Reaction of diphenyl ditelluride with 2,3-dichloroprop-1-ene in the system hydrazine hydrate-KOH

Article abstract of DOI:10.1134/S1070428014020055

Diphenyl ditelluride reacts with 2,3-dichloroprop-1-ene in the system hydrazine hydrate-KOH along several parallel routes. Beside the nucleophilic chlorine substitution at the sp ³-hybridized carbon atom resulting in 2-chloro-3-phenyltellanylprop-1-ene the elimination of both chlorine atoms occurs affording a mixture of allene and methylacetylene. The reasons of the dual elimination reaction paths are considered.

Full text of DOI:10.1134/S1070428014020055

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 2, pp. 175178. Pleiades Publishing, Ltd., 2014.
Original English Text  E.P. Levanova, V.S. Vakhrina, V.A. Grabel’nykh, I.B. Rozentsveig, N.V. Russavskaya, A.I. Albanov, N.A. Korchevin, 2014, published in
Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 2, pp. 186189.
Reaction of Diphenyl Ditelluride with 2,3-Dichloroprop-1-ene
in the System Hydrazine Hydrate–KОН
E. P. Levanova, V. S. Vakhrina, V. A. Grabel’nykh, I. B. Rozentsveig,
N. V. Russavskaya, A. I. Albanov, and N. A. Korchevin
Faworsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk,664033 Russia
е-mail: venk@irioch.irk.ru
Received September 20, 2013
Abstract—Diphenyl ditelluride reacts with 2,3-dichloroprop-1-ene in the system hydrazine hydrate–KОН along
several parallel routes. Beside the nucleophilic chlorine substitution at the sp3-hybridized carbon atom resulting in
2-chloro-3-phenyltellanylprop-1-ene the elimination of both chlorine atoms occurs affording a mixture of allene
and methylacetylene. The reasons of the dual elimination reaction paths are considered.
DOI: 10.1134/S1070428014020055
At the treatment with “soft” nucleophiles, in
particular, with chalcogen-containing anions, of geminal
dihalides besides the reactions of classic nucleophilic
substitution an abnormal redox process can occur
involving the elimination of both halogen atoms as anions
with the formation of an alkene and the oxidation of the
nucleophilic reagent [1]. The interest in these reactions
is not only caused by their application to the synthesis
of unsaturated compounds and protection of double
bonds [2], but also by the solution of important theoretic
issues of organic chemistry, first of all regarding the
problem of the competition between the substitution
and the elimination. At the use of chalcogen-containing
nucleophiles the theoretic interest consists also in the
effect of the nature of the chalcogen atom (in going from
sulfur to selenium and tellurium) on the direction of
the process. At the treatment with the sulfur-containing
nucleophilic reagents the elimination proceeds at the
use of aprotic polar solvents [3] or phase-transfer
catalysts [4, 5]. In the system hydrazine hydrate–alkali
1,2-dichloroethane reacted with potassium disulfide
to give only substitution products (sulfur-containing
oligomers), and with potassium diselenide and ditelluride
only the elimination was observed [6]. The elimination
occurs the most often in reactions with dihalides where
the halogen atoms are bound to sp3-hybridized carbon
atoms, yet some examples exist of debromination of
bromine linked to sp2-hybridized carbon atoms [3].
However from cis-1,2-dichloroethene and sodium
selenide in the presence of a phase-transfer catalyst a
series of unsaturated selenacrown ethers was obtained
(the substitution process proceeded exclusively) [7].
As the most conventional mechanism of vicinal de-
halogenation the synchronous mechanism is accepted
involving a halophilic attack of the nucleophile on one
of the halogen atoms [8]. When both halogen atoms are
bound to carbon atoms in the same hybridization state
the direction of the halophilic attack either is equally
probable, or is governed mainly by steric factors. The
reaction output therewith is the same: the formation of
an unsaturated compound. In event the halogen atoms
are linked to carbon atoms of different hybridization,
the direction of the halophilic attack is ambiguous. The
simplest compound with one chlorine atom attached to
sp3-hybridized carbon atom and another, to sp2-hybridized
carbon atom, is 2,3-dichloroprop-1-ene (I). The well
known “inertness” of halogens at the double bond in the
reactions of nucleophilic substitution [9] essentially af-
fects the direction of 2,3-dichloroprop-1-ene (I) reactions
with chalcogen-containing nucleophiles.
We formerly demonstrated that the elemental sulfur
activated in the system hydrazine hydrate–KОН into
S22– anions reacted with dichloropropene I to give bis(2-
chloroprop-1-en-3-yl) sulfide (a single chlorine atom
bound to the sp3-hybridized carbon was involved in the
reaction) [10]. At the use of the system hydrazine hy-
drate–aminoethanol we obtained from sulfur and dichlo-
175

LEVANOVA et al.
176
ropropene I bis(2-chloroprop-2-ene-1-yl) disulfide [11].
Selenium in both basic reduction systems afforded only
bis(2-chloroprop-2-ene-1-yl) selenide [12]. Elemental tel-
lurium in the system hydrazine hydrate–KОН (activation
to Te22–) reacted with compound I with the elimination of
both chlorine atoms and the formation of allene [10, 13].
the formation of allene or methylacetylene and regenera-
tion of the initial diphenyl ditelluride.
Regardless the relative high temperature (50°С) only
_
I + 2PhTe
(3)
_2Cl _,
_Ph2Te2
)
(
The reaction of Ph2S2 [14] and Ph2Se2 [15] with
dichloropropene I proceeds as a series of successive
transformations including the nucleophilic substitution
of the chlorine atom at the sp3-hybridized carbon, the
dehydrochlorination of the compound obtained into an
allene derivative, the allene-acetylene rearrangement, and
the addition of anions PhS– and PhSe– to the triple bond
(domino-reaction).
the first stage occurs of the previously observed [14, 15]
domino-reaction (2). The yield of compound II reaches
80% with respect to the reacted Ph2Te2. Ph2Te2 formed in
reaction (3) suffers again the reductive cleavage (1) in the
presence in the reaction mixture of alkali and hydrazine,
and thus obtained anions PhTe– enter reactions (2) and
(3). Therefore the completion of the process requires
excess of reagent I. It should be taken into account that
a part of 2,3-dichloroprop-1-ene (I) is consumed by
reaction (2) and by the formation of propenylhydrazine
III (reaction 4).
It is well known [16] that the chemical behavior of
2Ph2Te2 + 4KOH + N2H4 H2O
(1)
4PhTeK + N2 + 5H2O
Therefore the overall yield of allene and methylacety-
organotellurium compounds often is unlike that of the
corresponding sulfur and selenium compounds. Here
we report on the study on the direction of the reaction
of diphenyl ditelluride with 2,3-dichloroprop-1-ene (I).
Diphenyl ditelluride was brought into the reaction with
dichloropropene I after its preliminary dissolution in the
system hydrazine hydrate–alkali. The system is an effi-
cient reducer for the activation of elemental chalcogens
and organic dichalcogenides [17]. Potassium phenyltellu-
rolate obtained in reaction (1) was used without isolation
directly as a solution in hydrazine hydrate. At 50°С gas
liberation was observed; the latter proved to be a mixture
of allene and methylacetylene in 2:1 ratio (1Н NMR data).
In order to collect a considerable amount of gas we were
obliged to add to the reaction mixture a 4-fold excess of
dichloropropene I. After that the reaction was stopped,
and we isolated from the extract a mixture of three com-
pounds: [(2-chloroprop-2-ene-1-yl)tellanyl]benzene (II),
(2-chloroprop-2-en-1-yl)hydrazine (III), and diphenyl
ditelluride in the molar ratio 1:0.5:0.1.
Cl
Cl
+ NH2NH2
Cl
NHNH2 (4)
III
I
lene calculated with respect to dichloride I consumed only
in reaction (3) reaches 72%.
Thus the reaction of 2,3-dichloroprop-1-ene (I) with
diphenyl ditelluride can be summarized in expression (5).
2–
In the reaction of anions Te2 with dichloride I
Cl
Cl
_
PhTe
Cl
I
TePh
(5)
Ph2Te2
Ph2Te2
II
C3H4
N2H4 H2O_KOH
[13] even in more severe conditions (85°С) allene was
obtained practically free of methylacetylene impurity.
Consequently, the formation of a mixture of allene and
methylacetylene in reaction (3) is evidently not caused
by the isomerization of allene in methylacetylene, but by
elimination chlorine atoms in two ways distinguished by
the direction of the primary halophilic attack. We showed
formerly [18] that the reaction of (2-chloroprop-2-en-1-
yl)isothiuronium chloride containing a single chlorine
atom covalently bound to an sp2-hybridized carbon atom
Hence the reaction of 2,3-dichloro-prop-1-ene (I) with
PhTe– anions takes two main directions: the nucleophilic
substitution (2) of the chlorine at the sp3-hybridized car-
bon, and the elimination (3) of both chlorine atoms with
Cl
Cl
+ PhTe_
TePh
(2)
Cl
_
_Cl
I
II
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014

REACTION OF DIPHENYL DITELLURIDE
PhTe_
177
PhTe_
Cl
a
a
_PhTeCl, _Cl _
Cl
Cl
A
Cl
Cl
_
PhTe
_
b
Cl
H
b
PhTe_
CH2
_Cl_
(6)
_PhTeCl
Cl
H
B
C
with Te22– anions was also accompanied with allene for-
mation. It was therefore concluded that the ditelluride
anion attacked prevailingly the chlorine atom at the sp2-
hybridized carbon atom.Allene obtained in [18] also was
practically free of methylacetylene.
EXPERIMENTAL
The purity of initial 2,3-dichloroprop-1-ene was
checked and the products obtained were analyzed by GLC
on a chromatograph LKhM 80-MD-2 (column 2000 ×
3 mm, stationary phase silicone ХЕ-60, 5% on the car-
rier Chromaton N-AW-HMDS, ramp from 30 to 230°С
at a rate 12 deg/min, carrier gas helium). IR spectra were
recorded on a spectrophotometer Bruker IFS from thin
films. 1Н, 13С, and 125Te NMR spectra were registered on
a spectrometer Bruker DPX-400 (operating frequencies
400.13, 100.61, and 126.2 МHz respectively) in CDCl3,
internal reference TMS [(CH3)2Te for 125Те].
However sufficiently bulky and easily polarizable
PhTe– anions can apparently attack both chlorine atoms
in the molecule of 2,3-dichloroprop-1-ene (I) thus lead-
ing to the formation of allene and methylacetylene (6).
The elimination Е2 (a) proceeds synchronously (А),
as is common in such processes (see, e.g., [6, 8]), and the
halophilic attack in this case is aimed at the chlorine atom
possessing a partial positive charge due to the mesomeric
interaction with the multiple bond. The path b proceeding
apparently through the transition state B may occur not
synchronously but with a partial delay of the cleavage of
the second chlorine atom with the intermediate formation
of a kinetically independent carbocation C. This direction
may be interpreted in the framework of the concept of the
nucleophilic substitution at the chlorine atom [19]. In this
case the process may be accompanied with a rearrange-
ment involving a proton transfer from the carbon atom at
the double bond to the anion site resulting finally in the
formation of methylacetylene. Apparently the route a is
preferable, therefore allene is formed in a higher yield.
Mass spectra were obtained on a GC-MS instrument
Shimadzu GCMS-QP5050A (column SPB-5, 60000 ×
0.25 mm), film of the stationary phase 0.25 μm thick;
injector temperature 250°С, carrier gas helium, flow rate
0.7 mL/min, ramp from 60 to 260°С at a rate 15 deg/min.
Detector temperature 250°С, quadrupole mass analyzer,
electron impact, ionizing electrons energy 70 eV, tem-
perature of ion source 200°С, range of mass detected
34–650 Da.
Reaction of dichloropropene I with diphenyl ditel-
luride. In 8 ml of hydrazine hydrate containing 1.71 g
(0.0305 mol) of KOH was dissolved 2.5 g (0.0061 mol)
of diphenyl ditelluride at 80–85°С. The solution obtained
was cooled to 30°С, the reaction vessel was connected
to two cooled traps (–30 and –85°С). The reaction mix-
ture was heated to 45–50°С and simultaneously 2.8 g
(0.025 mol) of dichloropropene I was added dropwise.
In the second trap 0.37 g of colorless liquid was collected
containing according to 1Н NMR data 0.25 g [49% with
respect to dichloropropene consumed in reaction (3)] of
allene and 0.12 g (yield 23%) of methylacetylene. The
reaction mixture after the end of gas condensation was
extracted with dichloromethane (2×10 ml). The combined
Hence in the reaction of diphenyl ditelluride with
2,3-dichloroprop-1-ene along with the nucleophilic
substitution of the allyl chlorine the chlorine elimina-
tion can proceed in two direction with the formation of a
mixture of allene and methylacetylene. The elimination
in this case is an undesirable process just because of
the formation of the mixture of isomers С3Н4 and is of
interest only from the theoretical viewpoint. Unsaturated
organotelluric compounds II may be applied as important
reagents in the organic synthesis.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014

LEVANOVA et al.
178
Sukhomazova, E.N., Klyba, L.V., Zhanchipova, E.R.,
Albanov, A.I., Tatarinova, A.A., Elaev, A.V.,
Deryagina, E.N., Korchevin, N.A., and Trofimov, B.A.,
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extracts were dried with MgSO4. On removing the solvent
the residue (3.14 g) contained according to 1Н NMR data
2.36 g of compound II (yield 80% with respect to reacted
Ph2Te2), 0.44 g of (2-chloroprop-2-ene-1-yl)hydrazine
(III) (yield 16% with respect to used propenedichloride
I) and 0.34 g of diphenyl ditelluride (conversion 86%).
Spectral characteristics of allene are identical to data of
[13]. Spectral characteristics of (2-chloroprop-2-ene-1-
yl)hydrazine (III) are in agreement with our previous
data [10].
7. Shimizu, T., Kawaguchi, M., Tsuchiya, T., Hirabayashi, K.,
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1
Methylacetylene. Н NMR spectrum, δ, ppm: 1.805 s
(1Н, СН≡), 1.811 s (3Н, СН3). 13С NMR spectrum, δ,
ppm: 3.16 (СН3), 67.42 (СН≡), 80.01 (–С≡).
[(2-Chloroprop-2-ene-1-yl)tellanyl]benzene
(II). 1Н NMR spectrum, δ, ppm: 3.76 s (2Н, СН2Те,
2JТе,Н 14.4 Hz), 4.95 s, 4.97 s (2Н, СН2=), 7.11–7.77 m
(5Н, Ph). 13С NMR spectrum, δ, ppm: 16.56 (СН2Те,
1JС,Те 88.2 Hz), 112.34 (СН2=), 139.57 (ССl=), we failed
to reliably assign the signals of the carbon atoms of the
benzene ring. 125Те NMR spectrum, δ, ppm: 616.5 {for
Ph2Te2 125Те 421.5 ppm (420.8 ppm [20])}. Mass spec-
trum was not possible to register apparently due to the
thermal instability of compound II in the chromatographic
column of the GC-MS instrument.
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Rozen-tsveig, I.B., Tarasova, O.A., and Korchevin, N.A.,
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ACKNOWLEDGMENTS
The principal results were obtained on the equipment
of the Baikal analytical center in general use of the Si-
berian Department of the Russian Academy of Sciences.
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