Chalcogen-containing analogs of ethylene glycol and its derivatives

Article abstract of DOI:10.1134/S1070363208040166

Ethylene chlorohydrin when reacted with elemental chalcogens or dimethyl dichalcogenides in the hydrazine hydrate-alkali system forms chalcogen-containing analogs of ethylene glycol and its derivatives (dichalcogenated β-diglycols, chalcogenated ethanols, and chalcogenated methyl cellosolves).

Full text of DOI:10.1134/S1070363208040166

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 4, pp. 608–613. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.Yu.Vshivtsev, E.P. Levanova, V.A. Grabel’nykh, E.A. Sukhomazova, A.I. Albanov, L.V. Klyba, E.R. Zhanchipova,
N.V. Russavskaya, N.A. Kochervin, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 4, pp. 627–632.
Chalcogen-containing Analogs
of Ethylene Glycol and Its Derivatives
V. Yu.Vshivtsev, E. P. Levanova, V. A. Grabel’nykh, E. A. Sukhomazova,
A. I. Albanov, L.V. Klyba, E. R. Zhanchipova, N.V. Russavskaya, and N. A. Kochervin
Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
Abstract—Ethylene chlorohydrin when reacted with elemental chalcogens or dimethyl dichalcogenides in the
hydrazine hydrate–alkali system forms chalcogen-containing analogs of ethylene glycol and its derivatives
(
dichalcogenated β-diglycols, chalcogenated ethanols, and chalcogenated methyl cellosolves).
DOI: 10.1134/S1070363208040166
Ethylene glycol and its ethers (cellosolves and
glymes) are important ligands for complex formation,
and they are widely used as effective solvents
possessing specific solvation ability [1]. Replacement
of oxygen in these compounds by chalcogens (S, Se, or
Te) enhances their donor power, especially with
respect to heavy metal cations [2]. Ethylene glycol and
its monothio analog (2-sulfanylethanol) are used in
multistage organic syntheses for protection of the
carbonyl group, and, therewith, 2-sulfanylethanol is
more effective both for introducing and removing the
protective group [3]. The use of 2-sulfanylethanol in
organic synthesis opens the way to functionalized
sulfides and sulfoxides [4]. It was found just recently
that 2-sulfanylethanol is a stabilizing ligand for
preparing semiconductor zinc sulfide nanoparticles [5].
However, sulfur-containing and, moreover, selenium-
or tellurium-containing analogs of ethylene glycol and
its simplest derivatives still remain hardly accessible
compounds.
of anions with a required x value, the Y : KOH ratio is
2–
varied. To form dichalcogenide anions Y , a 1:1
2
Y:KOH ratio is needed. In the case of sulfur or
selenium, the reaction is performed in the presence of
water as solvent, and in the case of tellurium, excess
hydrazine hydrate is used [6].
4Y + 4 KOH + N H ·H O → 2 K Y + N + 5 H O. (1)
2
4
2
2
2
2
2
To prevent conversion of chalcogens to compounds
with a positive oxidation degree, an excess of hyd-
razine hydrate with respect to the stoichiometry of
reaction (1) was used in all cases.
In the reaction of ethylene chlorohydrin with ele-
mental sulfur activated according to reaction (1), the
organosulfur compounds that are formed do not
separate as an organic phase, evidently due to their
high solubility in the water–hydrazine medium.
Extraction of the reaction mixture with methylene
chloride allows two main products to be isolated in a
total yield of about 60%. Dithio-β-diglycol Ia is
formed in 29% yield.
We have developed convenient methods for syn-
thesis of dichalcogenated β-diglycols (HOCH CH )Y
2
2
2
(
Y = S, Se, Te) Ia–Ic and hetero analogs of ethylene
glycol HOCH CH YH (Y = S, Se) IIa, IIb and methyl
2
2
K2S2
cellosolve HOCH CH YCH (Y=S, Se, Te) IIIa–IIIc,
2 ClCH CH OH
(HOCH CH ) S .
(2)
2
2
3
2
2
2
2 2 2
–
2 KCl
based on reactions of ethylene chlorohydrin with
elemental chalcogens and dimethyl dichalcogenides in
the hydrazine hydrate–alkali system (Table 1).
Ia
Along with this disulfide product, 2-sulfanylethanol
IIa) was obtained in a fairly high yield (30%). Thiol
IIa is evidently formed by reductive cleavage of
The hydrazine hydrate–alkali redox system activ-
ates elemental chalcogens via formation of poly-
chalcogenide anions Yx [6]. For preferred formation
(
2
–
608

CHALCOGEN-CONTAINING ANALOGS
Table 1. Physicochemical characteristics of compounds I–III
609
Comp.
no.
bp., °С
Found, %
Calculated, %
Formula
(p, mm Hg)
С
Н
Y
С
Н
Y
Ia
Ib
152–156 (2)
185–190 (2)
31.51
19.01
6.56
3.98
S 40.87
Se 63.80
C
C
4
4
H
H
10
O
O
2
S
2
31.17
19.36
6.49
4.03
41.56
63.70
10
2
Se
2
a
IIa
70–72 (29)
81–82 (31)
93–94 (50)
89–90 (23)
84–85 (5)
31.03
18.92
38.98
25.95
19.32
7.78
4.83
8.56
5.80
4.45
S 41.00
Se 63.07
S 34.82
Se 56.84
Te 67.73
C
C
C
C
C
2
2
3
3
3
H
6
H
6
H
8
H
8
H
8
OS
30.77
19.20
39.13
25.91
19.19
7.69
4.80
8.69
5.75
4.26
41.02
63.20
34.78
56.82
68.02
IIb
OSe
OS
IIIa
IIIb
IIIc
OSe
OTe
a
Characteristics of compound IIa agree with published data [13].
disulfide Ia with excess hydrazine present in the
water–hydrazine phase.
(IIb). Note also that diselenides are more difficult to
reduce with hydrazine than disulfides [7]. Only traces
of monoseleno-β-diglycol IVb were found in this
1
77
2
Ia + N
2
H
4
·H
2
O → 4 HOCH
2
CH
2
SH + N
2
+ H
2
O. (3)
reaction by means of H and Se NMR spectroscopy
IIa
(δ CH SeC 2.75 ppm, t; δSe 105.73 ppm), what agrees
2
with the observation in [8] that selenium is less am-
biguously, compared to sulfur, activated in the aqueous
hydrazine–alkali system [8].
Disulfides are known to be readily reduced with
hydrazine hydrate even in the absence of alkali [7].
The most facile reaction occurs, when disulfide and
hydrazine hydrate are present in the same phase, which
is the case in reaction (3).
Tellurium dissolved in the hydrazine hydrate–alkali
system when reacted with ethylene chlorohydrin forms
ditelluro-β-diglycol Ic in 32% yield. Regeneraton of
the elemental tellurium is observed in the course of the
reaction (conversion 48%). Monotelluro-β-diglycol
IVc is formed in 11% yield, most probably, from di-
telluride Ic which is unstable, like many ditellurides [9].
By GC–MS we also detected in the dichloro-
methane extract of the reaction mixture monothio-β-
diglycol IVa (yield ~1% yield). Most probably, this
product is formed due to partial transformation of
sulfur in reaction (1) to the monosulfide anion.
K
2
Te
2
K
2
S
2 ClCH
2
CH
2
OH
2 2 2 2
(HOCH CH ) Te
–
2 KCl
2
ClCH
2
CH
2
OH
(HOCH
2
CH
2
)
2
S.
(4)
–
2 KCl
Ic
IVa
(
HOCH
2
CH
2
)
2
Te.
(6)
–
Te
IVc
The reaction of selenium with ethylene chloro-
hydrin in the hydrazine hydrate–alkali system proceeds
more unambiguously as compared to sulfur. Diseleno-
β-diglycol Ib separates as an organic layer in 75%
yield.
1
Compounds Ic and IVc were characterized by H
NMR spectroscopy (Table 2). Behavior of the
molecular ions of Ib, IIb, IIIb, and IIIc , formed
under electron impact, was studied. The fragmentation
di-seleno-β-diglycol Ib and 2-
selanylethanol (IIb) is sim-ilar to that of their sulfur-
K
2
Se
2
2
ClCH
2
CH
2
OH
(HOCH
2
CH
2
)
2
Se
2
.
(5)
–
2 KCl
pattern of
Ib
containing analogs [10, 11], though the molecular ion
The lower solubility of product Ib in the water–
hydrazine medium hinders, under the conditions of
reaction (5), reduction of Se–Se bonds with excess
hydrazine hydrate and formation of 2-selanylethanol
is very unstable (in both cases, W 2) (Scheme 1).
M
By contrast, 2-methylselanyl- and 2-methyltella-
nylethanols (IIIb, IIIc) form stable molecular ions
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 4 2008

6
10
VSHIVTSEV et al.
Table 2. Spectral characteristics of compounds I–III
NMR spectrum, δ, ppm
Comp.
no.
–
1
Mass spectrum, m/z (I, %, of the total ion
32 80 130
IR spectrum, cm
current) S, Se, Te
1
13
Н
С
+
·
Ia
3312 (νОН); 2922, 2873 (νСН); 1654 2.84 t (СН
2
S), 3.82 t 40.87 (СН
2
S), 60.03 154 (3) [M] [10]
(
δ
ОН); 1461, 1400, 1286 [δ(СН2)]; 1218, (СН
155, 1060, 1045, 1007, 819, 640,
85
2
О), 4.16 br.s (ОН) (СН О)
2
1
4
+
·
+ ·
Ib
3300 (νОН); 2900, 2845 (νСН); 1440, 3.09 t (СН
2
Sе), 3.91 t 32.58 (СН
2
Sе),
250 (1) [M] , 204 (1) [C
2
H
5
ОSе
2
] , 188
1
+ ·
+
1
1
5
390, 1245 [δ(СН2)]; 1110, 1040, (СН
015, 980, 950, 900, 770, 710, 620,
20, 425
2
О), 2.82 s (ОН)
J
С–Sе 75.7 Hz;
(2) [C H Sе ] , 175 (2) [CH Sе ] , 160
2
4
2
3
2
а
+ ·
+
61.75 (СН
2
О)
2 2 3
(10) [Sе ] , 107 (4) [C H Sе] , 93 (10)
+
+
+
[CHSе] , 80 (5) [Sе] , 45 (40) [C
2
H
5
О] ,
+
·
+
4
4 (5) [C H О] , 43 (15) [C H О] , 42 (3)
2 4 2 3
+
·
2 2
[C H О]
Ic
3332, 3189 (νОН); 2924, 2861 (νСН); 2.84 t, 3.31 t (СН
2
Tе), 7.46, 8.70 (СН
2
Tе);
О)
–
2
1
1
630, 2033, 1611 (δОН); 1459, 1402, 3.83 m (СН
361 [δ(СН2)]; 1264, 1104, 1066, (ОН)
2
О), 3.18 br.s 63.30, 64.28 (СН
2
038, 1003, 888, 714, 615
3
+·
IIа
IIb
3353 (νОН); 2934, 2874 (δСН); 2556 1.51 t (SН), JН–S–С–Н 8.2 Hz; 27.26 (SСН
2
), 63.77 78 (12) [M] [11]
(
[
ν
2 2
S–Н); 1635 (δОН); 1463, 1417, 1384 2.68 m (SСН ), 3.70 t (ОСН )
3
δ(СН2)]; 1293, 1236, 1169, 1062, (ОСН
2
), JН–С–С–Н 5.9 Hz
1
048, 1014, 941, 908, 758, 661, 471
3
+·
+ ·
3327 (νОН); 2979, 2938, 2871 (νС–Н); –0.68 t (SeН), JН–Se–С–Н 21.13
(SеСН
2
), 126 (2) [M] , 108 (20) [C
H
4
Sе] , 95, 93
2
+
+
+
2
1
1
4
299 (νSe–Н); 1637 (δОН); 1461, 1413, 7.5 Hz; 2.74 m (СН
2
Se), 63.98 (ОСН
2
)
(17) [CH
3
Sе] , [CHSе] , 81, 80 (28) [HSе] ,
3
+
381 [δ(СН2)]; 1277, 1201, 1153, 3.73 t (СН
2
О), JН–С–С–Н
[Se]
067, 1046, 1011, 933, 862, 799, 651, 6.2 Hz; 2.00 (ОН)
56
IIIа
3 3
3385 (νОН); 2962, 2920, 2878 (νСН); 2.10 s (СН S), 2.68 t 14.89 (СН S), 36.90 [14]
2
1
1
6
041, 1720, 1654, 1638 (δОН); 1460, (СН
2
S), 2.88 s (ОН),
(СН
2
S), 59.73 (ОСН
2
)
427, 1322, 1288, 1228 [δ(СН2)]; 3.72 t (ОСН
169, 1044, 958, 939, 816, 770, 699,
54, 470
2
)
2
1
+·
+
IIIb
3366 (νОН); 2994, 2967, 2925, 2872, 1.99 s (СН
3
Se),
J
Н–Se 3.65 (СН
3
Sе), JС–Se 140 (11) [M] , 109 (12) [M – CH
3
О] , 95,
+
+
2
827 (νС–Н); 2176, 2041, 1865, 1610 10.39 Hz; 2.71 t (СН
2
Se), 61.62 Hz; 28.37 93 (32) [CH
3
Sе, CHSе] , 80 (10) [Sе] , 45
1
+
(
δ
ОН); 1463, 1423, 1407, 1385, 1341, 3.21 s (ОН), 3.75 t (ОСН
269 [δ(СН2)]; 1194, 1156, 1065,
043, 1002, 972, 902, 811, 793, 739,
72, 591, 455
2
) (СН
2
Sе),
2 5
JС– Se (18) [C H O]
1
1
6
61.81 Hz; 60.52
b
2
(ОСН )
2
125
+·
IIIc
3345 (νОН); 2970, 2922, 2868 (νС–Н); 1.82 s (СН
3 3
Te), JН–С– Te –22.12 (СН Tе), 190 (9) [M] , 162 (8), 145–143 (21)
1
125
+
+
2
427, 2031, 1654 (δОН); 1416, 1264, 20.23 Hz; 2.73 t (СН
2
Te), JС– Te 157.8 Hz; [CH
3
Tе, CHTе] , 130 (14) [Tе] , 45 (32)
+
1
9
221[δ(СН2)]; 1150, 1061, 1037, 995, 2.77 s (ОН), 3.72 t (ОСН
2
) 8. 16 (СН Tе), [C H O]
2
2 5
1
125
44, 922, 833, 708, 624, 523
J
С– Te 156.6 Hz;
c
6
2
3.3 (ОСН )
a 77
b 77
c 125
Se NMR spectrum, δSe 268.88 ppm. Se NMR spectrum, δSe 21.29 ppm.
Te NMR spectrum, δTe 28.63 ppm.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 4 2008

CHALCOGEN-CONTAINING ANALOGS
611
Scheme 1.
+
(SeCH2)2
+ (CH O)
3
2
m/z 188 (2)
+
Se
Se
OH
Se2+ + (C H OH)
2 4 2
HO
Ib: M+ 250 (2)
m/z 160 (10)
Se+
m/z 80 (5)
CHSe+
C H Se + C H O Se
+
2
3
2 7 2
m/z 93 (4)
m/z 107 (4)
HSe+ + C H
CHSe+
2
3
m/z 93 (17)
m/z 81 (28)
+
SeH
+
C H Se + H O
HO
2
4
2
IIb: M+ 126 (2)
m/z 108 (20)
+
Se+ + C H
CH Se
3
2
4
m/z 95 (17)
m/z 80 (28)
+
·
[
M ] (Table 2). Their main fragmentation patterns
Acidification of solution of chalcogenolates Va,
Vb under mild conditions (0°, argon) provides 2-
sulfanylethanol (IIa) and 2-selanylethanol (IIb) in
yields of 65 and 47%, respectively.
involve cleavage of C–C and C–Y bonds (Scheme 2).
Scheme 2.
+
Thiol IIa is fairly widely used in organic synthesis,
while selenol IIb (like most other selenols [12]) is a
scarcely accessible compound, even though its syn-
thetic potential is as inexhaustible as that of thiol IIb.
H3C
Y
CH2 CH2 OH
+
+
M+
C H O + CH Y
CH Y CH + CH O
3
5
3
3
2
3
All three dichalcogenated β-diglycols Ia–Ic under
2
-Tellanylethanol (IIc) could not be prepared by
reaction (7), evidently due to its extreme instability [9,
2].
the action of the hydrazine hydrate–alkali system
without an additional solvent undergo reductive
cleavage by the Y–Y bond to form chalcogenolates
Va–Vc.
1
Treatment of solutions of chalcogenolates Va–Vc
with methyl iodide gave chalcogenated analogs of
methyl cellosolve IIIa–IIIc. Their yield decreases in
going from selenium IIIb (63%) to sulfur IIIa (41%)
and tellurium IIIc (20%) derivatives.
N H H O/KOH
2
4
2
_
Ia Ic
2 HOCH CH YK
2 2
_
Va Vc
+
H+
Considering the possible perspectives of ap-
plication of compounds IIIb, IIIc (by analogy with
sulfide IIIa) in organic synthesis and in the chemistry
HOCH CH YH
2
2
_K+
IIa, IIb (Y = S, Se)
of coordination compounds, a new procedure of their
+
CH3I
HOCH CH YCH
3
(7) synthesis was developed. The procedure is based on
2
2
_KI
_
IIIa IIIc
reductive activation of dimethyl dichalcogenides with
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 4 2008

6
12
VSHIVTSEV et al.
the hydrazine hydrate–alkali system, followed by
reaction (without isolation of corresponding methane-
chalcogenolates) with ethylene chlorohydrin.
solution, and the resulting mixture was kept for 2 h at
80°–85° and cooled to 40°. Ethylene chlorohydrin,
22.5 g, was then added to the mixture, and it was
stirred for 1.5 h at 55–60°C, cooled to 25°, and treated
with methylene chloride (2 × 30 ml). The extract was
dried over magnesium sulfate, and the solvent was
removed. The residue was distilled in a vacuum to
obtain 6.1 g of compound Ia as a colorless liquid
crystallising in the condenser, mp 35°, and 6.3 g of 2-
sulfanylethanol (IIa). The characteristics of the com-
pounds obtained are listed in Tables 1 and 2.
2
(CH
3
)
2
Y
2
+ N
2
H
4
·H
2
O + 4 KOH
+ 5 H O,
→
4 CH
3
YK + N
2
2
(8)
(9)
CH
3
YK + ClCH
2
CH
2
OH → IIIb, IIIc,
Y = Se, Te.
Compound IIIb, IIIc were prepared by reactions
8) and (9) in yields of 61 and 57 %, respectively.
Bis(2-hydroxyethyl) diselenide (Ib) was obtained
analogously from 31.4 g of KOH, 14 g of hydrazine
hydrate, 30 ml of water, 44.2 g of powdered selenium,
and 45.1 g of ethylene chlorohydrin. The organic layer
formed was separated, washed with water, dried over
(
Hence, we offered simple and effective methods
for preparing chalcogen-containing derivatives of
ethylene glycol, promising reagents for organic
synthesis and ligands for complex formation, based on
the use of the hydrazine hydrate–alkali system.
MgSO , and distilled in a vacuum to obtain 52 g of
4
compound Ib as a viscous light yellow oil. Its
characteristics are listed in Tables 1 and 2.
EXPERIMENTAL
Bis(2-hydroxyethyl) ditelluride (Ic) was obtained
analogously from 15.7 g of KOH, 140 g of hydrazine
hydrate, 35.7 g of powdered tellurium (in the absence
of water), and 22.5 g of ethylene chlorohydrin.
Precipitation of elemental tellurium (18.5 g) was
observed in the course of the reaction. It was removed,
and the reaction mixture was treated with methylene
The IR spectra were obtained on Specord IR-75 and
Bruker IFS-25 spectrometers in thin layer. The H, C,
Se, and Te NMR spectra were taken on a Bruker
1
13
77
125
DPX-400 spectrometer (400.1, 100.6, 76.3, and 126.2 MHz
respectively) in CDCl , CD OD, and mixtures of these
3
3
solvents; internal reference HMDS.
chloride. The extract was dried over MgSO , and the
4
The mass spectra were measured on a Shimadzu
GCMS-QP5050A instrument (SPB -5 column, 60000 ×
solvent was distilled off to obtain 10.62 g of a dark red
TM
1
13
liquid residue. According to the H and C NMR
spectra, it is a mixture of compounds Ic and IVc. Their
characteristics are listed in Table 2.
0
.25 mm, film thickness 0.25 μm). Injector tempera-
–
1
ture 250°; carrier gas helium, flow rate 0.7 ml min ;
–
1
temperature program 60°–260°, heating rate 15 deg min ;
detector temperature 250°; ionization energy 70 eV,
ion source temperature 200°; detected mass range 34–
2
-Selanylethanol (IIb). Compound Ib, 5.91 g, was
dissoled in a mixture of 21 g of hydrazine hydrate and
h of KOH at 75°–80° for 2.5 h. The reaction mixture
7
6
50 D.
Analysis of liquid reaction products was carried
out on a Tsvet-500 chromatograph (steel column,
000 × 5 mm, packing XE-60 on Inerton N-AW-
HMDS; linear temperature programming from 30° to
was cooled to 25° and poured with stirring under argon
into a mixture of ice and 90 ml of conc. HCl. The
mixture obtained was extracted with methylene
2
chloride and dried over MgSO , the solvent was
4
distilled off, and the residie, 2.3 g, was distilled in a
vacuum. The fraction with bp 81° (31 mm Hg)
contained a practically pure compound IIb, 1.3 g,
colorless liquid. Its characteristics are listed in Tables 1
and 2.
–
1
2
30° at a rate 12 deg min ; carrier gas helium) and on
an LKhM 80-MD-2 chromatograph (column 2000 × 3
mm, packing 5% XE-60 on Inerton AW-HMDS; linear
–
1
temperature programming at a rate 12 deg min ;
carrier gas helium).
2-(Methylsulfanyl)ethanol (IIIa). Compound Ia,
Bis(2-hydroxyethyl) disulfide (Ia). Potassium
hydroxide, 15.7 g, hydrazine hydrate, 7 g, and 15 ml of
water were placed in a flask equipped with a stirrer, a
reflux condenser, a thermometer, and a reagent supply
system. Powdered sulfur, 9 g, was added to the
2.06 g, was dissolved in a mixture of 20.1 g of
hydrazine hydrate and 4.5 g of KOH at 80°–85° for 2.5 h.
The reaction mixture was cooled to room temperature,
and 9.51 g of methyl iodide was slowly added. The
mixture was heated at 33–37°C for 3.5 h, extracted
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 4 2008

CHALCOGEN-CONTAINING ANALOGS
613
with methylene chloride, and the extract was dried
distilled in a vacuum was described above to obtain
over MgSO . The solvent was removed, and the residue,
1.65 g of pure compound IIIb.
4
1
9
.5 g, was distilled in a vacuum. The fraction with bp
3–94°C (50 mm Hg) contained a practically pure
REFERENCES
com-pound IIIa,
characteristics are listed in Tables 1 and 2.
1
g, colorless liquid. Its
1
. Comprehensive Organic Chemistry, Barton, D.H. and
Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 1.
Translated under the title Obshchaya organicheskaya
khimiya, Moscow: Khimiya, 1982, vol. 2.
2
-(Methylselanyl)ethanol (IIIb). a. Compound Ib,
3
.02 g, was dissolved in a mixture of 18.3 g of
hydrazine hydrate and 4.1 g of KOH at 80–85°C for 2.5 h. The
reaction mixture was cooled to room temperature, and
2. Garnovskii, A.D., Sadimenko, A.P., Osipov, O.A., and
Tsintsadze, G.V., Zhestko-myagkie vzaimodeistviya v
koordinatsionnoy khimii (Soft–Hard Interactions in
Coordination Chemistry), Rostov-on-Don: Rost. Univ.,
5
.2 g of methyl iodide was slowly added. The mixture
was heated for 35–40°C for 1.5 h, extracted with
methylene chloride, and the extract was dried over
1
986.
MgSO . The solvent was removed, and the residue was
distilled in a vacuum to give a fraction with bp 89–90° C
3. Protective Groups in Organic Chemistry, McOmie, J.F.W.,
Ed., London: Plenum, 1973.
4
(
23 mm Hg), containing a practically pure compound
4
5
6
. Moise, J., Goumont, R., Magnier, E., and Wakselman, C.,
Synthesis, 2004, no. 14, p. 2297.
IIIb, 2.12 g, colorless liquid. Its characteristics are
listed in Tables 1 and 2.
. Gubin, S.P., Kataeva, N.A., and Khomutov, G.B., Izv.
Ross. Akad. Nauk, Ser. Khim., 2005, no. 4, p. 811.
b. To a solution of 3.13 g of potassium hydroxide in
1
4 g of hydrazine hydrate, 2.1 g of dimethyl diselenide
was added, and the mixture was stirred for 2 h at 75–
0°C. After that, 1.8 g of ethylene chlorohydrin was
. Deryagina. E.N., Russavskaya. N.V., Papernaya, L.K.,
Levanova, E.P., Sukhomazova, E.N., and Korchevin, N.A.,
Izv. Ross. Akad. Nauk, Ser. Khim., 2005, no. 11,
p. 2395.
8
slowly added dropwise at 40°, and the reaction mixture
was stirred for 2.5 h at 55–60°C, extracted with
methylene chloride, and the extract was dried over
7
. Turchaninova, L.P., Korchevin, N.A., Deryagina, E.N.,
Trofimov, B.A., and Voronkov, M.G., Zh. Obshch.
Khim., 1992, vol. 62, no. 1, p. 152.
MgSO . The solvent was removed, and the residue was
4
distilled in a vacuum as described above to obtain 1.9 g
of pure compound IIIb.
8
. Russavskaya, N.V., Levanova, E.P., Sukhomazova, E.N.,
Grabel’nykh, V.A., Klyba, L.V., Zhanchipova, E.P.,
Albanov, A.I., and Korchevin, N.A., Zh. Obshch. Khim.,
2
-(Methyltellanyl)ethanol (IIIc ). a. Compound
2
006, vol. 76, no. 2, p. 243.
Ic was dissoloved in a mixture of 13.1 g of hydrazine
hydrate and 2.94 g of KOH at 80–85°C for 2.5 h. The
reaction mixture was cooled to room temperature, and
9. Sadekov, I.D., Maksimenko, A.A., and Minkin,V.I., Khi-
miya telluroorganicheskikh soedinenii (Chemistry of
Organo-tellurium Compounds), Rostov-on-Don: Rost.
Univ., 1983.
3
.72 g of methyl iodide was slowly added to it. The
mixture was kept at 35–40°C for 1 h and extracted
with methylene chloride. The extract was dried over
10. Kostiainen, O., Encyclopaedia of Analytical Chemistry,
Meyers, R.A., Ed., Chichester: Wiley, 2000, p. 963.
MgSO . The solvent was removed, and the residue was
4
distilled in a vacuum to obtain 0.65 g of a fraction with
bp 84–85°C (5 mm Hg), containing a practically pure
compound IIIc, a reddish clear transparent liquid. Its
characteristics are listed in Tables 1 and 2.
1
1
1. Ramsey, J.D. and Flanagan, R.J., J. Chromatogr., 1982,
vol. 240, p. 423.
2. Comprehensive Organic Chemistry, Barton, D.H. and
Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 3.
Translated under the title Obshchaya organicheskaya
khimiya, Moscow: Khimiya, 1982, vol. 5.
b. Dimethyl ditelluride, 2.21 g, was added to a
solution of 2.6 g of potassium hydroxide in 11.6 g of
hydrazine hydrate, and the resulting mixture was
stirred for 2 h at 80°C. After that 1.25 g of ethylene
chlorohydrin was slowly added dropwise at 40°C. The
mixture was stirred for 2.5 h at 55–60°C, cooled, and
extracted with CH Cl . The extract was dried over
13. Svoistva organicheskikh soedinenii. Spravochnik (Proper-
ties of Organic Compounds. A Handbook), Potekhin, A.A.,
Ed., Leningrad: Khimiya, 1984.
14. Hansen, M., Buttery, R.G., Stern, D.J., Cantwell, M.L.,
and Ling, L.C., J. Agr. Food Chem., 1992, vol. 40, no. 5,
p. 850.
2
2
MgSO , the solvent was removed, and the residue was
4
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