Reaction of tellurium with dichloromethane in the system hydrazine hydrate-alkali

Article abstract of DOI:10.1134/S1070363209110073

Tellurium reacts with dichloromethane in the system hydrazine hydrate-alkali substituting one chlorine atom by tellurium whereas the second chlorine atom undergoes reductive substitution by hydrogen leading to the formation of methyltellanyl derivatives.

Full text of DOI:10.1134/S1070363209110073

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 11, pp. 2321–2327. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © E.P. Levanova, V.A. Grabel’nykh, N.V. Russavskaya, L.V. Klyba, A.I. Albanov, N.A. Korchevin, 2009, published in Zhurnal
Obshchei Khimii, 2009, Vol. 79, No. 11, pp. 1800–1806.
Reaction of Tellurium with Dichloromethane
in the System Hydrazine Hydrate–Alkali
E. P. Levanova, V. A. Grabel’nykh, N. V. Russavskaya,
L. V. Klyba, A. I. Albanov, 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 April 24, 2009
Abstract—Tellurium reacts with dichloromethane in the system hydrazine hydrate–alkali substituting one
chlorine atom by tellurium whereas the second chlorine atom undergoes reductive substitution by hydrogen
leading to the formation of methyltellanyl derivatives. Tentative mechanism of reduction is discussed. The
discovered reaction allows the preparation of organotellurium compounds containing the MeTe group,
including those involving other chalcogens.
DOI: 10.1134/S1070363209110073
The chlorine atoms in dichloromethane can be
easily enough substituted by the action of chalcogen-
containing nucleophiles. The reaction of dichloro-
methane and elemental chalcogens led to the formation
of polymethylenedisulfides [1], polymethyleneselen-
ides and diselenides [2]. However, as was mention in
[3], Na2Te2 prepared from elemental tellurium in the
system hydrazine hydrate–alkali does not form with
CH2Cl2 organotellurium or polymer products but rather
the regeneration of tellurium metal in 87% yield
occurs. Even at the use of dibromo- or diiodomethane,
the polymer (СН2Те)n was obtained in as low as 3%
yield [4]. Anomalous behavior of tellurium was observed
also in investigating the reactions of dichloromethane
with chalcogens and dimethylchalcogenides in the
system hydrazine hydrate–alkali [5]. The formation of
methyltellanyl derivatives was detected in these
reactions.
added to the obtained solution at 40–42°С, after 0.5 h
about 10% of tellurium taken into the reaction accord-
ing to Eq. (1) is precipitated on the walls of the
reaction flask with retention of the color of the solu-
tion. After extraction of the obtained alkaline aqueous–
hydrazine solution with dichloromethane, the follow-
ing compounds were identified in the extract (the yields
were calculated on the tellurium taken into the reaction
(1) from the GC and chromatomass-spectrometry data):
dimethyltelluride I (traces), methylchloromethyltel-
luride II (4%), dimethylditelluride III (17%), bis-
(methyltelluro)methane IV (3%), and trace amounts of
unidentified products. Compounds I, III, and IV were
identified by comparing their spectral characteristics
with those of the authentic samples [5, 6], compound II,
which belongs to the class of extremely unstable α-
chlorotellurides, by the method of chromatomass
spectrometry (see Experimental). Therefore, in the
reaction of potassium telluride (prepared from elemen-
tal tellurium in the solution hydrazine hydrate–KOH)
with dichloromethane, unexpectedly, the formation of
methyltellanyl derivatives rather than polymer pro-
ducts is observed. Hence in the reaction under inves-
tigation one chlorine atom of СН2Сl2 is substituted by
tellurium atom and the second one, by the hydrogen
atom, which can be summarized as follows:
With all this in mind, we have studied the reaction
of CH2Cl2 with tellurium in the system hydrazine
hydrate–KOH in more detail. For this, tellurium was
converted into K2Те [6].
2Te + N2H4·H2O + 4KOH → 2K2Te + N2 + 5H2O. (1)
At the molar ratio KOH : Те = 6 : 1 and larger
tellurium is practically completely converted into the
anion Те2–, which imparts the solution a crimson-violet
color. When equimolar amount of dichloromethane is
2Te2– + 2CH2Cl2 + 2OH– + N2H4·H2O
→ 2 MeTe– + 4 Cl– + N2 + 3 H2O.
(2)
2321

2322
LEVANOVA et al.
2 MeTe– + N2H4 + 2 H2O
In reactions (1) and (2) the alkali is consumed that
→ Me2Te2 + 2NH3 + 2OH–.
(4)
leads to a decrease in the alkalinity of the solution. It
was stressed in [6] that tellurium can exist in the
anionic form Те2– only at high alkalinity of the
solution and its decrease, apparently, causes the forma-
tion of polytelluride anions (Тех2–, where x = 2 and
larger) and even precipitation of tellurium metal.
Air oxygen can also act as an oxidizer in reac-
tions (3) and (4) but carrying out the reaction in the
argon atmosphere does not have a notable effect on the
yields of the products. Nevertheless, the effect of
oxygen cannot be ruled out, in particular, in the stage
of treatment of the reaction mixture.
Earlier we have shown [7] that hydrazine acting as
a strong reducing agent under alkaline conditions can
become an oxidizing agent when the alkalinity of the
medium is reduced. For example, it can oxidize
hydrogen sulfide to polysulfide anions (Sn2–). Tellu-
rium-containing anions (Te2–, MeTe–, etc.) are
undoubtedly stronger reducers than hydrogen sulfide
[8], therefore, under the reaction conditions the oxida-
tive processes shown in Eqs. (3) and (4) can occur.
Apparently, the formation of elemental tellurium is
the main process when using Na2Te2 generated at the
ratio NaOH:Te = 1:1, as in [3]. Identification of
chloromethyltelluride II in the excess of Te2– ions
suggests a higher reactivity of anions MeTe– (whose
concentration in the reaction mixture is small) relative
to Te2– ions with respect to dichloromethane. This,
probably, is the reason preventing the formation of
polymer products.
2Te2– + N2H4 + 2H2O → Te22– + 2NH3 + 2OH–,
(3)
MeTe−
CH2Cl2
MeTe_
MeTeCH2Cl
II
MeTeCH2TeMe
_Cl−
IV
+Te2−
_Cl−
MeTeCH2Te_
The data of extraction of the reaction mixture (see
above) accounts for only 24% of the products of
transformations of tellurium. Therefore, if after
addition of one equivalent of dichloromethane to the
solution of K2Te to add ethyl bromide to the reaction
mixture containing, apart from compounds I–IV, the
nonreacted K2Te and the formed according to reac-
tions (2) and (3) MeTeK and K2Te2, the formation of
the following products is observed: telluride I (2%),
telluride II (traces), Me2Te2 III (2%), bis(methyltel-
luro)methane IV (3%), ethylchloromethyltelluride V
(traces), methylethyltelluride VI (39%), diethyl-
telluride VII (20%), diethylditelluride VIII (8%), 2,4-
ditellurahexane IX (8%), 3,5-ditelluraheptane X (4%).
The formation of products I–X, apart from the above
schemes, can be presented by schemes (5) and (6).
CH2Cl2
II
_
MeTe_
MeTeEt
EtBr
_Br _
(5)
_Cl
VI
EtBr
_Br _
ox
(EtTe)2
Et2Te
(6)
VII
VIII
EtBr + Te2_
CH2Cl2
EtTe_
EtTeCH2Cl
V
EtTe_
+II
_Cl_
EtTeCH2TeMe
IX
EtTeCH2TeEt
X
In addition to chromatomass-spectrometry, pro-
ducts I, III, IV, VI, VII, and VIII were identified by
comparing with authentic samples prepared by us
earlier [6, 9]. Taking into account the role of mass-
spectrometric identification of the obtained compounds
we have carefully analyzed their mass spectra. Ac-
cording to the type of degradation of the molecular ion,
compounds II–X were divided into three groups;
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REACTION OF TELLURIUM WITH DICHLOROMETHANE
2323
general directions of fragmentation are given in
Schemes (7)–(9). The intensities (% from total ion
current) and the values of m/z of the fragment ions
formed are given in the experimental part. Compounds
VIII and IX are isomers but their mass spectra are
substantially different. Thus, in the mass spectrum of
2,4-ditellurohexane IX the peak of ion m/z 173
[EtTeCH2]+ (130Te) is observed, which is absent in the
spectrum of diethylditelluride VIII. A similar ion is
formed upon fragmentation of the molecular ion
EtSCH2SMe [10]. Besides, in the mass spectrum of
compound IX the peaks of the odd-electron ion
[CH2Te2]+· with m/z 274 (130Te) and cation [MeTe]+
with m/z 145 are present, also lacking in the mass
spectrum of compound VIII. Therefore, these ions can
be considered as diagnostic ions for mass-
spectrometric confirmation of the structure of the
compounds [schemes (7) and (8)].
+
R1
Te
R2
[R1CH2Te]+
[R1CH2TeH]+ + CHR2
[TeH]+
+
CH2R2
[TeCH2R2]+ + R1CH2
Te+
[CH2Te]+
~H
+
CH2R2
R2
(7)
For VI, VII
+
CH2R1
+
II: R1 = H, R2 = Cl; V: R1 = Me, R2 = Cl; VI: R1 = H, R2 = Me; VII: R1 = R2 = Me.
+
R1
Te
Te
R2
[R2CH2Te]+
+
[TeCH2R1]
R1CH2 + [Te2CH2R2]+
Te+2 CH2R2
CHR1 + [CH3Te2R2]+
+
CH2R2
[CH2Te]+ + R2
[CHTe]+ HR2
+
(8)
~H
~H
For VIII
+
[HTe2]+
III: R1 = R2 = H; VIII: R1 = R2 = Me.
+
R1
Te
Te
R2
[R1CH2Te] + [R2C2H4Te]+
[R2CH2Te] + [R1C2H4Te]+
[R1C2H4Te2]+
+
CH2R2
(9)
[CH2Te2]+
+
CH2R1
[CH2Te]+
+
CH2R1
IV: R1 = R2 = H; IX: R1 = H, R2 = Me; X: R1 = R2 = Me.
Compound X was obtained independently from
diethylditelluride VIII and dichloromethane.
The target product X was isolated from reac-
tion (10) in 84% yield. In this reaction, in spite of the
presence of dichloromethane no formation of methyl-
tellanyl derivatives was observed in the system
hydrazine hydrate–alkali. At the same time, taking into
account the yields of compounds VI and IX in
reactions (4) and (5) it is presumable that the products
of reduction and the chlorine substitution in dichloro-
2Et2Te2 + N2H4 H2O + 4 KOH
4 EtTeK + N2 + 5H2O,
(10)
X.
2 EtTeK + CH2Cl2
_2 KCl
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 11 2009

2324
LEVANOVA et al.
methane, anions MeTe–, play the key role in the
reaction of K2Te with dichloromethane in the system
hydrazine hydrate–alkali [reaction (2)].
Formation of ions МеТе– as a kinetically inde-
pendent nucleophilic species from the earlier pos-
tulated by us solvate complex A was suggested in [5].
H
H
H
H
H
H
H
H
N
N
N
N
MeTe_ .
H
H
(11)
H
N
N
+ CH2Cl2
_Cl_
H
_N2H2
_HCl
Cl
Cl
Te2_
CH2
Te_
CH2
Cl
Te2_
B
C
A
The key point in this scheme is that after
nucleophilic substitution of chlorine in СН2Cl2 (A →
B → C) the molecule of hydrazine remains bound to
the fragment ClСН2Те– thus stimulating its further
transformations. When anions EtTe– are used in the
reaction with СН2Cl2 [reaction (10)], after the nucleo-
philic substitution the uncharged species EtТеСН2Cl V
is formed, which loses the bond with the molecule of
hydrazine and no reduction of the СН2Cl fragment
occurs.
system hydrazine hydrate–KOH undergoes reductive
splitting of the S–S bond [6].
In the reaction of potassium propanethiolate PrSK
and K2Те [prepared by scheme (1)] with dichloro-
methane, the main product is sulfidotelluride PrSTeMe
(XI), which is formed in 30% yield, apparently, due to
joint oxidation of anions MeTe– and PrS–. The pres-
ence of peaks of ions [MeTe]+ with m/z 145 and [PrS]+
with m/z 75 in the mass spectrum of compound XI can
be considered as a confirmation of the fact that the
propyl group is attached to the sulfur atom and the
methyl group to the tellurium atom. Symmetrical
products of oxidation, dimethylditelluride III and
dipropyldisulfide XII, are formed in 4 and 9% yield,
respectively. The product of the “normal” reaction of
dipropyldisulfide with dichloromethane, bis(propylthio)-
methane XIII, is formed in 18% yield.
Diimide N2H2 evolved in the course of the reaction
in scheme (11) is extremely unstable and rapidly
decomposes with the liberation of nitrogen [11].
Although, according to our reasoning, the complex of
type A can be formed also in the case of sulfur or
selenium [10], only for tellurium, perhaps, there are
favorable conditions for realization of the cyclic
transition state C shown in scheme (11). Nevertheless,
the formation of trace amounts of EtSCH2SMe was
reported in the reaction of elemental sulfur and
diethyldisulfide with dichloromethane in the system
hydrazine hydrate–NaOH [12].
2 PrSK + CH2Cl2
PrSCH2SPr.
–2 KCl
XIII
The product of cross coupling, 1-tellura-3-thiahep-
tane XIV, was also identified (2% yield).
Other examples of the reduction of fragments
RCHCl2 during synthesis of organochalcogen com-
pounds were reported in the literature. Thus, the
formation of dibenzyldiselenide from phenyldichloro-
methane and selenium in the presence of sodium hyd-
ride was reported in [13], and the formation of methyl-
sulfanyl derivatives was detected in the electro-
chemical synthesis of sulfides in the presence of
CH2Cl2 [14].
PrSK + MeTeK + CH2Cl2
MeTeCH2SPr.
–2 KCl
XIV
A notable yield of chloromethyltelluride II in this
reaction (12%) as compared to reaction (5) is an addi-
tional indication of a low reactivity of anions MeTe–
and PrS– with respect to dichloromethane. Much easier
these anions undergo oxidation.
Anions MeTe– generated in the system CH2Cl2/Te/
N2H4·H2O/KOH can be used in the synthesis of more
complex organotellurium compounds, for example,
sulfidotellurides, as we have shown on the example of
the reaction of dipropyldisulfide and elemental tellu-
rium with dichloromethane. Dipropyldisulfide in the
Therefore, the reaction of tellurium with dichloro-
methane in the system hydrazine hydrate–alkali,
instead of formation of polymer products, allows to
generate potassium methanetellurolate, which can be
used without isolation in the synthesis of various
organotellurium compounds.
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REACTION OF TELLURIUM WITH DICHLOROMETHANE
2325
143 [MeTe]+, [CHTe]+ (38.0), 130 [Te]+ (15.8), 49
EXPERIMENTAL
1
[CH2Cl]+ (8.8). H NMR spectrum of compound IV (δ,
2
The reactions were monitored and the liquid
products formed were analyzed on GLC instruments
LKhM 80 MD-2 (column 2000×3 mm, liquid phase
DC-550, 5% on Chromaton N-AW-HMDS, linear tem-
perature programming with the rate of 12 deg/min,
carrier gas helium) and Tsvet 500 (steel columns
2000×5 mm, liquid phase ХЕ-60, 5% on Chromaton
N-AW-HMDS, linear temperature programming with
ppm): 1.99 s (3H, MeTe, JH–Te 21.2 Hz); 3.39 s (2H,
TeCH2Te, 2JH–Te 25.5 Hz). Mass spectrum, m/z (130Te) (I,
% from total ion current): 304 [M]+· (26.2), 289 [M –
Me]+ (9.1), 274 [CH2Te2]+· (9.1), 260 [Te2]+· (3.8), 159
[C2H5Te]+ (24.1), 144, 143 [CH2Te]+·, [CHTe]+ (16.1),
131,130 [HTe]+, [Te]+ (11.6).
Reaction of potassium telluride with
dichloromethane and ethyl bromide. To the solution
of potassium telluride prepared from 1 g of powdered
tellurium and 2.65 g of KOH in 25 ml of hydrazine
hydrate 0.66 g of dichloromethane was slowly added at
room temperature and stirred for 0.5 h at 40–42ºС. The
reaction mixture was cooled to room temperature,
1.73 g of ethyl bromide was added, and the mixture
was stirred for 3 h at 37–38ºС. After cooling, the
reaction mixture, whose color turned from dark to
light-red, was extracted with methylene chloride, dried
over MgSO4. According to the GLC and chromato-
mass spectrometry data the residue obtained after
removal of solvent (1.27 g) contained the following
compounds: dimethyltelluride I, methylchloromethyl-
telluride II, dimethylditelluride III, bis(methyltelluro)-
methane IV, ethylchloromethyltelluride V, methyl-
ethyltelluride VI, diethyltelluride VII, diethylditel-
luride VIII, 2,4-ditellurahexane IX, and 3,5-ditel-
luraheptane X. Mass spectra of compounds II, IV and
the 1H NMR spectrum of compound IV are given above.
Mass spectrum of telluride V, m/z (35Cl, 130Te) (I, %
from total ion current): 208 [M]+· (14.6), 180, 179 [M –
Et]+, [M – C2H4]+· (19.8), 159 [EtTe]+ (8.7), 144, 143
[CH2Te]+·, [CHTe]+ (18.5), 131, 130 [HTe]+, [Te]+
(17.8), 49 [CH2Cl]+ (11.7), 43 [C3H7]+ (4.6), 41 [C3H5]
+(4.3). Mass spectrum of telluride VI: 174 [M]+· (25.6),
159 [M – Me]+ (6.0), 146, 145 [M – Et]+, [M – C2H4]+·
(37.9), 131, 130 [HTe]+, [Te]+ (25.5), 43 [C3H7]+ (2.8),
41 [C3H5]+ (2.2). Mass spectrum of compound VII: 188
[M]+· (24.9), 159, 160 [M – Et]+, [M – C2H4]+· (24.5),
131, 130 [HTe]+, [Te]+ (46.4), 43 [C3H7]+ (2.7), 41
[C3H5]+ (1.5). Mass spectrum of ditelluride VIII: 318
[M]+· (23.0), 290, 289 [M – Et]+, [M – C2H4]+· (24.4),
260 [Te2]+· (30.2), 159 [EtTe]+ (7.1), 131, 130 [HTe]+,
[Te]+ (15.3). Mass spectrum of compound IX: 318 [M]+·
(15.2), 290, 289 [M – Et]+, [M – C2H4]+· (9.8), 274
[CH2Te2]+· (12.5), 173 [M – MeTe]+ (8.4), 159 [EtTe]+
(10.1), 144, 143 [CH2Te]+, [CHTe]+ (18.7), 131, 130
[HTe]+, [Te]+ (10.1), 43 [C3H7]+ (10.1), 41 [C3H5]+
(5.1). Mass spectrum of compound X: 332 [M]+· (13.1),
303 [M – Et]+ (8.2), 274 [CH2Te2]+· (23.4), 173 [M –
the rate of 12 deg min–1, carrier gas helium). H, 13C,
1
and 125Te NMR spectra were registered on a Bruker
DPX 400 spectrometer (working frequencies 400.13,
100.62, and 126.2 MHz, respectively) in CDCl3 solu-
tions, internal references HMDS and dimethyltelluride.
Mass spectra were obtained on a chromatomass
spectrometer Shimadzu GCMS-QP5050A, column SPB-
5, 60000×0.25 mm), film of liquid phase of 0.25 μm,
temperature of injector 250°С, carrier gas helium, rate
0.7 ml min–1, temperature programming from 60 to
260°С with the rate of 15 deg min–1. Temperature of
detector 250°С, quadruple mass analyzer, electron
ionization, energy of electrons 70 eV, temperature of
the ionic source 200°С, the range of detected masses
34-650 D.
Reaction of elemental tellurium with dichloro-
methane in the system hydrazine hydrate–KOH. To
the solution of 5.3 g of KOH in 50 ml of hydrazine
hydrate 2 g of powdered tellurium were added by
portions at 75–85°С and stirred for 2.5 h at 85°С. After
cooling to room temperature 1.33 g of dichloro-
methane was slowly added into the reaction mixture
and stirred for 0.5 h at 40–42ºС. The precipitation of a
black powder was observed while the reaction mixture
remained dark. The reaction mixture was cooled, the
precipitated black powder filtered off, washed with
water, alcohol, ether, dried in vacuum. 0.19 g of the
precipitate was obtained, which was found to be
elemental tellurium. Found: Te 99.5%. The alkaline
aqueous-hydrazine layer was extracted with methylene
chloride, dried over MgSO4. According to the data of
GLC and chromatomass spectrometry the extract
contained the following compounds: dimethyltelluride
I, methylchloromethyltelluride II, dimethylditelluride
III, bis(methyltelluro)methane IV. The residue
obtained after removal of solvent (1 g) was analyzed
1
by GLC, chromatomass spectrometry, and H NMR
spectroscopy. Mass spectrum of compound II, m/z
(35Cl, 130Te) (I, % from total ion current): 194 [M]+·
(22.5), 179 [M – Me]+ (6.7), 159 [M – Cl]+ (8.2), 145,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 11 2009

2326
LEVANOVA et al.
MeTe]+ (8.7), 144, 143 [CH2Te]+·, [CHTe] (16.0), 131,
130 [HTe]+, [Te]+ (8.0), 43 [C3H7]+ (14.2), 41 [C3H5]+
(8.4). Distillation of the residue gave the fraction with
bp 112–120ºС (0.33 g), which according to the data of
combined, 6.63 g of dichloromethane was slowly
introduced at vigorous stirring, the mixture was stirred for
7 h at 40–42ºС, diluted with water, extracted with
dichloromethane, the extract was dried over MgSO4.
After removal of solvent and evacuation, the residue
was obtained (3.22 g) as a dark-red liquid, which
according to the GLC and chromatomass spectrometry,
consisted of the following compounds: dimethyl-
ditelluride III, 4-thia-5-tellura-hexane XI, dipropyl-
disulfide XII, iso(propylthio)-methane XIII, and 4-thia-
6-tellura-heptane XIV. Mass spectrum of compound XI,
m/z (130Te) (I, % from total ion current): 220 [M]+·
(16.9), 178 [M – C3H6]+· (24.0), 162 [STe]+· (6.4), 145
[CH3Te]+ (8.6), 130 [Te]+ (3.7), 77, 75 [SPr]+ (0.8), 47
[MeS]+ (6.9), 46 [CH2S]+· (2.2), 45 [CHS]+ (5.7), 43
[C3H7]+ (8.7), 42 [C3H6]+ (1.3), 41 [C3H5]+ (8.6), 39
[C3H3]+ (6.2). Mass spectrum of compound XIV: 234
[M]+· (34.6), 191 [M – Pr]+ (2.6), 177 [CH3STe]+ (5.4),
159 [C2H5Te]+ (5.2), 145, 143 [MeTe]+, [TeCH]+
(31.5), 130 [Te]+ (14.6), 43 [Pr]+ (6.1). Vacuum
distillation of the residue gave the fraction with bp 96–
97ºС (0.88 g), which, according to the GC,
1
GLC, H, 13C, 125Te NMR and chromatomass spectro-
metry consisted of methylethyltelluride VI and diethyl-
telluride VII (in the ratio of 1:2). 1H NMR spectrum of
3
compound VI (δ, ppm): 1.59 t (3H, CH3CH2, JH–H
7.0 Hz), 1.90 s (3H, MeTe), 2.60 m (2H, CH2CH3). 13С
NMR spectrum (δ, ppm): –23.5 (MeTe), –6.41
(CH2Te), 16.98 (CH3CH2C). 125Te NMR spectrum (δ,
ppm): 161.06. 1H NMR spectrum of compound VII (δ,
3
ppm): 1.58 t (3H, CH3CH2Te, JH–H 7.0 Hz), 2.60 m
(2H, CH2CH3). 13С NMR spectrum (δ, ppm): –5.52
(CH2Te), 17.41 (CH3CH2). 125Te NMR spectrum (δ,
ppm): 350.12.
3,5-Ditelluraheptane (X). To the solution of 1.7 g
of KOH in 7.6 ml of hydrazine hydrate 1.9 g of
diethylditelluride was added at 60ºС, and the mixture
was stirred for 3 h at 85–88ºС. After cooling to room
temperature, 1.34 g of dichloromethane was slowly
added into the reaction mixture which had dark-claret
color, and it was stirred for 0.5 h at 40–41ºС. The
reaction mixture was cooled, the organic layer was
separated as a dark-red oily liquid (1.13 g), the
aqueous–hydrazine layer was extracted with methylene
chloride, the extract was dried over MgSO4. The
residue obtained after removal of solvent (1 g) was
combined with the organic layer, analyzed by GLC
method, and distilled. The fraction with bp 93–94ºС
1
chromatomass spectrometry, and H, 13C, 125Te NMR
spectroscopy is the 1:1 mixture of compounds XIII
1
and XIV. H NMR spectrum of compound XIII (δ,
3
ppm): 0.99 t (3H, CH3CH2CH2, JH–Н 7.3 Hz), 1.61 m
3
(2H, CH3СH2CH2), 2.60 t (2H, CH3CH2CH2S, JH–Н 7.4
Hz), 3.61 s (2H, CH2S). 13С NMR spectrum (δ, ppm):
13.26 (CH3CH2CH2), 22.18 (CCH2C), 32.61 (CCH2S),
35.10 (SCS). 1H NMR spectrum of compound XIV (δ,
ppm): 1.01 t (3H, CH3CH2CH2), 1.66 m (2H,
CH3CH2CH2), 2.0 s (3H, MeTe), 2.52 t (2H,
CH3CH2CH2), 3.63 s (2H, SCH2Te). 13С NMR spectrum
(δ, ppm): –19.81 (MeTe), 0.77 (SCH2Te), 13.26
(CH3CH2CH2), 21.67 (CCH2C), 37.19 (CCH2S). 125Te
NMR spectrum (δ, ppm): 182.27.
1
(2 mm Hg), according to GLC, H, 13C, 125Te NMR
and chromato-mass spectrometry, contained >98% of
1
3,5-ditellura-heptane X. H NMR spectrum (δ, ppm):
3
1.65 t (3H, CH3CH2Te, J 6.8 Hz), 2.65–2.77 m (2H,
CH2CH3), 3.46 s (2H, TeCH2Te). 13C NMR spectrum
(δ, ppm, J, Hz): –49.56 (TeCH2Te, 1JC–Te 212.6 Hz),
0.76 (CH2Te, 1JC–Te 151.1 Hz), 16.78 (CH3CH2Te).
125Te NMR spectrum (δ, ppm): 397.65. Mass spectrum
of com-pound X is fully identical to that described
above. Found, %: C, 18.42; H, 3.64; Te, 77.61.
C5H12Te2. Calculated, %: C, 18.34; H, 3.67; Te, 77.99.
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