Polar cycloaddition of 2-pyridinetellurium trichloride to multiple bonds

Article abstract of DOI:10.1007/s11172-013-0139-5

A reaction of 2-pyridinetellurium trichloride with unsaturated hydrocarbons leads to [1,3]tellurazolo[3,2-a]pyridinium-4 derivatives - the products of polar cycloaddition of tellurium-containing electrophile at the multiple bond.

Full text of DOI:10.1007/s11172-013-0139-5

Russian Chemical Bulletin, International Edition, Vol. 62, No. 4, pp. 1042—1043, April, 2013
1042
Polar cycloaddition of 2ꢀpyridinetellurium trichloride to multiple bonds*
A. V. Borisov, Zh. V. Matsulevich, V. K. Osmanov, and G. N. Borisova
aR. E. Alekseev Nizhny Novgorod State Technical University,
24 ul. Minina, 603950 Nizhny Novgorod, Russian Federation.
Fax: +7 (831) 436 2311. Eꢀmail: avb1955@rambler.ru
A reaction of 2ꢀpyridinetellurium trichloride with unsaturated hydrocarbons leads to [1,3]telꢀ
lurazolo[3,2ꢀa]pyridiniumꢀ4 derivatives — the products of polar cycloaddition of telluriumꢀ
containing electrophile at the multiple bond.
Key words: 2ꢀpyridinetellurium trichloride, alkenes, acetylenes, cycloaddition, [1,3]tellurꢀ
azolo[3,2ꢀa]pyridiniumꢀ4 derivatives.
Scheme 1
It is known that the reaction of arenetellurium triꢀ
halides ArTeHal3 with alkenes and acetylenes usually gives
the products of 1,2ꢀaddition at the multiple bonds, ꢀhaloꢀ
alkyl(vinyl)tellurium dihalides1—5 or the products of
transannular cyclization with the ring closure by the elecꢀ
tronꢀdonating center of the functional group containing
in the molecule of the unsaturated substrate, lactones,
ordinary cyclic ethers, pyrrolidine and piperidine derivaꢀ
tives.1,2,6—11
In the present work, we synthesized 2ꢀpyridinetelluriꢀ
um trichloride (1), the first representative of hetarenetelꢀ
lurium trihalides containing a nitrogen base as the hetaryl
substituent and studied its reactions with norbornene (2),
cyclopentene (3), and pꢀmethoxyphenylacetylene (4). The
indicated reactions in dichloromethane at 20 C were found
to result in the formation of the heterocyclization
products with the ring closure by the nitrogen atom of
the pyridine ring in the starting electrophilic agent, i.e.,
salts 5—7, in 95, 82, and 96% yields, respectively (Scheme 1).
It can be suggested that the formation of the conꢀ
densed heterocyclic systems 5—7 follows the scheme of
polar cycloaddition similarly to the reactions of 2ꢀpyridineꢀ
tellurenyl chloride with alkenes studied by us earlier12
,
since we did not observe the formation of the 1,2ꢀaddition
products of reagent 1 to unsaturated compounds 2—4 even
in the trace amounts.
The structure of compounds obtained was confirmed
Experimental
1
by the H NMR spectroscopic, ESI mass spectrometric,
1
and elemental analysis data. The signals in the H NMR
Di(2ꢀpyridyl) ditelluride was obtained according to the
known procedure.17 Other reagents were purchased from Acros
Organics (Belgium) and used without preliminary purification.
The solvent CH2Cl2 was purified by distillation over P2O5. 1H NMR
spectra of were recorded on a Bruker AMꢀ300 spectrometer
(300 MHz) in DMSOꢀd6. Mass spectra ESI were obtained on a Finꢀ
nigan MAT INCOS 50 quadrupole mass spectrometer (70 eV).
In the mass spectra, the m/z values for the peaks of the maximal
intensity in the Teꢀcontaining isotope cluster are reported.
spectra were assigned based on the spectral characterisꢀ
tics of cycloaddition products of chalcogenꢀcentered
electrophiles to unsaturated compounds obtained by us
earlier, whose structure was confirmed by Xꢀray crystalꢀ
lography.12—16
* Dedicated to academician of the Russian Academy of Sciences
I. P. Beletskaya on the occasion of her anniversary.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 1041—1042, April, 2013.
1066ꢀ5285/13/6204ꢀ1042 © 2013 Springer Science+Business Media, Inc.

Derivatives of [1,3]tellurazolo[3,2ꢀa]pyridiniumꢀ4
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 4, April, 2013
1043
2ꢀPyridinetellurium trichloride (1). A solution of sulfuryl chloꢀ
ride (0.1 g, 0.75 mmol) in dichloromethane (5 mL) was added to
a solution of di(2ꢀpyridyl) ditelluride (0.103 g, 0.25 mmol) in
dichloromethane (5 mL) at 20 °C. After 1 h, compound 1 was
filtered off as white crystals. The yield was 0.155 g (97%), m.p.
240—242 C (decomp.). Found (%): C, 19.18; H, 1.24; N, 4.42.
C5H4Cl3NTe. Calculated (%): C, 19.24; H, 1.29; N, 4.49. MS,
m/z (Irel (%)): 313 [M]+• (1.6), 278 [C5H4NTeCl2]+• (2.0); 243
H(2)); 8.86 (d, 1 H, H(8), 3J = 7.3 Hz); 9.02 (d, 1 H, H(5),
3J = 7.3 Hz).
The authors are grateful to A. O. Chizhov (N. D. Zeꢀ
linsky Institute of Organic Chemistry, Russian Academy
of Sciences, Moscow) for the discussion on the results of
massspectrometric studies and his help in the preparation
of the paper.
[C5H4NTeCl]+ (4.1); 208 [C5H4NTe]+ (3.4); 200 [TeCl2]+
•
•
•
(3.3); 196 [C4H3NTe]+ (1.8); 165 [TeCl]+ (4.1); 130 [Te]+
•
•
(7.9); 113 [C5H4NCl]+• (0.6); 78 [C5H4N]+ (100); 51 [C4H3]+
(47.6); 39 [C3H3]+ (7.8); 38 [HCl]+• (1.6); 36 [HCl]+• (4.8).
Reaction of tellurium trichloride 1 with unsaturated comꢀ
pounds 2—4 (general procedure). A solution of unsaturated comꢀ
pound 2—4 (0.25 mmol) in CH2Cl2 (5 mL) was added to a susꢀ
pension of tellurium trichloride (1) (0.078 g, 0.25 mmol) in
CH2Cl2 (10 mL) at 20 C. The reaction mixture was kept for 24 h
at 20 C, the solvent was evaporated at reduced pressure. Comꢀ
pounds 5—7 were obtained after recrystallization of the residue
from CH2Cl2.
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exoꢀcisꢀ9,9ꢀDichloroꢀ9ꢀtelluraꢀ3ꢀazoniatetracycloꢀ
[9.2.1.02,10.03,8]tetradecaꢀ3,5,7ꢀtriene chloride (5). The yield
was 95%, white crystals, m.p. 243—245 C. Found (%): C, 35.37;
H, 3.41; N, 3.39. C12H14Cl3NTe. Calculated (%): C, 35.48;
H, 3.47; N, 3.45. 1H NMR, : 1.27 (d, 1 H, Hsyn(14), J= 11.7 Hz);
1.37 (m, 2 H, H(12)); 1.63 (d, 1 H, Hanti(14), J = 11.7 Hz); 1.80
(m, 2 H, H(13)); 3.09 (s, 1 H, H(11)); 3.12 (s, 1 H, H(1)); 3.86
(d, 1 H, H(10), J = 7.3 Hz); 5.70 (d, 1 H, H(2), J = 7.3 Hz); 8.22
(dd, 1 H, H(5), J = 7.3 Hz, J = 5.9 Hz); 8.58 (t, 1 H, H(6),
J = 7.3 Hz); 8.66 (d, 1 H, H(7), J = 7.3 Hz); 9.32 (d, 1 H, H(4),
J = 5.9 Hz). MS, m/z (Irel (%)): 370 [C12H14NTeCl2]+ (0.4);
300 [C12H14NTe]+ (0.6); 278 [C5H4NTeCl2]+ (10.2); 243
[C5H4NTeCl]+ (14.6); 208 [C5H4NTe]+ (7.0); 200 [TeCl2]+
•
•
12. A. V. Borisov, Zh. V. Matsulevich, V. K. Osmanov, G. N.
Borisova, V. I. Naumov, G. Z. Mammadova, A. M. Maharꢀ
ramov, V. N. Khrustalev, V. V. Kachala, Russ. Chem. Bull.
(Int. Ed.), 2012, 61, 91 [Izv. Akad. Nauk, Ser. Khim.,
2012, 89].
(10.2); 130 [Te]+• (15.1); 165 [TeCl]+ (13.1); 113 [C5H4NCl]+
•
(9.9.); 94 [C7H10]+ (10.6); 91 [C7H7]+ (7.9); 78 [C5H4N]+ (85.6);
66 [C5H6]+ (100); 51 [C4H3]+ (48.7); 39 [C3H3]+ (43.1);
•
36 [HCl]+• (13).
cisꢀ4,4ꢀDichloroꢀ2,3,3a,9aꢀtetrahydroꢀ1Hꢀcyclopenta[4,5]ꢀ
[1,3]tellurazolo[3,2ꢀa]pyridiniumꢀ9 chloride (6). The yield was
82%, yellow crystals, m.p. 57—58 C. Found (%): C, 31.51;
H, 3.11; N, 3.60. C10H12Cl3NTe. Calculated (%): C, 31.59; H, 3.18;
13. A. V. Borisov, Zh. V. Matsulevich, V. K. Osmanov, G. N.
Borisova, G. Z. Mammadova, A. M. Maharramov, V. N.
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Borisova, G. Z. Mammadova, A. M. Maharramov, V. N.
Khrustalev, Khim. Geterotsikl. Soedin., 2012, 1034 [Chem.
Heterocycl. Compd. (Engl. Transl.), 2012].
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Khrustalev, Khim. Geterotsikl. Soedin., 2012, 1167 [Chem.
Heterocycl. Compd. (Engl. Transl.), 2012].
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Borisova, G. Z. Mammadova, A. M. Maharramov, V. N.
Khrustalev, Khim. Geterotsikl. Soedin., 2012, 1180. [Chem.
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1
N 3.68. H NMR, : 1.71 (m, 2 H, CH2); 2.07 (m, 1 H, CH2);
2.42 (m, 1 H, CH2); 2.63 (m, 1 H, CH2); 2.89 (m, 1 H, CH2);
4.57 (dd, 1 H, H(3a), J = 15.8 Hz, J = 8.5 Hz); 6.27 (dd, 1 H,
H(9a), J = 15.8 Hz, J = 8.5 Hz); 8.23 (dd, 1 H, H(7), J = 7.3 Hz,
J = 6.1 Hz); 8.59 (dd, 1 H, H(6), J = 8.0 Hz, J = 7.3 Hz); 8.69
(d, 1 H, H(5), J = 7.3 Hz); 9.24 (d, 1 H, H(8), J = 6.1 Hz). MS,
m/z (Irel (%)): 278 [C5H4NTeCl2]+ (2.9); 243 [C5H4NTeCl]+
•
(16.4); 208 [C5H4NTe]+ (10.1); 200 [TeCl2]+• (4.3); 165 [TeCl]+
(10.4); 130 [Te]+• (17.1); 113 [C5H4NCl]+• (9.4); 78 [C5H4N]+
(100); 67 [C5H7]+ (77.9); 51 [C4H3]+ (37.4); 39 [C3H3]+ (38.6);
36 [HCl]+• (33.2).
1,1ꢀDichloroꢀ3ꢀ(4ꢀmethoxyphenyl)[1,3]tellurazolo[3,2ꢀa]ꢀ
pyridiniumꢀ4 chloride (7). The yield was 96%, orange crystals,
m.p. 130—132 C. Found (%): C, 37.74; H, 2.68; N, 3.10.
C14H12Cl3NOTe. Calculated (%): C, 37.85; H, 2.72; N, 3.15.
1H NMR, : 3.87 (s, 3 H, CH3O); 7.18 (d, 2 H, H(3´), H(5´)),
3J = 8.8 Hz); 7.57 (d, 2 H, H(2´), H(6´)), 3J = 8.8 Hz); 7.72 (t, 1 H,
H(7), 3J = 7.3 Hz); 7.98 (t, 1 H, H(6), 3J = 7.3 Hz); 8.78 (s, 1 H,
17. L. Engman, M. P. Cava, Organometallics, 1982, 1, 470.
Received December 31, 2012;
in revised form March 14, 2013