Synthesis and crystal structure of (Z)-1-(phenylsulphenyl)-2-phenylethenyl p-toluenesulfonate

Article abstract of DOI:10.1023/A:1009571720193

The reaction between 1-phenylsulphenyl-2-phenylethyne and p-toluenesulfonic acid in methylene chloride gives (Z)-1-(phenylsulphenyl)-2-phenylethenyl p-toluenesulfonate (1) in good yields. This reaction is both a regio -and a stereospecific cis addition, confirmed by X-ray crystal structure analysis of the title compound. 1 crystallizes in the monoclinic space group P2₁/n with the lattice parameters a = 10.556(3), b = 9.730(3), c = 19.687(3) A, β = 105.05(2)°, V = 1952.7(8) A³, and Z = 4. The results of elemental analysis, IR and NMR spectroscopy are included.

Full text of DOI:10.1023/A:1009571720193

Journal of Chemical Crystallography, Vol. 29, No. 6, 1999
Synthesis and crystal structure of (Z)-1-(phenylsulphenyl)-
2-phenylethenyl p-toluenesulfonate
Antonio Luiz Braga,(1)* Oscar E.D. Rodrigues,(1) Daniel J. Emmerich,(1)
Claudio C. Silveira,(1) Manfredo Horner,(1)* and Ezequiel M. Vazquez-Lopez(2)
¨
Received July 3, 1998
The reaction between 1-phenylsulphenyl-2-phenylethyne and p-toluenesulfonic acid in meth-
ylene chloride gives (Z)-1-(phenylsulphenyl)-2-phenylethenyl p-toluenesulfonate (1) in good
yields. This reaction is both a regio- and a stereospecific cis addition, confirmed by X-ray
crystal structure analysis of the title compound. 1 crystallizes in the monoclinic space group
˚
P21/n with the lattice parameters a ϭ 10.556(3), b ϭ 9.730(3), c ϭ 19.687(3) A, ͱ ϭ 105.05(2)Њ,
3
˚
V ϭ 1952.7(8) A , and Z ϭ 4. The results of elemental analysis, IR and NMR spectroscopy
are included.
KEY WORDS: Vinilic sulfides; thioacetylenes; tosylates; X-ray structure.
Introduction
Experimental
Vinilic sulfides are intermediates of great syn-
Elemental analysis was performed with a Carlo
Erba 1108 analyzer. The IR spectrum was registered
using KBr pellets on a Bruker IFS28 spectrometer,
and NMR spectra were acquired on a Bruker AC 80
spectrometer. A Bu¨chi apparatus was used for the
melting point determination.
All reagents were purchased from Aldrich and
used directly from original packages. The starting
material, 1-phenysulphenyl-2-phenylethyne, was pre-
pared according to literature.4
thetic potential, since they combine the ability of the
double bond to form single carbon-carbon bonds with
the functional transformation achieved by the well
known reactions of organosulfur compounds.1 (Z)-
Ͱ-sulfenylvinyl p-sulfonates are known,2 but not yet
studied in detail. The crystal structure of this com-
pound was undertaken because a knowledge of its
stereochemistry is required to predict successive reac-
tion pathways, and it is not trivial to assign the stereo-
chemistry of trisubstituted olefins by other methods.3
In this paper we describe the synthesis and the crystal
and molecular structure of Ph(H)CuC[OS(O2)
C6H4CH3]SPh (1), which is a very important precur-
sor for the synthesis of unsaturated and carbonyl
compounds.
Preparation of (Z)-1-(phenylsulphenyl)-2-
phenylethenyl p-toluenesulfonate
A mixture of the 1-phenysulphenyl-2-phenyleth-
yne (210 mg, 1 mmol) and p-toluenesulfonic acid (390
mg, 2.5 mmol) in methylene chloride (5 mL) was
stirred at 0ЊC for 30 min and overnight at room tem-
perature. The reaction mixture was filtered through
Al2O3 and K2CO3 columns and the solvent evapo-
rated. The residue was recrystallized (ethyl ether/
(1) Departamento de Qu´ımica, Universidade Federal de Santa Ma-
ria, Caixa Postal 5071, 97.105-900 Santa Maria-RS, Brazil.
(2) Departamento de Qu´ımica Inorga´nica, Universidad de Vigo, E-
36200 Vigo, Spain.
* To whom correspondence should be addressed.
677
1074-1542/99/0600-0677$16.00/0 1999 Plenum Publishing Corporation

678
Braga, Rodrigues, Emmerich, Silveira, Horner, Vazquez-Lopez
¨
hexane) to give the product (332 mg, 87%); mp ϭ
62.63ЊC; Anal. Found: C, 65.92; H, 4.75%. C21H18O3S2
requires: C, 65.95; H, 4.74%. IR (KBr): ␯ (cmϪ1):
2975, 1580, 1470, 1370, 1275, 1000. 1H NMR (80 MHz,
CDCl3): 7.64 (d, 2H, J ϭ 8Hz), 7.14-7.28 (m, 12H),
6.95 (1H, s), 2.32 (3H, s). 13C NMR (20 MHz, CDCl3):
145.12, 140.81, 133.36, 132.53, 131.21, 129.89, 129.50,
129.34, 129.20, 128.98, 128.70, 128.49, 128.29,
127.33, 21.63.
methods indicated a cell belonging to the monoclinic
crystal system with a P lattice. X-ray intensity data
were recorded with a scan speed of 45 sec/reflection.
Every 60 min, the intensity and orientation of three
standard reflections were confirmed; the observed
intensity decay was less than 1.5% over the data col-
lection. From the Bravais lattice and observed reflec-
tions conditions, the space group was chosen to be
P21/n. A semi-empirical absorption correction based
on psi-scans was made on the the intensity data.5
The structure was solved using direct methods
employing SHELXS-977 program and all nonhydro-
gen atoms were located by subsequent Fourier dif-
ference synthesis. For structure refinement the
SHELXL-978 program was employed and the full-
matrix least-squares method minimized on ⌺w
(F2oϪF2c)2 where w is a weighting scheme indicated
Crystallographic section
Single crystals of 1 were grown from a diethyl
ether/n-hexane mixture. A colorless crystal was
mounted on a glass fiber and used for intensity data
collection. Automatic intensity search and indexing
Table 1. Crystal Data and Summary of Intensity Data Collection and Structure Refinement
Compound
Ph(H)CuC[OS(O2)C6H4CH3]SPh
CCDC deposit no.
Color/shape
CCDC-1003/5557
Colorless/prismatic
Formula weight
Space group
382.47
P21/n
20
Temperature, ЊC
Cell constantsa
˚
a, A
10.556(3)
9.730(3)
19.687(3)
˚
b, A
˚
c, A
ͱ, deg
Cell volume, A
105.05(2)
1952.7(8)
3
˚
Formula units/unit cell
4
Dcalc , g cmϪ3
1.301
2.90
Ȑcalc , cmϪ1
Diffractometer/scan
Radiation, graphite monochromator
Max. crystal dimensions, mm
Scan width
Enraf-Nonius CAD-46/Ͷ-2␪
MoKͰ (␭ ϭ 0.71073 A)
0.35 ϫ 0.30 ϫ 0.15
0.60 ϩ 0.48 tan ␪
˚
Standard reflections
Decay of standards
Reflections measured
2␪ range, deg
208; 43-5; 2-3-2
Ϯ1.5%
2729
4.70 Յ 2␪ Յ 45.52
Range, of h, k, l
Ϫ11 Յ h Յ 11, Ϫ 10 Յ k Յ 0, 0 Յ l Յ 21
Reflections observed
1037
[I Ͼ 2␴(I)]b
Computer programsc
Structure solution
No. of parameters varied
GOF
SHELXL-978
SHELXS-977
239
1.008
R ϭ ͚ʈFo͉ Ϫ ͉Fcʈ/͚͉Fo͉
Rw
0.0464
0.0797
Extinction
Largest feature final diff. map
0.00006(8)
Ϫ3
0.198 eϪ
A
˚
a Least-squares refinement of [(sin␪)/␭]2 values for 25 reflections ␪ Ͼ 20 deg.
b Corrections: Lorentz-polarization.
c Neutral scattering factors and anomalous dispersion corrections.

(Z)-1-(phenylsulphenyl)-2-phenylethenyl p-toluenesulfonate
679
Table 2. Atomic Coordinates (ϫ104) and Equivalent Isotropic
below. All nonhydrogen atoms were refined using
anisotropic thermal parameters. Hydrogen atom sites
were obtained geometrically and their displacement
parameters were refined isotropically on a groupwise
basis. The hydrogen atom bound to the C(2) atom
was found in a difference Fourier map and refined
isotropically. The final refinement of the structure
includes an isotropic extinction correction and con-
verge to R ϭ 4.64% and Rw ϭ 7.97% with the
weighting scheme, w ϭ 1/[s2(Fo2) ϩ (0.0608P)2 ϩ
2.3183P], where P ϭ (F2o ϩ 2F2c)/3. Table 1 summa-
rizes the crystal data and structure refinement param-
eters for 1.
2
Displacement Parameters (A ϫ 103) for Ph(H)CuC[OS(O2)
˚
C6H4CH3]SPh
x
y
z
U(eq)a
S(1)
S(2)
O(1)
O(2)
O(3)
C(1)
C(2)
C(3)
C(4)
C(5)
5405(2)
2892(1)
3856(3)
6011(3)
5456(4)
3372(5)
3365(6)
2847(7)
3467(6)
3001(8)
1881(8)
1240(7)
1699(7)
5932(5)
5627(5)
6097(6)
6879(7)
7179(6)
6725(6)
7376(6)
1406(5)
702(6)
1889(2)
426(2)
1628(4)
700(5)
3175(5)
352(8)
1170(1)
1997(1)
1020(2)
977(2)
828(2)
1219(3)
810(4)
861(3)
656(3)
688(4)
910(4)
1092(4)
1074(3)
2079(3)
2375(3)
3086(4)
3512(4)
3212(4)
2493(4)
4298(3)
1737(3)
1053(3)
907(4)
72(1)
71(1)
65(1)
91(1)
87(1)
60(2)
66(2)
64(2)
80(2)
101(2)
104(3)
92(2)
74(2)
57(2)
67(2)
74(2)
73(2)
82(2)
77(2)
116(3)
56(2)
77(2)
96(3)
107(3)
108(3)
77(2)
Ϫ716(9)
Ϫ2104(8)
Ϫ3223(9)
Ϫ4534(9)
Ϫ4770(9)
Ϫ3648(10)
Ϫ2342(8)
2118(7)
3305(7)
3522(7)
2576(9)
1387(8)
1147(7)
2797(7)
1363(6)
1535(7)
2259(8)
2745(8)
2560(8)
1880(7)
C(6)
C(7)
C(8)
Results and discussion
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
Molecular structure of 1
Figure 1 shows the ZORTEP9 plot of the molec-
ular structure and atom numbering of 1. Atomic posi-
tional parameters for non-hydrogen atoms are listed
in Table 2 and selected bond distances and bond
angles are presented in Table 3. The X-ray structure
clearly demonstrates the Z geometry for 1.
Ϫ475(7)
Ϫ956(7)
Ϫ268(8)
908(6)
1429(6)
2114(5)
2265(3)
˚
The C(1)UC(2) distance of 1.314(7) A confirms
the expected double-bond character between these
atoms. This value is in good agreement with other
analogous ethylene compounds, e.g., the observed
a U(eq) is defined as one third of the trace of the orthogonalized
Uij tensor.
˚
CUC distance of 1.316 A in (E)-1-chloro-1-(tosy-
10
˚
loxy)-3,3-dimethyl-1-butene and 1.34(1) A in dichl-
oro[(Z)-2-chloro-2-phenylvinyl]-(4-methoxyphenyl)
tellurium(IV).11 A slight deviation from planarity of
the trisubstituted ethylene fragment is observed with
a C(3)UC(2)UC(1)US(2) torsion angle of 6.1(10)Њ.
The CuCUSPh and PhUCuC bond angles open-
ing up to 128.1(6) and 129.0(7)Њ, and the Cu
CUOS(O2) Utol bond angle decreasing to 117.6(5)Њ.
According to the torsion angles defined by the atoms
C(8)UC(3)UC(2)UC(1)
[37.0(9)Њ],
C(16)U
C(11)US(1)UO(1) [111.6(4)Њ], and C(22)U
C(21)US(2)UC(1) [18.0(6)Њ], the pȏ–pȏ interaction
between the C(2) atom and the C(3)UC(8) phenyl
ring and the dȏ–pȏ interactions between the S(1)
atom and the C(11)UC(16) phenyl ring and the S(2)
atom and the C(21)UC(26) phenyl ring are weak-
ened. Therefore, the bond lengths C(3)UC(2) ϭ
1.470(8), S(1)UC(11) ϭ 1.746(5), and S(2)UC(21)
Fig. 1. ZORTEP9 drawing with atom-labeling scheme of the struc-
ture of Ph(H)CuC[OS(O2)C6H4CH3]SPh; displacement ellipsoids
at the 30% probability level.
˚
ϭ 1.770(5) A, are slightly shorter in comparision with
the respective sums of the covalent radii (CиииC ϭ

680
Braga, Rodrigues, Emmerich, Silveira, Horner, Vazquez-Lopez
¨
˙
shell electron-pair-repulsion model (VSEPR)12 the
C(1)US(2)UC(21) angle of 101.3(9)Њ becomes ap-
preciably deviated from the ideal internal angle of a
tetrahedron as result of the repulsion between both
of the lone pairs of electrons and from those on the
SUC bonds. The three phenyl rings are essentially
planar with an average RMS deviation of 0.0068 A
and their interplanar angles are 84.8(2)Њ between
the C(3)UC(8) and C(11)UC(16) phenyl rings and
Table 3. Selected Bond Lengths (A), Angles (Њ)
and Torsional Angles (Њ) for Ph(H)Cu
C[OS(O2)C6H4CH3]SPh
S(1)UO(1)
1.604(3)
1.421(4)
1.428(4)
1.746(5)
1.736(6)
1.770(5)
1.435(6)
1.314(7)
1.470(8)
0.88(4)
S(1)UO(2)
S(1)UO(3)
S(1)UC(11)
˚
S(2)UC(1)
S(2)UC(21)
O(1)UC(1)
33.6(2)Њ
between
the
C(11)UC(16)
and
C(1)UC(2)
C(2)UC(3)
C(21)UC(26) phenyl rings.
C(2)UH(2)
O(2)US(1)UO(3)
O(2)US(1)UO(1)
O(3)US(1)UO(1)
O(2)US(1)UC(11)
O(3)US(1)UC(11)
O(1)US(1)UC(11)
C(1)US(2)UC(21)
C(1)UO(1)US(1)
C(2)UC(1)UO(1)
C(2)UC(1)US(2)
O(1)UC(1)US(2)
C(1)UC(2)UC(3)
C(1)UC(2)UH(2)
C(3)UC(2)UC(1)US(2)
C(8)UC(3)UC(2)UC(1)
C(16)UC(11)U(1)UO(1)
C(22)UC(21)US(2)UC(1)
O(2)UO(3)UO(1)UC(11)
120.9(3)
109.3(2)
102.3(2)
109.4(3)
109.3(3)
104.3(2)
101.9(3)
120.4(3)
117.6(5)
128.1(6)
114.3(5)
129.0(7)
114(3)
Acknowledgments
The authors thank the CNPq for financial sup-
port, and Prof. Dr. Alfonso Castin˜eiras Campos, Uni-
versity of Santiago de Compostela, Spain for the dif-
fractometer facilities.
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6.1(10)
37.0(9)
111.6(4)
18.0(6)
70.0(2)
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Refinement; University of Go¨ttingen: Germany, 1997.
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Crystallogr. 1995, C51, 861.
˚
1.54 and SиииC ϭ 1.80 A). The S(1) atom shows a
distorted tetrahedral configuration, with a O(2)U
O(3)UO(1)UC(11) torsion angle of 70.0(2)Њ. The
˚
S(1)UO(1) distance [1.604(3) A] and the
O(1)UC(1) distance [1.435(6) A] are in good
˚
agreement with the values found for analogous
bonds in (E)-1-Chloro-1-(tosyloxy)-3,3-dimethyl-1-
butene.10 Two lone pairs together with the C(1) and
the C(21) atoms impose a typical tetrahedral config-
uration to the S(2) atom. As expected by the valence-
12. Gillespie, R.J. Molecular Geometry; van Nostrand-Rein-
hold, 1972.