Complexes of Macroheterocyclic Compounds Derived from Substituted 1,2,4-Triazoles with Tetravalent Metals

Article abstract of DOI:10.1023/A:1024716810867

Symmetrical marcoheterocyclic compounds derived from substituted 1,2,4-triazoles were reacted with tin(IV) and titanium(IV) chlorides to prepare the corresponding metal complexes. Macroheterocyclic compounds insoluble in organic solvents give mixtures of

Full text of DOI:10.1023/A:1024716810867

Russian Journal of General Chemistry, Vol. 73, No. 2, 2003, pp. 308 311. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 2, 2003,
pp. 331 335.
Original Russian Text Copyright
2003 by Yagodarova, Danilova, Smirnov.
Complexes of Macroheterocyclic Compounds Derived
from Substituted 1,2,4-Triazoles with Tetravalent Metals
L. D. Yagodarova, E. A. Danilova, and R. P. Smirnov
Ivanovo State University of Chemistry Technology, Ivanovo, Russia
Received February 1, 2001
Abstract Symmetrical marcoheterocyclic compounds derived from substituted 1,2,4-triazoles were reacted
with tin(IV) and titanium(IV) chlorides to prepare the corresponding metal complexes. Macroheterocyclic
compounds insoluble in organic solvents give mixtures of products on complex formation.
Metal complexes of macroheterocyclic compounds
exhibit practically important properties. However, the
information available at present relates mostly to
complexes with divalent metals, such as Cu, Ni, Co,
Zn, etc. In the present work we report on the synthesis
of complexes with tetravalent metals (Sn and Ti).
form (Fig. 1) contains three principal bands at 344,
358, and 379 nm, as well as a medium-intensity band
at 368 nm and a shoulder at 349 nm. These data are
consistent with data for a macroheterocyclic com-
pound containing a 1-dodecyl-1,2,4-triazole fragment
[3]. The IR spectrum of compound III (Fig. 2) dis-
1
plays a strong band at 3300 cm , characteristic of
Macroheterocyclic compounds I and II were
prepared by known procedures [1]. As the starting
diamine in the synthesis of compound III we used
1-decyl-1,2,4-triazole obtained by alkylation of
guanazole [2] with decyl bromide in the presence of
sodium methoxide. After purification, 1-decyl-1,2,4-
triazole was reacted with o-phthalonitrile in ethylene
glycol under reflux to obtain compound III. The elec-
tronic absorption spectrum of the product in chloro-
stretching vibrations of the imino group. The absorp-
1
tion bands at 2920 and 2856 cm relate to stretching
vibrations of alkyl C H bonds [4].
The reactions of compounds I III comprising
substituted 1,2,4-triazole fragments with tin(IV) or
titanium(IV) chlorides were used to prepare metal
complexes IV IX.
R
R
Cl
N N
N N
Cl
N
N
N
N
N
N
N
N
MCl4
2HCl
HN
NH
M N
N
N
N
N
N
N
N
N
N
R
R
I III
IV IX
R = H (I, IV, VII), Ph (II, V, VIII), Dec (III, VI, IX); M = Sn (IV, VI), Ti (VII IX).
Complexes IV IX as extra ligands contain two
chlorine atoms which may locate on the same side or
on opposite sides of the molecular plane, which is an
important factor in the synthesis of sandwich struc-
tures. To explore this question, we performed quan-
tum-chemical calculations for compound IV by the
AM-1 method with full geometry optimization. The
molecular model is represented in Fig. 3. The metal
atom deviates from the plane defined by the four exo-
Deceased.
1070-3632/03/7302-0308$25.00 2002 MAIK Nauka/Interperiodica

COMPLEXES OF MACROHETEROCYCLIC COMPOUNDS DERIVED
309
log
4.5
cyclic nitrogen atoms by 37.5 ; this corresponds to a
constant of this plane of 0.94 . The isoindole frag-
ments deviate from this plane in opposite directions.
The triazole fragments deviate from the macroring
plane by 17 . The mean radius of the macrohetero-
cyclic window is 1.97 . Therewith, the chlorine
atoms locate symmetrically with respect to the metal
atom and at the same distance from it (2.4 ). This
structure is quite suitable for the synthesis of sand-
wich compounds.
1
2
4.3
3
4.1
3.9
The principal electronic absorption bands of com-
plexes IV, V, VII, and VIII are shifted slightly red
compared with those of the parent heterocycles I and
II [5] and are diffuse, which is probably associated
with the presence of metal and is consistent with
the theory of chromaticity of organic compounds. At
the same time, compounds VI and IX give a new
absorption band at 440 and 450 nm, respectively
(Fig. 1). Introduction of long alkyl residues into
macroheterocycle III allowed us to increase the solu-
bility of the macrocycle as such and of its metal com-
plexes in organic solvents, which made it possible to
apply present-day purification techniques and to
obtain a better resolved absorption spectrum.
300
400
, nm
Fig. 1. Electronic absorption spectra of (1) macrohetero-
cycle III and complexes (2) VI and (3) IX.
cycles and their complexes (Fig. 2) show common
absorption bands at 760, 1040, 1104, 1304 1316,
1408, and 1500 1504 cm , which points to a
1
common macroheterocyclic system (shown with
The IR spectra of the resulting metal-free macro-
compounds III and IV). At the same time, some dif-
T, %
60
1
40
2
20
4000
3000
2000
1500
1000
500
, cm
1
Fig. 2. IR spectra of (1) macroheterocycle III and (2) complex VI.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003

310
YAGODAROVA et al.
Cl
Cl
H
C
H
C
H
C
C
H
C
C
C
Sn
N
C
N
C
N
N
N
C
N
C
H
N
N
N
H
C
C
C
C
N
N
C
C
H
C
C
C
H
H
H
Fig. 3. Calculated molecular model of complex IV.
ferences can be noted. Thus, for instance, complexes
VI IX give no band at 3300 cm , characteristic of
dropwise over the course of 2 h and the mixture was
refluxed for 6 h and poured into 500 ml of cold water.
The oil layer was collected from the water surface and
steamed until the condensate no longer smelled of
decyl bromide. The hot residue was poured into
500 ml of cold water. The precipitate was filtered off
and dried at room temperature to obtain a pale-yellow
powderlike substance, 73%, mp 75 78 C; the sub-
stance is insoluble in acetone and readily soluble in
acetone, chloroform, and diethyl ether. IR spectrum,
1
stretching vibrations of the imino group. As shown in
[3], in going from a metal-free compound to a com-
1
plex, the absorption band at 1660 1670 cm , charac-
teristic of imino C=N stretching vibrations, shifts to
1
1550 1580 cm . Thus, the corresponding band for
1
complex VI is at 1580 cm and for the metal-free
1
compound III, at 1668 cm .
Upon isolation of complexes IV, V, VII, and VIII,
derived from macrocycles I and II, we, probably,
have a mixture of the starting and final products, since
the IR spectra of the isolated materials show not only
1
, cm : 2920, 2848, 1648, 1488, 1448, 1376, 1088.
Found, %: C 60.3; H 10.5; N 29.2. C12H25N5. Cal-
culated, %: C 60.1; H 10.8; N 29.1.
1
new bands at 1560 cm , but also imino C=N bands at
2,4,5,7,16,18,19,21,29,30,31,32-Dodecaazahept-
acyclo[20.6.1.13,6.18,15.117,20.09,14.023,28]dotriaconta-
1,3,6(32),7,9,11,13,15,17,20(30),21,23,25,27-tetra-
decaene (I) and 5,19-diphenyl-2,4,5,7,16,18,19,21,29,
30,31,32-dodecaazaheptacyclo[20.6.1.13,6.18,15.117,20.-
1
1660 cm , while slightly weaker.
As shown by electronic and IR spectroscopy and
atomic absorption analysis, complexes VI and IX are
individual compounds.
0
9,14.023,28]dotriaconta-1,3,6(32),7,9,11,13,15,17,
20(30),21,23,25,27-tetradecaene (II) were prepared by
the procedure in [1].
EXPERIMENTAL
The IR spectra were measured on a Specord M-80
spectrophotometer (4000 400 cm ) in KBr. The elec-
tronic absorption spectra were obtained on a Specord
M-40 spectrophotometer (300 700 nm) in DMF.
5,19-Didecyl-2,4,5,7,16,18,19,21,29,30,31,32-do-
decaazaheptacyclo[20.6.1.13,6.18,15.117,20.09,14.023,28]-
dotriaconta-1,3,6(32),7,9,11,13,15,17,20(30),21,23,
25,27-tetradecaene (III). A solution of 10 g 3,5-di-
amino-1-decyl-1,2,4-triazole and 5.4 g of phthalo-
nitrile in 100 ml of ethylene glycol predried by azeo-
tropic distillation. The mixture was stirred for 8 h
under reflux. The precipitate that formed was filtered
off, washed with water, twice recrystallized from
120 ml of DMF, and dried at 100 120 C to obtain a
reddish-brown substance, 20%, mp 215 217 C; the
substance is readily soluble in chloroform, benzene,
and methanol and insoluble in acetone and water.
Electronic absorption spectrum, max, nm (log ): 344
1
The metal contents were determined by flame-
ionization spectroscopy on a Saturn device.
Quantum-chemical calculations were performed by
the HYPERCHEM-4 program.
3,5-Diamino-1-decyl-1,2,4-triazole. A mixture
of 100 ml of methanol, 2.32 g of metallic sodium, and
10 g of 3,5-diamino-1,2,4-triazole was stirred under
reflux for 1 h. Decyl bromide, 24.5 g, was then added
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003

COMPLEXES OF MACROHETEROCYCLIC COMPOUNDS DERIVED
311
(4.27), 349, 358 (4.56), 368, 379 (4.35). IR spectrum,
, cm : 3296, 2920, 2856, 1668, 1616, 1488, 1456,
1444, 1372, 1344, 1300, 1096, 1056, 888, 768, 720.
Found, %: C 68.3; H 7.8; N 23.9. C40H52N12. Cal-
culated, %: C 68.5; H 7.5; N 24.0.
11,13,15,17,20(30),21,23,25,27-tetradecaene (VIII),
yield 81%, does not melt up to 450 C. Brown sub-
stance, sparingly soluble in DMF and pyridine and
insoluble in other organic solvents. Electronic absorp-
tion spectrum, max, nm: 352, 371, 394. IR spectrum,
1
1
, cm : 1664, 1580, 1596, 1500, 1408, 1304, 1100,
Metal complexes IV, V, VII, and VIII. A mixture
of 1.19 mmol of macroheterocycle I or II, 3.57 mmol
of tin or titanium chloride, and 30 ml of dry nitro-
benzene was stirred under reflux for 6 h. The preci-
pitate was filtered off, washed with benzene and
acetone, and suspended in 10% hydrochloric acid. The
precipitate was filtered off, washed with distilled
water to Cl -free washings (AgNO3 test), dried at
110 C, and purified by treatment with acetone.
1016, 762, 616. Found, %: S 63.0; H 4.3; Cl 1.9; N
28.5; Ti 2.3. C32H20Cl2N12Ti. Calculated, %: C 55.6;
H 2.9; Cl 10.3; N 24.3; Ti 6.9.
Metal complexes VI and IX. Macrocycle III,
4
7.13 10 mol, tin or titanium tetrachloride, 21.4
4
10 mol, and 30 ml of 1-chloronaphthalene were
stirred at 200 C for 20 h. After cooling, the reaction
mixture was diluted with heptane. The precipitate that
formed was washed with acetone and purified by
treatment with acetone.
29,31-Dichlorotin-2,4,5,7,16,18,19,21,29,30,31,32-
dodecaazaheptacyclo[20.6.1.13,6.18,15.117,20.09,14
0
.
23,28]dotriaconta-1,3,6(32),7,9,11,13,15,17,20(30),
29,31-Dichlorotin-5,19-didecyl-2,4,5,7,16,18,19,
21,29,30,31,32-dodecaazaheptacyclo[20.6.1.13,6.
21,23,25,27-tetradecaene (IV), yield 68%, does not
melt up to 450 C. Dark brown substance; sparingly
soluble in DMF and pyridine and insoluble in other
1
8,15.117,20.09,14.023,28]dotriaconta-1,3,6(32),7,9,11,
13,15,17,20(30),21,23,25,27-tetradecaene (VI), yield
44%, does not melt up to 300 C. Brown substance;
moderately soluble in hot chloroform, readily soluble
in DMF, and insoluble in acetone and water. Elec-
tronic absorption spectrum, max, nm: 275, 359 (4.5),
organic solvents. Electronic absorption spectrum,
,
max
1
nm: 352, 367, 402. IR spectrum, , cm : 1648, 1560,
1364, 1304, 1184, 1100, 1044, 764. Found, %: C 47.5;
H 3.6; Cl 4.3; N 34.0; Sn 10.6. C20H10Cl2N12Sn.
Calculated, %: S 39.5; H 1.7; Cl 11.7; N 27.6;
Sn 19.5.
1
379 (4.27), 440 (3.9). IR spectrum, , cm : 2920,
2856, 1580, 1512, 1468, 1376, 1312, 1100, 888, 760,
704. Found, %: S 54.2; H 5.3; Cl 8.0; N 19.2; Sn 13.3.
C40H50Cl2N12Sn. Calculated, %: C 54.0; H 5.6; Cl
8.5; N 18.9; Sn 13.0.
29,31-Dichlorotin-5,19-diphenyl-2,4,5,7,16,18,19,
21,29,30,31,32-dodecaazaheptacyclo[20.6.1.13,6.
1
8,15.117,20.09,14.023,28]dotriaconta-1,3,6(32),7,9,11,
29,31-Dichlorotitanium-5,19-didecyl-2,4,5,7,16,
18,19,21,29,30,31,32-dodecaazaheptacyclo[20.6.1.
13,6.18,15.117,20.09,14.023,28]dotriaconta-1,3,6(32),7,9,
11,13,15,17,20(30),21,23,25,27-tetradecaene (IX),
yield 44%, does not melt up to 300 C. Brown sub-
stance; moderately soluble in hot chloroform, readily
soluble in DMF, and insoluble in acetone and water.
Electronic absorption spectrum, max, nm: 280, 360
13,15,17,20(30),21,23,25,27-tetradecaene (V), yield
68%, does not melt up to 450 C. Brown substance,
sparingly soluble in DMF and pyridine and insoluble
in other organic solvents. Electronic absorption spec-
1
trum, max, nm: 352, 371, 394. IR spectrum, , cm :
1664, 1580, 1596, 1500, 1408, 1304, 1100, 1016, 762,
616. Found, %: S 56.0; H 3.9; Cl 4.3; N 27.7; Sn 8.1.
C32H20Cl2N12Sn. Calculated, %: C 50.4; H 2.6; Cl 9.4;
N 22.0; Sn 15.6.
1
(4.54), 380 (4.31), 450 (3.94). IR spectrum, , cm :
2920, 2856, 1580, 1511, 1470, 1376, 1310, 1100, 888,
762, 706. Found, %: S 59.0; H 5.3; Cl 8.1; N 6.2; Ti
6.4. C40H50Cl2N12Ti. Calculated, %: C 58.8; H 6.1;
Cl 8.5; N 20.6; Ti 6.0.
29,31-Dichlorotitanium-2,4,5,7,16,18,19,21,29,
30,31,32-dodecaazaheptacyclo[20.6.1.13,6.18,15.-
1
17,20.09,14.023,28]dotriaconta-1,3,6(32),7,9,11,13,15,
17,20(30),21,23,25,27-tetradecaene (VII), yield 81%,
does not melt up to 450 C. Brown substance, sparing-
ly soluble in DMF and pyridine and insoluble in other
soluble. Electronic absorption spectrum, max, nm:
REFERENCES
1. US Patent 2765308, Ref. Zh. Khim., 1959, no. 12,
43365 P.
1
332, 352, 367. IR spectrum, , cm : 1648, 1560,
2. Pellizarri, G., Zbl., 1886, vol. 55, p. 435.
3. Diaz-Garcia, M.A., Ledoux, I., Fernandoz-Lazaro, L.,
Sastre, A., Torres, T., Aggullo-Lopez, F.A., and Zyss, J.,
J. Phys. Chem., 1994, vol. 98, no. 17, p. 4495.
4. Bellamy, L.J., Advances in Infra-red Group Fre-
quencies, London: Methuen, 1966.
1364, 1304, 1184, 1100, 1044, 764, 688. Found, %:
C 54.2; H 3.0; Cl 4.6; N 36.4; Ti 1.8. C20H10Cl2N12Ti.
Calculated, %: C 44.7; H 1.9; Cl 13.2; N 31.3; Ti 8.9.
29,31-Dichlorotitanium-5,19-diphenyl-2,4,5,7,16,
18,19,21,29,30,31,32-dodecaazaheptacyclo[20.6.1.
13,6.18,15.117,20.09,14.023,28]dotriaconta-1,3,6(32),7,9,
5. Elvidge, J.A. and Golden, J.H., J. Chem. Soc., 1957,
no. 5, p. 700.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003