Synthesis of 3,3,5,5-tetrabenzyl-1,2,4-trithiol and 1,2-dis(1,3-arylpropan- 2-yl)disulfane

Article abstract of DOI:10.1016/j.cclet.2013.05.041

Novel sulfur-containing compounds (3a-3c, 4a-4c) were obtained in ethanol with 1,3-diphenyl-2-propanone as the starting material. The advantages of this procedure were mild reaction conditions, simple protocol, and high yields. The structures of the products were characterized by IR, ¹H NMR, MS and elementary analysis. The crystal of the new compound 4a belongs to monoclinic, space group C2 with a = 18.727(3), b = 6.5179(9), c = 13.7576(18) ?, β = 131.0610(10), V = 1266.2(3)?³, Z = 2, Dc = 2.136 g/cm³, μ = 1.078 mm^-1, F(0 0 0) = 843, R = 0.0490 and wR = 0.1247 for 3211 observed reflection with I > 2σ(I). X-ray analysis reveals that the molecule is not symmetrical, the molecular structure is stabilized by weak π-π stacking interactions, and no classical hydrogen bonds can be observed.

Full text of DOI:10.1016/j.cclet.2013.05.041

Chinese Chemical Letters 24 (2013) 909–911
Contents lists available at SciVerse ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
Original article
Synthesis of 3,3,5,5-tetrabenzyl-1,2,4-trithiol and
1,2-dis(1,3-arylpropan-2-yl)disulfane
*
Fu Feng, Meng Huang, Zheng-Chao Duan, Wei-Bing Hu
School of Chemistry and Environmental Engineering, Hubei Institute for Nationalities, Enshi 445000, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Novel sulfur-containing compounds (3a–3c, 4a–4c) were obtained in ethanol with 1,3-diphenyl-2-
propanone as the starting material. The advantages of this procedure were mild reaction conditions,
simple protocol, and high yields. The structures of the products were characterized by IR, 1H NMR, MS
Received 4 March 2013
Received in revised form 28 April 2013
Accepted 8 May 2013
and elementary analysis. The crystal of the new compound 4a belongs to monoclinic, space group C2
3
˚
˚
with a = 18.727(3), b = 6.5179(9), c = 13.7576(18) A,
Dc = 2.136 g/cm3, = 1.078 mmÀ1
reflection with I > 2 (I). X-ray analysis reveals that the molecule is not symmetrical, the molecular
b
= 131.0610(10)8, V = 1266.2(3)A , Z = 2,
Keywords:
m
, F(0 0 0) = 843, R = 0.0490 and wR = 0.1247 for 3211 observed
1,3-Diphenyl-2-propanone
Synthesis
s
structure is stabilized by weak
observed.
p–p stacking interactions, and no classical hydrogen bonds can be
Sulfur-containing compounds
ß 2013 Wei-Bing Hu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights
reserved.
1. Introduction
analysis instrument. Melting point was measured on a XT4A
melting-point apparatus with microscope and uncorrected. Single
Mercapto-compounds are important intermediates in organic
synthesis, dye, and are widely used for the synthesis of medicines,
polymeric materials, aluminum alloy corrosion inhibitors and
analytical reagents for heavy metal ion complexation [1,2].
Moreover, sulfur-containing compounds are widely used spices
in food flavor and play an important role in improving the quality
and grade of flavors [3,4]. So, a great number of studies have
appeared on sulfur-containing compounds [5]. In this paper, we
first synthesized 1,3-diphenylpropane-2,2-dithiol using 1,3-diphe-
nyl-2-propanone as the starting material. Several related novel
compounds (3a–3c, 4a–4c) were then also synthesized. The
procedures required only mild reaction conditions and simple
protocols but gave high yields. The crystal structure of compound
4a was determined by X-ray diffraction. The synthetic route to
produce compounds 3–4 is shown in Scheme 1.
crystal X-ray diffraction data were collected on a BRUCKER SMART
APEX-CCD diffractometer equipped with a graphite-monochro-
˚
matic Mo K radiation (l = 0.71073 A). 1,3-Diphenyl-2-propanone
a
and other chemicals were purchased from commercial sources.
2.1. Synthesis of compounds 3a–3c
A solution of 0.01 mol of iodine in 50 mL of benzene was added,
with stirring, to 0.01 mol of 1,3-diarylpropane-2,2-dithiol (2) in
100 mL of benzene in an ice bath. The first portion of the iodine was
rapidly decolorized, but the color soon persisted. The flask was
allowed to warm to room temperature and stirring continued for 2
days. The unchanged iodine was then destroyed by washing the
benzene solution with aqueous sodium bisulfite. The pale yellow
benzene layer was washed with saturated sodium chloride
solution. Evaporation of the benzene at reduced pressure gave a
reddish semisolid, which was extracted with hot n-hexane. The
crude material was recrystallized from n-hexane-chloroform to
give pure products 3a–3c.
2. Experimental
Infrared spectra were measured on
a Nicolet 360 FT-IR
3,3,5,5-Tetrabenzyl-1,2,4-trithiole (3a): White solid, yield 83%,
instrument using KBr pellet in the 4000–400 cmÀ1 range. 1H-
NMR spectra were collected on a Mercury Plus-400 MHz spec-
trometer in DMSO-d6 solution with TMS as an internal standard.
Elemental analysis was performed by a Vario EL III elementary
mp 144–146 8C; 1H NMR (400 MHz, DMSO-d6):
d
2.79(s, 8H, CH2),
7.31–7.37 (m, 12H, Ar-H), 7.43–7.48 (m, 8H, Ar-H); IR (KBr, cmÀ1):
3032, 2917, 1611, 1593; EI-MS (m/z): 91 (100%), 484 (M+, 4.29%).
y
Anal. Calcd. for C30H28S3: C 73.38, H 5.79; Found: C 73.52, H 5.71.
3,3,5,5-Tetra(4-bromobenzyl)-1,2,4-trithiole (3b): White solid,
yield 77%, mp 173–175 8C; 1H NMR (400 MHz, DMSO-d6):
8H, CH2), 7.33–7.37 (m, 8H, Ar-H), 7.59–7.64 (m, 8H, Ar-H); IR (KBr,
d
2.80 (s,
* Corresponding author.
E-mail address: fengfu04971118@163.com (W.-B. Hu).
1001-8417/$ – see front matter ß 2013 Wei-Bing Hu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
http://dx.doi.org/10.1016/j.cclet.2013.05.041

910
F. Feng et al. / Chinese Chemical Letters 24 (2013) 909–911
ArCH2
CH2Ar
S S
S
1,2-Dis(1,3-diphenylpropan-2-yl)disulfane (4a): white solid,
yield 90%, mp 126–128 8C; 1H NMR (400 MHz, DMSO-d6):
2.75 (d,
J = 7.2 Hz, 8H, CH2), 3.28–3.31 (m, 2H, CH), 7.26–7.29 (m, 12H, Ar-
C
C
I2
d
CH Ar
ArCH2
2
H), 7.41–7.45 (m, 8H, Ar-H); IR (KBr, cmÀ1):
y 3019, 2917, 1593; EI-
O
SH
3
MS (m/z): 91 (100%), 454 (M +, 3.19%). Anal. Calcd. for C30H30S2: C
79.30; H 6.61. Found: C 79.58, H 6.43.
ArCH2 C CH2Ar
ArCH2 C CH Ar
2
SH
1,2-Dis[1,3-di(4-bromophenylpropan)-2-yl]disulfane (4b): White
ArCH2
ArCH2
CH2Ar
CH2Ar
solid, yield 81%, mp 143–145 8C; 1H NMR (400 MHz, DMSO-d6):
d
2.76
1
H+
2
CH S S CH
(d, J = 7.2 Hz, 8H, CH2), 3.27–3.29 (m, 2H, CH), 7.31–7.34 (m, 8H, Ar-H),
7.57–7.61 (m, 8H, Ar-H); IR (KBr, cmÀ1):
y3021, 2911, 1597; EI-MS (m/
z): 169 (100%),766 (M +, 1.02%). Anal. Calcd. for C30H26Br4S2: C 47.00, H
3.39; Found: C 47.12, H 3.47.
4
1,2-Dis[1,3-di(4-nitrophenylpropan)-2-yl]disulfane (4c): White
solid, yield 83%, mp 197–199 8C; 1H NMR (400 MHz, DMSO-d6):
3a: Ar=C6H5 ;
4a: Ar=C6H5 ;
3b: Ar=4-BrC6H4 ;
4b: Ar=4-BrC6H4 ;
3c: Ar= 4-NO2C6H4
4c: Ar= 4-NO2C6H4
d
2.91 (d, J = 7.2 Hz, 8H, CH2), 3.35 (m, 2H, CH), 7.38 (m, 8H, Ar-
Scheme 1. Synthetic route of compounds 3a–3c and 4a–4c.
H), 8.19 (m, 8H, Ar-H); (KBr, cmÀ1):
y
3021, 2907, 1599; EI-MS
+
(m/z): 136 (100%), 634 (M
, 5.71%). Anal. Calcd. for
cmÀ1):
y
3025, 2917, 1607, 1591; EI-MS (m/z): 169 (100%), 796
C30H26N4O8S2: C 56.78, H 4.10, N 8.83; Found: C 56.93, H
4.02, N 8.76.
(M+, 1.45%). Anal. Calcd. for C30H24Br4S3: C 45.23, H 3.02; Found: C
45.37, H 3.11.
3,3,5,5-Tetra(4-nitrobenzyl)-1,2,4-trithiole (3c): White solid,
3. Results and discussion
yield 73%, mp 201–203 8C; 1H NMR (400 MHz, DMSO-d6):
d
2.90 (s,
8H, CH2), 7.37–7.40 (m, 8H, Ar-H), 8.21–8.25 (m, 8H, Ar-H); (KBr,
The synthesis of compound 2 followed literature procedures [6]
and the isolated yield was in agreement with the literature report.
The 1H NMR, IR and elemental analysis data of these products
supported their proposed chemical structures. A white single
cmÀ1):
y 3047, 2911, 1611, 1597; EI-MS (m/z): 136 (100%), 664
(M+, 3.46%). Anal. Calcd. for C30H24N4O8S3: C 54.22, H 3.61, N 8.43;
Found: C 54.41, H 3.54, N 8.59.
crystal
of
compound
4a
with
dimensions
of
2.2. Synthesis of compounds 4a–4c
0.16 mm  0.15 mm  0.10 mm was chosen for X-ray diffraction
analysis performed on a BRUCKER SMART APEX-CCD diffractome-
A solution of 1,3-diarylpropane-2,2-dithiol (0.01 mol) in 50 mL
of absolute alcohol was saturated with hydrogen chloride at 0–
5 8C, and the mixture was stirred at 78 8C. After 1.5 h, the flask was
stored in a refrigerator overnight and a white solid appeared. The
crude product was recrystallized from ethanol to give pure
products 4a–4c.
An alcohol solution of compound 4a was allowed to stand at
room temperature and the alcohol was allowed to slowly
evaporate. White crystals suitable for X-ray diffraction analysis
were isolated one week later.
ter equipped with a graphite-monochromatic Mo K radiation
a
˚
(
l
= 0.71073 A) radiation at 298(2) K. A total of 5119 reflections
were collected in the range of 1.968 <
scan mode with 3278 independent ones (Rint = 0.0464), in which
3211 with I > 2 (I) were observed and were used in the
u < 30.008 by using a c–v
s
subsequent refinements. The data set was corrected by SADABS
program, the structure was solved by direct methods and
expanded by Difference Fourier techniques with SHELXS-97 [7].
The non-hydrogen atoms were refined anisotropically and the
hydrogen atoms were added according to the theoretical models.
Fig. 1. Molecular structure of compound 4a.

F. Feng et al. / Chinese Chemical Letters 24 (2013) 909–911
911
stacking interactions and there no classical hydrogen bonds can be
observed.
4. Conclusion
In conclusion, a series of novel sulfur-containing compounds
were synthesized in ethanol using 1,3-diphenyl-2-propanone as
the starting material. The advantages of this procedure include
mild reaction conditions, simple protocols, and high yields. The
crystal structure of the new compound 4a was obtained. Other
properties of these compounds are being studied.
Acknowledgments
We are grateful for the Natural Science Foundation of Hubei
Province (No. 2012FFB01103), the Hubei Provincial Department of
Education (No. Q20131905), the National Natural Science Founda-
tion of China (No. 21262011), and the Fund of Ethnic Affairs
Commission of China (No. 12HBZ010).
Fig. 2. Packing diagram of compound 4a.
References
The structure was refined by the full-matrix least-squares method
on F2 with SHELXL-97 [8]. The final refinement gave R = 0.0490,
[1] J.M. Khurana, K.S. Prabhat, Chemoselective alkylation of thiols: a detailed inves-
tingation of reactions of thiols with halides, Synth. Commun. 22 (1992) 1691–
1702.
[2] E.S. Paul, Inorganic halide salt catalysts for hydroxyalkylation of phenols or
thiophenols, US 4341905, 1982.
[3] I. Katz, W.J. Evers, A.S. Highlands, Flavoring compositions and processesutilizing
alpha-ketothiols, US 3773524, 1973.
[4] W.J. Evers, H.H. Heinsohn, F.L. Schmitt, alpha-Oxy(oxo)mercaptan perfume and
cologne compositions, US 4070308, 1978.
[5] D. Craig, K. Daniels, Additive pummerer reactions of vinylic sulphoxides. Synthesis
of 2-(phenylsulphenyl) aldehydes and primary alcohols, Tetrahedron Lett. 32
(1991) 6973–6976.
[6] F. Feng, W.B. Hu, H.X. Liu, Study on synthesis of 1, 3-diphenyl-2,2-dithiol, J. Hubei
Inst. Nationalities 24 (2006) 69–70.
[7] G.M. Sheldrick, SHELXS-97, Program for Crystal Structure Solution, University of
Go¨ttingen, 1990.
[8] G.M. Sheldrick, SHELXL-97, Program for Crystal Structure Refinement, University
of Go¨ttingen, 1997.
wR = 0.1247
(w = l/[s2(Fo2)+(0.0682P)2+1.7325P],
where
max = 2.403 and
P = (FO2+2FC2)/3, S = 1.059,(
D
/
s)max = 0.001, (Dr
)
3
˚
(
Dr) min = À0.296/A .
The molecular structure and packing diagram are depicted in
Figs. 1 and 2, respectively. In the crystal structure, the bond length
(1.834(2)) of C(8)-S(1) is longer than that (1.533(3)) of C(7)-C(8)
and the bond length of S(1)-S(1a)(2.0284(9)) is the longest.
Moreover, there is no center of symmetry and symmetry plane in
the molecule. So the molecule is not symmetrical. In the aromatic
rings in the molecule, the molecular dimensions are as expected
with the aromatic C–C bond distances between 1.388(4) and
˚
1.408(4) A, and these bond lengths are even. The aromatic C–C–C
bond angles ranging from 118.1(2) to 121.14(18)8 are almost
within the normal ranges [9]. Each of the rings is nearly planar. It
can be seen that the molecular structure is stabilized by weak p–p
[9] F. Feng, Solvent-free Michael addition reaction of fluorene with chalcon, Chin.
Chem. Lett. 22 (2011) 29–32.