Synthesis and crystal structure of diethyl tosyloxybenzylphosphonate

Article abstract of DOI:10.14233/ajchem.2014.16607

Diethyl tosyloxybenzylphosphonate was synthesized by the reaction of hydroxybenzylphosphonate with p-toluenesulfonyl chloride characterized by NMR spectroscopy, elemental analyses and X-ray single-crystal diffraction. The possessing parameters: m.f. C₁₈H₂₃O₆PS, monoclinic, P2(1)/n, a = 8.1087(9) ?, b = 20.215(2) ?, c = 12.5201(12)?, α= 90°, β= 98.7380(10)°, γ= 90°, V = 2028.5(4) ?3, Z = 4, Mr = 398.39, D_c = 1.305 g/cm³, μ = 0.268 mm^-1, F(000) = 840, T = 298(2) K, R₁ = 0.0462, wR₂ = 0.1076 for 3579 observed reflections with I >2σ;(I).

Full text of DOI:10.14233/ajchem.2014.16607

Asian Journal of Chemistry; Vol. 26, No. 7 (2014), 2138-2140
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.16607
Synthesis and Crystal Structure of Diethyl Tosyloxybenzylphosphonate
1,*
2
2
DU-LIN KONG , GUO-ZHU LI and REN-DIE LIU
1School of Pharmaceutical Sciences, Hainan Medical University, Haikou 571199, Hainan Province, P.R. China
2College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, Hainan Province, P.R. China
*Corresponding author: Tel/Fax: +86 898 66893826; E-mail: 173548977@qq.com
Received: 30 October 2013;
Accepted: 3 December 2013;
Published online: 22 March 2014;
AJC-14978
Diethyl tosyloxybenzylphosphonate was synthesized by the reaction of hydroxybenzylphosphonate with p-toluenesulfonyl chloride
characterized by NMR spectroscopy, elemental analyses and X-ray single-crystal diffraction. The possessing parameters: m.f. C18H23O6PS,
monoclinic, P2(1)/n, a = 8.1087(9) Å, b = 20.215(2) Å, c = 12.5201(12)Å, α = 90º, β = 98.7380(10)º, γ = 90º, V = 2028.5(4) Å3, Z = 4,
Mr = 398.39, Dc = 1.305 g/cm3, µ = 0.268 mm-1, F(000) = 840, T = 298(2) K, R1 = 0.0462, wR2 = 0.1076 for 3579 observed reflections
with I >2σ(I).
Keywords: Diethyl tosyloxybenzylphosphonate, Synthesis, Crystal structure.
points were determined on a Yanaco apparatus and they are
INTRODUCTION
uncorrected. NMR spectral data were collected on a Brucker
The biological importance of phosphonates was recognized
400 MHz with TMS as an internal standard.
in the past decade1. Among them, α-substituted phosphonates
Synthesis: To a solution cooled to 0 °C of 10 mL methy-
are particularly important in connection with their remarkable
lene chloride, (2.44 g, 10 mmol) diethyl hydroxybenzyl-
biological activities2-4. The widespread uses of phosphonates
phosphonate and 2.81 mL of triethylamine was added dropwise
are as enzyme inhibitors5-7, botryticides8, anti-HIV agents9-10
antibacterial agents11 and haptens for catalytic antibodies12.
,
over 0.5 h a solution of p-toluenesulfonyl chloride (1.91 g,
10 mmol) in 10 mL of methylene chloride. The reaction
temperature did not exceed 25 °C during the addition. After
an additional 0.5 h of stirring the reaction was allowed to warm
to room temperature and stir overnight, filtration and evapo-
ration afforded 3.90 g (98 %) of the title compound as a white
In our recent researches, we require p-toluenesulfonyl
chloride as the intermediate to synthesize a series of α-oxophos-
phonic acid derivatives in the hope of looking for new
biological compounds.As an extension of the work on structure
characterization of α-oxophosphonic acid derivatives, a single
crystal of the title compound was subjected to X-ray diffraction
experiment.
l
solid, as shown in Scheme-I. m.p. 63-65 °C. H NMR (400
MHz, CDCI3): 01.21 (6H, m) 2.34 (3H, s), 4.03 (4H, m), 5.65
(lH, d, 1 = 16 Hz) and 7.35 (9H, m); 13C NMR (50 MHz,
CDCI3 ): 016.4 (m), 21.6, 63.5 (m), 75.8, 79.2,128.0, 128.2,
128.3, 128. 4, 128. 5, 129.0, 129.1, 129.5, 131.8, 133.8 and
144.8. Anal. Calcd for C18H23O6PS: C, 54.26; H, 5.82. Found:
C, 54.12; H, 5.73.
EXPERIMENTAL
Starting materials were obtained from commercial supp-
liers and were used without further purification. All melting
CH3
OH
O
P
O
triethylamine
O S O
OCH2CH3
H3C
S Cl
O
+
O
OCH2CH3
O
P OCH2CH3
OCH2CH3
Scheme-I

Vol. 26, No. 7 (2014)
Synthesis and Crystal Structure of Diethyl Tosyloxybenzylphosphonate 2139
Determination of crystal structure:A colourless crystal
having approximate dimensions of 0.45 mm × 0.32 mm ×
0.30 mm was selected for X-ray diffraction study. Diffraction
experiments were performed on a Siemens SMART CCD area-
detector diffractometer with graphite-monochromatic MoKα
radiation (λ = 0.71073 Å) at 298 2 K, scan technique 2.60º
≤ θ ≤ 25.02º. A total of 10016 reflections were collected, of
which 3579 reflections were unique with Rint = 0.0292. Lp
effects and empirical absorption were applied in data correc-
tions. The structure was solved by direct methods and expanded
using Fourier techniques and SHELXS-97 program system
was used in the solution and refinement of the structure. The
nonhydrogen atoms were refined anisotropically. Hydrogen
atoms were added according to theoretical model. The final
full-matrix least-squares refinement including 258 variable
parameters for 3579 reflections with I > 2σ(I) and converged
with unweighted and weighted agreement factors of R1 =
0.0462 and wR2 = 01076, where w = 1/[σ2(F02) + (0.0466P)2 +
2
1.0491P] and P = (F02 + 2FC )/3. The maximum and minimum
peaks on the final difference fourier map are corresponding to
0.264 and -0.264e/A3, respectively.
RESULTS AND DISCUSSION
Figs. 1 and 2 show the molecular structure and packing
diagram of the title compound, respectively. Selected bond
distances and angles are listed in Table-1. In the title compound,
the dihedral angle formed by the two benzene planes is 6.1
(1)° The atom P(1) has a distorted tetrahedral configuration.
The widening of angle O(3)-P(1)-O(1)(115.76(13)°) and
narrowing of angle O(1)-P(1)-C(1)(101.62(12)°) from the ideal
tetrahedral value are attributed to the Thrope-Ingold effect .
The bond P(1)-O(3) (1.454(2)Å) of is much shorter than P(1)-
O(1) (1.561(2)Å ) and P(1)-O(2)(1.562(2)Å ). This is result
of the (d-p)π bonding between 3d vacant orbital of the P atom
and the lone electron pair of the O(2) atom. These values are
basically identical with that of the reference13. The two ethoxy
groups on the phosphorus atom were unequivalent symmetry.
The angular disposition of the bond about atom S(1) shows a
significant deviation from that of a regular tetrahedron, with
the largest deviation for the O-S-O angle. The widening of the
O(5)-S(1)-O(6) angle, to 120.43(16) in the title compound,
from the ideal tetrahedral value is presumably the result of the
repulsive interaction between the short S=O bonds, similar to
that observed in related structures14-15. The bond length of S(1)-
C(12)(1.749(3)Å) is shorter than that of general S-C(1.81Å),
which may be attributed to the conjugation of all carbon-carbon
bonds in benzene ring and exocyclic sulfur-oxygen double
bonds. The orientation of the benzene ring substituent is
Fig. 1. Molecular structure of the title compound
Fig. 2 Packing diagram of the title compound
TABLE –1
SELECTED BOND LENGTHS (Å) AND ANGLES (º) FOR THE COMPOUND
Bond
O(1)-C(8)
O(1)-P(1)
O(2)-C(10)
Lengths
1.41(3)
1.561(2)
1.431(4)
Angles
Bond
Lengths
1.5863(19)
1.419(2)
1.421(2)
Angles
Bond
P(1)-C(1)
S(1)-C(12)
C(1)-C(2)
Bond
Lengths
1.822(3)
1.749(3)
1.512(3)
Angles
O(4)-S(1)
O(5)-S(1)
O(6)-S(1)
Bond
Bond
C(8)-O(1)-P(1)
C(8')-O(1)-P(1)
O(4)-C(1)-C(2)
127.9(13)
120.3(14)
110.3(2)
O(4)-C(1)-H(1)
C(7)-C(2)-C(3)
C(3)-C(2)-C(1)
109.4
118.7(3)
121.8(2)
C(4)-C(3)-H(3)
C(2)-C(7)-C(6)
O(1)-C(8)-C(9)
119.5
120.2(3)
116(2)

2140 Kong et al.
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of the phenyl ring bound to the sulfonyl group is governed by
a C(13)-H(13)...O(6) interaction, defined by the O(4)-S(1)-
C(12)-C(13) torsion angle.
ACKNOWLEDGEMENTS
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The authors are grateful to Natural Science Foundation
of Hainan Province of China (No: 211020) for financial sup-
ports.
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