2856
A. V. Golovchenko et al.
PAPER
Dimethyl 5-Hydrazino-2-styryl-1,3-oxazol-4-ylphosphonate
(9c)
Diethyl 5-(Anilino-1,3,4-thiadiazol-2-yl)(cinnamoylamino)me-
thylphosphonate (10e)
Compound 10e was prepared following the general procedure from
9e (3.37 g) and phenyl isothiocyanate (1.49 g). The product was pu-
rified by recrystallization from EtOH; yield: 3.63 g (77%); pale yel-
low crystals; mp 171–173 °C.
Compound 9c was prepared as described before.16
Diethyl 5-Hydrazino-2-phenyl-1,3-oxazol-4-ylphosphonate (9d)
Compound 9d was prepared following the general procedure from
8d (3.88 g). After evaporating the solvent in vacuo, the residue was
treated with hexane, filtered off, and recrystallized from benzene;
yield: 2.6 g (84%); colorless crystals; mp 78–80 °C.
Anal. Calcd for C22H25N4O4PS: C, 55.92; H, 5.33; N, 11.86; P, 6.56;
S, 6.79. Found: C, 56.10; H, 5.58; N, 11.74; P, 6.42; S, 6.60.
Anal. Calcd for C13H18N3O4P: C, 50.16; H, 5.83; N, 13.50; P, 9.95.
Found: C, 50.33; H, 6.02; N, 13.45; P, 9.91.
Dimethyl (4-Methylbenzoylamino)[5-(4-toluidino)-1,3,4-thiadi-
azol-2-yl]methylphosphonate (10f)
Compound 10f was prepared following the general procedure from
9b (2.97 g) and 4-methylphenyl isothiocyanate (1.64 g). The prod-
uct was purified by recrystallization from MeOH; yield: 2.91 g
(65%); colorless crystals; mp 130–132 °C.
Diethyl 5-Hydrazino-2-styryl-1,3-oxazol-4-ylphosphonate (9e)
Compound 9e was prepared following the general procedure from
8e (4.14 g); yield: 3.13 g (93%); pale yellow oil which was used
without purification in the preparation of 10e.
Anal. Calcd for C20H23N4O4PS: C, 53.81; H, 5.19; N, 12.55; P, 6.94;
S, 7.18. Found: C, 53.97; H, 4.91; N, 12.45; P, 6.82; S, 7.03.
Anal. Calcd for C15H20N3O4P: C, 53.41; H, 5.98; N, 12.46; P, 9.18.
Found: C, 53.62; H, 6.13; N, 12.45; P, 9.31.
X-Ray Structure Determination of 5d
Dialkyl 5-(Arylamino-1,3,4-thiadiazol-2-yl)(acylamino)meth-
ylphosphonates 10a–f; General Procedure
A solution of compound 9a–e (10 mmol) and aryl isothiocyanate
(11 mmol) in dioxane (10 mL) was boiled for 12 h. The precipitate
formed was filtered off, dried in vacuo, and recrystallized from
MeOH or EtOH (Table 1).
Crystal Data: C19H18N4O3S, M = 382.44, monoclinic, a = 9.747(3),
b = 20.078(7), c = 9.931(2) Å, = 100.85(3), V = 1908.8 Å3, Z = 4,
d = 1.331 gcm–3, space group P21/c, = 1.87 cm–1, F(000) = 800.6,
sphere with d = 0.36 mm.
Data Collection: All crystallographic measurements were per-
formed at 20 °C on a CAD-4 Enraf-Nonius diffractometer operating
in the -2 scan mode (the ratio of the scanning rates /2 = 1.2).
Intensity data were collected within the range 2 < < 25° , (0 < h <
11, 0 < k < 23, –11 < l < 11) using graphite-monochromated Mo-K
radiation ( = 0.71069 Å). Intensities of 3674 reflections (3341
unique reflections, Rint = 0.033) were measured. Data were correct-
ed for Lorentz and polarization effects, and an empirical absorption
correction based on azimuthal scan data was applied.23
Dimethyl 5-(Anilino-1,3,4-thiadiazol-2-yl)(benzoylamino)meth-
ylphosphonate (10a)
Compound 10a was prepared following the general procedure from
9a (2.83 g) and phenyl isothiocyanate (1.49 g). The product was
purified by recrystallization from MeOH; yield: 3.3 g (79%); color-
less crystals; mp 194–195 °C.
Anal. Calcd for C18H19N4O4PS: C, 51.67; H, 4.58; N, 13.39; P, 7.40;
S, 7.66. Found: C, 51.83; H, 4.61; N, 13.31; P, 7.40; S, 7.66.
Structure Solution and Refinement: The structure was solved by di-
rect methods and refined by full-matrix least-squares technique in
the anisotropic approximation using the CRYSTALS program
package.24 In the refinement 1655 reflections with I >3 (I) were
used.
Dimethyl 5-(Anilino-1,3,4-thiadiazol-2-yl)(4-methylbenzoyl-
amino)methylphosphonate (10b)
Compound 10b was prepared following the general procedure from
9b (2.97 g) and phenyl isothiocyanate (1.49 g). The product was pu-
rified by recrystallization from MeOH; yield: 3.07 g (71%); color-
less crystals; mp 133–135 °C.
All hydrogen atoms were located in the difference Fourier maps and
included in the final refinements with fixed positional and thermal
parameters [only H (3) and H(4) atoms participating in hydrogen
bonding were refined isotropically]. Convergence was obtained at
R1 = 0.053 and wR2 = 0.053, GOF = 1.162 (252 refined parame-
ters; obs/variabl. = 6.6; the largest and minimal peaks in the final
difference map, 0.33 and –0.27 eÅ–3). Chebyshev weighting
scheme25 with the parameters 1.26, 0.82, and 1.00 was used.26
Anal. Calcd for C19H21N4O4PS: C, 52.77; H, 4.89; N, 12.96; P, 7.16;
S, 7.41. Found: C, 52.58; H, 5.08; N, 12.79; P, 7.05; S, 7.31.
Dimethyl 5-(Anilino-1,3,4-thiadiazol-2-yl)(cinnamoylami-
no)methylphosphonate (10c)
Compound 10c was prepared following the general procedure from
9c (3.09 g) and phenyl isothiocyanate (1.49 g). The product was pu-
rified by recrystallization from MeOH; yield: 3.34 g (75%); pale
yellow crystals; mp 160–161 °C.
References
(1) Adlington, R. M.; Baldwin, J. E.; Catteric, D.; Pritchard, G.
J. J. Chem. Soc., Perkin Trans. 1 1999, 855.
(2) Adlington, R. M.; Baldwin, J. E.; Catteric, D.; Pritchard, G.
J. J. Chem. Soc., Perkin Trans. 1 2000, 299.
Anal. Calcd for C20H21N4O4PS: C, 54.05; H, 4.76; N, 12.61; P, 6.97;
S, 7.21. Found: C, 54.15; H, 4.58; N, 12.52; P, 6.86; S, 7.10.
(3) Jones, R. C. F.; Berthelot, D. J. C.; Iley, J. N. Chem.
Commun. 2000, 2131.
(4) Adlington, R. M.; Baldwin, J. E.; Catteric, D.; Pritchard, G.
J.; Tang, L. T. J. Chem. Soc., Perkin Trans. 1 2000, 2311.
(5) Adlington, R. M.; Baldwin, J. E.; Catteric, D.; Pritchard, G.
J. J. Chem. Soc., Perkin Trans. 1 2001, 668.
(6) Stensbol, T. B.; Uhlmann, P.; Morel, S.; Eriksen, B. L.;
Felding, J.; Kromann, H.; Hermit, M. B.; Greenwood, T. R.;
Bräuner-Osborne, H.; Madsen, U.; Junager, F.; Krogsgaard-
Larsen, P.; Begtrup, M.; Vedso, P. J. Med. Chem. 2002, 45,
19.
Diethyl 5-(Anilino-1,3,4-thiadiazol-2-yl)(benzoylamino)meth-
ylphosphonate (10d)
Compound 10d was prepared following the general procedure from
9d (3.11 g) and phenyl isothiocyanate (1.49 g). The product was pu-
rified by recrystallization from EtOH; yield: 3.48 g (78%); pale yel-
low crystals; mp 186–187 °C.
Anal. Calcd for C20H23N4O4PS: C, 53.81; H, 5.19; N, 12.55; P, 6.94;
S, 7.18. Found: C, 54.11; H, 5.43; N, 12.43; P, 6.83; S, 7.09.
(7) Myers, A. G.; Gleason, J. L. J. Org. Chem. 1996, 61, 813.
Synthesis 2003, No. 18, 2851–2857 © Thieme Stuttgart · New York