Synthesis of 2-(2-methyltetrazol-5-yl)-2,2-dinitroacetonitrile and its reaction with substituted nitrile N-oxides

Article abstract of DOI:10.1134/S1070428014020237

A procedure of synthesis of 2-(2-methyltetrazol-5-yl)-2,2- dinitroacetonitrile has been developed and its reaction with substituted nitrile N-oxides has been investigated, proceeding by the mechanism of 1,3-dipolar cycloaddition and affording 2-methyl-5-[(1,2,4-oxadiazol-5-yl)(dinitro)methyl]- 2H-tetrazoles. The latter react with KOH in ethanol forming the potassium salt of 2-methyltetrazol-5-yldinitromethane and substituted 5-hydroxy-1,2,4- oxadiazoles.

Full text of DOI:10.1134/S1070428014020237

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 2, pp. 280−284. © Pleiades Publishing, Ltd., 2014.
Original English Text © M.А. Abdelrakhim, А.G. Tyrkov, Е.А. Yurtaeva, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 2, pp. 287−291.
Synthesis of 2-(2-Methyltetrazol-5-yl)-2,2-dinitroacetonitrile
and Its Reaction with Substituted Nitrile N-Oxides
M. А. Abdelrakhima, А. G. Tyrkova, and Е. А. Yurtaevab
aAstrakhan State Universty, Astrakhan, Russia, 414000 Russia
bResearch Institute of Lepra Studies, Ministry of Public Health of the Russian Federation, Astrakhan, Russia
e-mail: tyrkov@rambler.ru
Recieved March 29, 2013
Abstract—A procedure of synthesis of 2-(2-methyltetrazol-5-yl)-2,2-dinitroacetonitrile has been developed and
its reaction with substituted nitrile N-oxides has been investigated, proceeding by the mechanism of 1,3-dipolar
cycloaddition and affording 2-methyl-5-[(1,2,4-oxadiazol-5-yl)(dinitro)methyl]-2H-tetrazoles. The latter react with
KOH in ethanol forming the potassium salt of 2-methyltetrazol-5-yldinitromethane and substituted 5-hydroxy-
1,2,4-oxadiazoles.
DOI: 10.1134/S1070428014020237
Trinitroacetonitrile [1], dinitrochloroacetonitrile [2], of dinitroacetonitriles, 2-(2-methyltetrazol-5-yl)-2,2-
and ethylnitrochloroacetonitrile [3] react with aromatic
nitrile N-oxides and form products of 1,3-dipolar cyclo-
addition, 3,5-substitued 1,2,4-oxodiazoles.
dinitroacetonitrile (III). The preparation procedure for
compound III is underlain by the introduction of a cyano
group in the dinitromethyl fragment of 2-methyltetrazol-
5-yldinitromethane silver salt (II) obtained from potas-
sium salt I.
In order to investigate the degree of generality of this
reaction we have tried to extend it to a new specimen
C(NO2)2K
C(NO2)2Ag
C(NO2)2CN
N
N
N
AgNO3
_KNO3
BrCN
_AgBr
N
N
N
N
N
N
N
N
N
Me
Me
Me
I
II
III
The structure of silver salt II has been established from
IR, UV-Vis, 13С NMR spectra, and the composition, by
the elemental analysis. In the IR spectrum the absorption
bands are present with intricate contour apparently cor-
trinitromethane, and dinitroacetonitrile (~137.7 ppm).
At the same time the structure of salt II depends on the
polarity of the environment. So in the IR spectrum of the
salt in benzene (possessing lower dielectric permeability,
ε 2.3, than acetone, ε 20.7) the absorption band νas NO2
is shifted with respect to that in acetone (1590 cm–1 in
benzene, 1490 cm–1 in acetone), and its intensity is higher.
It is probably due to the gradual deviation of the geminal
nitro groups and the tetrazole ring from the coplanarity as
the dielectric permeability of the environment decreases
with the corresponding reduction in the delocalization of
the anion charge and its concentration on the carbon atom.
As a result this process, apparently, leads to the formation
–
responding to the C(NO2)2 moiety (1540, 1490, 1462,
1370, 1260, 1143 cm–1) and the bands of tetrazole ring at
1045, 1033 cm–1, in good agreement with the data of [4].
These findings do not also contradict the close position
of the signal of the central carbon atom in the 13С NMR
spectrum of salt II (δ 36.2 ppm), recorded in the water,
to the signals of the carbon atom of gem-dinitromethyl
group in the spectra of similar compounds: potassium
salts of 5-dinitromethyl-3-phenyl-1,2,4-oxodiazole,
280

SYNTHESIS OF 2-(2-METHYLTETRAZOL-5-YL)-2,2-DINITROACETONITRILE
281
of the covalent bond Ag–C that may be observed in salt
II solution in benzene.
between the asymmetric and symmetric stretching vibra-
tionsΔ(NO2) is 320 cm–1, which is typical for dinitroace-
tonitriles.As known, the position of the absorption bands
of the nitro groups in the IR spectrum and the value of
Δ(NO2) may be used in analytical purposes to distinguish
between mono-, gem-dinitro, and trinitroalkanes [8]. The
value ofΔ(NO2) for nitro groups of dinitroacetonitrile III
is much larger than that of mono- (~180 cm–1) and gem-
dinitroalkanes (~250 cm–1), and it is close to the frequency
difference typical of polynitroalkanes (300 cm–1). It is
evidently caused by the electron-acceptor influence on
the dinitromethyl group produced by the cyano group
and the tetrazole ring. In the 13С NMR spectrum of
compound III the signal of the carbon atom of the gem-
dinitromethyl group appears at 118.1 ppm corresponding
to the δ values of similar fragments in the molecules of
analogous compounds, trinitroacetonitrile (113.2 ppm)
[9] and 2,2-dinitrobutanonitrile (105.9 ppm) [10]. In ni-
trile III the electronic spectum apart from the absorption
band of the tetrazole ring at 250 nm contains a specific
absorption band at 280 nm, typical of nitroacetonitriles
and corresponding to a forbidden n → π*-transition. Its
intensity (logε 2.08) is closer to the intensity of similar
band in the spectrum of dinitroacetonitriles (2,2-dinitro-
butanonitrile or trinitroacetonitrile (logε 2.06–2.17), than
of gem-dinitroalkanes (logε 1.76) [8].
The same trend can be seen in the electronic spectrum
of salt II. With the decrease in the polarity of the environ-
ment in the series water−ethanol –benzene a blue shift
of the absorption maximum is observed from 330 nm
(logε 4.13) in water (ε 78.3) to ~290 nm (logε 2.10)
in benzene that may also indicate the formation of the
covalent bond Ag–C in the benzene surroundings. The
silver salt of 5-dinitromethyl-2-methyl-2Н-tetrazole can
be regarded as a polydentate anion whose charge may be
localized either on the oxygen atom of the nitro group,
or on the carbon atom attached to the nitro groups, or on
the nitrogen atoms of the tetrazole ring. Consequently,
in the reaction with electrophilic reagents O-, C- or
N-alkylation may occur [5].
The treatment of salt II with excess of cyanogen
bromide at 40°С for 20 h resulted in С-alkylation, and
nitrile III formed in 70% yield that allows regarding this
procedure as preparative. The cyanation of silver salts of
trinitromethane with cyanogen iodide or of substitued
dinitromethane with cyanogen bromide occurs in the
same way [6].
The structure of compound III was established from
IR, UV-vis, 1Н and 13С NMR spectra, and its composition
was proved by the elemental analysis. In its IR spectrum
a weak absorption band was observed of the stretching
vibrations of the cyano group at 2255 cm–1 [7]. Besides
the IR spectrum contains intensive absorption bands of
the stretching vibrations of the gem-dinitromethyl group
at 1600 (νas) and 1280 cm–1 (νs), the frequency difference
Nitrile III reacts with active N-oxides of aromatic ni-
triles IV–IX or acetonitrile N-oxide (X) in mild conditions
along the mechanism of 1,3-dipolar cycloaddition form-
ing unknown before 2-methyl-5-[(1,2,4-oxodiazol-5-yl)-
(dinitro)methyl]-2H-tetrazoles XI–XVII in small yields.
HO
NO2
NO2
R
N
N
0oC
N
N
N
O
N
KOH
EtOH
+
+
I
III
R C N
O
O
Et2O
N
R
N
Me
IV_X
XI_XVII
XVIII_XXIV
R = Ph (IV, XI, XVIII), 4-MeOC6H4 (V, XII, XIX), 3-MeOC6H4 (VI, XIII, XX), 2-MeOC6H4 (VII, XIV, XXI), 4-MeC6H4 (VIII, XV,
XXII), 2-MeC6H4 (IX, XVI, XXIII), Me (X, XVII, XXIV).
Nitrile III behaves in this reaction as a dipolarophile
activated with dinitrotetrazolylmethyl group, and the ni-
trile N-oxides IV–X act as 1,3-dipoles. The nitrile oxides
with acceptor substituents in the benzene ring are inert
with respect to compound III probably due to insufficient
dipolarophile activity of the nitrile group in reagent III.
This reaction provides an opportunity to incorporate into
the main part of molecule III of the 1,2,4-oxadiazole ring
as a result of a one-pot process.
The structure of the cycloaddition products XI–XVII
1
was established from IR, Н, 13С NMR spectra, from
chemical transformations, and the composition was
proved by the elemental analysis. The IR spectral pattern
is typical of polynitromethyl compounds, for instance,
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ABDELRAKHIM et al.
282
the absorption bands of the stretching vibrations of the
nitriles IV–IX were obtained by dehydrohalogenating the
corresponding chlorides of aryl hydroxamic acids with
triethylamine by procedure [12]. Acetonitrile N-oxide
(X) was generated by treating with acetyl chloride the
sodium salt of nitroethane by the method [13], and it was
introduced into the reaction with compound III in situ.
NO2 group are recorded in the region 1580–1600 (νas)
1
and 1280–1300 cm–1 (νs). In the Н NMR spectra the
signals of the aromatic protons appear in the region
6.92–7.74 ppm (in case of compounds XI–XVI) and of
the СН3 group, at 2.52 ppm (compound XVII). In the
13С NMR spectra the signals of atoms С5' and С3' of the
oxadiazole ring are registered respectively at 171–172 and
164–166 ppm, in agreement with the published data [10].
Silver salt of 5-(dinitromethyl)-2-methyl-2H-tetra-
zole (II). To 2.10 g (10 mmol) of tetrazole I potassium salt
in 10 mLof water at 40°С was added a solution of 2.550 g
(15 mmol) of AgNO3 in minimal quantity of water. The
solution was cooled to 0°С and kept for 20 min, the
precipitate of salt II was filtered off, washed twice with
small amount of water, and dried in a vacuum-desiccator
for 3 h. Yield 2.419 g (82%), white crystals, temperature
of decomposition 160–163°С. IR spectrum, ν, cm–1:
1540, 1462, 1370, 1260 sh, 1143 [C(NO2)2–]. Found, %:
С 12.04; H 0.87; N 28.31. С3Н3AgN6O4. Calculated, %:
C 12.20; H 1.02; N 28.48.
The electrophilic nature of compounds XI–XVII made
it possible to carry out their reaction with KOH in ethanol.
The salt formation takes place in mild conditions with the
1,2,4-oxydiazole ring elimination and leads to the known
compounds: salt of 2-methyltetrazol-5-yldinitromethane
(I) and 5-hydroxyderivatives of 1,2,4-oxadiazole XVIII–
XXIV.
This reaction direction may be caused by the pres-
ence in the initial compounds of two strong neighboring
electron-acceptor groups that effect strong deshielding
of both С5' atom of the oxadiazole heterocycle and the
carbon atom of the dinitromethyl group thus weakening
the С5'–С(NO2)2 bond. In the electronic spectrum of salt
I apart from the absorption band of the tetrazole ring at
245 nm the absorption band with the maximum at 365 nm
is present, typical of the salts of gem-dinitroalkanes [4].
2-(2-Methyltetrazol-5-yl)-2,2-dinitroacetonitrile
(III). Into an ampule of tick glass was charged a mixture
of 1.475 g (5 mmol) of salt II and 0.636 g (6 mmol) of
cyanogen bromide. The ampule was sealed, placed into
an explosion-safe box and heated for 20 h at 80°С. After
cooling the content of the ampule was extracted with
diethyl ether (2 × 10 mL), the extract was evaporated in
a vacuum, the residue was chromatographed on a column
(10 × 250 mm) filled with activated silica gel of Silicagel
100/400μ grade, using the solvents of the Trappe series,
eluent benzene. Yield 0.746 g (70%), white crystals,
mp 71–73°С. IR spectrum, ν, cm–1: 2255 (CN); 1600,
1280 (NO2). UV spectrum, λmax, nm (logε): 250 (4.14),
280 (2.08).1Н NMR spectrum, δ, ppm: 4.52 s (3Н, СН3).
13C NMR spectrum, δ, ppm: 39.8 (СН3), 108.2 (CN),
118.1 [C(NO2)2], 147.3 (C5). Found, %: C 22.36; H 1.25;
N 45.84. С4H3N7O4. Calculated, %: C 22.54; H 1.41;
N 46.01.
Reaction of 2-(2-methyltetrazol-5-yl)-2,2-dinitro-
acetonitrile (III) with N-oxides of aromatic nitriles
IV–IX. To a solution of 1.065 g (5 mmol) of compound
III in 10 mL of dried diethyl ether at –10°С was added
dropwise while stirring 0.595–0.745 g (5 mmol) of com-
pound IV–IX in 50 mL of the same solvent. The reaction
mixture was left standing for 24 h at 25°С, the solvent was
distillated in a vacuum, the residue was chromatographed
on a column (10 × 500 mm) as described above. Eluent
for compounds XI–XVI benzene.
Hence, 2-(2-methyltetrazol-5-yl)-2,2-dinitroacetoni-
trile (III) can be regarded as a convenient synthon for
preparation of various azaherocyclic compounds on its
basis.
EXPERIMENTAL
The IR spectra were recorded on a spectrophotometer
InfraLUM FТ-02 from tablets with KВr or from solutions
in CHCl3 (for compounds XI, XVII). The electronic
spectrum of compound III was recorded on a spectro-
photometer Cary-50 from solution in CCl4 of concn.
0.3 mg mL–1. 1Н, 13С NMR spectra were registered on a
spectrometer BrukerAvance II 300 SF (300 and 75 MHz
respectively) in DMSO-d6, internal reference HMDS. The
elemental analysis was carried out on a CHNS-analyzer
Euro EA-3000 of Euro Vector. The course of the reaction
and the individuality of the obtained compounds were
controlled by TLC on Silufol UV-254 plates in the sys-
tem of the solvents acetone-hexane, 2 : 3, development
in iodine vapor. The potassium salt of tetrazole I was
synthesized by the known method [4]. Cyanogen bromide
was obtained by the method [11]. N-Oxides of aromatic
5-[Dinitro(3-phenyl-1,2,4-oxadiazol-5-yl)-methyl]-
2-methyl-2H-tetrazole (XI). Yield 0.963 g (58%), light-
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SYNTHESIS OF 2-(2-METHYLTETRAZOL-5-YL)-2,2-DINITROACETONITRILE
283
yellow oily substance, nD20 1.4850. IR spectrum, ν, cm–1:
1580, 1300 (NO2). Н NMR spectrum, δ, ppm: 4.51 s
(57%), white crystals, mp 41–42°С (hexane). IR spec-
trum, ν, cm–1: 1580, 1300 (NO2). Н NMR spectrum,
1
1
(3Н, СН3), 7.62–7.74 m (5Н, Ph). 13С NMR spectrum,
δ, ppm: 39.7 (СН3), 122.3 (С6), 124.3–133.2 (Саrom),
147.4 (С5), 166.5 (С3'), 171.3 (С5а). Found, %: C 39.58;
H 2.29; N 33.55. C11H8N8О5 . Calculated, %: C 39.76;
H 2.41; N 33.73.
δ, ppm: 2.32 s (3Н, СН3), 4.51 s (3Н, СН3), 7.12–7.51 m
(4Н, С6Н4). 13С NMR spectrum, δ, ppm: 19.2 (СН3), 39.6
(СН3N), 119.6–139.7 (Саrom), 122.6 (С6), 147.5 (С5),
166.6 (С3'), 171.4 (С5а). Found, %: C 41.48; H 2.76;
N 32.15. C12H10N8О5. Calculated, %: C 41.62; H 2.89;
N 32.37.
2-Methyl-5-[3-(4-methoxyphenyl-1,2,4-oxadiazol-
5-yl)(dinitro)methyl]-2H-tetrazole (XII). Yield 1.086 g
(60%), white crystals, mp 71–72°С (CCl4). IR spectrum,
ν, cm–1: 1580, 1300 (NO2). 1Н NMR spectrum, δ, ppm:
3.81 s (3Н, СН3О), 4.52 s (3Н, СН3), 6.95–7.72 m (4Н,
С6Н4). 13С NMR spectrum, δ, ppm: 39.6 (СН3N), 60.3
(СН3О), 115.5–159.7 (Саrom), 122.5 (С6), 147.4 (С5),
165.4 (С3'), 171.2 (С5а). Found, %: C 39.61; H 2.64;
N 30.78. C12H10N8О6. Calculated, %: C 39.78; H 2.76;
N 30.94.
2-Methyl-5-[(3-methyl-1,2,4-oxadiazol-5-yl)-
(dinitro)methyl]-2H-tetrazole (XVII). To the solution
of 0.491 g (5 mmol) of nitroethane sodium salt in 30 mL
of anhydrous DMAA was added at 20°С while stirring
0.393 g (5 mmol) of acetyl chloride.After 15 min 1.065 g
(5 mmol) of compound III in 10 mL of the same solvent
was added, the mixture was stirred for 12 h, 50 mL of the
mixture of ice water and benzene, 3 : 1, was added, and
the mixture was stirred for 30 min. The aqueous layer
was extracted with benzene (2 × 15 mL), the extract was
dried with Na2SO4, evaporated in a vacuum, the residue
was chromatographed by the method described above,
eluent chloroform. Yield 0.608 g (45%), light-yellow
oily substance, nD20 1.4738. IR spectrum, ν, cm–1: 1580,
2-Methyl-5-[3-(3-methoxyphenyl-1,2,4-oxadiazol-
5-yl)(dinitro)methyl]-2H-tetrazole (XIII). Yield 0.905 g
(50%), white crystals, mp 67–68°С (CCl4). IR spectrum,
ν, cm–1: 1580, 1300 (NO2). 1Н NMR spectrum, δ, ppm:
3.83 s (3Н, СН3О), 4.51 s (3Н, СН3), 6.94–7.65 m (4Н,
С6Н4). 13С NMR spectrum, δ, ppm: 39.7 (СН3N), 55.3
(СН3О), 118.4–159.7 (Саrom), 122.5 (С6), 147.5 (С5),
166.5 (С3'), 172.5 (С5а). Found, %: C 39.62; H 2.59;
N 30.75. C12H10N8О6. Calculated, %: C 39.78; H 2.76;
N 30.94.
1
1300 (NO2). Н NMR spectrum, δ, ppm: 2.52 s (3Н,
СН3), 4.51 s (3Н, СН3). 13С NMR spectrum, δ, ppm:
39.6 (СН3N), 48.7 (СН3), 121.3 (С6), 147.2 (С5), 164.5
(С3'), 172.2 (С5а). Found, %: C 26.53; H 2.06; N 41.32.
С6H6N8O5. Calculated, %: C 26.67; H 2.22; N 41.48.
2-Methyl-5-[3-(2-methoxyphenyl-1,2,4-oxadiazol-
5-yl)(dinitro)methyl]-2H-tetrazole (XIV). Yield 1.177 g
(65%), white crystals, mp 37– 38°С (hexane). IR spec-
Reaction of 2-methyl-5-[(1,2,4-oxadiazol-5-yl)(dini-
tro)methyl]tetrazoles XI–XVII with KОН in ethanol.
To the solution of 0.810–1.086 g (3 mmol) of compound
XI–XVII in 10 mL of ethanol was added dropwise at
20°С excess of saturated alcohol solution of KОН, the
mixture was maintained for 1 h at 0°С, the precipitate
was filtered off and recrystallized. In the synthesis of
compounds XVIII–XXIV the yield of salt I (yellow
crystals [4]) was respectively 65, 67, 62, 70, 62, 68, 55%.
1
trum, ν, cm–1: 1580, 1300 (NO2). Н NMR spectrum,
δ, ppm: 3.80 s (3Н, СН3О), 4.52 s (3Н, СН3), 6.92–7.35 m
(4Н, С6Н4). 13С NMR spectrum, δ, ppm: 39.6 (СН3N),
55.7 (СН3О), 114.9–159.2 (Саrom), 122.4 (С6), 147.4
(С5), 166.8 (С3'), 171.7 (С5а). Found, %: C 39.60; H 2.64;
N 30.78. C12H10N8О6. Calculated, %: C 39.78; H 2.76;
N 30.94.
The mother liquor was evaporated in a vacuum, the
residue was chromatographed by the method described
above, eluent for compounds XVIII–XXIV diethyl ether.
2-Methyl-5-[3-(4-tolyl-1,2,4-oxadiazol-5-yl)(dini-
tro)methyl]-2H-tetrazole (XV). Yield 0.952 g (55%),
white crystals, mp 77–78°С (CCl4). IR spectrum, ν, cm–1:
1
5-Hydroxy-3-phenyl-1,2,4-oxadiazole (XVIII).
Yield 0.107 g (22%), white crystals, mp 203°С (CCl4)
[14].
1580, 1300 (NO2). Н NMR spectrum, δ, ppm: 2.35 s
(3Н, СН3), 4.52 s (3Н, СН3), 7.15–7.56 m (4Н, С6Н4).
13С NMR spectrum, δ, ppm: 21.3 (СН3), 39.8 (СН3N),
122.7 (С6), 129.2–141.3 (Саrom), 147.4 (С5), 166.4
(С3'), 172.3 (С5а). Found, %: C 41.46; H 2.78; N 32.19.
C12H10N8О5. Calculated, %: C 41.62; H 2.89; N 32.37.
5-Hydroxy-3-(4-methoxyphenyl)-1,2,4-oxadiazole
(XIX). Yield 0.144 g (25%), white crystals, mp 208°С
(CCl4) [15].
2-Methyl-5-[3-(2-tolyl-1,2,4-oxadiazol-5-yl)-
(dinitro)methyl]-2H-tetrazole (XVI). Yield 0.986 g
5-Hydroxy-3-(3-methoxyphenyl)-1,2,4-oxadiazole
(XX). Yield 0.121 g (21%), white crystals, mp 85–86°С
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ABDELRAKHIM et al.
284
(CCl4). IR spectrum, ν, cm–1: 3620 (ОН). 1Н NMR spec-
trum, δ, ppm: 3.82 s (3Н, СН3О), 5.65 br.s. (1Н, ОН),
6.95–7.62 m (4Н, С6Н4). Found, %: C 56.08; H 4.02;
N 14.42. С9H8N2O3. Calculated, %: C 56.25; H 4.17;
N 14.58.
Khim. Tekhnol., 1994, vol. 37, p. 131.
3. Tyrkov,A.G. and Suikhanova, B.G., Zh. Org. Khim., 1999,
vol. 35, p. 1330.
4. Terpigorev, A.N., Tselinskii, I.V., Makarevich, A.V.,
Frolova, G.M., and Mel’nikov,A.A., Zh. Org. Khim., 1987,
vol. 23, p. 244.
5-Hydroxy-3-(2-methoxyphenyl)-1,2,4-oxadiazole
(XXI). Yield 0.115 g (20%), white crystals, mp 51–52°С
5. Altukhov, K.V. and Perekalin, V.V., Russ. Chem. Rev.,
1976, vol. 45, p. 2052; Shevelev, S.A., Dalinger, I.L.,
Vinogradov, V.M., and Fainzil’berg, A.F., Izv. Akad.
Nauk SSSR, Ser. Khim., 1990, p. 1816; Zeng, Z., Gao, H.,
Twamley, B., and Shreeve, J.M., J. Mater. Chem., 2007,
vol. 17, p. 3819.
1
(hexane). IR spectrum, ν, cm–1: 3620 (ОН). Н NMR
spectrum, δ, ppm: 3.80 s (3Н, СН3О), 5.62 br.s (1Н, ОН),
6.92–7.65 m (4Н, С6Н4). Found, %: C 56.11; H 3.98;
N 14.38. С9H8N2O3. Calculated, %: C 56.25; H 4.17;
N 14.58.
5-Hydroxy-3-(4-tolyl)-1,2,4-oxadiazole (XXII).
Yield 0.106 g (20%), white crystals, mp 220°С (CCl4)
[15].
6. Hantzsch, A. and Rickenberger, A., Ber., 1899, vol. 32,
p. 628; Shevtsova, I.A. and Tyrkov, A.G., Russ. J. Org.
Khim., 2007, vol. 43, p. 1742.
5-Hydroxy-3-(2-tolyl)-1,2,4-oxadiazole (XXIII).
Yield 0.121 g (23%), white crystals, mp 94– 95°С (CCl4).
7. Parker, C.O., Emmons, W.D., Rolewicz, H.A., and
McCallum, K.S., Tetrahedron, 1962, vol. 17, p. 79;
Parker, S.O. Tetrahedron, 1962, vol. 17, p. 109.
1
IR spectrum, ν, cm–1: 3620 (ОН). Н NMR spectrum,
δ, ppm: 2.31 s (3Н, СН3), 5.67 br.s. (1Н, ОН), 7.14–
7.52 m (4Н, С6Н4). Found, %: C 61.19; H 4.38; N 15.73.
С9H8N2O2. Calculated, %: C 61.36; H 4.55; N 15.91.
8. Slovetskii, V.I., Shlyapochnikov, V.A., Shevelev, S.A.,
Fainzil’berg, A.A., and Novikov, S.S., Izv. Akad. Nauk
SSSR, 1961, p. 330; Shlyapochnikov, V.A., Kolebatel’nye
spektry alifaticheskikh nitrosoedinenii (Vibrational Spectra
ofAlifatic Nitrocompounds), Ivshin, V.P., Ed., Ioshkar-Ola:
Izd. Udm. Gos. Iniv., 2007.
5-Hydroxy-3-methyl-1,2,4-oxadiazole (XXIV).
Yield 0.066 g (22%), white crystals, mp 62°С (hexane)
[15].
9. Ladyzhnikova, T.D., Solov’ev, N.A., Altukhov, K.V., and
ACKNOWLEDGMENTS
Perekalin, V.V., Zh. Org. Khim., 1988, vol. 24, p. 644.
10. Tyrkov,A.G., Doctoral Sci. (Chem.) Dissertation, Saratov,
This study was carried out with the financial support of
Ministry of Science and Education of Russian Federation
(program “Developement of innovating infrastructure in
Russian Universities,” grant no. 13.G37.31.0038) using
the scientific equipement of the R&D Center “Biotech-
nologies for creating original pharmacologic substances.”
2005.
11. Rubtsov, M.V. and Baichikov, A.G., Sinteticheskie
khimiko-farmatsevticheskie preparaty (Synthetic Chemical
Pharmaceitucal Medicines), Moscow: Meditsina, 1971.
12. Rheinboldt, H., Lieb. Ann., 1927, vol. 451, p. 161.
13. Harada, K., Kaji, E., and Zen, S., Chem. Pharm. Bull.,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014