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Journal Name
New Journal of Chemistry
DOI: 10.1039/C5NJ00200A
frequency shifts of functional groups in an aromatic ring
depends on its position in the aromatic ring and on the
vibrational mode considered.
Acknowledgements
Authors acknowledge CONICET (Consejo Nacional de
Investigaciones Científicas y Técnicas) and UNT (Universidad
Nacional de Tucumán) for the financial support. Authors also
kindly acknowledge staff from LISA (Laboratorio de
Investigación y ServiciosAnalíticos) for NMR and GC/MS
measurements.
References
aINQUINOA (CONICETꢀUNT) Ayacucho 471, (4000) Tucumán,
República Argentina.
bInstituto de Química Física, Facultad de Bioquímica, Química
y
Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, (4000)
Tucumán, República Argentina.
cInstitut für Physikalische und Theoretische Chemie, Universität
Tübingen, 72076 Tübingen, Germany.
1
2
K. Krieze and G. van Koten, Recl. Trav. Chim. Pays-Bas., 1980, 99,
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Fig. 6. Major fragmentation patterns of m/z peaks for mꢀ
fluorosulfinylaniline.
a) Hꢀ.G. Mack, H. Oberhammer and C.O. Della Vedova, J. Mol.
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3
a) R. M. Romano and C. O. Della Védova, J. Mol. Struct., 1998, 440,
43; b) R. M. Romano, C. O. Della Vedova and A. Pfeiffer, J. Mol.
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Conclusions
A new member of the sulfinylaniline family of compounds has
been prepared by reacting ꢀfluoroaniline and SOCl2. The
4
5
R.M. Romano and C.O. Della Védova, J. Mol. Struct.,2000, 522, 1.
G. Cerioni, N. Culeddu and A. Piumitallo, Tetrahedron, 1993, 49,
2957.
m
highly reactive and corrosive liquid compound obtained was
characterized by using nuclear magnetic resonance
spectroscopy (1H and 13C), gasꢀchromatography/mass
spectrometry, vibrational spectra and quantum chemical
calculations. Although at least two stable conformers might be
expected around the N=S bond (syn and anti of the C–N bond
with respect to the S=O bond) and also two stable structures
were predicted taking into account the orientation of the
N=S=O and fluorine substituents, all experimental spectra
evidence the presence of a single conformer, since no additional
signals were observed to account for several forms in
equilibrium at room temperature. Theoretical calculations using
B3LYP with different basis sets confirmed that only the syn
conformation of the N=S=O moiety can be observed in the
liquid phase, predicting global CS symmetry of this compound
in agreement with the properties observed for the parent
sulfinylaniline. The unexpected syn configuration adopted by
all R‒N=S=O compounds reported so far, might be rationalized
in terms of orbital interactions. In fact, larger interaction
6
7
a) A. Michaelis andR. Hertz, Ber. Deutsch. Chem. Ges., 1891, 24,
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a) R. M. Romano, C. O. DellaVédova and R. Boese, J. Mol. Struct.
,
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Hildebrandt, J. Mol. Struct., 1999, 508, 5; c) R. Meij, A. Oskam and
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8
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K. O. Christe, M. Gerken, R. Hages, S. Schneider, T. Schroer, F.S.
Tham and A. Vij, Solid State Sci., 2002, 4, 1529.
E. V. Ivanova and H. M. Muchall, J. Phys. Chem. A, 2011, 115, 3095.
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11 A. L. Páez Jerez, A. Flores Antognini, E. H. Cutin and N. L. Robles,
Spectrochim. Acta A,2015, 137, 300.
12 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
Robb, J. R. Cheeseman, J. A. Montgomery Jr., T. Vreven, K. N.
Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V.
Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.
A.Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R.
Fukuda, J. Hasegawa,M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H.
Nakai, M. Klene, X. Li, J. E. Knox,H. P. Hratchian, J. B. Cross, V.
Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.Stratmann, O.
Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski,
energies were predicted for the syn configuration of
mꢀ
fluorosulfinylaniline compared to the anti structure, according
to Natural Bond Orbital analysis. Thus, the thermodynamic
preference of the syn form can be rationalized as a result of the
influence of stabilizing anomeric interactions.
From the analysis of the vibrational frequencies of the
pꢀ and
m
ꢀfluorosulfinylaniline compounds reported up to the moment,
we may state that the influence of a fluorine atom on the
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