Synthesis and structure of a novel disulfide-containing aniline

Article abstract of DOI:10.1081/SCC-200046525

A novel disulfide-containing aniline, 5,8-dihydro-1H,4H-2,3,6,7- tetrathiaanthracen-9-ylamine (6) was synthesized. The structures of the target compound and the intermediates have been identified by ¹H NMR, MS, IR, Raman and elemental analysis. In addition, the structure of 9-Nitro-5,8-dihydro-1H,4H-2,3,6,7-tetrathiaanthracene (5) was determined by single X-ray analysis.

Full text of DOI:10.1081/SCC-200046525

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Synthesis and Structure of a
Novel Disulfide‐Containing
Aniline
Shi‐Ren Deng a , Lei Wu a , Hao Wang a , Bin Zhou a
,
Wai‐Kwok Wong b , Jian‐ping Guo b , Zao‐Ying Li a
Yun‐Hong Zhou a
&
a Department of Chemistry , Wuhan University ,
Wuhan, 430072, P. R. China
b Department of Chemistry , Hong Kong Baptist
University , Hong Kong, P. R. China
Published online: 05 Aug 2006.
To cite this article: Shi‐Ren Deng , Lei Wu , Hao Wang , Bin Zhou , Wai‐Kwok Wong ,
Jian‐ping Guo , Zao‐Ying Li & Yun‐Hong Zhou (2005) Synthesis and Structure of a Novel
Disulfide‐Containing Aniline, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 35:1, 129-135, DOI: 10.1081/
SCC-200046525
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Synthetic Communicationsw, 35: 129–135, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1081/SCC-200046525
Synthesis and Structure of a Novel
Disulfide-Containing Aniline
Shi-Ren Deng, Lei Wu, Hao Wang, Bin Zhou,
Zao-Ying Li, and Yun-Hong Zhou
Department of Chemistry, Wuhan University, Wuhan, P. R. China
Wai-Kwok Wong and Jian-ping Guo
Department of Chemistry, Hong Kong Baptist University,
Hong Kong, P. R. China
Abstract: A novel disulfide-containing aniline, 5,8-dihydro-1H,4H-2,3,6,7-tetrathia-
anthracen-9-ylamine (6) was synthesized. The structures of the target compound and
1
the intermediates have been identified by H NMR, MS, IR, Raman and elemental
analysis. In addition, the structure of 9-Nitro-5,8-dihydro-1H,4H-2,3,6,7-tetrathia-
anthracene (5) was determined by single X-ray analysis.
Keywords: Alkylbromination, thioesterification, selective reduction, disulfide
A series of organodisulfide compounds[1,2] having two mercapto groups
within the molecules are recently being considered as new energy storage
materials in lithium batteries because of their high specific energy, whereby
energy exchange occurs based on the reversible polymerization-depolymeri-
zation process (2S2 $ S-S). At the same time, polyaniline (PANI) as one
of the most promising intrinsically conducting polymers due to its straight-
forward polymerization, chemical and environmental stability, and relatively
high conductivity, has been widely studied for electronic and optical
Received in Poland August 20, 2004
Address correspondence to Zao-Ying Li, Department of Chemistry, Wuhan Univer-
sity, Wuhan 430072, P. R. China. E-mail: zyliwuc@whc.edu.cn

130
S.-R. Deng et al.
applications.[3] Since the 1990s, Naoi[4] found that the PANI could act as an
effective electrocatalyst to speed up the redox of the disulfide, the researches
on syntheses and properties of disulfide-containing aniline have been widely
reported with relative satisfying results as a new kind of highly potential
anode material.[5–7]
In this paper, we report the synthesis and structure of a new aniline deriva-
tive, which has two condensed aliphatic rings containing two disulfur bonds.
Its high disulfide density and intramolecular S-S bonds can lead to a promising
advantage of high effectivity as a potential battery material.[6]
The total synthetic steps for target compound 5,8-dihydro-1H,4H-2,3,6,
7-tetrathia- anthracen-9-ylamine (6) is achieved in four steps starting from
1,2,4,5-tetramethyl-benzene(1) as outlined in Scheme 1. Bromination of 1
(NBS, CCl4, reflux) is followed by nitration of the bromide 2 (HNO3,
CHCl3, 308C) to afford the 1,2,4,5-tetrabromomethyl-3-nitrobenzene (3). In
contrast, attempted nitration of 1 followed by bromination of the nitro
compound failed to give the pure nitro compound 3, a hardly isolated
mixture of nitro benzylic bromide. It is noteworthy that during the course of
nitration, the 3,6-dinitro-1,2,4,5-tetrabromomethyl-benzene was never
obtained in this process. Either the mononitro compound results, or else
unchanged starting material and oxidation product was generated, no matter
how much the nitric acid was used.
The benzylic bromide 3 was then converted to a kind of sodium alkylthio-
sulfate (4) (Na2S2O3, H2O/EtOH, 808C) as an intermediate which, without
purification, was oxidized by I2 in the same condition as above to form a
tricyclic structure 5. Sodium alkylthiosulfate (Bunte salts) has been reported
as a generally used regent to form disulfide compound by reaction with
iodine[8] and hydrogen peroxide.[9] In this case, we completed the reaction
with iodine but failed with hydrogen peroxide. Furthermore, to prove the
existence of the thioesterification product (4), the above reaction was inter-
1
rupted before the addition of iodine, and the H NMR(D2O) spectrum of the
fine white solid mixture resulting from the evaporation of the above
Scheme 1.

Synthesis and Structure of a Novel Disulfide-Containing Aniline
131
solution was obtained. From its water solubility and the dataa of its NMR
spectrum, we can easily confirm the formation of this intermediate.
Finally, the nitro compound 5 was selectively reduced to amine 6 (Fe/
NH4Cl, H2O/EtOH, reflux), preventing the ring opening at the S-S bond.
Fe/NH4Cl have been reported as a kind of specific reductant in neutral
medium for the nitro group, along with other reducible group such as the
nitrile and keto unaffected.[10] In this case, we successfully reduced the
nitro group to the amino group with Fe/NH4Cl in a EtOH/H2O (1 : 1)
mixed solution, without any change to disulfide bond. It is mentionable that
if the medium of reduction changed to acid condition, the disulfide bond
will be reduced to mercapto group.
Sulfur-rich compounds give very intense Raman spectra since the valence
electrons in S-S bonds are highly polarizable.[11] Therefore, Raman spec-
troscopy has always been a powerful research tool in this area. In this work,
the Raman spectra of compound 5 and 6, both containing S-S bonds, were
recorded. Their S-S stretching vibrations are observed at 522 and 525 cm21
respectively, which was similar to the character of other disulfide
compounds.[12,13]
Our attempt of getting the single crystal of 6 failed, but we successfully
grew a single crystal of 5 from CHCl3 and submitted it to X-ray crystallogra-
phy. The ORTEP drawing of the compound 5 is shown in Fig. 1, from which
we can see clearly that the molecule has a nonplanar structure. The relative
crystal data are presented in the Experimental section.
In conclusion, a four-step synthesis of a novel disulfide-containing
aniline, 5,8-dihydro-1H,4H-2,3,6,7-tetrathia-anthracen-9-ylamine(6) has
been developed. During the synthesis of 6, three new compounds, 3, 5, 6
were first prepared, and the single-crystal X-ray analysis of 5 confirmed its
structure. The designed molecular is a kind of potential material when it is
to be polymerized and used as the cathode material of the secondary
lithium batteries. The corresponding research work on polymerization is
under way.
EXPERIMENTAL
1,2,4,5-Tetramethyl-benzene (1) and N-bromosuccinimide (NBS) were
recrystallized from MeOH and H2O, respectively. Other commercially
available reagents were used without further purification, unless otherwise
noted. All solvents used for extractions or reactions were dried according to
standard procedures and kept over molecular sieves. 1,2,4,5-Tetrabromo-
methyl- benzene (2) was prepared according to literature[14] procedure.
Melting-points were taken on a micro-melting apparatus and uncorrected.
a1H NMR(D2O) d 7.63(s, 1H, ph-H), 4.37(s, 4H, o-ph-CH2), 4.24(s, 4H, m-ph-CH2).

132
S.-R. Deng et al.
Figure 1. ORTEP Drawing of the molecular structure of 5. CCDC reference number
235626.
NMR spectra were obtained on Varian Mercury-VX 300 spectrometers.
Spectra were recorded in CDCl3, using TMS as internal standard at 300
1
MHz for H and 125 Hz for 13C at 298 K if not stated otherwise; d values
are given in ppm and coupling constants are reported in Hz. FT-IR spectra
were recorded on a Shimadzu Infred spectrophotometer (as KBr disc,
values in cm21). Raman spectra were recorded on a NEXUS670 spectro-
photometer. Mass spectra were obtained on a Thermo Finnigan TRACE
MS PLUS (EI) and Finnigan LCQ advantage (electrospray). The element
analyses were measured with a Finnigan FLASH 1112 SERIES EA. The
crystal data were collected with a Bruker AXS SMART 1000 CCD. Chroma-
tographic separations were performed using silica gel G (200–300 mesh,
Qingdao, China).
1,2,4,5-Tetrabromomethyl-3-nitrobenzene (3)
12.6 g (196 mmol) of fuming nitric acid was added over 10 min into a magne-
tically stirred mixture of 9.0 g (20 mmol) 2 in 120 mL of CHCl3 and 90 mL of
98% H2SO4 at 08C. After heating at 308C for 4 h, the reaction mixture was
cooled to room temperature and poured into a separatory funnel to remove
the mixed acid layer, and the upper organic layer was immediately washed
with 10% NaOH and H2O and dried over MgSO4. Removal of the solvent
gave a white solid residue, which was recrystallized from CHCl3/EtOH to
1
afford 4.5 g (46%) of 2, mp 187–1888C, H NMR (CDCl3) d 7.55(s, 1H,

Synthesis and Structure of a Novel Disulfide-Containing Aniline
133
ph-H), 4.62(s, 4H, o-ph-CH2), 4.47(s, 4H, m-ph-CH2), FT-IR(KBr) 3038,
2921(nC-H), 1525, 1327(nN55O), 601(nC-Br) cm21, Anal. for C10H9Br4NO2
Calcd: C, 24.27; H, 1.83; N, 2.83, Found: C, 24.22; H, 1.83; N, 2.80.
9-Nitro-5,8-dihydro-1H,4H-2,3,6,7-tetrathia-anthracene (5)
The compound 3 (2.0 g 4.0 mmol) and sodium thiosulphate (4.0 g 16.1 mmol)
were dissolved in 80 mL of EtOH/H2O (1 : 1). The mixture was refluxed with
stirring until the solution was homogeneous. The iodine was then added in
small portions until the color remained. Then a sodium bisulfite solution
was added to remove the excess iodine. After filtration, the yellow precipi-
tation was washed with water and then dried in vacuum at 808C and then
extracted by 100 mL of boiling CHCl3. Evaporation of solvent left a yellow
solid, which was purified using silica gel chromatography (chloroform/
petroleum ether 10 : 3) to give 0.64 g (53%) of 5 as a yellow solid: mp
1
136–1378C; H NMR (CDCl3) d 6.99(s, 1H, ph-H), 4.05(s, 4H, o-ph-CH2),
3.85(s, 4H, m-ph-CH2); FT-IR (KBr) 2960, 2914(nC-H), 1532, 1363(nN55O
)
cm21; Raman 525(nS-S) cm21; ESMS m/z 301.6[M-H]þ; Anal. for
C10H9NO2S4 Calcd: C, 39.58; H, 2.99; N, 4.62, Found: C, 39.64; H, 3.02;
N, 4.58.
9-Amino-5,8-dihydro-1H,4H-2,3,6,7-tetrathia-anthracene (6)
A hot solution of 0.2 g (0.66 mmol) of 5 in 80 mL of EtOH was added to a
refluxing mixture of 7.0 g(125 mmol) of iron powder and 6.0 g (112 mmol)
of NH4Cl in 80 mL of H2O under nitrogen atmosphere. After heating at
reflux for 4 h, the reaction mixture was cooled and filtered and the filtrate
was extracted with CHCl3 (3 ꢀ 30 mL), the combined extracts were washed
with H2O (3 ꢀ 30 mL), dried over Na2SO4 and purified using silica gel chrom-
atography (CHCl3) to give 0.14 g (78%) of 6 as a light yellow solid: mp 1268C
(dec); 1H NMR (CDCl3) d 6.36(s, 1H, ph-H), 4.01(s, 4H, o-ph-CH2),
3.72(s, 4H, m-ph-CH2), 3.61(s, 2H, broad, NH2); 13C NMR (CDCl3) d
142.8, 131.4, 122.0, 116.4, 36.2, 28.4; FT-IR(KBr) 3463, 3386, 1625(nN-H
)
cm21; Raman 522(nS-S) cm21; MS (EI) 273[M]þ; Anal. for C10H11NS4
Calcd: C, 43.92; H, 4.05; N, 5.12, Found: C, 44.05; H, 4.07; N, 5.08.
X-Ray Crystallographic
The crystal structures of compound 5 were determined using data collected
at 293 K with Mo Ka radiation on a Bruker AXS CCD diffractometer. The
structure was solved by direct methods (SHELXS-97) and refined using
full-matrix least-squares on F2.

134
S.-R. Deng et al.
Slight yellow crystal of 5 was obtained by slow crystallization (CHCl3) at
0–48C over 1 week. A crystal of dimensions 0.20 ꢀ 0.20 ꢀ 0.10 mm3 was
selected and found to crystallize in the orthorhombic space group Pbca,
˚
˚
˚
a ¼ 14.9439(10) A, b ¼ 8.1770(6) A, c ¼ 19.8869(13) A, a ¼ 908, b ¼ 908,
g ¼ 908, V ¼ 2430.1(3) A , Z ¼ 8, dcalc ¼ 1.659 Kg m23,T ¼ 293 K. 13674
3
˚
reflections were measured, 2911 unique (Rint ¼ 0.0501). The final wR(F2)
was 0.0898 for all data, R1(F) was 0.0373 where I . 2s(I). Goodness of fit
on F2 is 1.016.
Complete crystallographic data (excluding structure factors) have been
deposited at the Cambridge Crystallographic Data Centre under the
reference number CCDC 235626. Copies of the data can be obtained, free
of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK [fax: þ44-1223-336033 or e-mail: deposit@ccdc.cam.ac.uk].
ACKNOWLEDGMENT
We gratefully acknowledge financial support by the National Natural Science
Foundation of China (No. 29833090).
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