Synthesis of polynuclear nonfused azoles

Article abstract of DOI:10.1023/B:RUJO.0000019746.10504.f3

Polynuclear blocks consisting of nonfused heterocycles of the azole series, connected through methylene bridges, were synthesized by successive addition of azole units via cycloaddition of organic azides to the triple bond of N-(2-propynyl)azoles, as well

Full text of DOI:10.1023/B:RUJO.0000019746.10504.f3

Russian Journal of Organic Chemistry, Vol. 39, No. 12, 2003, pp. 1792 1796. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 12, 2003,
pp. 1863 1867.
Original Russian Text Copyright
2003 by Verkhozina, Kizhnyaev, Vereshchagin, Rokhin, Smirnov.
Synthesis of Polynuclear Nonfused Azoles
O. N. Verkhozina, V. N. Kizhnyaev, L. I. Vereshchagin,
A. V. Rokhin, and A. I. Smirnov
Institute of Petrochemical and Coal-Chemical Synthesis, Irkutsk State University,
ul. Lermontova 126, P.O. Box 4020, Irkutsk, 664033 Russia
e-mail: kizhnyaev@chem.isu.ru
Received October 30, 2002
Abstract Polynuclear blocks consisting of nonfused heterocycles of the azole series, connected through
methylene bridges, were synthesized by successive addition of azole units via cycloaddition of organic azides
to the triple bond of N-(2-propynyl)azoles, as well as via reaction of azide ion at the cyano group of cyano-
methylazoles. Initial N-(2-propynyl)azoles were prepared by reaction of 2-propynyl bromide with 1,2,3-tri-
azoles, benzotriazole, and tetrazoles; cyanomethylazoles were obtained by alkylation of azoles with chloro-
acetonitrile. An analogous scheme was used to add heterocyclic units to 2-phenyl-1,2,3-triazole-4-carbonitrile.
In this case, the first two heterocyclic units are linked through the ring carbon atom.
The chemistry of polynuclear systems has been
reviewed in [1] in sufficient detail. We previously
demonstrated [2] the possibility of synthesizing non-
fused polynuclear triazole- and tetrazole-containing
systems. In continuation of these studies, in the
present work we examined a version of synthesis of
nonfused polynuclear blocks consisting of hetero-
cyclic units of the azole series, which are linked
through methylene bridges. The procedure is based on
alkylation of azoles with 2-propynyl bromide or
chloroacetonitrile, followed by cycloaddition of
organic or inorganic azides to the triple bond of the
alkylation product. As a result, an additional triazole
or tetrazole ring is built up.
For this purpose, a number of N-(2-propynyl)- and
N-cyanomethylazoles were synthesized. As a rule,
the alkylation was performed with preliminarily pre-
pared potassium or sodium salts of azoles. Despite
some similarity of the alkylation processes, the reac-
tions with different azoles required different condi-
tions. 4-Nitro-N-(2-propynyl)-1,2,3-triazole (Ia) was
obtained from 2-propynyl bromide and 4-nitro-1,2,3-
triazole (IIa) potassium salt. By contrast, the alkyla-
tion of 5-phenyltetrazole (IIb) and benzotriazole (IIc)
with 2-propynyl bromide was more successful than
the corresponding triethylammonium salts were used.
The reaction gives a mixture of isomeric products. In
some cases, we succeeded in isolating particular
isomers by fractional crystallization or by column
chromatography on aluminum oxide.
Unsuccessful attempts to effect cyanomethylation
of unsubstituted tetrazole and 5-phenyltetrazole (IIb)
with chloroacetonitrile were reported previously [3].
However, by reaction of ammonium salts of azoles
IIb, IIc, and III with chloroacetonitrile we obtained
mixtures of isomeric cyanomethylazoles IVa, IVb,
and V in satisfactory yields (Scheme 1). In some
cases, the fraction of one (minor) isomer was so small
that it was lost during the isolation procedure. Never-
theless, some individual isomers were isolated by
fractional crystallization or column chromatography.
1
The H NMR spectra of 2-propynylazoles Ia Ic
contain signals at 2.6 3.3 ppm from the terminal
acetylenic proton. In the region 8 9 ppm we ob-
served two signals from protons of the triazole ring
in isomer Ia. According to the data of [4], the signal
from the triazole ring proton of the 1,4-isomer is
located in a weaker field than that of the correspond-
ing 1,5-isomer. The chemical shifts of the methylene
protons in both propynyl- and cyanomethylazoles
range from 5.5 to 6.5 ppm; these protons appear as
two signals from isomeric azoles.
4-Phenyl-1,2,3-triazol-1-ylacetonitrile (VI) was
synthesized by cycloaddition of azidoacetonitrile (VII)
to phenylacetylene. It should be noted that the IR
spectra of all prepared N-cyanomethylazoles, regard-
less of the position of the cyanomethyl group, lack
absorption band typical of the C N bond. The spec-
tral pattern does not change in going to nonpolar
1070-4280/03/3912-1792$25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS OF POLYNUCLEAR NONFUSED AZOLES
1793
Scheme 1.
I, II, XR2 = CH, R1 = NO2 (a); XR2 = N, R1 = Ph (b); X = C, R1R2 = benzo (c); IV, XR2 = N, R1 = Ph, n = 1 (a), X = C, R1R2 =
benzo, n = 1 (b); XR2 = N, R1 = Ph, n = 2 (c); IX, XR2 = CH, R1 = NO2, R3 = Ph (a); XR2 = CH, R1 = NO2, R3 = Bzl (b);
X = C, R1R2 = benzo, R3 = Bzl (c); XR2 = N, R1 = Ph, R3 = CH2CN (d); XR2 = N, R1 = Ph, R3 = Bzl (e); XIII, XR2 = N, R1 = Ph.
Scheme 2.
solvents, though the 13C NMR spectra contain the
corresponding carbon signal. On the other hand, the
IR spectra of compounds where the cyano group is
attached to carbon atom, e.g., as in 2-phenyl-1,2,3-tri-
azole-4-carbonitrile (VIII), or is separated from the
ring by two methylene groups, as in 3-(5-phenyltetra-
zol-2-yl)propionitrile (IVc), contain a strong absorp-
N-cyanomethyl fragment. In any case, this problem
requires additional study. Polynuclear blocks were
built up by successive addition of azole units via
cycloaddition of an organic azide to the triple bond
of N-(2-propynyl)azoles Ia Ic, as well as via reaction
of sodium azide at the C N bond of cyanoazoles
IV VI, VIII, and IXd (Schemes 1, 2). The reactions
of azides with propynylazoles were carried out in
boiling ethanol or toluene. The products were com-
pounds IXa IXe whose molecules consist of two
1
tion band at 2250 cm , which belongs to the cyano
group. Presumably, this is the result of prototropic
rearrangement like CH2 C N
CH C NH in the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

1794
VERKHOZINA et al.
heterorings bridged by a methylene group. Depending
on the initial propynylazole, structures containing two
triazole rings (compounds IXa IXc) and two different
heterocycles (III, Xa, XI) were obtained. The addition
of 5-azidomethyltetrazole (XII) to phenylacetylene
afforded 5-(4-phenyl-1,2,3-triazol-1-ylmethyl)tetrazole
(XI). Propynylazole Ib reacted with azidoacetonitrile
(VII) to give 2-[4-(5-phenyltetrazol-2-ylmethyl)-1,2,3-
triazol-1-yl]acetonitrile (IXd). The presence in the
latter of a cyanomethyl group makes it possible to add
new azole rings. On the other hand, the reaction of
propynylazoles with aromatic azides is a dead end
from the veiwpoint of further addition of heterocyclic
units. In this case, only bicyclic compounds IXa IXc
and IXe were formed. The products contain no NH
moiety; therefore, they cannot be brought into further
alkylation. The reaction of sodium or ammonium
azide with cyanoazoles IV VI, VIII, and IXd leads
to formation of new heterocycles possessing a proton
at the ring nitrogen atom. These products are capable
of undergoing alkylation, and hence one more hetero-
cyclic unit can be attached to the existing polynuclear
block. As a result, we obtained structures XIII and
XIV which include a sequence of three heterocycles.
reduced pressure, and the residue was recrystallized.
By fractional crystallization from ethanol we isolated
two isomers in an overall yield of 4.2 g (63%). Light
yellow crystals, isomer ratio 1:1. 4-Nitro isomer:
mp 110 111 C (from EtOH); 5-nitro isomer: mp 51 C
(from EtOH). H NMR spectrum, , ppm: 8.5 s (1H,
CH, 4-nitro isomer), 9.1 s (1H, CH, 5-nitro isomer),
1
5.5 s (2H, CH2), 3.3 s (1H, CH). IR spectrum,
,
1
cm : 3260 (C H); 2100 (C C); 1560, 820 (NO2).
Found, %: C 40.12; H 2.50; N 36.75. C5H4N4O2.
Calculated, %: C 39.5; H 2.63; N 36.8.
5-Phenyl-1(2)-(2-propynyl)tetrazole (Ib). A solu-
tion of 10.2 g (0.07 mol) of tetrazole IIb and 7.6 g
(0.075 mol) of triethylamine in 20 ml of acetone
was stirred for 30 min at room temperature, 8.9 g
(0.075 mol) of 2-propynyl bromide in 7 ml of acetone
was added, and the mixture was stirred for 5 7 h at
20 25 C. The precipitate was filtered off, the solvent
was distilled off from the filtrate under reduced pres-
sure, and the residue was distilled in a vacuum.
A fraction with bp 135 140 C (1 mm) was collected,
1
9.8 g (76%). According to the H NMR data, it con-
tained 53% of 5-phenyl-1-(2-propynyl)tetrazole and
47% of 5-phenyl-2-(2-propynyl)tetrazole. By column
chromatography we isolated 2-(2-propynyl) isomer Ib
Initial azidoacetonitrile (VII) was synthesized from
chloroacetonitrile and sodium azide under conditions
of phase-transfer catalysis (in the presence of benzyl-
triethylammonium chloride). Compound VII is
a highly inflammable substance which requires careful
handling. Azole XII was prepared from nitrile VII
and sodium azide.
1
with mp 45 47 C (from EtOH). H NMR spectrum,
, ppm: 5.36 s (2H, CH2), 2.67 s (1H, CH), 7.6 8.1 m
(5H, Harom). Found, %: C 65.13; H 4.24; N 30.40.
C10H8N4. Calculated, %: C 65.22; H 4.35; N 30.43.
Following an analogous procedure, oily 1-(2-pro-
pynyl)benzotriazole (Ic) was synthesized from 5.95 g
(0.05 mol) of benzotriazole (IIc), 6.06 g (0.06 mol)
of triethylamine, and 7.4 g (0.06 mol) of 2-propynyl
bromide in 7 ml of benzene. Yield 4.8 g (61%).
1H NMR spectrum, , ppm: 2.7 s (1H, CH), 5.38 s
(2H, CH2), 6.2 7.4 m (4H, Harom).
EXPERIMENTAL
The IR spectra were recorded on a Specord M80
instrument from samples dispersed in mineral oil. The
1H and 13C NMR spectra were recorded on a Bruker
VXR-500S spectrometer at 500 and 125.6 MHz, re-
spectively from solutions in acetone-d6 or DMSO-d6.
The progress of reactions was monitored by TLC on
Silufol plates using ethyl acetate hexane (2:3) as
eluent; spots were detected under UV light or by treat-
ment with iodine vapor. Compounds IVc [3], IIa [5],
and IIb [2] were synthesized by known methods.
4(5)-Nitro-1-(2-propynyl)-1,2,3-triazole (Ia).
Potassium hydroxide, 2.5 g (0.044 mol), was added
to a solution of 5 g (0.044 mol) of triazole IIa in
20 ml of ethanol, the mixture was stirred until it
became homogeneous, and 5.24 g (0.044 mol) of
2-propynyl bromide was added. The mixture was
heated with stirring for 3 h under reflux and cooled,
the precipitate of potassium bromide was filtered off,
the solvent was distilled off from the filtrate under
1-Benzotriazolylacetonitrile (IVb). A mixture of
21.42 g (0.18 mol) of benzotriazole (IIc) and 20.2 g
(0.2 mol) of triethylamine in 10 ml of benzene was
stirred for 30 min, 15.1 g (0.2 mol) of chloroaceto-
nitrile in 3 ml of benzene was added, and the mixture
was heated for 5 7 h under reflux with stirring. The
mixture was cooled, the precipitate was filtered off,
the solvent was distilled off from the filtrate under
reduced pressure, and the residue was recrystallized.
We thus obtained a mixture of benzotriazole IVb
isomers at a ratio of 1:10, which were separated
by column chromatography on aluminum oxide of
activity grade II using ethyl acetate hexane (2:3)
as eluent. Yield of 1-benzotriazolylacetonitrile (IVb)
1
12.2 g (57%), mp 75 76 C (from EtOH). H NMR
spectrum, , ppm: 6.09 s (2H, CH2), 7.5 8.1 m (4H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

SYNTHESIS OF POLYNUCLEAR NONFUSED AZOLES
1795
H
arom). Found, %: C 60.54; H 3.75; N 35.29. C8H6N4.
N 28.76. C16H14N6. Calculated, %: C 66.21; H 4.83;
N 28.97.
Calculated, %: C 60.76; H 3.8; N 35.44.
5-Phenyl-2-tetrazolylacetonitrile (IVa) was syn-
thesized in a similar way using 7.3 g (0.05 mol) of
tetrazole IIb, 5 g (0.05 mol) of triethylamine in 30 ml
of acetone, and 3.8 g (0.05 mol) of chloroacetonitrile.
4-(5-Phenyltetrazol-2-ylmethyl)-1,2,3-triazol-1-
ylacetonitrile (IXd) was synthesized from 3.0 g
(0.016 mol) of tetrazole (Ib) and 1.5 g (0.018 mol)
of azidoacetonitrile (VII) in 5 ml of ethanol. Yield
2.5 g (59%), mp 105 C (from butyl acetate hexane,
1 : 1). 1H NMR spectrum, , ppm: 5.42 s (2H,
CH2CN), 5.84 s (2H, CH2N), 7.5 8.34 m (5H, Harom),
7.61 s (1H, CH in triazole). Found, %: C 54.12;
H 3.70; N 42.15. C12H10N8. Calculated, %: C 54.14;
H 3.76; N 42.11.
1
Yield 5.3 g (57%), mp 75 77 C. H NMR spectrum,
, ppm: 6.15 s (2H, CH2), 7.6 8.15 m (5H, Harom).
13C NMR spectrum, C, ppm: 166.54 (CH), 42.25
(CH2). Found, %: C 58.02; H 3.69; N 37.48. C9H7N5.
Calculated, %: C 58.38; H 3.78; N 37.84.
Azidoacetonitrile (VII). Sodium azide, 9.7 g
(0.15 mol), and benzyltriethylammonium chloride,
0.5 g, were slowly added with stirring at 20 25 C to
a dispersion of 10 g (0.13 mol) of chloroacetonitrile in
20 ml of water. The mixture was heated to 45 50 C,
stirred for 3 h, cooled, and extracted with ether
(3 30 ml). The extract was dried over CaCl2, the
solvent was distilled off, and the residue was distilled
in a vacuum. Yield 8.1 g (75%), bp 70 C (17 mm),
n2D5 = 1.4470.
2-(1-Benzyl-1,2,3-triazol-4-ylmethyl)-5-phenyl-
tetrazole (IXe) was prepared from 3.0 g (0.016 mol)
of tetrazole Ib and 2.4 g (0.018 mol) of benzyl azide
in 5 ml of ethanol. Yield 2.7 g (53%), mp 132 133 C
1
(from EtOH). H NMR spectrum, , ppm: 6.6 s (2H,
CH2N), 5.65 s (2H, CH2Ph), 7.58 7.7 m (5H, Harom
,
benzyl), 7.4 7.6 m (5H, Harom), 8.2 s (1H, CH in
triazole). Found, %: C 64.12; H 4.48; N 30.87.
C17H15N7. Calculated, %: C 64.35; H 4.73; N 30.91.
4-Nitro-1-(1-phenyl-1,2,3-triazol-4-ylmethyl)-
1,2,3-triazole (IXa). A solution of 0.3 g (3 mmol)
of N-(2-propynyl)triazole Ia and 0.48 g (4 mol) of
azidobenzene in 4 ml of toluene was heated for 5 h
under reflux. The solvent was distilled under reduced
pressure, and the residue was recrystallized. Yield
4-Phenyl-1,2,3-triazol-1-ylacetonitrile (VI) was
synthesized from 2.0 g (0.0196 mol) of phenylace-
tylene and 1.6 g (0.0196 mol) of azidoacetonitrile
1
(VII) in 10 ml of toluene. The H NMR spectrum
of the product contained signals from two isomers
at a ratio of 1:10. By fractional crystallization we
succeeded in isolating 4-phenyl-1,2,3-triazol-1-yl-
acetonitrile. Yield 1.5 g (42%), mp 69 71 C.
1H NMR spectrum, , ppm: 5.71 s (2H, CH2), 7.6
7.8 m (5H, Harom), 7.87 s (1H, CH in triazole). Found,
%: C 65.13; H 4.41; N 30.27. C10H8N4. Calculated,
%: C 65.22; H 4.35; N 30.43.
1
0.22 g (21%), mp 137 138 C (from EtOH). H NMR
spectrum, , ppm: 8.8 s (1H, CH in phenyltriazole),
9.5 s (1H, CH in nitrotriazole), 6.0 s (2H, CH2),
7.5 8 m (5H, Harom). Found, %: C 49.03; H 3.46;
N 35.8. C11H9N7O2. Calculated, %: C 48.7; H 3.32;
N 36.2.
Compounds IXb IXe and VI were synthesized in
1-(Tetrazol-5-ylmethyl)benzotriazole (Xb).
A suspension of 0.65 g (0.01 mol) of sodium azide in
10 ml of DMF was heated for 30 min at 100 105 C
under stirring. It was then cooled to 40 50 C, 1.1 g
(0.010 mol) of diethylamine hydrochloride was added,
the mixture was stirred for 30 min, 1.26 g (8 mmol)
of benzotriazole IVb was added, and the mixture was
stirred for 4 5 h at 110 115 C, cooled, and poured
into 50 ml of cold water. The aqueous solution was
washed with ether and acidified to pH 2 3 with dilute
hydrochloric acid. The precipitate was filtered off,
washed with cold water, and recrystallized. Yield
a similar way.
1-(1-Benzyl-1,2,3-triazol-4-ylmethyl)-4-nitro-
1,2,3-triazole (IXb) was obtained from 1.0 g
(7 mmol) of propynyltriazole Ia and 1.06 g (8 mmol)
of benzyl azide in 5 ml of toluene. Yield 1.05 g
1
(56%), mp 175 C (from EtOH). H NMR spectrum,
, ppm: 8.99 s (1H, CH in nitrotriazole), 8.19 s (1H,
CH in benzyltriazole), 5.9 s (2H, CH2N), 5.65 s (2H,
CH2Ph), 7.3 7.4 m (5H, Harom). Found, %: C 50.26;
H 3.9; N 34.05. C12H11N7O2. Calculated, %: C 50.53;
H 3.85; N 34.39.
1-(1-Benzyl-1,2,3-triazol-4-ylmethyl)benzotri-
azole (IXc) was obtained from 1.77 g (0.01 mol) of
propynylbenzotriazole Ic and 1.6 g (0.012 mol) of
benzyl azide in 15 ml of ethyl acetate. Yield 0.7 g
1
1.4 g (87%), mp 196 C (from EtOH). H NMR spec-
trum, , ppm: 6.45 s (2H, CH2), 7.5 7.6 m (4H,
Harom). Found, %: C 47.67; H 3.62; N 48.61. C8H7N7.
1
Calculated, %: C 47.76; H 3.48; N 48.76.
(21%), mp 158 160 C (from EtOH). H NMR spec-
Compounds III, Xa, Xc, XI (method a), and XIII
were synthesized in a similar way.
trum, , ppm: 5.6 s (2H, CH2Ph), 6.2 s (2H, CH2N),
7.2 7.4 m (5H, C6H5). Found, %: C 66.11; H 4.44;
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

1796
VERKHOZINA et al.
5-(2-Phenyl-1,2,3-triazol-4-yl)-2-(tetrazol-5-yl-
5-(2-Phenyl-1,2,3-triazol-4-yl)tetrazole (III) was
methyl)tetrazole (XIV). Triethylamine, 0.56 g
(5 mmol), was added with stirring to a solution of
1.07 g (5 mmol) of compound III in 6 ml of acetone;
after 30 min, 0.4 g (5 mmol) of chloroacetonitrile in
2 ml of acetone was added. The mixture was heated
for 2 days under reflux and cooled, the precipitate
was filtered off, and the filtrate was evaporated under
reduced pressure. A suspension of 0.195 g (3 mmol)
of sodium azide and 0.19 g (3 mmol) of ammonium
chloride in 5 ml of DMF was added to the residue
(0.7 g), and the mixture was stirred for 5 h at 110 C,
poured into 50 ml of cold water, washed with ether,
and acidified to pH 2 3 with dilute hydrochloric acid.
The precipitate was filtered off, washed with cold
water, and recrystallized. Yield 0.59 g (72%),
obtained from 1.09 g (6 mmol) of triazole VIII,
0.78 g (0.012 mol) of sodium azide, and 0.64 g
(0.012 mol) of ammonium chloride in 5 ml of DMF.
1
Yield 1.1 g (83%), mp 214 215 C (from EtOH). H
NMR spectrum, , ppm: 8.59 s (1H, CH in triazole),
7.5 8.1 m (5H, Harom). Found, %: C 50.57; H 3.13;
N 46.21. C9H7N7. Calculated, %: C 50.70; H 3.29;
N 46.01.
4-(5-Phenyltetrazol-2-ylmethyl)-1-(tetrazol-5-yl)-
1,2,3-triazole (XIII) was synthesized from 0.27 g
(4 mmol) of sodium azide, 0.46 g (4 mmol) of di-
ethylamine hydrochloride, and 0.98 g (4 mmol) of
compound IXd in 5 ml of DMF. Yield 0.91 g (79%),
mp 164 166 C (from EtOH). 1H NMR spectrum,
, ppm: 6.08 s (2H, CH2Ntriazole), 6.13 s (2H,
CH2Ntetrazole), 8.47 s (1H, CH in triazole), 7.6 8.1 m
(5H, Harom). Found, %: C 46.54; H 3.47; N 49.75.
C12H11N11. Calculated, %: C 46.60; H 3.56; N 49.84.
5-Phenyl-2-[2-(tetrazol-5-yl)ethyl]tetrazole (Xc)
was synthesized from 5 g (0.025 mol) of tetrazole
IVc, 2.44 g (0.038 mol) of sodium azide, and 4.2 g
(0.038 mol) of diethylamine hydrochloride in 20 ml
of DMF. Yield 3.2 g (49%), mp 143 144 C (from
EtOH). 1H NMR spectrum, , ppm: 5.27 t (2H,
CH2N), 3.85 t (2H, CH2C), 7.5 8.3 m (5H, Harom).
Found, %: C 49.67; H 4.02; N 46.12. C10H10N8.
Calculated, %: C 49.59; H 4.13; N 46.28.
1
mp 182 C (from EtOH). H NMR spectrum, , ppm:
6.54 s (2H, CH2), 8.5 s (1H, CH in triazole), 7.5
7.6 m (5H, Harom). Found, %: C 44.68; H 3.11;
N 52.25. C11H9N11. Calculated, %: C 44.75; H 3.05;
N 52.20.
5-Azidomethyltetrazole (XII). A solution of
1.96 g (0.024 mol) of azidoacetonitrile (VII) in
2 ml of DMF was added to a suspension of 1.95 g
(0.03 mol) of sodium azide and 3.3 g (0.03 mol) of
diethylamine hydrochloride in 10 ml of DMF, which
was prepared as described avobe. The mixture was
carefully heated (a sharp temperature rise with tarring
is possible). For this purpose, the mixture was main-
tained at 50 55 C over a period of 30 min using
a cold water bath. The cooling bath was removed, and
the mixture sharply warmed up to 105 110 C. It was
kept for 1 h at 100 C, cooled, washed with ether, and
acidified to pH 2 3 with dilute hydrochloric acid.
5-Phenyl-2-(tetrazol-5-ylmethyl)tetrazole (Xa)
was synthesized from 2.1 g (0.01 mol) of tetrazole
IVa, 0.78 g (0.012 mol) of sodium azide, and 1.3 g
(0.012 mol) of diethylamine hydrochloride in 10 ml
of DMF. Yield 1.92 g (79% ), mp 178 179 C (from
1
1
EtOH). H NMR spectrum, , ppm: 5.8 s (2H, CH2),
Yield 1.9 g (64%), mp 56 C (from EtOH). H NMR
spectrum, , ppm: 4.91 s (2H, CH2). 13C NMR spec-
trum, C, ppm: 44.9 (CH2), 157.5 (NCN). Found, %:
C 18.84; H 2.21; N 78.56. C2H3N7. Calculated, %:
C 19.2; H 2.4; N 78.4.
7.5 8.3 m (5H, Harom), 14 (1H, NH). Found, %:
C 47.15; H 3.41; N 49.07. C9H8N8. Calculated, %:
C 47.37; H 3.51; N 49.12.
4-Phenyl-1-(tetrazol-5-ylmethyl)-1,2,3-triazole
(XI). a. Compound XI was synthesized from 7.3 g
(0.039 mol) of triazole VI, 3.0 g (0.045 mol) of
sodium azide, and 5 g (0.045 mol) of diethylamine
hydrochloride in 25 ml of DMF. Yield 7.84 g (87%),
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1
mp 173 174 C (from EtOH). H NMR spectrum, ,
ppm: 6.05 s (2H, CH2), 7.8 s (1H, CH in triazole),
7.5 7.6 m (5H, Harom). Found, %: C 52.69; H 4.03;
N 43.11. C10H9N7. Calculated, %: C 52.86; H 3.96;
N 43.17.
b. A solution of 2.5 g (0.02 mol) of 5-azido-
methyltetrazole (XII) and 6.12 g (0.06 mol) of
phenylacetylene in 10 ml of ethanol was kept for
2 days at 80 C. The solvent was distilled off under
reduced pressure, and the residue was recrystallized.
Yield 2.3 g (50.6%), mp 173 174 C (from EtOH).
5. Eagles, T.E., Khan, M.A., and Lynch, B.M., Org.
Prep. Proced. Int., 1970, p. 117.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003