Reaction of O-phenylchloromethylisothiocyanatothiophosphonate with aliphatic diamines

Full text of DOI:10.1134/S1070363209020285

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 2, pp. 328–329. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © M.A. Pudovik, R.Kh. Bagautdinova, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 2, pp. 338–339.
LETTERS
TO THE EDITOR
Reaction of O-Phenylchloromethylisothiocyanatothiophosphonate
with Aliphatic Diamines
M. A. Pudovik and R. Kh. Bagautdinova
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
fax: (8432) 752253
e-mail: pudovik@iopc.knc.ru
Received July 8, 2008
DOI: 10.1134/S1070363209020285
It has been shown earlier that chloromethylisothio-
cyanatothiophosphonates add aliphatic and aromatic
amines to form phosphorylated thioureas which can
closure cycle yielding 1,3,4-thiazaphosphols [1, 2]. We
carried out some reactions of О-phenyl chloromethyl-
isothiocyanatothiophosphonate I with aliphatic di-
amines for the purpose of continuing this line of
studying. We assumed that on using of equimolar
reagents quantities the secondary amino group will
play a role of internal base to provide heterocyclization
of urea or thiourea.
phorylated thioureas IIIa and IIIb. It suggests that
they transform rapidly into the end cyclic products.
2-(2-Ammonium chloride)ethylamino-4-thioxo-
4-phenoxy-1,3,4-thiazaphosphol (IVа). To a solution
of 2.07 g of isothiocyanate I in 20 ml of benzene was
added 0.47 g of ethylenediamine IIa at stirring and
cooling to 5ºC. This mixture was kept for 3 days at 20°С.
Then precipitate was separated and washed with
benzene. Yield 1.36 g (54%), mp 161.5–163°С. IR
spectrum (KBr), ν, сm–1: 1242 (POPh), 1463 (Ph),
+
S
1565 (C=N), 2521, 2576, 2677, 2712 (NH3 ), 3423
PhO
1
(NH). Н NMR spectrum ((СD3)2СO), δ, ppm: 3.27
PNCS + H2N(CH2)nNH2
2
br.m (4H, CH2N), 3.54 d.d (1H, РCH2, JPH 3.3 Hz,
ClCH2
2
2
2JHH 13.57 Hz), 3.99 d.d (1H, РCH2, JPH = JHH
I
IIа, IIb
+
12.84 Hz), 7.16–7.39 m (5H, Ph), 9.08 s (3H, NH3 ).
S
31Р NMR spectrum (С6H6), δР, ppm: 117.31. Found, %:
C 37.05; H 4.51; N 12.69; P 9.52. C10H15ClN3OPS2.
Calculated, %: С 37.10; H 4.68; N 12.98; P 9.56.
PhO
ClCH2
PNHC(S)NH(CH2)nNH2
IIIа, IIIb
2-(3-Ammonium chloride)propylamino-4-thioxo-
4-phenoxy-1,3,4-thiazaphosphol (IVb) was prepared
similarly from 1.02 g of isothiocyanate I and 0.28 g of
diamine IIb. Yield 0.62 g (48%), mp 218–220°С. IR
spectrum (KBr), ν, сm–1: 1220 (POPh), 1470 (Ph),
S
N
PhO P
CHNH(CH2)nNH3+ Cl _
S
IVа, IVb
+
1595 (C=N), 2425, 2552, 2650, 2705 (NH3 ), 3436
II–IV: n = 2 (a), n = 3 (b).
(NH). 31Р NMR spectrum (С6H6), δР, ppm: 117.42.
Found, %: C 38.97; H 4.95; N 12.38; P 8.99.
C11H17ClN3OPS2. Calculated, %: С 39.11; H 5.08; N
12.44; P 9.16.
Reaction of isothiocyanate I with diamines IIa and
IIb proceeds smoothly at room temperature producing
with high yield 1,3,4-thiazaphosphols IVa and IVb
containing ammonium fragment. We failed to isolate
or register spectrally the intermediately formed phos-
The IR spectra were registered on a UR-20 spec-
trometer in the range of 400–3600 сm–1 (vaseline oil).
328

REACTION OF O-PHENYLCHLOROMETHYLISOTHIOCYANATOTHIOPHOSPHONATE
329
The 1H NMR spectra were measured on a Bruker WM-
REFERENCES
250 spectrometer (250.132 МHz) relative to internal
TMS. The 31Р NMR spectra were taken on a Bruker
MSL-400 NMR-Fourier spectrometer (100.62 MHz).
ACKNOWLEDGMENTS
1. Khailova, N.A., Bagautdinova, R.Kh., Kataeva, O.N.,
Pudovik, M.A., Alfonsov, V.A., and Pudovik, A.N.,
Synlett., 2006, no. 10, p. 1613.
2. Khaylova, N.A., Krepysheva, N.E., Saakyan, G.M.,
Bagautdinova, R.Kh., Shaymardanova, А.А., Zyab-
likova, Т.А., Аzancheev, N.M., Litvinov, I.A., Gubay-
dullin, A.T., Zverev, V.V., Pudovik, М.А., and Pudo-
vik, А.N., Zh. Obshch. Khim., 2002, vol.72, no. 7, p. 1145.
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 06-03-
32085).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 2 2009