Synthesis and crystal structure determination of 2,2′-sulfinyl-bis(4- methyl phenol) and 2,2′-thio-bis(4-methyl phenol)

Article abstract of DOI:10.1080/714040965

2,2′-Sulfinyl-bis(4-methyl phenol) 3 and it's thio derivative have been synthesized in this work. The reduction process of sulfoxide 3 to its thio derivative 5 was accomplished in the presence of Zn/AcOH/SiO₂, under microwave irradiation. The s

Full text of DOI:10.1080/714040965

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Phosphorus, Sulfur, and Silicon and the Related
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Synthesis and Crystal Structure Determination of 2,2′-
Sulfinyl-bis(4-methyl Phenol) and 2,2′-Thio-bis(4-
methyl Phenol)
Abbas Shockravi a , Robabeh Alizadeh a , Hossein Aghabozorg a , Abolghasem Moghimi b ,
Esmael Rostami a & Samad Bavili a
a Teacher Training University, Tehran, Iran
b Imam Hossein University, Tehran, Iran
Published online: 18 Jun 2010.
To cite this article: Abbas Shockravi , Robabeh Alizadeh , Hossein Aghabozorg , Abolghasem Moghimi , Esmael Rostami &
Samad Bavili (2003) Synthesis and Crystal Structure Determination of 2,2′-Sulfinyl-bis(4-methyl Phenol) and 2,2′-Thio-bis(4-
methyl Phenol), Phosphorus, Sulfur, and Silicon and the Related Elements, 178:12, 2519-2527, DOI: 10.1080/714040965
To link to this article: http://dx.doi.org/10.1080/714040965
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Phosphorus, Sulfur, and Silicon, 178:2519–2527, 2003
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500390248006
SYNTHESIS AND CRYSTAL STRUCTURE
DETERMINATION OF 2,2ꢀ-SULFINYL-BIS(4-METHYL
PHENOL) AND 2,2ꢀ-THIO-BIS(4-METHYL PHENOL)
Abbas Shockravi,a Robabeh Alizadeh,a Hossein Aghabozorg,a
Abolghasem Moghimi,b Esmael Rostami,a and Samad Bavilia
Teacher Training University, Tehran, Irana and Imam Hossein
University, Tehran, Iranb
(Received April 4, 2003; accepted June 26, 2003)
2,2ꢁ-Sulfinyl-bis(4-methyl phenol) 3 and it’s thio derivative have been
synthesized in this work. The reduction process of sulfoxide 3 to its
thio derivative 5 was accomplished in the presence of Zn/AcOH/SiO2,
under microwave irradiation. The structures have been confirmed by
spectroscopic (IR, 1HNMR, 13CNMR) and single crystal x-ray diffrac-
tion methods. 2,2ꢁ-Sulfinyl-bis(4-methyl phenol) 3 crystallizes in the
space group Cc of the monoclinic system with four molecules in the unit
˚
˚
˚
cell of dimensions a = 11.425(2) A, b = 13.530(2) A, c = 9.5215(17) A,
ꢁ
˚
β = 117.289(4) A, and 2,2 -thio-bis(4-methyl phenol) 5 crystallizes in the
space group P 212121 of the orthorhombic system with four molecules
˚
˚
in the unit cell of dimensions a = 9.021(1) A, b = 10.523(2) A, c =
˚
13.607(2) A, α = 90. The structures have been refined to final values for
the crystallographic R factor of 0.0189(3) and 0.0248(5) based on 2999
and 3720 observed independent reflections respectively.
Keywords: Friedel-Crafts; microwave; sulfide; sulfinyl; sulfoxide
The symmetric diaryl sulfides and their sulfoxide derivatives have
been synthesized by many groups using different conditions.1 Friedel-
Crafts method is generally used for the synthesis of these com-
pounds. Treatment of p-cresol 1 with thionyl chloride 2 and anhy-
drous aluminium chloride in dichloromethane afforded sulfoxide 3.
Recently, catalytic oxygenation of organosulfur compounds have found
increased applications in asymmetric synthesis.2 Also, metal catalyzed
reactions of organosulfur compounds are of biological and industrial
Address correspondence to Abbas Shockravi, Faculty of Chemistry, Teacher Training
University, No. 49, Dr. Mofateh Ave., Tehran 15614, Iran. E-mail: Abbas Shockravi@
yahoo.co.uk; shockravi@saba.tum.ac.ir
2519

2520
A. Shockravi et al.
importance.3 Rehder and coworkers have examined the vanadium-
catalyzed oxygenation of sulfides to sulfoxides and sulfones.4 Because
of the importance of these compounds we were interested in the syn-
thesis and crystal structure determination of them. We synthesized
the sulfoxide 3 by using the same strategy in very good yield with
some modifications in temperature and time interval of the reac-
tion. In the 1HNMR spectrum, the hydroxyl groups have appeared
at 9.3 ppm and the aromatic hydrogens absorbed at 6.3–7.0 ppm
(Scheme 1).
SCHEME 1
The reduction of sulfoxide group to sulfide has been reported in dif-
ferent conditions; e.g., Zn/AcOH,5 pph3/I2,6 LAH/THI,7 LAH/Et2C,8 and
recently hv(300 nm)/NaOCH3/CH3OH.9 We found that in this case the
reduction process can be carried out in the presence of Zn/AcOH/SiO2
and microwave irradiation. This reaction took only five minutes with
100% yield. Absence of absorption band at 950–1050 cm−1 in the IR
spectrum proved that the reduction of sulfoxide to sulfide group had
1
taken place. In the HNMR spectrum, the hydroxyl group absorbs at
8.5 ppm and the aromatic hydrogens appeared at 7–8 ppm. Crystal data
˚
for 5 (C14H14O2S): space group P212121, a = 9.021(1) A, b = 10.523(2)
◦
˚
˚
A, c = 13.607(2) A, α = 90 .

2521

2522
A. Shockravi et al.
TABLE II Selected Torsion Angles (◦) for 3 and 5
3
5
O1 S1 C1 C6
O1 S1 C8 C9
O1 S1 C1 C2
O1 S1 C8 C13
C8 S1 C1 C6
C1 S1 C8 C9
C8 S1 C1 C2
C1 S1 C8 C13
S1 C1 C2 O2
S1 C8 C9 O3
S1 C1 C2 C3
S1 C8 C9 C10
S1 C1 C6 C5
−88.40
−172.27
88.58
C8 S1 C1 C6
C8 S1 C1 C2
S1 C1 C2 O1
S1 C1 C2 C3
S1 C1 C6 C5
C1 S1 C8 C13
C1 S1 C8 C9
S1 C8 C9 O2
S1 C8 C9 C10
O2 C9 C10 C11
S1 C8 C13 C12
92.66
−89.66
2.00
−178.60
178.39
−89.03
95.01
3.10
20.60
78.33
−162.38
−106.30
0.30
−4.45
175.40
−179.92
−175.67
−8.00
−178.84
174.18
177.99
S1 C8 C13 C12 −175.02
C6 C1 C2 O2
C13 C8 C9 O3
177.40
176.60
RESULTS AND DISCUSSION
Molecular Structures
Crystallization of 2,2ꢁ-sulfinyl-bis(4-methyl phenol) 3 from ethanol at
room temperature afforded colorless crystals whereas suitable crystals
of 2,2ꢁ-thio-bis(4-methyl phenol) 5 have been obtained by slow evapora-
tion of a toluene solution.
The perspective views of the molecular structure for 3 and 5 and
the crystal packing diagrams are shown in Figures 1–4. The selected
bond lengths and angles, selected torsion angles and intermolecular
hydrogen bond distances are listed in Tables I–III.
The most important feature in the crystal structure of sulfinyl com-
pound 3 is that the two phenyl rings possessing an OH group are anti
to each other, while for the thio compound 5 these two groups are in
◦
˚
TABLE III Hydrogen Bond Distances (A) and Angles ( ) for 3 and 5
. . .
. . .
D
H
A
d(D H) d(H A)
<DHA
Symmetry transformation
3
. . .
O(2) H(2O) O(1)
0.93
0.93
1.82
1.74
148
167
[x, −y − 1, z − 1/2]
. . .
O(3) H(3O) O(1)
[x − 1/2, −y − 1/2, z− 1/2]
5
. . .
O(1) H(1O) O(2)
0.81
0.84
1.96
2.04
173
162
[x + 1/2, −y − 1/2, −z − 1]
. . .
O(2) H(2O) O(1)
Intermolecular

Sulfinyl-Bis(Methyl Phenol)
2523
FIGURE 1 ORTEP drawing of the sulfoxide 3.
FIGURE 2 Unit cell packing diagram of the sulfoxide 3.

2524
A. Shockravi et al.
FIGURE 3 ORTEP drawing of the sulfide 5.
one side and syn to each other (Figures 1 and 3). This can be related
to the steric constraints within the compound 3 which is caused by
the S O group. Therefore the hydrogen-bonding pattern is completely
different (Figures 2 and 4; Table III). There is an intramolecular hydro-
gen bonding between two hydroxyl groups for compound 5 (Figures 3
and 4). The <C S C angles are comparable in the two compounds.
One important feature in the crystal structure of the thio compound 5
is the presence of three crystallographically independent molecules of
2,2ꢁ-thio bis(4-methyl phenol), (Figure 4), which are connected to each
other with strong hydrogen bonding interaction (Table III) while for
compound 3 there is hydrogen bonding between the O atom of the S O
group and the OH group, providing an extended organic network in
both case.
EXPERIMENTAL
X-ray Structure Analysis
Analysis on single crystals of 3 and 5 were carried out on a Bruker
SMART CCD area detector diffractometer (Mo Kα radiation, graphite
◦
˚
monochromator, λ = 0.71073 A) at −163 C (110K). Diffracted data were
corrected for absorption using the SADABS program. Some softwares10
including SMART (data collection), SAINT+ (cell refinement and data
reduction), SHELXTL (version 5.10, structure solution and refine-
ment; molecular graphics and publication material) and SHELXL-97
were used. A crystal of dimensions 0.35 × 0.20 × 0.15 mm3 (3) and

Sulfinyl-Bis(Methyl Phenol)
2525
FIGURE 4 (a) Hydrogen bonding and (b) unit cell packing diagram of the
sulfide 5.

2526
A. Shockravi et al.
TABLE IV Crystallographic Data for 3 and 5
3
5
Empirical formula
fw
Space group
C14H14O3S
262.31
Cc
110(2)
0.71073
11.425(2)
13.530(2)
9.522(2)
90◦
C14H14O2S
246.31
P212121
110(2)
0.71073
9.021(2)
10.523(2)
13.607(2)
90◦
T,k
˚
λ(Mo kα), A
˚
a, A
˚
b, A
˚
c, A
α, deg
β, deg
117.29(4)
90◦
γ , deg
90◦
90◦
1291.7(2)
4
1.267
1.237
3
˚
V, A
1308.0(4)
4
1.332
Z
Dcalcd, g cm−3
µ, mm−1
0.244
Independent reflections 2999 [R(int) = 0.0189] 3720 [R(int) = 0.0248]
R1/wR2 (obs data)a
R1/wR2 (all data)a
0.0443/0.1149b
0.0470/0.1178b
0.0473/0.1065c
0.0565/0.1112c
a R1 =
Fo| − |F
/
|Fo|; wR2 = [ w(Fo2 − F2)2/ w(Fo2)2]1/2
.
bw = 1/[σ2(Fo2) +c(0.0830P)2 + 0.5854P]; P = c(Fo2 + 2F2)/3.
c
cw = 1/[σ2(Fo2) + (0.0500P)2 + 0.8000P].
0.6 × 0.5 × 0.4 mm3 (5) were mounted in a glass capilary, and the data
were collected in the range 2.51 ≤ θ ≤ 28.99◦ (3) and 2.45 ≤ θ ≤ 30.02◦
(5), with −15 ≤ h ≤ 15, −18 ≤ k ≤ 6, −11 ≤ 1 ≤ 12 (3) and −12 ≤ h ≤
10, −14 ≤ k ≤ 12, −18 ≤ l ≤ 17 (5). The structures were solved by di-
rect method and refined by full-matrix least-squares based on F 2. The
crystallographic data are listed in Table IV.
REFERENCES
[1] a) S. Smiles and L. Rossignal, J. Chem. Soc., 93, 745 (1908); b) M. Gazdar and S.
Smiles, J. Chem. Soc., 97, 2248 (1910); c) W. S. Gump and J. C. Vitucci, J. Am.
Chem. Soc., 67, 238 (1945); d) M. E. Jung, D. Jachiet, I. Khan Saeed, and C. Kim,
Tetrahedron Lett., 36, 361 (1995).
[2] D. A. Cogan, G. Liu, K. Kim, B. J. Backes, and J. A. Ellman, J. Am. Chem. Soc., 120,
8011 (1998).
[3] E. I. Stiefel, Transition Sulfur Chemistry: Biological and Industrial Significance
and Key Trends, edited by E. I. Stiefel (American Chemical Society, Washington,
DC, 1996), pp. 2–38.
[4] H. Schmidt, M. Bashirpoor, and D. Rehder, J. Chem. Soc., Dalton Trans., 3865 (1996).
[5] Vogel’s Texbook of Practical Organic Chemistry, 5th ed., 1989, p. 231.
[6] C. Jouen, M. C. Lasne, and J. C. Pammelet, Tetrahedron Lett., 37, 2413 (1996).

Sulfinyl-Bis(Methyl Phenol)
2527
[7] G. Solladie, G. Demailly, and C. Greck, J. Org. Chem., 50, 1552 (1985).
[8] E. N. Karaulova and G. D. Gal’Pern, C. A., 54, 120960 (1960).
[9] J. W. Cubbage, T. A. Tetzlaff, H. Groundwater, R. D. McCulla, M. Nag, and W. S.
Jenks, J. Org. Chem., 66, 8621 (2001).
[10] a) Bruker (1998a), SAINT+, Program for Data Reduction and Correction, ver. 6.01,
Bruker Axs, Madison, WI; b) Bruker (1998b), SMART, Bruker Molecular Analysis
Research Tool, ver. 5.059, Bruker Axs, Madison, WI; c) G. M. Sheldrick (1998a),
SADABS, Bruker/Siemens Area Detector Absorption Correction Program, ver. 2.01,
Bruker Axs, Madison, WI; d) G. M. Sheldrick (1998b), SHELXTL, Structure Deter-
mination Software Suite, ver. 5.10, Bruker Axs, Madison, WI.