Synthesis of 1,3,4-thiazaphospholines containing primary amino-group in the molecule

Full text of DOI:10.1134/S1070363209020297

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 2, pp. 330–331. © 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. 340–341.
LETTERS
TO THE EDITOR
Synthesis of 1,3,4-Thiazaphospholines
Containing Primary Amino-group in the Molecule
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 August 22, 2008
DOI: 10.1134/S1070363209020297
2-(2-Aminoethyl)amino-4-thioxo-4-phenoxy-1,3,4-
thiazaphosphol-2-ine (IIIа). A mixture of 1.0 g of
isothiocyanate I, 0.23 g of ethylenediamine, 0.52 g of
triethylamine and 20 ml of benzene was kept for 2 days
at 20°С. Triethylamine hydrochloride was separated
and solution was washed with water and dried over
anhydrous sodium sulfate. Then solvent was removed.
Yield 0.42 g (39%), mp 69–72°С. IR spectrum (KBr),
ν, сm–1: 1485 (Ph), 1568 (C=N), 3242 (NH2). 1Н NMR
spectrum [(СD3)2СO], δ, ppm: 3.55 d. d (1H, РCH2,
2JPH 3.49 Hz, 2JHH 13.95 Hz), 3.94 d. d (1H, РCH2, 2JPH
Chloromethylisothiocyanatothiophosphonates are
known to add aliphatic and aromatic amines to form
the phosphorylated thioureas. The latter closure cycle
in the presence of base yielding 1,3,4-thiazaphosphols
[1, 2]. We carried out reactions of О-phenyl chloro-
methylisothiocyanatothiophosphonate I with aliphatic
diamines IIа and IIb in the presence of triethylamine
and prepared 1,3,4-thiazapospholines containing primary
amino group IIIа and IIIb.
S
PhO
2
+
H2N(CH2)nNH2
PNCS
2.22 Hz, JHH 12.98 Hz), 3.70 m (4Н, CH2N), 7.28 m
31
(5H, Ph). Р NMR spectrum (С6H6), δР, ppm: 118.07.
ClCH2
Found, %: C 41.62; H 4.51; N 14.49; P 10.52.
C10H14N3OPS2. Calculated, %: С 41.79; H 4.92; N
14.63; P 10.78.
I
IIa, IIb
S
Et3N
N
PhOP
.
Et3N HCl
2-(3-Aminopropyl)amino-4-thioxo-4-phenoxy-
1,3,4-thiazaphosphol-2-ine (IIIb) was prepared si-
milarly from 1.09 g of isothiocyanate I, 0.30 g of 1,3-
propylenediamine IIb, 0.56 g of triethylamine and 50 ml
of benzene. Yield 0.66 g (53%), mp 94–96°С. IR
spectrum (KBr), ν, сm–1: 1487 (Ph), 1566 (C=N),
CNH(CH2)nNH2
S
IIIa, IIIb
II, III: n = 2 (a); n = 3 (b).
1
3241 (NH2). Н NMR spectrum [(СD3)2СO], δ, ppm:
Thiazaphospholines IIIа and IIIb can readily
undergo further modification due to the presence of
primary amino group in the molecule. Thus, 1,3,4-thiaza-
phospholine IV containing urea fragment was obtained
by reaction of phospholine IIIa with phenylisocyanate.
2
1.29 m (2Н, СН2), 3.53 d. d (1H, РCH2, JPH 4.50 Hz,
2
2JHH 13.20 Hz), 3.92 d. d (1H, РCH2, JPH 4.03 Hz,
2JHH 13.21 Hz), 3.69 m (4Н, СН2N), 7.29 m (5H, Ph).
31Р NMR spectrum (С6H6), δР, ppm: 118.07. Found, %:
C 43.55; H 5.11; N 13.69; P 9.92. C11H16ClN3OPS2.
Calculated, %: С 43.89; H 5.31; N 13.95; P 10.29.
S
N
2-(2-Phenylaminocarbonylethyl)amino-4-thioxo-
4-phenoxy-1,3,4-thiazaphosphol-2-ine (IV). A mix-
ture of 0.34 g of IIIа, 0.14 g of phenylisocyanate and
10 ml of benzene was refluxed for 5 h at 80°С. The
PhOP
CNH(CH2)2NHC(O)NHPh
IIIa
PhNCO
+
S
IV
330

SYNTHESIS OF 1,3,4-THIAZAPHOSPHOLINES
331
formed product was separated as powder and washed
ACKNOWLEDGMENTS
thrice with benzene. Yield 0.13 g (30%), mp 181–
183.5°С. IR spectrum (KBr), ν, сm–1: 1480 (Ph), 1553
(C=N), 1719 (СО), 3188, 3216, 3275 (NH). 31Р NMR
spectrum [(СD3)2CO], δР, ppm: 118.50. Found, %: C
50.01; H 4.28; N 13.69; P 7.52. C17H19N4O2PS2.
Calculated, %: С 50.24; H 4.67; N 13.79; P 7.63.
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 06-03-
32085).
REFERENCES
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., Zyabli-
kova, 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.
The IR spectra were registered on a UR-20 spec-
trometer in the range of 400-3600 сm–1 (vaseline oil).
The 1H NMR spectra were measured on a Bruker WM-
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).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 2 2009