MECHANISM OF SULFUR TRANSFER FROM 1,2,4-DITHIAZOLIDINE-3,5-DIONES TO TRIPHENYLPHOSPHINES
Compound 1f
EXPERIMENTAL
C8H4N2O4S2, M = 256.25, monoclinic, P 21, a = 7.8220(3), b = 7.8601(2),
Syntheses
c = 7.9299(3) Å, b = 92.726(3) ꢀ, Z = 2, V = 486.99(3) Å3, Dc = 1.748 g ꢃ cm–3
,
All the 1,2,4-dithiazolidine-3,5-diones (1a–g) were synthesized and
purified according to published general procedures[31] in two steps from
phenyl isothiocyanate (see Supporting Information).
m = 0.545 mm–1, Tmin/Tmax = 0.887/0.932; –9 ≤ h≤ 10, –10 ≤ k≤ 8, –8 ≤ l ≤ 10;
3535 reflections measured (Ymax = 27.5 ꢀ), 3515 independent (Rint
=
0.0242), 1875 with I > 2s(I), 145 parameters, S = 1.090, R1(obs.
data) = 0.0194, wR2(all data) = 0.0497; max., min. residual electron
density = 0.270, –0.191 eǺ–3
.
In the crystal packing of 1f (Fig. 4), no interesting interatomic
interactions were observed except of non-classical H-bonding
and short contacts between C–H ꢃ ꢃ ꢃ O and N = O ꢃ ꢃ ꢃ S–S atoms or
moieties, respectively.
Kinetic measurements
The kinetic measurements were carried out on a Diode Array Stopped-Flow
SX.18 MV-R (Applied Photophysics) spectrophotometer or on a Hewlett
Packard HP 8453 Diode Array spectrophotometer at 25 ꢀC in 1 cm closable
cells under pseudo-first order conditions (triphenylphosphines in large
excess) in ACN, DCM, THF and TOL. The observed pseudo-first order rate
constants kobs were calculated from the measured time dependence
of the absorbance at 336 nm with the help of an optimization program
(See Tables 3–9 in Supporting Information). In all kinetic runs, the stan-
dard deviation in the fit was always less than 5% of the quoted value and
was more usually between 0.2 and 0.4% of the quoted value. Solvents
used for kinetic measurements were of HPLC quality and were dried
and distilled under argon prior to use. All triphenylphosphines were
from commercial sources and were used as received because the
amount of corresponding oxidation product or another phosphorus-
containing compound was only negligible according to 31P NMR
spectrum. Due to potential oxidation of triphenylphosphines, all the
solutions were freshly prepared just before kinetic measurements.
SUPPORTING INFORMATION
Supporting information may be found in the online version of
this article.
Acknowledgement
The authors thank the Ministry of Education, Youth and Sports of
the Czech Republic for the institutional support.
REFERENCES
[1] G. Zumach, W. Weiss, E. Kühle, Belgian Patent 682991, June
23, 1966.
NMR measurements
[2] G. Zumach, E. Kühle, Angew. Chem. Int. Ed. Engl. 1970, 9, 54.
[3] G. Barany, R. B. Merrifield, J. Am. Chem. Soc. 1977, 99, 7363.
[4] G. Barany, F. Albericio, J. Am. Chem. Soc. 1985, 107, 4936.
[5] F. Albericio, G. Barany, Int. J. Pept. Protein Res. 1987, 30, 177.
[6] E. Meinjohanns, M. Meldal, H. Paulsen, H. Bock, J. Chem. Soc., Perkin
Trans. 1995, 1, 405.
1H, 13C and 31P NMR spectra were recorded on a Bruker Avance 3 400 MHz
instrument. Chemical shifts (d) are referenced to solvent residual peaks
d(DMSO-d6) = 2.50 (1H) and 39.6 ppm (13C), and d(CDCl3) = 7.27 (1H) and
77.0 (13C).[31] P NMR shifts are referenced to 85% phosphoric acid (external
standard).
[7] E. Meinjohanns, A. Vargas-Berenguel, M. Meldal, H. Paulsen, K. Bock,
J. Chem. Soc., Perkin Trans. 1995, 1, 2165.
[8] E. Meinjohanns, M. Meldal, A. Schleyer, H. Paulsen, K. Bock, J. Chem.
Soc., Perkin Trans. 1 1996, 985.
[9] K. J. Jensen, P. R. Hansen, D. Venugopal, D. G. Barany, J. Am. Chem.
Soc. 1996, 118, 3148.
[10] E. Meinjohanns, M. Meldal, T. Jensen, O. Werdelin, L. GalliStampino,
S. Mouritsen, K. Bock, J. Chem. Soc., Perkin Trans. 1 1997, 871.
[11] M. Planas, E. Bardaji, K. J. Jensen, G. Barany, J. Org. Chem.
1999, 64, 7281.
[12] D. J. Cane-Honeysett, M. D. Dowle, M. E. Wood, Synlett 2000, 1622.
[13] M. E. Wood, D. J. Cane-Honeysett, M. D. Dowle, S. J. Coles,
M. B. Hursthouse, Org. Biomol. Chem. 2003, 1, 3015.
[14] M. E. Wood, V. M. Annis, C. D. Jones, Org. Biomol. Chem. 2008,
6, 4099.
X-ray crystallography of compound 1f
The yellowish single crystals of 1f suitable for X-ray determination
were grown from hot diethyl ether and petroleum ether solution. The X-
ray data for 1f were obtained at 150 K using an Oxford Cryostream low-
temperature device on a Nonius KappaCCD diffractometer with Mo Ka
radiation (l = 0.71073 Å), a graphite monochromator, and the Φ and w scan
modes. Data reductions were performed with the DENZO-SMN.[32] The
absorption was corrected by integration methods.[33] Structures were solved
by direct methods (Sir92)[34] and refined by full matrix least-squares based on
F2 (SHELXL97).[35] The hydrogen atoms were mostly localized on a difference
Fourier map: however, to ensure uniformity of the treatment of the crystals,
all hydrogen atoms were recalculated into idealized positions (riding model)
and assigned temperature factors Hiso(H) = 1.2 Ueq(pivot atom) with C–
H = 0.93 Å for the hydrogen atoms in the aromatic ring.
[15] M. E. Wood, D. J. Cane-Honeysett, M. D. Dowle, J. Chem. Soc., Perkin
Trans. 2002, 1, 2046.
[16] D. J. Cane-Honeysett, M. D. Dowle, M. E. Wood, Tetrahedron 2005,
61, 2141.
[17] A. Blencowe, A. Clarke, M. G. B. Drew, W. Hayes, A. Slark, P. Woodward,
React. Funct. Polym. 2006, 66, 1284.
[18] R. K. Gessner, K. Chibale, Synlett 2009, 2839.
[19] Q. Xu, K. Musier-Forsyth, R. P. Hammer, G. Barany, Nucleic Acids Res.
1996, 24, 1602.
[20] O. Ponomarov, A. P. Laws, J. Hanusek, Org. Biomol. Chem.
2012, 10, 8868.
[21] J. Hernandez, F. M. Goycoolea, D. Zepeda-Rivera, J. Juarez-Onofre, K.
Martinez, J. Lizardi, M. Salas-Reyes, B. Gordillo, C. Velazquez-
Contreras, O. Garcia-Barradas, S. Cruz-Sanchez, Z. Dominguez, Tetra-
hedron 2006, 62, 2520.
2
2
2
Rint ¼ Σ j Fo ꢁ Fo;mean j =ΣFo
;
h ꢀ
ꢁ
i
GOF ¼ Σ wðFo ꢁ Fc
Þ
= Ndiffrs ꢁ Nparams §for all data;
ꢂ
ꢃ
2
2
2
RðFÞ ¼ Σ jj Fo j ꢁ j Fc jj =Σ j Fo j for observed data;
wRðF2Þ ¼ Σ wðFo ꢁ Fc
h ꢀ
ꢁ ꢀ
ꢁi
2
2
2
2
2
Þ
= ΣwðFo
Þ
§for all data:
[22] K. A. Chernyshev, L. B. Krivdin, Russ. J. Org. Chem. 2011, 47, 355.
[23] J. Hanusek, M. A. Russell, A. P. Laws, P. Jansa, J. H. Atherton, K. Fettes,
M. I. Page, Org. Biomol. Chem. 2007, 5, 478.
[24] P. D. Bartlett, G. Meguerian, J. Am. Chem. Soc. 1956, 78, 3710.
[25] J. R. Lloyd, N. Lowther, G. Zsabo, C. D. Hall, J. Chem. Soc., Perkin Trans.
2 1985, 1813.
Crystallographic data for structural analysis have been deposited with
the Cambridge Crystallographic Data Centre, CCDC no. 921142. Copies of
this information may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EY, UK (fax: +44-1223-336033;
[26] W. A. Henderson Jr., C. A. Streuli, J. Am. Chem. Soc. 1960, 82, 5791.
J. Phys. Org. Chem. 2013, 26 560–564
Copyright © 2013 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/poc