Synthesis of new 1,2,3-triazolo[1,5-a]quinazolinones

Article abstract of DOI:10.1002/jhet.321

(Chemical Equation Presented) Synthesis of novel 3-substituted-1,2,3- triazolo[1,5-a]quinazolinones in high yields was performed via anionic hetero-domino reaction of appropriate substituted 2-azidobenzoates prepared from isatines and acetonitriles activated by 1,3-thiazole, 1,3-benzothiazole, 1,3,4-oxadiazole, and 1,2,4-oxadiazole rings. It was shown that acetonitriles exhibited high reactivity and were convenient methylenic compounds for such reactions providing rapid structural variation.

Full text of DOI:10.1002/jhet.321

March 2010
Synthesis of New 1,2,3-Triazolo[1,5-a]quinazolinones
415
Nazariy T. Pokhodylo* and Vasyl S. Matiychuk
Department of Organic Chemistry, Ivan Franko National University of Lviv, Lviv 79005, Ukraine
*E-mail: pokhodylo@gmail.com
Received August 18, 2009
DOI 10.1002/jhet.321
Published online 4 March 2010 in Wiley InterScience (www.interscience.wiley.com).
Synthesis of novel 3-substituted-1,2,3-triazolo[1,5-a]quinazolinones in high yields was performed via
anionic hetero-domino reaction of appropriate substituted 2-azidobenzoates prepared from isatines and
acetonitriles activated by 1,3-thiazole, 1,3-benzothiazole, 1,3,4-oxadiazole, and 1,2,4-oxadiazole rings. It
was shown that acetonitriles exhibited high reactivity and were convenient methylenic compounds for
such reactions providing rapid structural variation.
J. Heterocyclic Chem., 47, 415 (2010).
INTRODUCTION
triles activated by (het)aryl substituents is a perspective
synthetic approach. The exclusive examples of the reac-
tion of arylazides with (5-methylisoxazol-3-yl)acetoni-
trile [1] and phenylacetonitrile [5] have been described.
In addition, introduction of new heterocyclic fragments
to the C-3 position may extend the spectrum of biologi-
cal activity of such compounds.
1,2,3-Triazolo[1,5-a]quinazolines are an important
class of heterocycles, which have been the subject of
great interest because of their biological activities. For
instance, in the works of Jones and coworkers [1] the
synthesis and evaluation of the biological affinity of a
large number of C-5 substituted 1,2,3-triazolo[1,5-a]qui-
nazolines are reported. It was shown that compounds of
the current class were new ligands for GABAA receptors
and potentially pharmaceutically acceptable for treat-
ment of Alzheimer’s disease. Moreover, Biagi et al [2].
found the activity of some 3-ethoxycarbonyl- or 3-phe-
nyl-substituted 1,2,3-triazolo[1,5-a]quinazolines towards
benzodiazepine, A1 and A2A adenosine receptors. The
promising biological activity and the unique structure of
these families make them attractive synthetic targets.
Furthermore, in the article [1b,c] it was underlined that
1,2,3-triazolo[1,5-a]quinazolines were first synthesized
in 1966 [3], however, this class of compounds has sub-
sequently received little attention [1,4]. Their syntheses,
using readily available raw materials with short and fac-
ile routes, continue to be challenging endeavors.
Recently, we have reported [6] the synthesis of 1H-
1,2,3-triazole derivatives by cyclization of arylazides
with (1,3-benzothiazol-2-yl)/(4-aryl-1,3-thiazol-2-yl)ace-
tonitriles. It was shown that (1,3-benzothiazol-2-yl)ace-
tonitrile undergoes an anionic domino reaction with
methyl 2-azidobenzoate or 2-azidobenzonitrile to give
[1,2,3]triazolo[1,5-a]quinazoline derivatives [6a]. Fur-
thermore, it was found that acetonitrile possesses high
reactivity, as an active methylenic compound for such
reactions, for construction of [1,2,3]triazolo[1,5-a]pyri-
midines system [6b] with heterocyclic substituents.
RESULTS AND DISCUSSION
In the current work we present the results of a study
of hetarylacetonitriles in the reaction with substituted
methyl 2-azidobenzoates. Starting hetarylacetonitriles
were obtained by several synthetic procedures. First the
required precursors 1a–d, 2 were synthesized in moder-
ate to good yields according to the literature procedure
[7]. Then we developed a synthetic protocol for prepara-
tion of acetonitriles activated by 1,3,4-oxadiazole and
1,2,4-oxadiazole. Compounds containing the oxadiazole
It is noteworthy that more attention was drawn to syn-
thetic strategies, which have been developed to allow
easy variation of the C-5 position of triazoloquinazoli-
none [1]. On the contrary, diversification of other posi-
tions has been discussed insufficiently. 2-Azidobenzoic
acid and cyanoacetic acid derivatives were mostly used
for construction of triazoloquinazolinone framework [4].
At the same time, the reaction of azides with acetoni-
C
V
2010 HeteroCorporation

416
N. T. Pokhodylo and V. S. Matiychuk
Vol 47
Scheme 1
ring have been widely studied recently since they ex-
hibit biological activity [8] and possess some attractive
photophysical properties [9]. Initial (5-aryl-1,3,4-oxadia-
zol-2-yl)acetonitriles 5a–d were synthesized by one-pot
cyclization of diacylhydrazines prepared in situ by acy-
lation of cyanoacetic acid hydrazide 4 with the corre-
sponding substituted benzoyl chlorides 3a–d, via modifi-
cation of known procedures [10]. (5-Phenyl-1,2,4-oxa-
diazol-2-yl)acetonitrile 8 was prepared by heating phe-
nylamide oxime 6 with cyanoacetyl chloride 7 in anhy-
drous DMF in the presence of pyridine (Scheme 1).
The obtained hetarylacetonitriles 1a, 5a, 8 were
examined in the reaction with phenylazide in sodium
methoxide solution at room temperature. These condi-
tions allowed to avoid possible Dimroth rearrangement
[11] occurring when 5-aminotriazoles were heated in a
strong base medium. As a result, new triazole deriva-
tives 9a–c were isolated in high yields and no by-prod-
ucts were formed. The corresponding 1,2,3-triazoles 9a–
c precipitated in good yields from the reaction medium.
In an effort to diversify the azido component, the
method of 2-azidobenzoate synthesis from isatines, pre-
pared from the corresponding anilines 10 by the Sand-
meyer method [12], was used. By the reaction of ani-
lines 10a,b with chloral hydrate and hydroxylamine
hydrochloride in aqueous sodium sulfate, isonitrosoace-
tanilides were formed. The obtained isonitrosoacetani-
lides were treated with concentrated sulfuric acid and
yielded isatines 11b,c [12]. Compounds 11d,e were pre-
pared from isatine 11a by the reaction with brome [13]
or chlorine generated in situ from HCl and hydrogen
peroxide [14] correspondingly. Isatines 11a–e were oxi-
dated with alkaline hydrogen peroxide to form substi-
tuted 2-aminobenzoic acids [15], which were converted
into esters 12a–e by the following reaction with metha-
nol in the presence of sulphuric acid [16]. It is of note
that compound 12d can be prepared from commercially
available methyl anthranilate 12a via chlorization by the
use of calcium hypochlorite [17]. Finally, compound 12f
was prepared by subsequent nitration and reduction of
dimethyl benzene-1,4-dicarboxylate. Anthranilates 12a–f
were readily converted into 2-azidobenzoic acid esters
13a–f by diazotisation and displacement with sodium
azide (Scheme 2).
To obtain [1,2,3]triazolo[1,5-a]quinazolines, substi-
tuted methyl 2-azidobenzoates were allowed to react
with acetonitriles 1, 2, 5, 8. The reaction was carried
out using 1 equiv. of sodium methoxylate at room tem-
perature. It was found that the reaction exhibited an
appreciable exothermal effect and was completed within
1–2 min. In general, the reaction product was formed
immediately after mixing the reagents and precipitated
from the reaction medium. The polycyclic compounds
14a–o were isolated in excellent yields (84–98%) (Table
1). It is noteworthy that esters 13 used in such a reaction
are more convenient instead of 2-azidobenzoic acids. In
the reaction of 2-azidobenzoic acids, yields were lower
and the reaction required more time. Moreover, in some
cases the reaction mixture must be heated. For instance,
in the work [1a] triazoloquinazolinone framework was
prepared by treatment of an equimolar mixture of 2-azi-
dobenzoic acid with isoxazole acetonitrile in the pres-
ence of sodium ethoxide at 80ꢀC for 5 h. Bertelli et al.
[2b] reported that 2-carboxy-4/5-chloro-phenylazide
reacted with ethyl cyanoacetate in absolute ethanol in
the presence of two equivalents of sodium ethoxide at
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Scheme 2
Table 1
Physical and analytical data of compounds 14a–o.
Analysis %
Calcd./Found
Mp
(ꢀC)
Yield, IR, mmax
MS (CI):
[MþHþ]
Molecular
formula
a
Compound
R
C-3 substituent
%
(cmꢁ1 b
)
C
H
N
14a
H
4-methyl-1,3-thiazol-2-yl
>300
>300
>300
>300
90
1679
1683
1677
1680
284
362, 364
346
C13H9N5OS
55.11 3.20 24.72
55.28 3.02 24.93
14b
14c
14d
7-Br
H
–
92
96
95
C13H8BrN5OS 43.11 2.23 19.34
43.28 2.01 19.17
C18H11N5OS
4-phenyl-1,3-thiazol-2-yl
62.60 3.21 20.28
62.44 3.34 20.06
63.49 3.65 19.49
–
4-(4-methylphenyl)-1,3-
thiazol-2-yl
360
C19H13N5OS
63.36 3.37 19.66
18H10ClN5OS 56.92 2.65 18.44
14e
–
4-(4-chlorophenyl)-1,3-
thiazol-2-yl
>300
98
1671
380
C
57.08 2.41 18.38
14f
14g
14h
14i
7-Me
7-F
1,3-benzothiazol-2-yl
>300
>300
>300
>300
98
94
97
94
1674
1690
1678
334
338
354
378
C
17H11N5OS
61.25 3.33 21.01
61.15 3.19 21.77
56.97 2.39 20.76
56.84 2.30 20.52
–
–
–
C16H8FN5OS
7-Cl
C16H8ClN5OS 54.32 2.28 19.80
54.26 2.46 19.99
C18H11N5O3S
8-CO2Me
1724,
1680,
1276
57.29 2.94 18.56
57.19 2.78 18.44
61.82 3.05 25.44
61.73 2.92 25.35
62.79 3.51 24.41
14j
H
–
5-phenyl-1,3,4-oxadiazol-2-yl >300
87
84
1688
1672
330
345
C17H10N6O2
C18H12N6O2
14k
5-(4-methylphenyl)-1,3,4-
oxadiazol-2-yl
>300
>300
>300
62.87 3.39 24.28
60.00 3.36 23.32
14l
–
–
5-(4-methoxyphenyl)-1,3,4-
oxadiazol-2-yl
93
93
1684
1677
361
C18H12N6O3
60.15 3.15 23.41
49.90 2.22 20.54
14m
5-(4-bromophenyl)-1,3,4-
oxadiazol-2-yl
409, 411
C17H9BrN6O2
49.77 2.13 20.31
61.82 3.05 25.44
61.97 2.93 25.36
55.98 2.49 23.04
55.87 2.40 23.19
14n
14o
3-phenyl-1,2,4-oxadiazol-5-yl >300
– >300
90
97
1680
1686
331
365
C
17H10N6O2
7-Cl
C17H9ClN6O2
a Isolated yields.
b All compounds 14 showed a similar stretching peaks of associated NH (OH) groups with mmax approximately 3400 cmꢁ1
.

418
N. T. Pokhodylo and V. S. Matiychuk
Vol 47
Table 2
1H NMR spectra of products 14a–o (J, Hz) 500 MHz.
[1,2,3]triazolo[1,5-a]quinazoline protons
Compound Me
H-6
H-9
H-7
H-8
(Het)Aryl fragment
14a
2.42
2.41
8.18 (t, J 9.2)
8.15 (d, J 7.0)
8.22 (t, J 7.6)
7.78 (t, J 7.1)
–
7.75 (t, J 7.6)
7.52 (t, J 7.1)
7.94 (d, J 7.0)
7.49 (t, J 7.6)
7.08 (s, 1H)
7.09 (s, 1H)
14b
8.24 (s)
14ca
7.29 (t, J 7.4, 1H), 7.42 (t, J 7.6, 2H),
7.70 (s, 1H), 8.04 (d, J 7.2, 2H)
7.22 (d, J 8.0, 2H, H-3,5), 7.70 (s, 1H,
HTz), 7.86 (d, J 8.0, 2H, H-2,6)
14d
14e
14f
2.39
2.42
8.20–8.25 (m)
8.24 (t, J 8.0)
7.74 (t, J 7.4)
7.77 (t, J 7.6)
–
7.51 (t, J 7.6)
7.50 (t, J 7.6)
7.43 (d, J 8.8, 2H, H-3,5), 7.86 (s, 1H,
HTz), 8.02 (d, J 8.8, 2H, H-2,6)
7.89 (d, J 2.0)
7.87 (d, J 8.4)
7.62 (dd, J 8.4, 2.0), 7.32 (t, J 7.0, 1H, H-6), 7.44 (t, J 7.4,
1H, H-5), 7.99 (d, J 7.8, 1H, H-7),
8.05 (d, J 7.4, 1H, H-8)
14g
14h
14i
8.29 (dd, J 8.4, 3.9) 7.85 (dd, J 8.9, 1.7),
–
7.70 (dt, J 8.6, 2.5) 7.34 (t, J 7.0, 1H, H-6), 7.47 (t, J 7.4,
1H, H-5), 7.98 (d, J 8.0, 1H, H-7),
8.06 (d, J 7.4, 1H, H-8)
8.12 (s)
8.25 (d, J 8.4)
8.73 (s)
–
7.85 (d, J 8.7)
7.31-7.38 (m, 1H, H-6), 7.47 (t, J 7.1,
1H, H-5), 7.97 (d, J 7.2, 1H, H-7),
8.07 (d, J 7.0, 1H, H-8)
3.97
8.30 (d, J 7.6)
8.08 (d, J 7.6)
–
7.35 (t, J 7.1, 1H, H-6), 7.48 (t, J 6.7,
1H, H-5), 7.98 (d, J 7.4, 1H, H-7),
8.08 (d, J 7.3, 1H, H-8)
14ja
14k
14l
14m
14n
14o
8.35 (d, J 8.0)
8.34 (d, J 8.00)
8.37 (d, J 8.0)
8.22 (d, J 8.1)
8.34 (d, J 8.0)
8.14 (s)
8.26 (d, J 7.9)
8.28 (d, J 7.7)
8.25 (d, J 8.0)
8.09 (d, J 8.0)
8.27 (d, J 7.9)
8.27 (d, J 8.7)
7.94 (t, J 7.1)
7.94 (t, J 7.9)
7.97 (t, J 7.9)
7.80 (t, J 7.6)
7.97 (t, J 7.9)
–
7.65 (t, J 7.6)
7.67 (t, J 7.7)
7.70 (t, J 7.9)
7.56 (t, J 7.6)
7.64 (t, J 8.0)
7.83 (d, J 8.7)
7.57-7.62 (m, 3H), 8.19 (m, 2H)
7.40 (d, J 7.9, 2H), 8.04 (d, J 7.9, 2H)
7.12 (d, J 8.2, 2H), 8.09 (d, J 8.2, 2H)
7.86 (d, J 7.9, 2H), 8.03 (d, J 8.1, 2H)
7.53-7.59 (m, 3H), 8.17 (m, 2H)
7.55-7.62 (m, 3H), 8.19 (m, 2H)
2.47
3.88
a Recorded at 400 MHz.
room temperature, affording 1-(4- or 5-chloro-2-car-
boxy-phenyl)-4-ethoxycarbonyl-5-amino-1H-1,2,3-triazole
intermediates, and the corresponding triazoloquinazoli-
nones were formed after acidification of the alkaline so-
lution. The reaction of such azides with phenylacetoni-
trile required refluxing of the reaction mixture but it pro-
ceeded in the same manner [2b]. Obviously, replacement
of the carboxylic group into the carboxylate one
increased the rate of the reaction of the amino group in
the intermediate triazole A, which was formed at the first
stage of the reaction. The carboxylate function provided
the formation of the pyrimidine ring without any addi-
tional procedures.
a possibility of substituent variation in triazoloquinazo-
line framework. Moreover, new active methylenic com-
pounds were used for anionic domino reactions leading
to formation of triazoloquinazolines.
EXPERIMENTAL
All melting points were determined in capillary tubes in a
Thiele apparatus and are uncorrected. 1H NMR spectra were
recorded on a Varian Mercury 400 instrument (400 MHz for
1
1H) and Bruker 500 (500 MHz for H, 125 MHz for 13C) with
The structures of all new compounds were confirmed
by analytical and spectroscopic data (Tables 1 and 2,
Fig. 1). In the 1H NMR spectra of compounds 14a–o
there were characteristic shift values for the H6, H7,
H8, and H9 protons typical for the 1,2,3-triazolo[1,5-
a]quinazoline system (Table 2). Furthermore, aryloxa-
diazolyl fragments were easily identified via low-field
shifted aromatic protons ortho to the oxadiazole rings,
usually found at 8.03–8.19 ppm.
In conclusion, in the current work we described effi-
cient and economic routes to 1,2,3-triazolo[1,5-a]quina-
zolines from cheap abundant starting materials and with
Figure 1. 13C NMR chemical shifts of compounds 9a, 14b, 14g.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

March 2010
Synthesis of New 1,2,3-Triazolo[1,5-a]quinazolinones
419
TMS or deuterated solvent as an internal reference. Mass spec-
tra were run using Agilent 1100 series LC/MSD with an API-
ES/APCI ionization mode. IR spectra were recorded on a Spe-
cord 80M spectrophotometer in KBr pellets. The evolution of
the reactions and purity of the synthesized compounds were
monitored chromatographically on Silufol UV-254 plates. 13C
NMR spectra of product 9b,c and 14a, c–f, h–o are not
reported due to their very low solubility.
(5-Aryl-1,3,4-oxadiazol-2-yl)acetonitriles 5a–d (general
procedure). The solution of 21 mmol of substituted benzoyl
chloride 3 in 10 mL of anhydrous dioxane was added under
continuous stirring to the solution of 2.1 g (21 mmol) of 2-
cyanoacetohydrazide and 2.9 mL (21 mmol) of triethylamine
in 30 mL of anhydrous dioxane. The mixture was stirred for
0.5 h at room temperature and 10 mL of POCl3 was added.
The mixture was heated for 3 h at 80ꢀC, cooled to room tem-
perature and poured onto ice. The precipitate was filtered off
and dried in air. The crude product was purified by flash chro-
matography followed by recrystallization from ethanol.
suspension was filtered and the solid product was washed with
water and methanol to give the corresponding 1H-1,2,3-triazol-
5-amines 9a–c and [1,2,3]triazolo[1,5-a]quinazolin-5(4H)-ones
14a–o.
4-(4-Methyl-1,3-thiazol-2-yl)-1-phenyl-1H-1,2,3-triazol-5-
amine (9a). Yield: 2.2 g (87%); as white crystals; mp 168–
169ꢀC (DMF–EtOH); 1H NMR (DMSO-d6 400MHz): d 2.45
(s, 3H, Me), 6.47 (s, 2H, NH2), 6.95 (s, 1H, thiazole), 7.52 (t,
3
3J ¼ 7.1 Hz, 1H, HPh-4), 7.61 (t, J ¼ 7.2 Hz, 2H, HPh-3,5),
3
7.66 (d, J ¼ 7.2 Hz, 2H, HPh-2,6); MS: (CI) m/z (%) ¼ 258
(100%) [MþHþ]. Anal. Calcd. for C12H11N5S (257.31): C
56.01; H 4.31; N 27.22. Found: C 56.19; H 4.24; N 27.07.
1-Phenyl-4-(5-phenyl-1,3,4-oxadiazol-2-yl)-1H-1,2,3-triazol-
5-amine (9b). Yield: 2.8 g (93%); as white crystals; mp 214–
215ꢀC (DMF–EtOH); 1H NMR (DMSO-d6 400MHz): d 6.58
(s, 2H, NH2), 7.50–7.72(m, 8H, arom.), 8.11–8.16 (m, 2H,
HPh-2,6); MS: (CI) m/z (%) ¼ 305 (100%) [MþHþ]. Anal.
Calcd. for C16H12N6O (304.31): C 63.15; H 3.97; N 27.62.
Found: C 63.01; H 3.74; N 27.48.
1-Phenyl-4-(3-phenyl-1,2,4-oxadiazol-5-yl)-1H-1,2,3-triazol-
5-amine (9c). Yield: 2.7 g (90%); as white crystals; mp 230–
231ꢀC (DMF–EtOH); 1H NMR (DMSO-d6 400MHz): d 6.80
(s, 2H, NH2), 7.52–7.59 (m, 5H, arom.), 7.63–7.66 (m, 3H,
arom.), 8.16–8.18 (m, 2H, HPh-2,6); MS: (CI) m/z (%) ¼ 305
(100%) [MþHþ]. Anal. Calcd. for C16H12N6O (304.31): C
63.15; H 3.97; N 27.62. Found: C 63.06; H 3.88; N 27.64.
(3-Phenyl-1,2,4-oxadiazol-5-yl)acetonitrile 8. Cyanoacetyl
chloride 6 (0.52 g, 5 mmol) was added to the solution of 5
mmol of N’-hydroxybenzenecarboximidamide 7 in 2 mL of
pyridine. The mixture was kept for 0.5 h and 5 mL of DMF
was added. The mixture was heated for 3 h at 80ꢀC, cooled to
room temperature and mixed with 30 mL of water. The precip-
itate was filtered off, washed with water on a filter, recrystal-
lized from alcohol and dried in air.
Azides 13a–f preparation. The solution of sodium nitrite
(7.1 g, 0.1 mol) in water (30 mL) was added dropwise to a
stirred solution of substituted anthranilic esters (0.1 mol) in 40
mL of concentrated HCl and 20 mL of water keeping the tem-
perature below 5ꢀC. After that the mixture was stirred for 10
min and rapidly filtered. To the obtained solution NaN3 (6.5 g,
0.1 mol) in water (125 mL) was added dropwise. The mixture
was stirred for 15 min at 0ꢀC and then for 30 min at room
temperature. Azides 13a,b were extracted by diethyl ether (3
ꢂ 10 mL). Ether was evaporated in vacuo. Azides 13c–f were
filtered and washed with water twice. Azides were used with-
out subsequent cleaning: methyl 2-azidobenzoate 13a, yield
11.5 g, 65%; dark red oil; MS: (CI) m/z (%) ¼ 178 (100%)
[MþHþ]; methyl 2-azido-5-methylbenzoate 13b, yield 13.7
g, 72%; dark red oil; MS: (CI) m/z (%)¼ 192 (100%)
[MþHþ]; methyl 2-azido-5-fluorobenzoate 13c, yield 13.8 g,
71%; pink solid, mp: 28–29ꢀC; MS: (CI) m/z (%)¼ 196
(100%) [MþHþ]; methyl 2-azido-5-chlorobenzoate 13d,
yield 16.7 g, 79%; white pink solid, mp: 50–52ꢀC; MS: (CI)
m/z (%) ¼ 212(100%) [MþHþ]; methyl 2-azido-5-bromoben-
zoate 13e, yield 20.8 g, 81%; white solid, mp: 71–72ꢀC; MS:
(CI) m/z (%) ¼ 256 (100%) [MþHþ], 258 (100%) [MþHþ];
dimethyl 2-azidobenzene-1,4-dicarboxylate 13f, yield 17.7 g,
75%; white solid, mp: 83–85ꢀC; MS: (CI) m/z (%) ¼ 236
(100%) [MþHþ]. (Caution! All azides are potentially explo-
sive and should not be heated).
REFERENCES AND NOTES
[1] (a) Bryant, H. J.; Chambers, M. S.; Jones, P.; MacLeod, A.
M.; Maxey, R. J. WO Patent 0,144,250, 2001; (b) Jones, P.; Chambers,
M. Tetrahedron, 2002, 58, 9973; (c) Bryant, H. J.; Chambers, M. S.;
Jones, P.; MacLeod, A. M.; Maxey, R. J. US Patent 7,144,887 B2,
2006.
[2] (a) Biagi, G.; Giorgi, I.; Livi, O.; Scartoni, V.; Velo, S.;
Lucacchini, A.; Senatore, G.; De Santis, B.; Martinelli, A. Farmaco
1996, 51, 131; (b) Bertelli, L.; Biagi, G.; Giorgi, I.; Livi, O.; Manera,
C.; Scartoni, V.; Lucacchini, A.; Giannaccini, G.; Barili, P. L. Eur J
Med Chem 2000, 35, 333.
[3] Tennant, G. J Chem Soc (C) 1966, 2290.
[4] (a) Shaban, M. A. E.; Taha, M. A. M.; Sharshira, E. M. Adv
Heterocycl Chem 1991, 52, 1; (b) Krivopalov, V. P.; Shkurko, O. P.
Russ Chem Rev 2005, 74, 339.
[5] Da Settimo, A.; Livi, O.; Biagi, G.; Primofiore, G.; Masoni,
G. Farmaco, 1982, 37, 728.
[6] (a) Pokhodylo, N. T.; Matiychuk, V. S.; Obushak.M. D.
Chem Heterocycl Compds 2009, 45, 483; (b) Pokhodylo, N. T.; Matiy-
chuk, V. S.,Obushak, M. D. Tetrahedron 2009, 65, 2678.
[7] (a) Saito, K.; Kambe, S.; Nakano, Y. Synthesis 1983, 210;
(b) Volovenko, Y. M.; Resnyanska, E. V.; Tverdokhlebov, A. V. Col-
lect Czech Chem Commun 2002, 67, 365.
[8] Obushak, N. D.; Pokhodylo, N. T.; Pidlypnyi, N. I.; Matii-
chuk, V. S. Russ J Org Chem 2008, 44, 1522.
[9] (a) Xu, Z.; Li, Y.; Ma, X.; Gao, X.; Tian, H. Tetrahedron
2008, 64, 1860; (b) Paul, P. K.; Hussain, S. A.; Bhattacharjee, D. J
Luminescence 2008, 128, 41; (c) Feng, L.; Wang, X.; Chen, Z. Spec-
trochimica Acta Part A: Mol Biomol Spectrosc 2008, 71, 312; (d)
Ono, K.; Ito, H.; Nakashima, A.; Uemoto, M.; Tomura, M.; Saito, K.
Tetrahedron Lett 2008, 49, 5816; (e) Xiao, F.; Liu, Y.; Hu, Z.; Gan,
Q.; Wang, L.; Wen, Z.; Zhu, M.; Zhu, W. Synth Met 2009, 159, 1308;
(f) Hegde, P. K.; Adhikari, A. V.; Manjunatha, M. G.; Suchand San-
deep, C. S.; Philip, R. Synth Met 2009, 159, 1099.
General procedure for the synthesis of 1H-1,2,3-triazol-
5-amines 9a–c and [1,2,3]triazolo[1,5-a]quinazolin-5(4H)-
one 14a–o. To the solution of sodium methoxide (540 mg,
10.0 mmol) in dry methanol (20 mL) an appropriate substi-
tuted acetonitrile 1, 2, 5 or 8 (10.0 mmol) was added. To this
solution substituted methyl 2-azidobenzoate 2 (10.0 mmol) in
dry methanol (2 mL) was added dropwise and the solid started
to precipitate. The mixture was stirred for 1 h. The resulting
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

420
N. T. Pokhodylo and V. S. Matiychuk
Vol 47
[10] (a) Ignatenko, O. A.; Kuznetsov, M. A.; Selivanov, S. I.
[13] Bayer, O.; Eckert, W. In Methoden der organischen
Chemie (Houben-Weyl), Bd. 7/4, S.5, Thieme Verlag: Stuttgart,
1968.
Russ J Org Chem 2007, 43, 1042; (b) Ol’khovik, V. K.; Pap, A. A.;
Vasilevskii, V. A.; Galinovskii, N. A.; Tereshko, S. N. Russ J Org
Chem 2008, 44, 1172.
[14] Leulier, P. Bull Soc Chim France 1924, 35, 1328.
[15] (a) Cassebaum, H. J Prakt Chem 1964, 23, 301; (b) Kambli,
E. Helv Chim Acta 1964, 47, 2155; (c) Prinz, W.; Kayle, A.; Levy, P.
R. J Chem Res (S) 1978, 116.
[11] (a) Dimroth, O.; Michaelis, W. Lieb Ann Chem 1927, 459,
39; (b) El Ashry, E. S. H.; El Kilany, Y.; Rashed, N.; Assafir, H. Adv
Heterocycl Chem 1999, 75, 79.
[12] (a) Sandmeyer, T. Helv Chim Acta 1919, 2, 230; (b) Da Silva,
J. F. M.; Garden, S. J.; Pinto, A. C. J Braz Chem Soc 2001, 12, 273.
[16] Falcao da Fonseca, L. Rev Portug Farmac 1965, 15, 317.
[17] Okabe, M.; Sun, R.-C. Tetrahedron 1995, 51, 1861.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet