2-Hydroxy-3-mercaptopropaneselenol-1

Full text of DOI:10.1134/S1070363208050356

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 5, pp. 1019–1020. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © E.P. Levanova, E.N. Sukhomazova, V.A. Grabel’nykh, I.A. Zemirova, N.V. Russavskaya, A.I. Albanov, E.R. Zhanchipova, L.V. Klyba,
N.A. Korchevin, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 5, pp. 877–878.
LETTERS
TO THE EDITOR
2-Hydroxy-3-mercaptopropaneselenol-1
E. P. Levanova, E. N. Sukhomazova, V. A. Grabel’nykh, I. A. Zemirova, N. V. Russavskaya,
A. I. Albanov, E. R. Zhanchipova, L. V. Klyba, and N. A. Korchevin
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: venk@irioch.irk.ru
Received February 5, 2008
DOI: 10.1134/S1070363208050356
Derivative of glycerol containing in one molecule
ОН, SH and SeH groups, 2-hydroxy-3-mercapto-
propaneselenol-1 (I), was not described in the literature.
For its synthesis we have used elemental sulfur and
selenium, 1,3-dichloropropanol-2 (II) and the appro-
aches described in [1]. Preactivation of sulfur and
selenium was performed in the system hydrazine
hydrate–monoethanolamine where S22– and Se22– anions
are generated from these elements.
Oligomer III was subjected to reductive splitting in
the system hydrazine hydrate–KOH that led to the
formation of three types of chalcogenolates VIIа–VIIc.
Mild acidification of the solution of dichalcogenolates
VII results in the formation of a mixture of
dichalcogenols I, VIIIа, and VIIb. Fractions enriched
with compounds VIIIа, I, and VIIIb were isolated by
vacuum distillation.
N2H4
H2O/KOH
KY1CH2CH(OH)CH2Y2K
III
4 Y + N2H4·H2O + 4 RNH2 → 2 (RNH3)2Y2 + N2 + H2O
VIIа−VIIc
Y = S, Se; R = CH2CH2OH.
H+
HY1CH2CH(OH)CH2Y2H,
I, VIIIa, VIIIb
0oC, Ar
Combined solutions of sulfur and selenium in the
system used were introduced into the reaction with
dichloride II to obtain oligomer product III (81% to
dichloride II brought into the reaction). Chromatomass
spectrometry of the dichloromethane extract of the
reaction mixture revealed the presence of 4-hydroxy-1,2-
dithiolane IV (М+· 122 m/z) (yield ~2%), 4-hydroxy-1-
thio-2-selenolane V (М+· 170 m/z for 80Se) (~1%), and 4-
hydroxy-1,2-diselenolane (VI) (М+· 218 m/z) (6 %).
VIIа, VIIIа, Y1 = Y2 = S; VIIb, I, Y1 = S, Y2 = Se; VIIc,
VIIIb, Y1 = Y2 = Se.
Separately prepared at 60–65°С solutions of 3.2 g
of sulfur and 7.8 g of selenium, each in the mixture of
15 ml of hydrazine hydrate and 1.8 ml of mono-
ethanolamine, were combined. To the obtained mixture
at 50–55°С 11.7 ml of dichloride II was added
dropwise. The reaction mixture was heated for 4.5 h at
65–75°С. The polymer formed was separated by
decanting, washed with water, ethanol and ether; 17 g
of brown polymer was obtained. The hydrazine layer
was treated with dichloromethane, the solvent was
removed, and the residue was analyzed by chroma-
tomass spectrometry. The prepared polymer (10 g) was
added to the solution of 16.5 g of KOH in 74 ml of
hydrazine hydrate and on complete dissolution of the
polumer the reaction mixture was poured in an argon
nClCH2CH(OH)CH2Cl
II
0.5n S22− + 0.5n Se22−
( SCH2CH(OH)CH2Se )n
−2n Cl−
III
H
OH
Se
H
S
OH
S
H
S
OH
Se
+
+
+
Se
VI
IV
V
1019

1020
LEVANOVA et al.
flow into a beaker with 100 g of ice and 175 ml of
conc. НСl. The content of the beaker in an argon flow
was extracted with dichloromethane, the extract was
dried over magnesium sulfate, the solvent was
removed, and the residue (6.8 g) containing, by the
94, 93 (9) [СН2Sе]+·, [СНSе]+, 77 (1) [М – СН3Sе]+, 73
(3) [М – Н2О – HSе]+, 59 (12) [М – Н2О – СН3Se]+, 47
(10) [СН3S]+, 45 (8) [СНS]+, 44 (3), 43 (7), 41 (9).
IR spectra were recorded on a Bruker IFS-25
instrument, 1Н and 13С NMR spectra, on a Bruker DPX-
400 spectrometer (at 400.12 and 100.63 MHz, res-
pectively) in CDCl3 solutions, internal standard HMDS.
Mass spectra were obtained on a Shimadzu GCMS-
QP5050A spectrometer with quadrupole mass-analyzer,
energy of ionizing electrons 70 eV.
1
data of H NMR analysis, 2.7 g of compound I, was
distilled in vacuum. Fraction with bp 115–120°С
(2.5 mm Hg) contained ca. 75% of compound I, its
1
yield being 27% to the polymer taken. H NMR
(CDCl3), δ, ppm: 0.49 t (1H, SeH), 1.54 t (1H, SH), 2.74
m (4H, CH2S, CH2Se), 3.2 br.s (1H, ОН), 3.72 m (1H,
СНО). 13С NMR (CDCl3), δС, ppm, (J, Hz): 23.3 (С–Se,
JC–Se 53.3), 30.4 (С–S), 72.6 (С–О). IR spectrum, cm–1:
2296 νSe–H, 2549 νS–H. Mass spectrum, m/z (Irel., 80Se):
170 (1) [М – H2]+·, 154 (12) [М – Н2О]+·, 125 (7) [М –
СН3S]+, 112 (10) [SSe]+·, 107 (8) [М – Н2О – СН2SH]+,
REFERENCES
1. Grabel’nykh, V.A., Sukhomazova, E.N., Levanova, E.P.,
Vshivtsev, V.Yu., Zhanchipova, E.R., Klyba, L.V.,
Albanov, A.I., Russavskaya, N.V., and Korchevin, N.A.,
Russ. J. Gen. Chem.. 2007, vol. 77, no. 10, p. 1817.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 5 2008