolates by treating 4-(2-hydroxyphenyl)-1,2,3-thia- and
selenadiazoles with bases [4–10]. This method of
benzo[b]furans synthesis is underlain by intramolecular
addition of an ortho-hydroxy group to the products of
1,2,3-thia- and selenadiazoles decomposition, thioketenes
and selenoketenes [5].
ethanone (I), was obtained via Fries rearrangement from
the resorcinol diacetate [12]. Reaction of compound I
with ethoxycarbonylhydrazine afforded successively its
ethoxycarbonylhydrazone (II) and bis(ethoxycarbonyl-
hydrazone) (III). Previously unknown 4,6-di(1,2,3-
thiadiazol-4-yl)-1,3-phenylenediol (IV) was obtained by
treating bis(ethoxycarbonylhydrazone) (III) with thionyl
chloride.
Treated with potassium carbonate bis(thiadiazole) IV
decomposed with nitrogen elimination giving rise to
furo[3',2':4,5]benzo[b]furan-2,6-dithiolate (V). Dithiolate
V formation was confirmed with the following experi-
ments: The decomposition of dithiadiazole IV effected by
potassium carbonate in the presence of butyl bromide fur-
nished 2,6-di(butylthio)furo[3',2':4,5]benzo-[b]furan (VI),
a similar reaction in the presence of benzyl chloride af-
forded 2,6-di(benzylthio)-furo[3',2':4,5]benzo[b]furan
(VII).
In an attempt to extend this method to the synthesis of
furo[3',2':4,5]benzo[b]furans we prepared 4,6-di(1,2,3-
thiadiazol-4-yl)-1,3-phenylenediol.Among benzene deriva-
tives containing more than one 1,2,3-thiadiazol-4-yl sub-
stituent only the 4-[3,5-di(1,2,3-thiadiazol-4-yl)phenyl]-
1,2,3-thiadiazole was known [11]. The initial compound
for the synthesis of 4,6-di(1,2,3-thiadiazol-4-yl)-1,3-
phenylenediol, 1-(5-acetyl-2,4-dihydroxyphenyl)-1-
1-(5-Acetyl-2,4-dihydroxyphenyl)-1-ethanone
ethoxycarbonylhydrazone (II). A mixture of 1.28 g
+2
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1+ 1+&2 (W
(W2 &+1+1
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2
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62&O
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. &2 ꢀꢀ0H&1
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5+OJ 56
6
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1070-4280/04/4011-1691Ó2004 MAIK “Nauka/Interperiodica”

PETROV et al.
1692
what darker to the end of the process. On cooling the
reaction mixture to 20–25°C the excess thionyl chloride
was distilled off in a vacuum. To the residue 30 ml of cold
water was added to decompose the traces of thionyl chlo-
ride. The separated precipitate was filtered off, washed
with water (5´20 ml), and dried. Yield of the crude reac-
tion product 1.8 g. It was extracted with boiling benzene
(3´15 ml), the substance precipitated from the extract
was filtered off, washed with a little benzene, and dried.
Yield of compound IV 0.7 g (52%). Light-yellow small
crystals, mp 270°C (decomp), Rf 0.54 (eluent chloroform–
(6.6 mmol) of 1-(5-acetyl-2,4-dihydroxyphenyl)-1-
ethanone (I) [13], 1.37 g (13.16 mmol) of ethoxy-
carbonylhydrazine, and 20 ml of toluene was boiled for
2 h while distilling off water into the Dean-Stark trap.
The reagents first dissolved giving a light-yellow solution,
and in 30 min a colorless precipitate of ethoxycarbonyl-
hydrazone separated. On completion of the reaction the
precipitate was filtered off, thoroughly washed with wa-
ter, and dried. Yield of ethoxycarbonylhydrazone II 1.76
g (95%). Fine crystalline powder, mp. 245–247°C, Rf 0.44
(eluent chloroform-acetone, 5:1).
1H NMR spectrum (DMSO-d6), d, ppm: 1.26 t
(CH3CH2), 2.35 s (CH3C=N), 2.62 s (CH3C=O), 4.2 q
(CH2CH3), 6.32 s (H6 ), 7.99 s ( H3 ), 10.72 s ( OH1),
12.56 s (NH), 14.03 s (OH5). 13C NMR spectrum
(DMSO-d6), d, ppm: 13.7 (CH3CH2), 14.8 (CH3C=N),
27.19 ( CH3C=O), 61.59 (CH2CH3), 104 (C6), 112.2 (C2),
113.24 (C4), 132.93 (C3), 154.38 (C=N), 164.23 (C1),
165.79 (C5), 203.1 (C=O). Mass spectrum, m/z (Irel, %):
M+ 280 (100). Found, %: C 55.87, 55.64; H 5.82, 5.93.
C13H16N2O5. Calculated, %: C 55.71; H 5.75.
1
acetone,5:1). H NMR spectrum (DMSO-d6), d, ppm:
6.83 s (H2), 9.27 s (H5), 9.33 s (H, Ht), 10.81 s (OH).
13C NMR spectrum (DMSO-d6), d, ppm: 103.43 (C4, C6),
110.13 (C2), 130.23 (C5, Ht), 132.83 (C4, Ht), 156.37 (C5),
158.07 (C1, C3). Mass spectrum, m/z (Irel, %): M+ 278
(95). Found, %: C 42.97, 43.21; H 2.24, 2.33.
C10H6N4O2S2. Calculated, %: C 43.16; H 2.16.
2,6-Di(butylthio)furo[3',2':4,5]benzo[b]-furan
(VI). A dispersion of 0.46 g (1.66 mmol) of compound
IV, 0.69 g (4.98 mmol) of freshly calcined potassium car-
bonate, 0.46 g (3.32 mmol) of butyl bromide, and 50 ml of
dry acetonitrile was boiled for 2 h at vigorous stirring.
Then the reaction mixture was filtered, and the filtrate
was evaporated in a vacuum. The residue was subjected
to chromatography on a column (3´10 cm) packed with
silica gel of the grade L 100/160, eluent carbon tetrachlo-
ride. From the first fraction on removal of the solvent we
obtained 0.23 g (42%) of viscous light-yellow oily com-
1-(5-Acetyl-2,4-dihydroxyphenyl)-1-ethanone
bis(ethoxycarbonylhydrazone) (III). A mixture of
2.8 g 10 mmol) of compound II, 5.2 g (50 mmol) of
ethoxycarbonylhydrazine, 1 ml of acetic acid, and 200 ml
of ethanol was boiled at vigorous stirring for 30 h. On
completion of the reaction the light-greenish precipitate
was filtered off, washed with ethanol (5´20 ml), and
dried. Yield of bis(ethoxycarbonylhydrazone) (III)
3.26 g (89%). Fine crystalline greenish powder, mp 275°C
1
pound VI, Rf 0.63 (eluent carbon tetrachloride). H NMR
spectrum (CDCl3), d, ppm: 0.91 t (CH3), 1.46 t. d
(SCH2CH2), 1.65 t.d (SCH2CH2CH2), 2.94 t.t (SCH2),
6.81 s (H3, H5), 7.47 s (H8), 7.51 s (H4). 13C NMR spec-
trum (CDCl3), d, ppm: 13.35 (CH3), 21.39 (CH2CH3),
31.57 (SCH2), 34.23 (SCH2CH2), 93.67 (C8), 109.48 (C4),
110.61 (C3, C5), 125.19 (C3a, C4a), 150.6 (C7a, C8a), 154.36
(C2, C6). Mass spectrum, m/z (Irel, %): M+ 334 (27).
Found, %: C 64.49, 64.67; H 6.45, 6.59. C18H22O2S2.
Calculated, %: C 64.41, H 6.54.
1
(decomp.), Rf 0.36 (eluent chloroform–acetone, 3:1). H
NMR spectrum (DMSO-d6), d, ppm: 1.26 t (CH3CH2),
2.32 C (CH3C=N), 4.19 q (CH2CH3), 6.28 s (H6), 7.59 s
( H3 ), 10.63 s (NH), 13.38 s (OH). 13C NMR spectrum
(DMSO-d6), d, ppm: 13.75 (CH3CH2), 14.83 (CH3C=N),
61.43 (CH2CH3), 104.52 (C6), 112.2 (C2 and C4), 128.68
(C3), 154.42 (C=N and C=O), 161.31 (C1 and C5). Mass
spectrum, m/z (Irel, %): M+ 366 (80). Found, %: C 52.36,
52.545; H 5.91, 5.79. C16H22N4O6. Calculated, %: C 52.45;
H 6.05.
2,6-Di(benzylthio)furo[3',2':4,5]benzo-[b]furan
(VII). Adispersion of 0.09 g (0.324 mmol) of 4,6-di(1,2,3-
thiadiazol-4-yl)-1,3-phenylenediol (IV), 0.134 g (0.971
mmol) of freshly calcined potassium carbonate, 0.082 g
(0.647 mmol) of benzyl chloride, and 5 ml of dry acetoni-
trile was boiled for 2 h at vigorous stirring. Then the re-
action mixture was filtered, and the filtrate was evapo-
rated in a vacuum. The residue was subjected to chro-
matography on a column (3´10 cm) packed with silica
gel of the grade L 100/160, eluent carbon tetrachloride.
From the first fraction on removal of the solvent we ob-
4,6-Di(1,2,3-thiadiazol-4-yl)-1,3-phenylenediol
(IV). In a flask equipped with a magnetic stirrer, a reflux
condenser, and a system for removal and absorption of
gases was added to 1.76 g (4.81 mmol) of 1-(5-acetyl-
2,4-dihydroxyphenyl)-1-ethanone bis(ethoxycarbonylhy-
drazone) (III) 30 ml of freshly distilled thionyl chloride.
The mixture was heated at reflux and stirring for 5 h; the
mixture became homogeneous about 5 min after the start
of reaction turning into a brown solution that got some-
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004

4,6-BIS(1,2,3-THIADIAZOL-4-YL)-1,3-BENZENEDIOL
1693
tained 0.05 g (39%) of 2,6-di(benzylthio)furo[3',2':4,5]-
REFERENCES
benzo[b]furan (VII). Fine crystalline powder, mp 95–
96°C, Rf 0.52 (eluent carbon tetrachloride). H NMR
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1
spectrum (CDCl3), d, ppm: 4.16 s (CH2), 6.69 s (H3, H5),
7.25 br.s (Ph), 7.43 s (H8), 7.54 s ( H4). 13C NMR spec-
trum (CDCl3), d, ppm: 39.32 (CH2), 93.74 (C8), 110.16
(C4), 111.89 (C3, C5), 125.15 (C3a, C4a), 127.21 (Ph, Cp),
128.37 (Ph, Co), 128.67 (Ph, Cm), 137.05 (Ph, Cipso),
149.58 (C7a, C8a), 154.65 (C2, C6). Mass spectrum, m/z
(Irel, %): M+ 402 (69). Found, %: C 71.72, 71.56; H 4.31,
4.29. C24H18O2S2. Calculated, %: C 71.64; H 4.48.
..
Melting points were measured on a Boetius heating
block. 1H and 13C NMR spectra were registered on spec-
trometers BrukerAvance (300 and 75 MHz) and Bruker
AMX-400 (400 and 100 MHz), as internal references
served signals of residual protons (1H) and carbon atoms
(13C) of deuterated solvents. Mass spectra were recorded
on a mass spectrometer Kratos MS 890 at a direct ad-
mission of a sample into the ion source, ionizing electrons
energy 70 eV, temperature in the ionization chamber
200°C. The reaction progress was monitored by TLC on
Silufol UV-254 plates, spots were visualized by UV irra-
diation or iodine vapor.All solvents used in the study were
purified and dried by standard procedures.
The study was carried out under financial support of
the Ministry of Education of the Russian Federation (grant
no. A03-2.11-3).
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004