Russian Journal of General Chemistry, Vol. 75, No. 12, 2005, p. 1975. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 12, 2005, p. 2065.
Original Russian Text Copyright
2005 by Sal’keeva, Nurmagambetova, Minaeva.
LETTERS
TO THE EDITOR
New Amidoesters of P(III) Acids
on the Basis of 2-Amino-4-phenylthiazole
L. K. Sal’keeva, M. T. Nurmagambetova, and E. V. Minaeva
Buketov Karaganda State University, Karaganda, Kazakhstan
Received April 5, 2005
Thiazole and its derivatives are the most important
synthons for preparing various biologically active
compounds. In detail, heterocyclic sulfanylamide
derivatives include norsulfazol (2-sulfanylamidothia-
zole), a widely known antimicrobial sulfanylamide
drug. With the purpose of searching for and synthesiz-
ing new medicines, we carried out purposeful che-
mical modification of 2-amino-4-phenylthiazole (I) to
obtain new P(III) amidoesters. Starting thiazole I was
prepared by the procedure in [1]. The reaction was
carried out by heating equimolar amounts of thiazole
I and tert-butyl tetraethylphosphorodiamidite (II) in
ethyl acetate with simultaneous distillation of the
evolving diethylamine (identified as hydrochloride).
Reaction progress was controlled by TLC. Comple-
tion of the reaction was judged about by the amount
of the hydrochloride obtained.
N
N
+ (Et2N)2POBu-t
+ Et2NH
NH P NEt2
NH2
S
S
OBu-t
III
I
II
tert-Butyl N,N-diethyl-N -[(4-phenyl)thiazol-2-yl]-
phosphorodiamidite (III) was purified by crystalliza-
tion from benzene. It is a white crystalline substance
readily soluble in water and polar organic solvents.
spectrum, , ppm: 7.22 7.48 m (C6H5, CH), 1.21 s
3
[9H, (CH3)3C], 1.07 t (6H, CH3, JHH 7 Hz), 2.59 m
(4H, CH2), 4.0 s (1H, NH). Found, %: C 58.45; H
7.22; N 11.78; P 8.69; S 8.98. C17H26N3OPS. Cal-
culated, %: C 58.21; H 7.40; 11.96; P 8.83; S 9.12.
During transamidation of phosphite II with 2 mol
of thiazole under the same conditions, only 1 mol of
diethylamine evolved. Upon addition of one more mole
of phosphite II, phosphorodiamidite III was isolated
and identified. Hence, we failed to introduce two
2-amino-4-phenylthiazole residues to the P(III) atom,
probably, by steric reasons. The phosphoramidite ob-
tained presents interes, since it provides wide possi-
bilities for chemical modification.
The IR spectra were measured on Specord IR-75
and Nicolet Avatar-360 spectrometers in thin layer in
1
1
the range 3700 400 cm . The H NMR spectra were
recorded on a Tesla BS-587 spectrometer (80 MHz) in
C6H6 against internal HMDS.
REFERENCES
tert-Butyl N,N-diethyl-N -[(4-phenyl)thiazol-2-
yl]phosphorodiamidite (III). Yield 85%, mp 141
1. Komarov, A.V., Yakovlev, I.P., Novikov, D.V., and
Zakhs, V.E., Zh. Obshch. Khim., 2003, vol. 73, no. 12,
p. 2043.
1
142 C. IR spectrum, , cm : 1475, 1620 (C=C),
1
1685 (C=N), 3435 (NH), 1020 (P O C). H NMR
1070-3632/05/7512-1975 2005 Pleiades Publishing, Inc.
Sal'keeva
