Reactions of chloromethyloxirane and dihalopropanols with chalcogens in basic reducing systems

Article abstract of DOI:10.1134/S1070428008040064

Chloromethyloxirane and 2,3-dibromopropan-1-ol reacted with a solution of selenium or tellurium in the system hydrazin hydrate-potassium hydroxide (K ₂Se₂, K₂Te₂) to give allyl alcohol; the reaction was accompanied by regeneration of the initial free chalcogen. 1,3-Dichloropropan-2-ol reacted with selenium in the same system to give oligomeric product having a 2-hydroxypropane-1,3-diyldiseleno monomeric unit, while the reaction with tellurium led to the formation of allyl alcohol and almost complete regeneration of initial tellurium. Probable reaction mechanisms are discussed. Polyselenide oligomers containing a hydroxy group in a monomeric unit were formed in reactions of chloromethyloxirane and 1,3-dichloropropan-2-ol with selenium in the system hydrazine hydrate-2-aminoethanol. Under analogous conditions 2,3-dibromopropan-1-ol was converted into allyl alcohol with regeneration of elemental selenium. Reductive cleavage of polyselenide oligomers gave Se-methyl derivatives of 2-hydroxypropane-1,3-diselenol.

Full text of DOI:10.1134/S1070428008040064

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 4, pp. 505–510. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.V. Elaev, V.A. Grabel’nykh, N.V. Russavskaya, E.P. Levanova, E.N. Sukhomazova, E.R. Zhanchipova, L.V. Klyba, A.I. Albanov,
N.A. Korchevin, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 4, pp. 510–515.
Reactions of Chloromethyloxirane and Dihalopropanols
with Chalcogens in Basic Reducing Systems
A. V. Elaev, V. A. Grabel’nykh, N. V. Russavskaya, E. P. Levanova, E. N. Sukhomazova,
E. R. Zhanchipova, L. V. Klyba, A. I. Albanov, and N. A. Korchevin
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: venk@irioch.irk.ru
Received September 5, 2006
Abstract—Chloromethyloxirane and 2,3-dibromopropan-1-ol reacted with a solution of selenium or tellurium
in the system hydrazin hydrate–potassium hydroxide (K2Se2, K2Te2) to give allyl alcohol; the reaction was
accompanied by regeneration of the initial free chalcogen. 1,3-Dichloropropan-2-ol reacted with selenium in
the same system to give oligomeric product having a 2-hydroxypropane-1,3-diyldiseleno monomeric unit,
while the reaction with tellurium led to the formation of allyl alcohol and almost complete regeneration of
initial tellurium. Probable reaction mechanisms are discussed. Polyselenide oligomers containing a hydroxy
group in a monomeric unit were formed in reactions of chloromethyloxirane and 1,3-dichloropropan-2-ol with
selenium in the system hydrazine hydrate–2-aminoethanol. Under analogous conditions 2,3-dibromopropan-1-
ol was converted into allyl alcohol with regeneration of elemental selenium. Reductive cleavage of poly-
selenide oligomers gave Se-methyl derivatives of 2-hydroxypropane-1,3-diselenol.
DOI: 10.1134/S1070428008040064
Chloromethyloxirane (I), 2,3-dibromopropan-1-ol
(II), and 1,3-dichloropropan-2-ol (III) were reported to
react with sulfur in the system hydrazine hydrate–
alkali–water, yielding polysulfide oligomers with hy-
droxy groups in their macromolecules [1]. The result-
ing oligomers underwent reductive cleavage at the S–S
bonds by the action of an alkaline solution of hydra-
zine hydrate with no other solvent. These transforma-
tions underlay simple preparative procedures for the
synthesis of dithioglycerols and their S-methyl deriva-
tives. In the reactions with any compound I–III, mix-
tures of isomeric dithioglycerols were formed, i.e., the
process was accompanied by migration of the hydroxy
group [1].
work we examined reactions of compounds I–III
with selenium and tellurium in hydrazine-based basic
reducing systems. We anticipated that these reactions
will lead to the formation of oligomeric polychalco-
genides having hydroxy groups, as well as selenium-
and tellurium-containing glycerol analogs which can
be regarded as valuable multidentate ligands for com-
plex formation and reagents for organic synthesis.
However, 2,3-dibromopropan-1-ol (II) reacted with
selenium activated in the systems hydrazine hydrate–
potassium hydroxide–water and hydrazine hydrate–
2-aminoethanol (in both cases, diselenide ions were
generated [2]) to give allyl alcohol (yield 50–74%)
with regeneration of elemental selenium (yield 66–
76%) (Scheme 1). The reaction follows a scheme
analogous to that reported for the reaction of 1,2-di-
chloroethane with potassium diselenide [3]. Separation
of elemental selenium was observed after addition of
a required amount dibromide II to a solution of sele-
nium in the above systems, but the mixture remains
intensely colored, indicating the presence of polysele-
nides. It is known [4] that polyselenides can be formed
from elemental selenium and hydrazine (Scheme 2);
i.e., a reaction reverse to the dissolution of selenium
With a view to reveal other relations holding in
reactions of polyelectrophilic chloromethyloxirane and
dihalopropanols with chalcogenide, in the present
Scheme 1.
Br
+ K2Se2
Br
OH
II
H2C
OH
+
2Se
–2 KBr
505

ELAEV et al.
dibromide II. The reaction resulted in regeneration of
506
Scheme 2.
2x Se
+
5 N2H4 · H2O
2 (N2H5)2Sex + N2 + 5 H2O
elemental selenium (60%) and formation of allyl alco-
hol (52%) and a small amount (2–3%) of 4-hydroxy-
1,2-diselenolane V. Likewise, in the reactions of all
compounds I–III with tellurium in the system hydra-
zine hydrate–KOH (K2Te2 [6]), tellurium was recov-
ered from the reaction mixtures almost quantitatively,
and the yield of allyl alcohol ranged from 58 to 62%.
No 4-hydroxy-1,2-ditellurolane was detected among
the products.
occurs. Presumably, this is the reason why regenera-
tion of elemental selenium in the reaction shown in
Scheme 1 is not complete.
Allyl alcohol was isolated by extraction of the
reaction mixture with diethyl ether and was identified
by 1H NMR spectroscopy. Apart from allyl alcohol, the
extract contained (according to the GC–MS data)
initial dibromide II (its amount corresponded to a con-
version of ~92%), bromomethyloxirane (IV) (~3%,
calculated on the initial dibromide II), and 4-hydroxy-
1,2-diselenolane (V) (yield 5%). Compounds IV and V
were likely to be formed according to Scheme 3. The
mass spectrum of bromomethyloxirane (IV) contained
the molecular ion peak as a doublet typical of the
presence of one bromine atom in the molecule
(m/z 136/138). The base peak in the spectrum had
an m/z value of 57; it originated from elimination of
bromine atom from the molecular ion.
We believe that in all cases the process involves the
corresponding halomethyloxirane [elimination of hy-
drogen bromide from 2,3-dibromopropan-1-ol (II) in
basic medium gives 2-bromomethyloxirane]. Halo-
methyloxiranes are capable of reacting with diselenide
and ditelluride ions along two pathways. The first of
these is common SN2 nucleophilic replacement of
halogen, and the second is halophilic attack by Y22– ion
on the halogen atom [3]. Taking into account higher
electronegativity of the oxygen atom as compared to
chlorine or bromine [7], halophilic attack by dichalco-
genide ion on halomethyloxirane through intermediate
state A (Scheme 5) should occur more readily than its
attack on 1,2-dihaloethane [3].
Scheme 3.
K2Se2, H2O
–KBr, –KOH
Se
Se
Br
OH
II
–HBr
O
IV
V
Scheme 5.
When the reaction of II with selenium was per-
X · · · Y22–
O
H2C
–Y2X–
formed for a longer time, the reaction mixture also
contained propan-1-ol which was formed via hydro-
genation of allyl alcohol with the system N2H4–
KOH–O2. It is known that the latter generates diimide
[5] (Scheme 4). The yield of propyl alcohol attains
38% when the reaction time is more than 3 h, and it
can even exceed the yield of allyl alcohol. The hydro-
genation of allyl alcohol is favored by its good solubil-
ity in the system hydrazine hydrate–alkali.
O
A
H2O
OH
H2C
–OH–
Y2X–
2Y
–X–
X = Cl, Br; Y = Se, Te.
The other reaction direction implies nucleophilic
attack by Y22– on the methylene carbon atom in the
oxirane ring; our results showed that this reaction path-
way is observed only for selenium (Scheme 6). Oligo-
meric products could be formed according to a similar
scheme. However, we detected no oligomeric products
Scheme 4.
2 N2H4 + O2
2 N2H2
+
2 H2O
OH
+
OH
N2H2
Me
H2C
–N2
In the mass spectrum of 1,2-diselenolane V the mo-
lecular ion gives rise to a low-intensity peak cluster
(m/z 218 for 80Se). The base peak belongs to the frag-
ment ion with m/z 58, which is formed as a result of
elimination of two selenium atoms from the molecular
ion. In addition, 1,2-diselenolane V was identified by
1H NMR spectroscopy (see Experimental).
Scheme 6.
O–
Se22–
+
X
Se2
X
O
H2O
Chloromethyloxirane (I) reacted with selenium in
the system hydrazine hydrate–alkali in a way similar to
V
–OH–, –X–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008

REACTIONS OF CHLOROMETHYLOXIRANE AND DIHALOPROPANOLS
507
Scheme 9.
in the reactions of compounds I and II with selenium
and tellurium in the system hydrazine hydrate–alkali.
N2H4 ·H2O/KOH
KSe
SeK
VI
Unlike compounds I and II, 1,3-dichloropropan-2-
ol (III) reacted with selenium in the system hydrazine
hydrate–potassium hydroxide–water to give oligomer
VI (Scheme 7).
OH
VII
2MeI
–2KI
MeSe
SeMe
OH
VIII
Scheme 7.
OH
OH
Se, H2O/N2H4 ·H2O/KOH
propan-2-ol (VIII) (Scheme 9). The structure of com-
pound VIII was confirmed by the 1H and 13C NMR and
mass spectra. Our results showed that only one isomer
of bis(methylselanyl)propanol VIII is formed with
1,3-arrangement of the selenium atoms. No 2,3-bis-
(methylselanyl)propan-1-ol was detected (cf. [1]).
Among the reaction products we also identified by
GC–MS 2-methoxy-1,3-bis(methylselanyl)propane
(IX, yield ~2%). Its fragmentation pattern under elec-
tron impact is illustrated by Scheme 10; it unambigu-
ously indicates that the methoxy group is attached to
the C2 atom.
Cl
Cl
Se
Se
n
III
VI
Compounds structurally related to VI can also be
obtained from chloromethyloxirane (I) and 1,3-di-
chloropropan-2-ol (III) by reaction with selenium in
the system hydrazine hydrate–2-aminoethanol at a mo-
lar ratio of 10:1 (Scheme 8).
Scheme 8.
Se, N2H4 ·H2O/H2NCH2CH2OH
I, III
VI
Scheme 10.
In all cases, oligomers VI were formed in nearly
quantitative yield (97–99%) as viscous orange–red
substances; they contained about 70% of selenium and
residual chlorine (see Experimental). Assuming that
the residual chlorine atoms are located at the ends of
the macromolecule, the molecular weight of the oligo-
meric product was estimated at 3330 a.m.u. The data
of elemental analysis are very consistent with the
general formula C48H96Cl2O16Se30.
m/z 109
m/z 153
+·
MeSe
SeMe
OMe
M+ (IX)
m/z 95
m/z 95
m/z 41
m/z 72
m/z 58
m/z 43
–OMe
–CH2
–Me
OH
OH
Taking into account the direction of reactions of
chloromethyloxirane derivatives with selenium and
tellurium in the systems hydrazine hydrate–base, the
absence of products with vicinal arrangement of the
selenium atoms (in the system hydrazine hydrate–
2-aminoethanol), and previously reported data on the
reactions of 1,2-dihaloethanes with selenium and tel-
lurium [3], we can conclude that the examined reac-
tions of 1,2-dielectrophiles with selenium- and telluri-
um-containing anions are fairly general. The driving
force of these processes is polarization of the dielec-
trophile molecule by the action of chalcogenide ion.
Cl
Se
Se
Cl
Se
Se
OH
(C48H96Cl2O16Se30
14
)
By extraction of the crude oligomeric product with
acetone or other organic solvents we isolated 4-hy-
droxy-1,2-diselenolane (V) which was likely to be
formed concurrently with the polycondensation proc-
ess. The yield of V, calculated on the initial selenium,
was about 5%. Despite poor yield, we succeeded in
isolating compound V as individual substance.
Like other diselenide oligomers [2], oligomer VI
underwent cleavage at the Se–Se bonds in the system
hydrazine hydrate–KOH; the reaction was accom-
panied by complete dissolution, and the resulting di-
selenolate VII was treated in situ with methyl iodide.
We thus isolated 48–52% of 1,3-bis(methylselanyl)-
2–
· · · ·
Yn
X
C
C
X'
On the other hand, the polarizing effect of Yn2– is
determined by its electron-donating power, i.e., it
decreases in the series Te > Se > S [7], which is very
consistent with our experimental data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008

ELAEV et al.
508
Thus, the systems hydrazine hydrate–alkali–water
tillation gave 1.5 g of allyl alcohol, bp 47–54°C
(115 mm). 1H NMR spectrum, δ, ppm: 4.10 d (CH2O),
5.12 d.d, 5.24 d.d (CH=), 5.95 m (=CH–), 3.23 br.s
and hydrazine hydrate–2-aminoethanol make it pos-
sible to obtain oligomeric poliselenides containing hy-
droxy groups from selenium and 1,3-dichloropropan-
2-ol. From chloromethyloxirane, such oligomers can
be obtained only in the system hydrazine hydrate–
2-aminoethanol. Reductive cleavage of polyselenide
oligomers provides a synthetic route to 2-hydroxy-
propane-1,3-diselenol derivatives.
(OH); Jcis = 10.5, Jtrans = 17.3, J = 5.1, 2J = 1.65, J =
1.6 Hz (ABCX2 spin system). Ppropan-1-ol was iden-
tified by 1H NMR as an impurity (yield 5%). When the
reaction time was increased to 10 h, the yield of
propan-1-ol reached 38%, while the yield of allyl al-
cohol fell down to 33%. 4-Hydroxy-1,2-diselenolane
(V) was identified among the products by GC–MS; its
1H NMR spectrum is given below.
3
4
EXPERIMENTAL
Reaction of 2,3-dibromopropan-1-ol (II) with
selenium in the system hydrazine hydrate–KOH–
H2O. A solution of potassium diselenide was prepared
from 2.8 g (0.05 mol) of potassium hydroxide, 2.5 g
(0.05 mol) of hydrazine hydrate, 15 ml of water, and
4.1 g (0.052 mol) of powdered selenium. The mixture
was heated for 2 h at 80–85°C and cooled to 45°C,
8.2 g (0.038 mol) of 2,3-dibromopropan-1-ol (II) was
slowly added, and the mixture was stirred for 7 h at
80–85°C. During the process, a black solid separated
and was filtered off, washed, dried under reduced
pressure, and identified as elemental selenium (2.7 g,
mp 210–215°C). The filtrate was extracted with diethyl
ether, the extract was dried over MgSO4, the solvent
was removed, the residue was cooled, and 0.31 g of
a crystalline product was separated. According to the
The progress of reactions was monitored, and the
liquid products were analyzed, by gas–liquid chroma-
tography on LKhM 80-MD-2 (2000×3-mm column
packed with 5% of DC-550 on Chromaton N-AW-
HMDS; linear oven temperature programming at a rate
of 12 deg/min; carrier gas helium) and Tsvet-500 in-
struments (2000×5-mm steel column packed with 5%
of XE-60 on Chromaton N-AW-HMDS; linear oven
temperature programming from 30 to 230°C at a rate
of 12 deg/min; carrier gas helium). The IR spectra
were measured on Specord 75IR and Bruker IFS-25
spectrometers from samples prepared as thin films.
1
The H and 13C NMR spectra were recorded on
a Bruker DPX-400 spectrometer at 400.1 and
100.6 MHz, respectively, using CDCl3 as solvent and
hexamethyldisiloxane as internal reference. The mass
spectra were obtained on a Shimadzu GCMS-
QP5050A instrument (SPB-5 column, 60000×0.25 mm,
film thickness 0.25 μm; injector temperature 250°C;
carrier gas helium, flow rate 0.7 ml/min; oven tem-
perature programming from 60 to 260°C at a rate of
15 deg/min; detector temperature 250°C; quadrupole
mass analyzer, electron impact, 70 eV; ion source tem-
perature 200°C; a.m.u. range 34–650).
1
GLC, GC–MS, and H NMR data, it was identified as
1
4-hydroxy-1,2-diselenolane (V). H NMR spectrum
of V [in a mixture with allyl alcohol, propan-1-ol, and
2,3-dibromopropan-1-ol (II)], δ, ppm: 5.35 m (CHO),
3.27 d and 3.40 d (CH2Se), 3.80 s (OH). Protons in the
CH2 group of compound V are differently oriented
with respect to the CHO proton; therefore, three spin–
spin couplings were detected with the following con-
stants: JAB = 10.48, JAX = 2.42, JBX = 2.96 Hz.
Reaction of 2-chloromethyloxirane (I) with sele-
nium in the system hydrazine hydrate–KOH–
H2O. A solution of potassium diselenide was prepared
from 5.6 g (0.1 mol) of potassium hydroxide, 5 g
(0.1 mol) of hydrazine hydrate, 30 ml of water, and
7.9 g (0.1 mol) of powdered selenium. The mixture
was heated for 2 h at 80–85°C and cooled to 40°C,
4.6 g (0.05 mol) of chloromethyloxirane (I) was slowly
added, and the mixture was stirred for 3 h at 60–70°C.
During the process, a black solid separated and was
filtered off, washed, dried under reduced pressure, and
identified as elemental selenium (4.74 g, mp 217–
222°C). The filtrate was extracted with diethyl ether,
the extract was evaporated, and the residue was ana-
Se
HA
HB
O
HC
The liquid part of the residue (after separation of
crystals) was distilled under reduced pressure. A frac-
tion with bp 51–53°C (115 mm), 1.27 g, was identified
by GLC and H NMR as allyl alcohol. Its spectral
parameters are given above.
1
Reaction of 1,3-dichloropropan-2-ol (III) with
selenium in the system hydrazine hydrate–KOH–
H2O. 1,3-Dichloropropan-2-ol (III), 4.86 g (0.038 mol),
was added dropwise to a solution of 3.95 g (0.05 mol)
of selenium in a mixture of 2.5 g (0.05 mol) of hydra-
1
lyzed by GLC, H NMR, and GC–MS. Vacuum dis-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008

REACTIONS OF CHLOROMETHYLOXIRANE AND DIHALOPROPANOLS
509
zine hydrate, 2.8 g (0.05 mol) of potassium hydroxide,
and 15 ml of water, prepared as described above, and
the mixture was stirred for 1 h at 60–70°C. An orange–
red solid separated and was filtered off, washed with
water and organic solvents, and dried under reduced
pressure. We thus isolated 5.2 g of oligomer VI with
mp 60–110°C (decomp.). IR spectrum, ν, cm–1: 3432,
2915, 2840, 1410, 1393, 1276, 1160, 740, 625, 435.
Found, %: Cl 2.05; Se 71.04. C48H96Cl2O16Se30. Cal-
culated, %: Cl 2.11; Se 70.35. The filtrate was ex-
tracted with diethyl ether, the extract was dried over
MgSO4, and the solvent was removed. The residue,
1.13 g, was analyzed by GC–MS, It was identified as
4-hydroxy-1,2-diselenolane (V).
described above from 2.8 g (0.05 mol) of potassium
hydroxide, 20 g (0.4 mol) of hydrazine hydrate, and
6.38 g (0.05 mol) of powdered tellurium. The mixture
was cooled to 45°C, 3.2 g (0.025 mol) of 1,3-dichloro-
propan-2-ol (III) was slowly added, and the mixture
was stirred for 2 h at 60–65°C. Elemental tellurium,
6.1 g, separated from the mixture. The filtrate was
treated as described above to isolate 0.89 g of allyl
alcohol. Neither initial 1,3-dichloropropan-2-ol (III)
nor 4-hydroxy-1,2-ditellurolane was detected..
Reaction of 2,3-dibromopropan-1-ol (II) with
selenium in the system hydrazine hydrat–2-amino-
ethanol. A solution of potassium diselenide was pre-
pared from 7.5 g (0.15 mol) of hydrazine hydrate,
0.92 g (0.015 mol) of 2-aminoethanol, and 3.95 g
(0.05 mol) of powdered selenium. The mixture was
heated for 2 h at 70–75°C and cooled to 50°C, 8.16 g
(0.037 mol) of 2,3-dibromopropan-1-ol (II) was added,
and the mixture was stirred for 1.5 h at 65–70°C.
During the process, a black solid separated and was
filtered off, washed, dried under reduced pressure, and
identified as elemental selenium (3 g, mp 210–216°C).
The filtrate was extracted with diethyl ether, the extract
was dried over MgSO4, and removal of the solvent left
a liquid residue which was subjected to vacuum distil-
lation to isolate 1.61 g of a fraction with bp 50–54°C
(115 mm). The product was identified as allyl alcohol
on the basis of the GLC and 1H NMR data.
Reaction of 2-chloromethyloxirane (I) with tellu-
rium in the system hydrazine hydrate–KOH. A so-
lution of potassium ditelluride was prepared from 1.4 g
(0.025 mol) of potassium hydroxide, 10 g (0.2 mol) of
hydrazine hydrate, and 3.19 g (0.025 mol) of powdered
tellurium. The mixture was heated for 2 h at 80–85°C
and cooled to 45°C, 1.15 g (0.0125 mol) of 2-chloro-
methyloxirane (I) was added, and the mixture was
stirred for 2.5 h at 50–52°C. During the process,
a black powder-like solid separated and was filtered
off, washed, dried under reduced pressure, and iden-
tified as elemental tellurium (3 g) (by elemental
analysis). The filtrate was extracted with diethyl ether,
the extract was dried over MgSO4, and the solvent was
removed to obtain a liquid residue which was distilled
under reduced pressure. A fraction with bp 68–70°C
(140 mm), 0.43 g, was identified as allyl alcohol on the
Oligomer VI. a. 2-Chloromethyloxirane (I), 4.6 g
(0.05 mol), was added dropwise to a solution of 7.9 g
(0.1 mol) of selenium in a mixture of 15 g (0.3 mol) of
hydrazine hydrate and 1.84 g (0.03 mol) of 2-amino-
ethanol, prepared as described above. The mixture was
heated for 9 h at 65–70°C, and the orange–red solid
was filtered off, washed with water and organic sol-
vents, and dried under reduced pressure. Yield 10.7 g,
mp 85–120°C (decomp.). IR spectrum, ν, cm–1: 3430,
2920, 2840, 1418, 1395, 1280, 1160, 740, 618, 436.
Found, %: C 17.07; H 2.88; Cl 2.13; Se 69.95.
C48H96Cl2O16Se30. Calculated, %: C 17.09; H 2.85;
Cl 2.11; Se 70.35. A 3.5-g (0.016-mol) portion of
oligomer VI was treated with a mixture of 23.7 g
(0.4 mol) of acetone and 1 g (0.009 mol) of o-xylene
(standard for GC), and the mixture was left to stand for
1 h. The extract was analyzed by GC–MS, and 4-hy-
droxy-1,2-diselenolane (V) was identified; yield 5%.
1
basis of the GLC and H NMR data. Neither initial
chloromethyloxirane (I) nor 4-hydroxy-1,2-ditelluro-
lane was detected.
Reaction of 2,3-dibromopropan-1-ol (II) with
tellurium in the system hydrazine hydrate–KOH.
A solution of potassium ditelluride was prepared as
described above from 2.8 g (0.05 mol) of potassium
hydroxide, 20 g (0.4 mol) of hydrazine hydrate, and
6.38 g (0.05 mol) of powdered tellurium. The mixture
was cooled to 45°C, 5.45 g (0.025 mol) of 2,3-di-
bromopropan-1-ol (II) was added, and the mixture was
stirred for 3 h at 60–70°C. Elemental tellurium, 6.2 g,
separated from the mixture. The filtrate was treated as
described above to isolate 0.84 g of allyl alcohol.
Neither initial 2,3-dibromopropan-1-ol (II) nor 4-hy-
droxy-1,2-ditellurolane was detected.
b. 1,3-Dichloropropan-2-ol (III), 12.8 g (0.1 mol),
was added to a solution of 7.9 g (0.1 mol) of selenium
in a mixture of 15 g (0.3 mol) of hydrazine hydrate and
1.84 g (0.03 mol) of 2-aminoethanol, prepared as
Reaction of 1,3-dichloropropan-2-ol (III) with
tellurium in the system hydrazine hydrate–KOH.
A solution of potassium ditelluride was prepared as
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008

ELAEV et al.
510
described above. The mixture was stirred for 1.5 h at
70°C, and the orange–red solid was filtered off,
washed with water and organic solvents, and dried
under reduced pressure. Yield 10.7 g, mp 85–120°C
(decomp.). IR spectrum, ν, cm–1: 3425, 2910, 2835,
1415, 1390, 1270, 1158, 740, 620, 435. Found, %:
C 17.11; H 3.05; Cl 2.07; Se 71.44. C48H96Cl2O16Se30.
Calculated, %: C 17.09; H 2.85; Cl 2.11; Se 70.35.
A small amount of oligomer VI was treated with
CDCl3, the mixture was kept for 17 h at room tempera-
[CH2CHONCH2]+, 57 (4) [CH2SONCH2]+, 43 (6)
[CH2CHO]+. Found, %: C 24.57; H 4.80; Se 64.38.
C5H12Se2O. Calculated, %: C 24.39; H 4.88; Se 64.23.
Reductive cleavage and methylation of oligomers VI
obtained in the other systems were carried out in
a similar way.
REFERENCES
1. Alekminskaya, O.V., Russavskaya, N.V., Korche-
vin, N.A., Deryagina, E.N., and Trofimov, B.A., Russ. J.
Gen. Chem., 2000, vol. 70, p. 732.
1
ture, and the solution was analyzed by H NMR to
identify 4-hydroxy-1,2-diselenolane (V).
2. Russavskaya, N.V., Levanova, E.P., Sukhomazova, E.N.,
Grabel’nykh, V.A., Klyba, L.V., Zhanchipova, E.R., Alba-
nov, A.I., and Korchevin, N.A., Russ. J. Gen. Chem.,
2006, vol. 76, p. 229.
1,3-Bis(methylselanyl)propan-2-ol (VIII). Oligo-
mer VI, 3 g (0.014 mol), prepared as described above
in a, was dissolved at 70°C in a mixture of 17 g
(0.034 mol) of hydrazine hydrate and 3.9 g (0.07 mol)
of potassium hydroxide (2 h). The mixture was cooled,
3.9 g (0.028 mol) of methyl iodide was slowly added,
the mixture was extracted with diethyl ether, and the
extract was dried over CaCl2 and evaporated. Accord-
ing to the GLC and GC–MS data, the residue, 1.76 g,
was almost pure 1,3-bis(methylselanyl)propan-2-ol
3. Russavskaya, N.V., Grabel’nykh, V.A., Levanova, E.P.,
Sukhomazova, E.N., Klyba, L.V., Zhanchipova, E.R.,
Tatarinova, A.A., Elaev, A.V., Deryagina, E.N., Korche-
vin, N.A., and Trofimov, B.A., Russ. J. Org. Chem.,
2006, vol. 42, p. 652.
4. Turchaninova, L.P., Korchevin, N.A., Deryagina, E.N.,
Trofimov, B.A., and Voronkov, M.G., Zh. Obshch. Khim.,
1992, vol. 62, p. 152.
1
(VIII). H NMR spectrum, δ, ppm: 2.03 s (CH3Se),
2.74 d.d (CH2Se), 2.83 br.s (OH), 3.85 m (CH).
5. Deryagina, E.N., Korchevin, N.A., Russavskaya, N.V.,
and Grabel’nykh, V.A., Izv. Ross. Akad. Nauk, Ser. Khim.,
1998, p. 1874.
1
13C NMR spectrum, δC, ppm: 5.02 (CH3, JSe, C
=
1
61.92 Hz), 32.61 (CH2Se, JSe,C = 64.87 Hz), 69.22
(CH). Mass spectrum, m/z for 80Se (I, % of the total ion
current): 248 (6) [M]+·, 233 (17) [M – CH3]+, 175 (9)
[CH3SeSe]+, 139 (5) [CH3SeCH2CHON]+, 137 (5)
[CH3SeCH2SO]+, 109 (17) [CH3SeCH2]+, 95 (9)
[CH3Se]+, 93 (7) [CHSe]+, 80 (3) [Se]+, 58 (4)
6. Vvedenskii, V.Yu., Deryagina, E.N., and Trofimov, B.A.,
Russ. J. Gen. Chem., 1996, vol. 66, p. 1539.
7. Ugai, Ya.A., Obshchaya i neorganicheskaya khimiya
(General and Inorganic Chemistry), Moscow: Vysshaya
Shkola, 2004, p. 527.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008