Reaction of 1-bromo-3-chloropropane with tellur and dimethyltelluride in the system of hydrazine hydrate-alkali

Article abstract of DOI:10.1134/S1070363206050112

A synthesis of oligomeric substance of thiocol type, the poly(trimethyleneditelluride), from 1-bromo-3-chloropropane and elemental tellurium is performed using a hydrazine hydrate-alkali system. Reductive splitting of the tellurocol followed by alkylation with methyl iodide give rise to preparation of bis(methyltelluro)propane, which was synthesized also from dimethyltelluride and 1,3-dihalopropanes using the N₂H ₄?H₂O/KOH system. Mass spectra of the synthesized low molecular weight organotellurium compounds are considered. Pleiades Publishing, Inc., 2006.

Full text of DOI:10.1134/S1070363206050112

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 5, pp. 726 729.
Pleiades Publishing, Inc., 2006.
Original Russian Text N.V. Russavskaya, E.P. Levanova, E.N. Sukhomazova, V.A. Grabelnykh, A.V. Elaev, L.V. Klyba, E.R. Zhanchipova, A.I. Albanov,
I.M. Korotaeva, D.S. Totyashinova, N.A. Korchevin, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 5, pp. 763 766.
Reaction of 1-Bromo-3-chloropropane
with Tellur and Dimethyltelluride
in the System of Hydrazine Hydrate Alkali
N. V. Russavskaya, E. P. Levanova, E. N. Sukhomazova,
V. A. Grabelnykh, A. V. Elaev, L. V. Klyba, E. R. Zhanchipova,
A. I. Albanov, I. M. Korotaeva, D. S. Totyashinova, and N. A. Korchevin
Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: venk@irioch.irk.ru
Received December 16, 2005
Abstract A synthesis of oligomeric substance of thiocol type, the poly(trimethyleneditelluride), from
1-bromo-3-chloropropane and elemental tellurium is performed using a hydrazine hydrate alkali system.
Reductive splitting of the tellurocol followed by alkylation with methyl iodide give rise to preparation of
bis(methyltelluro)propane, which was synthesized also from dimethyltelluride and 1,3-dihalopropanes using
the N2H4 H2O/KOH system. Mass spectra of the synthesized low molecular weight organotellurium com-
pounds are considered.
DOI: 10.1134/S1070363206050112
Organic compounds of tellurium are highly effec-
tive ligands for the complex formation [1 3] and
reagents for the synthesis of complicated organic
compounds [4, 5]. Polimeric materials containing
tellurium attract attention as the compounds for crea-
tion of new electronic components [6, 7]. Earlier we
by reaction of 1-bromo-3-chloropropane with ele-
mental sulfur [8, 9] and selenium [10] in the system
of hydrazine hydrate base obtained oligomeric
substances of thiocol type which were used for the
synthesis of various low molecular weight organo-
sulfur and organoselenium compounds.
From the results of elemental analysis we estimated
average molecular weight of the oligomer obtained
( 3400). Taking into consideration the residual
content of halides we propose for this substance struc-
ture I:
ClCH2CH2CH2Te(TeCH2CH2CH2Te)10TeCH2CH2CH2Br.
I
The IR spectrum (KBr) of compound I is typical
of polymeric materials. It contains the following
bands: 2956, 2919, 2850, 1435, 1400, 1330, 1248,
1
1168, 1118, 906, 787, 756, 693, 478 cm . The bands
In this communication we publish our results on
the study of behavior of tellurium and some of its
derivatives in the reaction with 1-bromo-3-chloro-
propane in the base-reducing system of hydrazine
hydrate alkali. In such a system tellurium is activated
at the ratio Te:KOH = 1:1 due to formation of Te22
anion [11]:
1
1168 and 693 cm
are the strongest. Existing data
on vibration spectra of organotellurium compounds
do not allow their unambiguous assignment.
Like the related thiocols [8, 9] and selenocols [10]
the system of hydrazine hydrate KOH splits oligomer
I forming a homogenous solution (reductive splitting
of Te Te bonds [12]).
4Te + 4KOH + NH2NH2 H2O
N2H4 H2O/KOH
2K2Te2 + N2 + 5H2O.
(1)
I
KTeCH2CH2CH2TeK.
(2)
Further reaction of K2Te2 (Te22 ) with 1-bromo-3-
chloropropane leads to formation of a black product.
II
Potassium ditellurate II without isolation from the
solution was methylated with methyl iodide. From
the organic layer formed 1,3-bis(methyltelluro)pro-
pane (III) was isolated in 47.5% yield (on the tel-
ClCH2CH2CH2Br
K2Te2
(TeCH CH CH Te
.
)
2
2
2
n
KCl, KBr
726

REACTION OF 1-BROMO-3-CHLOROPROPANE
lurium taken for the reaction1). Dimethyltellur is
727
H2O, [O]
formed in 25% yield.
.
II
2KOH Te Te
IV
2CH3I
(3)
II
CH3TeCH2CH2CH2TeCH3.
III
2KI
1
and mass-spectrometry. In its H NMR spectrum the
protons of CH3Te group induce a singlet at 1.84 ppm,
the CCH2C protons give a quintet centered at
Compound III is the most effective ligand among
the tellurium containing ones [3], therefore the de-
velopment of a simple method for its synthesis is
independently of practical importance.
3
2.10 ppm, J 7.3 Hz, the CH2Te protons induce a
triplet at 2.65 ppm. Mass-spectrum contains a family
of peaks of the molecular ion with the intensity
typical for the particles with two Te atoms. The
molecular ion III fragmentation is the same as in the
case of related thio [8] and selenium [10] analogs
(Scheme 1, m/z of the tellurium-containing ions is
given for 130Te, the intensities are scaled to overall
ion current).
According to the data of chromato-mass spec-
trometry, the organic layer in reactions 2 and 3 also
contains 1,2-ditellurolane (IV), m/z 302 for 130Te [13],
yield 3%. The the latter most probably is formed at
the oxidation of ditellurolate II.
Structure of 1,3-bis(methyltelluro)propane (III) is
1
confirmed by the methods of H NMR spectroscopy
Scheme 1.
m/z 39 (11), 41 (15)
+
+
Te
Te Me
Te Me
Me Te
[HCTe]+
Me
Me
C3H7Te
III, M+ , 332 (2)
m/z 317 (22)
m/z 143 (12)
+
MeTe=CH2
C3H6
C3H6
m/z 159 (6)
[Me Te2]+
m/z 275 (18)
[Me Te Te Me]+
[Te]
m/z 130 (6)
m/z 290 (3)
1,3-Bis(methyltelluro)propane (III) was also ob-
tained by us in an authentic synthesis in 86% yield
from dimethyltelluride and 1,3-dibromopropane ac-
cording to the following sequence:
occur those of V: 1.91 s (CH3Te), 2.13 quintet
(CCH2C), 2.73 t (CH2Te), 3.60 t (CH2Cl), J 7.0 Hz.
3
Mass-spectrum of compound V contains a family of
peaks of molecular ion with medium intensity, the
signal distribution typical of the presence of one tel-
lurium and one chlorine atom in the particle (for 130Te
and 35Cl m/z 222 [M]+). The most strong fragmental
peaks correspond to the ions [CH3TeCl]+ m/z 180,
[CH3Te]+ m/z 145, [CH2Te]+ m/z 144, Te+ m/z 130,
[CH2Cl]+ m/z 49, and [C3H5]+ m/z 41.
2Ne2Te2 + N2H4 H2O + 4KOH
4MeTeK + N2 + 5H2O,
2MeTeK + Br(CH2)3Br III.
(4)
(5)
2KBr
Then 1-bromo-3-chloropropane is involved in the
reaction (5) instead of 1,3-dibromopropane, a mixture
of two compounds is formed: III (yield 17% on the
dimethyltelluride taken into reaction) and methyl(3-
chloropropyl)telluride (V) (44%).
By the method of chromato-mass spectrometry
among the products formed in reaction (5) we also
detected methylallyltelluride (VI) (yield 1%). This
compound is probably formed through a partial de-
hydrochlorination of nonsymmetrical telluride V in
the basic-reductive system.
Cl(CH2)3Br
MeTeK
III + CH3TeCH2CH2CH2Cl.
(6)
V
KOH
V
CH3TeCH2CH=CH2.
1
In H NMR spectrum of the mixture of compounds
III and V in addition to the signals of compound III
KCl, H2O
VI
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 5 2006

728
RUSSAVSKAYA et al.
1
In the mass-spectrum of telluride VI the molecular
carrier gas helium, flow rate 0.7 mlmin , program-
med rise of temperature from 60 to 260 C 15 deg.
Temperature of detector 250 C, mass analyzer quad-
rupole, electron ionization, energy 70 eV, temperature
of ion source 200 C, the detectable mass range is 34
to 650 D.
peak appears as a typical cluster of isotopic peaks
([M]+ 186 m/z for 130Te) with intensity ratio charac-
terisitic of the presence of one tellurium atom. Its
fragmentation is shown in the Scheme 2.
Scheme 2.
Analysis of the formed liquid compounds was
performed on a LKhM 80-MD-2 chromatograph,
column 2000 3 mm, liqid phase XE-60 (5%), linear
temperature programming 12 deg min , carrier gas
helium.
+
[CHTe]+
m/z 143 (11)
Te
H
+
Te
1
M+ , 186 (12)
m/z 185
CH2Te
Te
Poly(trimethylditelluride) (I). To a solution of
2.8 g of KOH in 20 g of hydrazine hydrate at 75 C
was added 6.38 g of tellurium powder for 0.5 h. The
dark violet reaction mixture was kept for 2 h at 85 C
and cooled to room temperature. Then in 15 min
5.85 g of 1-bromo-3-chloropropane was added till
decolorization of the reaction mixture. The mixture
was kept for 1.5 h at 60 65 C, cooled, and tellurocol
dropped as sticky black mass was separated from
aqueous layer, washed repeatedly with cold and hot
water, and then dried in a vacuum. Yield 7.2 g (98%
on the taken tellurium), mp (decomp.) 55 90 C.
Found, %: C 12.45, H 2.05, (Br + Cl) 3.42, Te 81.88.
C36H72Te22BrCl. Calculated, %: C 12.60, H 2.10,
Br + Cl 3.36, Te 81.92.
[C3H5]+
[C4H7]+
m/z 41 (44)
m/z 55 (5)
Methylallyltelluride VI was prepared in 66.5%
yield by authentic route from allyl bromide and di-
methyltelluride in a hydrazine hydrate alkali system.
The potassium methyltellurate obtained in reaction
(2) was taken into reaction with allyl bromide and
only telluride VI was obtained.
MeTeK + BrCH2CH=CH2
VI.
KBr
Compound VI has been described in [14]. It was
prepared by reaction of allylmagnesium halides with
tellurium in an inert atmosphere at low temperature
followed by methylation with methyl iodide (00C).
Methylallyltelluride VI was isolated in dark in 56%
yield. The method of synthesis of telluride VI pro-
posed by us is based on the more available reagents
and is more useful in technological aspect.
1,3-Bis(methyltelluro)propane (III). a. A mixture
of 2.52 g KOH in 11.4 g of hydrazine hydrate and
2.7 of g poly(trimethyleneditelluride) (I) was stirred
for 1.5 h at 75 C to complete dissolving of the poly-
mer. Mixture was cooled to room temperature and
5.1 g of methyl iodide was added in 0.5 h. Stir was
continued for 0.5 h at 40 43 C and after cooling
organic layer (bottom) was separated (2.02 g). Ac-
cording to the data of GLC and chromato-mass spec-
trometry it contained compound III, dimethyltelluride
and 1,2-ditellurolane IV. Yield of compound III is
47.5%.
Thus, from 1-bromo-3-chloropropane and tellurium
in the system of hydrazine hydrate KOH can be
synthesized tellurocol which enters readily to reduc-
tive splitting, and this enables preparation of 1,3-bis-
(methyltelluro)propane. The latter compound can also
be synthesized from dihalopropane and dimethylt-
elluride.
b. To a solution of 1.17 g of KOH in 5 g hydrazine
hydrate 1.2 g of dimethyltelluride was added. The
mixture was heated with stirring for 1 h at 75-80 C,
then cooled to 30 C and for 15 min 1.7 g of 1,3-di-
bromopropane was added to it. The reaction mixture
was heated for 0.5 h at 60 62 C and after cooling the
bottom (organic) layer (1.0 g) was separated. Accord-
EXPERIMENTAL
IR spectra were registered on a Specord IR-75
instrument in thin layer and on a Bruker IFS-25 in
KBr pellets. H and 13C NMR spectra were registered
on a Bruker DPX-400 spectrometer (400.1 and 100.6
MHz, respectively) as solvents in CDCl3, internal
reference HMDS.
1
1
ing to GLC and H NMR data it consisted purely of
1,3-bis(methyltelluro)propane III, yield 80%.
c. To a solution of 3.5 g of dimethyltelluride in the
system of hydrazine hydrate (15 ml) KOH (3.4 g) ob-
tained in the b procedure was added at 50 C 3.8 g of
1-bromo-3-chloropropane. The mixture was stirred
for 1 h at 50 60 C, then cooled and organic layer
The mass spectra were registered on a chromato-
mass spectrometer Shimadzu GCMS-QP5050A
(SPBTM-5 column, 60000 0.25 mm), stationary
phase film 0.25 m, injector temperature 250 C,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 5 2006

REACTION OF 1-BROMO-3-CHLOROPROPANE
729
(3.2 g) was separated. The data of GLC, chromato-
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no. 1, p. 1.
1
cated the presence of compound III, methyl(3-chloro-
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Methylallyltelluride (VI). To a solution of 3.6 g
of KOH in 16 g of hydrazine hydrate 3.62 g of di-
methyltelluride was added and the mixture was stirred
for 2 h at 80 85 C to complete dissolving of dimethyl-
telluride. After cooling to 25 C, 3.05 g of allyl
bromide was added in 20 min, then stir was continued
for 1 h at room temperature and the bottom (organic)
layer (3.1 g) was separated. Compound VI was iso-
lated by distillation in a vacuum: bp 56 C (30 mm
Hg) (published: 41 C at 13 mm Hg) [14]). Found, %:
C 26.03, H 4.41, Te 68.74. C4H8Te. Calculated, %: C
1
26.14, H 4.36, Te 69.50. IR spectrum, cm : 3077,
3029, 3000, 2972, 2921, 2849, 1624, 1426, 1398,
1291, 1219, 1190, 1128, 1042, 984, 901, 849, 676,
1
524, 491. H NMR spectrum, , ppm: 1.86 s (CH3Te),
3.31 d (CH2Te), 4.80 m (CH2=), 5.94 m (CH=). 13C
NMR spectrum, C, ppm: ( 20.70) (CH3Te), 5.31
(CH2Te), 114.24 (CH2=), 136.02 (CH=).
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