New representatives of nitroamine-containing 1,2,4-triazoles: Synthesis and structure

Article abstract of DOI:10.1134/S1070363213090259

The interaction of 1-methyl-1-nitroso-2-nitroguanidine with carboxylic acid hydrazides results in formation of N-(2-nitroguanidino)amides that easily give 3(5)-nitroamino-5(3)-alkyl(aryl)-1,2,4-triazoles under refluxing in aqueous alkaline medium. We have developed a one-pot method to prepare such heterocyclic structures; the synthesis of one of the sample compound has given an example of the method applicability. The compounds structures have been confirmed by UV, IR, ¹H, and ¹³C-{¹H} NMR spectroscopy.

Full text of DOI:10.1134/S1070363213090259

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 9, pp. 1779–1786. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © T.P. Efimova, O.Yu. Ozerova, T.A. Novikova, I.V. Belik, V.M. Berestovitskaya, 2013, published in Zhurnal Obshchei Khimii, 2013,
Vol. 83, No. 9, pp. 1564–1571.
On the 100th anniversary of V.V. Perekalin
New Representatives of Nitroamine-Containing 1,2,4-Triazoles:
Synthesis and Structure
T. P. Efimova, O. Yu. Ozerova, T. A. Novikova, I. V. Belik, and V. M. Berestovitskaya
Herzen State Pedagogical University of Russia, Moyka emb. 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received April 22, 2013
Abstract—The interaction of 1-methyl-1-nitroso-2-nitroguanidine with carboxylic acid hydrazides results in
formation of N-(2-nitroguanidino)amides that easily give 3(5)-nitroamino-5(3)-alkyl(aryl)-1,2,4-triazoles under
refluxing in aqueous alkaline medium. We have developed a one-pot method to prepare such heterocyclic
structures; the synthesis of one of the sample compound has given an example of the method applicability. The
compounds structures have been confirmed by UV, IR, 1H, and 13C–{1H} NMR spectroscopy.
DOI: 10.1134/S1070363213090259
An increased interest to functionalized 1,2,4-
triazoles is due to the high practical importance of many
representatives of this class. They are used in medicine
(for instance, antifungal and antiviral agents Fluconazole
and Ribavirin [1]), as plant growth regulators [2, 3],
herbicides and fungicides (for example, Impact® and
Bayleton® [4]), and in photographic industry.
One of the methods to prepare the nitroamino-
containing 1,2,4-triazoles is cyclization of acyl
derivatives of nitroaminoguanidine [5, 6]. We have
developed a convenient method leading to new
representatives of nitroamino-containing 1,2,4-
triazoles, based on condensation of 1-methyl-1-nitroso-
2-nitroguanidine with the carboxylic acid hydrazides.
NO2
NO2
O
NO
O
N
N
N
N2H
+
H2N HN
R
−CH3OH
−N2
N1H
CH3
R
NH2
NH2
I−VI
H2O (OH−), Δ
NH
R
N
R = CH3
O2NHN
N
VII−XII
HO
OH
(III, IX),
OCH3
OCH3
OCH3
R = CH3 (I, VII), C7H15 (II, VIII),
(IV, X),
Br
(VI, XII).
(V, XI),
1779

1780
EFIMOVA et al.
Table 1. Yields, melting points and spectroscopic characteristics of carboxylic acids N-(2-nitroguanidino)amides I–VI
1Н NMR
(DMSO-d6), δ, ppm
IR, ν, cm–1 (vaseline oil)
Comp.
no.
Yield,
%
R
mp, ºС
NH
С=О
NH1
9.84
NH2
NH2
R
–СН3
191–192
156–158
66
65
3386
3239
3275
3193
1700
9.56
8.19
8.59
8.15
8.60
1.83 s
I
−C7H15
1711
9.80
9.55
0.81 m
1.2 m
II
1.6 m
2.18 m
HO
175–176
108–110
74
73
3388а
3335
3248
1694
1692
9.85 с 9.60 s 8.15
6.60–7.15 m
9.38 s
III
IV
CH2
CH2
8.62
CH2
3477а
3445
3220
9.85 с 9.57 s 8.12
1.70 m
2.20 m
3.38 m
4.60 s
CH2
Br
8.60
CH2
OH
179–180
216–217
95
63
3308
3170
1676
1663
10.70 с 9.90 s 8.45 7.50–8.25 m
V
8.70
OCH3
OCH3
OCH3
3385
3334
3199
10.43 с 9.78 s 8.34
3.68 s
3.80 s
7.22 s
VI
8.63
a In the cases of compounds III and IV, the absorption bands of NH and OH groups were observed in that spectral region.
Reactions of 1-methyl-1-nitroso-2-nitroguanidine
with hydrazides of aliphatic and aromatic carboxylic
acids performed in aqueous alcohol medium at 80–90°С
gave N-(2-nitroguanidino)amides of the corresponding
acids I–VI with yields up to 95%.
1,2,4-triazoles were colorless high-melting crystalline
substances.
The structures of I–XII were confirmed by 1Н, 13С–
{1H} NMR, IR, and UV spectroscopy (Tables 1 and 2)
as well as by comparison of the melting point of VII
with that of the reference sample prepared previously
by another method [8].
Refluxing of the obtained polynitrogen compounds
I–VI in aqueous alkaline medium resulted in their
intramolecular heterocyclization and thus formation of
3-nitroamino-5-alkyl(aryl)-1,2,4-triazoles VII–XII with
yields up to 92%. Noteworthily, the cyclization of
compounds I–VI occurred generally slower (within
several hours) than in the case of N-(2-nitroguanidino)-
amidooxalate (within 20 min, [7]).
1
In the H NMR spectra of the compounds, the
signals of all structural fragments were identified.
For example, in the 1H NMR spectrum of VI (Fig. 1),
the broad signals of magnetically nonequivalent
protons of primary NH2 (8.34 and 8.63 ppm) and
secondary NH1, NH2 (9.78 and 10.43 ppm) groups
were observed in the weak field [9], being
characteristic of the aminonitroguanidine structure.
The spectrum contained the singlet signals of aromatic
ring protons at 7.22 ppm and of those of methoxy
groups at 3.68 and 3.80 ppm as well. The validity of
the signals assignment was confirmed by 1Н–13С
HMQC and HMBC experiments [10, 11].
A possibility of one-pot synthesis of 5(3)-methyl-
3(5)-nitroamino-1,2,4-triazole VII was demonstrated
using condensation of 1-methyl-1-nitroso-2-nitro-
guanidine with N-(2-nitroguanidino)acetamide I as an
example. The reaction was performed by refluxing the
reagents mixture in aqueous alkaline medium for 2 h.
The so prepared 5(3)-alkyl(aryl)-3(5)-nitroamino-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 9 2013

NEW REPRESENTATIVES OF NITROAMINE-CONTAINING 1,2,4-TRIAZOLES
1781
Table 2. Yields, melting points and spectral characteristics of 5(3)-alkyl(aryl, amino)-3(5)-nitroamino-1,2,4-triazoles VII–
XII
1Н NMR
(DMSO-d6), δ, ppm
Electronic spectra (ethanol)
Comp.
no.
R
mp, ºС
Yield %
NH
R
λmax, nm
ε
–CH3
209–210
185–186
60
75
13.64 s
2.25
291
287
13000
17000
VII
−C7H15
13.90 s 0.65 m, 1.3 m,
1.6 m, 2.65 m
VIII
HO
214–215
75
13.90 s
2.95 s,
6.65–7.15 m,
9.40 s
283
14500
IX
CH2
CH2
CH2
CH2
196–199
197–199
65
71
13.90 s 1.80 t, 2.45 m,
2.70 m, 3.40 s
287
291
16000
16500
X
CH2
Br
OH
13.95 s
7.80–8.00 m
XI
OCH3
OCH3
OCH3
210–212
92
14.29 s
3.68 s,
3.81 s,
7.23 s
298
16500
XII
In particular, the HMQC spectrum of VI (Fig. 2)
contained the cross-peaks of proton signals at 3.68
ppm (3H, p-OCH3) and 3.80 ppm (6H, m-OCH3) with
the carbon signals of p- and m-methoxy groups at
60.69 and 56.62 ppm, respectively, as well as of
aromatic ortho-protons singlet at 7.22 ppm (2H) with
the carbons signal at 106.03 ppm (C2', C6'). In the
HMВC spectrum of VI (Fig. 3), the cross-peaks of
protons signal at 3.68 (p-ОСН3) with carbon signal at
were close to those in the spectra of the starting
compounds I–VI. In the 13С–{1Н} NMR spectra of
VII and XII, the 13С signals of all structural fragments
were identified. In particular, С5 and С3 atoms of
triazole ring (Fig. 5) were assigned to the signals at
148.30 (VII), 148.87 (XII) and 153.12 (VII), 153.72
ppm (XII), respectively. The validity of their
assignments was confirmed by the HMBC
experiments. In the HMBC spectra, the cross-peak of
the methyl group signal at 2.25 ppm with the signal at
148.30 ppm (VII) was present, along with the cross-
peak of the aromatic ring ortho-protons signals (7.23
ppm) with the signal at 148.87 ppm (XII), thus, those
signals could be assigned to С5 of triazole ring.
Analysis of other cross-peaks in the XII spectrum
allowed accurate assignment of all the carbon atoms,
similarly to the above-described for compound VI.
3
141.15 ppm (С4', J), 3.80 (m-ОСН3) with 153.08 ppm
3
(С3', С5', J), and 7.22 (ortho-H) with 153.08 ppm (С3',
2
С5', J) were observed. At the same time, the proton
signal at 7.22 ppm gave rise to three additional cross-
2
peaks, with the carbons signals at 127.65 (С1', J),
3
3
141.15 (С4', J), and 166.29 ppm (С=О, J). The
carbon signal with δС of 161.92 ppm with no cross-
peaks in both HMQC and HMBC spectra was assigned
to the С=NNO2 carbon atom.
In the IR spectra of heterocycles VII–XII, a set of
intense absorption bands was observed in the range of
1250–1630 cm–1. The strong band at 1600–1630 cm–1
could be probably assigned to the combination of
stretching of C=N and deformation of N–H bonds [13].
The absorption bands at 1550–1580 and 1260–
1320 cm–1 were due to stretching of NO2 group [14,
15]. The N–H valence vibrations were observed in the
range of 3100–3600 cm–1. In the cases of III and IV,
1
In the H NMR spectra of VII–XII (Fig. 4), there
were no proton signals of nitroguanidine fragment, the
only downfield broad singlet observed in the range of
13.90–14.29 ppm was assigned to the NH group of
triazole ring. Apparently, the signal of NHNO2 group
was absent due to its exchange, especially when
DMSO-d6 contained water admixture [12]. The
chemical shifts of alkyl and aryl protons of VII–XII
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 9 2013

1782
EFIMOVA et al.
6H
H3CO
H3CO
H3CO
O
3H
NH1 NH2
C
NH2
NNO2
2H
OCH3-m
OCH3-p
2H
1H
1H
δ, ppm
Fig. 1. 1Н NMR spectrum of compound VI in DMSO-d6.
the absorption band assigned to OH group was
observed in that region.
EXPERIMENTAL
The H, 13C–{1H}, H–13C HMQC, and HMBC
NMR spectra were recorded with Jeol ECX400A
spectrometer [399.78 (1H), 100.525 (13C) MHz] in
DMSO-d6; the signals of residual non-deuterated
solvent being the internal standard. The IR spectra
were recorded with IRPrestige-21 Fourier-spectro-
meter in KBr pellets. The electronic spectra were
recorded with Shimadzu UV2401PC spectrophotometer
in quartz cuvettes (l = 0.1 cm, c ~ 1.0×10–3 mol l–1 in
ethanol). Elemental analysis was performed with
Eurovector EA 3000 (CHN Dual mode) analyzer.
1
1
Electronic spectra of triazoles VII–XII contained
an absorption band at 283–298 nm (ε = 13000–17000),
being consistent with the data reported for the
structurally similar compounds [7, 9].
To conclude, the studied reactions of 1-methyl-1-
nitroso-2-nitroguanidine with carboxylic acid hydra-
zides were convenient methods to prepare the pre-
viously unknown 3(5)-5-nitroamino-5(3)-alkyl(aryl)-
1,2,4-triazoles, compounds of potential interest for the
medical applications. The obvious advantages of the
developed method were availability of the starting
materials, high yields of the target products, and
possibility of one-pot synthesis under conditions of
“green” chemical processes [16].
1-Methyl-1-nitroso-2-nitroguanidine was prepared
as described in [17]. Commercially available
hydrazides of octanoic, 4-hydroxybutanoic, 3-(2-hyd-
roxyphenyl)propanoic, 3-bromobenzoic, and 3,4,5-
trimethoxybenzoic acids were used.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 9 2013

NEW REPRESENTATIVES OF NITROAMINE-CONTAINING 1,2,4-TRIAZOLES
1783
m-OCH3
p-OCH3
δC, ppm
m-OCH3/m-OCH3
p-OCH3
p-OCH3
p-OCH3/m-OCH3
ortho-H
δH, ppm
Fig. 2. 1H–13C HMQC spectrum of compound VI DMSO-d6.
δC, ppm
ortho-H
p-OCH3
ortho-H
ortho-H
ortho-H
m-OCH3
δH, ppm
Fig. 3. 1H–13C HMBC spectrum of compound VI in DMSO-d6.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 9 2013

1784
EFIMOVA et al.
H
N N
N
OCH3
OCH3
HN
O2N
OCH3-m
OCH3-p
OCH3
δ, ppm
Fig. 4. 1Н NMR spectrum of compound XII in DMSO-d6.
m-OCH3
p-OCH3
δC, ppm
m-OCH3
p-OCH3
ortho-H
p-OCH3
ortho-H
ortho-H
ortho-H
m-OCH3
δH, ppm
Fig. 5. 1H–13C HMBC spectrum of compound XII in DMSO-d6.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 9 2013

NEW REPRESENTATIVES OF NITROAMINE-CONTAINING 1,2,4-TRIAZOLES
1785
N-(2-Nitroguanidino)amide of acetic acid (I).
23.52 g of 1-methyl-1-nitroso-2-nitroguanidine was
added in small portions to a solution of 12.39 g of
acetic acid hydrazide in 30 ml of water. The reaction
mixture was heated to 80°C. When the precipitate was
formed, the reaction mixture was kept for 10–15 h till
the reaction completion. The resulting precipitate was
filtered off, washed sequentially with cold water,
ethanol, ether, and dried in air. Yield 17 g (66%), mp
191–192°C (water). Found, %: C 26.25; H 4.05; N
49.50. C3H7N5O3. Calculated, %: C 22.36; H 4.35; N
43.48.
water was added to a solution of 1.61 g of acetic acid
N-(2-nitroguanidino)amide I in 30 ml of water, and the
reaction mixture was refluxed for 1–2 h till decoloura-
tion of the solution. Then the reaction mixture was
cooled down to room temperature and acidified with
concentrated hydrochloric acid to pH ~ 5. The
resulting precipitate was filtered off and washed with
water. Yield 1.14 g (60%), decomp. 212–213°C
(water) {decomp. 208°C (water) [7]}.
b. 5.88 g of 1-methyl-1-nitroso-2-nitroguanidine
was added in small portions to a solution of 3.31 g of
acetic acid hydrazide in 50 ml of water. The reaction
mixture was heated at 80ºC for 2 h. Then 2.24 g of
sodium hydroxide was added to the mixture. The
reaction mixture was heated for 1 h. After cooling
down to room temperature, the reaction mixture was
acidified with concentrated hydrochloric acid to pH
~ 5. The resulting precipitate was filtered off and
washed with water. Yield 3.14 g (55%), decomp. 209–
210°C (water). Melting point of the mixture of samples
prepared by the both methods was not depressed.
Found, %: C 25.17; H 3.49; N 48.95. C3H5N5O2.
Calculated, %: C 25.46, H 3.96; N 47.87.
N-(2-Nitroguanidino)amide of octanoic acid (II)
was prepared similarly from 2.07 g of octanoic acid
hydrazide and 1.92 g of 1-methyl-1-nitroso-2-nitro-
guanidine. Yield 2.07 g (65%), mp 156–158°C
(isopropanol–water, 1:1). Found, %: C 44.24; H 8.73;
N 27.78. C9H19N5O3. Calculated, %: C 44.00; H 7.90;
N 27.50.
N-(2-Nitroguanidino)amide of 3-(2-hydroxy-
phenyl)propanoic acid (III) was prepared similarly
from 2.6 g of 3-(2-hydroxyphenyl)propionic acid
hydrazide and 1.92 g of 1-methyl-1-nitroso-2-nitro-
guanidine. Yield 2.6 g (75%), mp 175–176°C (iso-
propanol–water, 1:1). Found N, %: 26.21. C10H13N5O4.
Calculated N, %: 26.20.
5(3)-Heptyl-3(5)-nitroamino-1,2,4-triazole (VIII).
A solution of 0.4 g of sodium hydroxide in 5 ml of
water was added to a solution of 2.27 g of octanoic
acid N-(2-nitroguanidino)amide II in 20 ml of water.
The reaction mixture was refluxed for 1–2 h till
decolouration of the solution. The reaction mixture
was cooled down to room temperature and acidified
with concentrated hydrochloric acid to pH ~ 5. The
resulting precipitate was filtered off and washed with
water. Yield 1.53 g (75%), mp 185–186°C (water).
Found, %: H 7.10; N 30.90. C9H17N5O2. Calculated,
%: H 7.48; N 30.83.
N-(2-Nitroguanidino)amide of 4-hydroxybutanoic
acid (IV) was prepared similarly from 1.56 g of 4-
hydroxybutanoic acid hydrazide and 1.95 g of 1-
methyl-1-nitroso-2-nitroguanidine. Yield 1.94 g (73%),
mp 108–110°C (water). Found, %: H 5.22; N 34.44.
C5H11N5O4. Calculated, %: H, 5.36; N 34.14.
N-(2-Nitroguanidino)amide of 3-bromobenzoic
acid (V) was prepared similarly from 0.52 g of 3-
bromobenzoic acid hydrazide and 0.35 g of 1-methyl-
1-nitroso-2-nitroguanidine. Yield 0.69 g (95%), mp
179–180°C (isopropanol–water, 1:1). Found, %: C
32.02; H 2.63; N 23.63. C9H11N5O3Br. Calculated, %:
C 31.78; H 2.64; N 23.17.
5(3)-(2-Hydroxyphenyl)-3(5)-nitroaminoethyl-1,2,4-
triazole (IX) was prepared similarly from 2.49 g of 3-
(2-hydroxyphenyl)propanoic acid N-(2-nitroguanidino)-
amide III and 0.4 g of sodium hydroxide. Yield 1.68 g
(75%), mp 214–215°C (water). Found, %: C 42.36; H
4.77; N 21.96. C10H11N5O3. Calculated, %: C 42.1; H
4.7; N 22.3.
N-(2-Nitroguanidino)amide of 3,4,5-trimethoxy-
benzoic acid (VI) was prepared similarly from 1.26 g
of 3,4,5-trimethoxybenzoic acid hydrazide and 0.82 g
of 1-methyl-1-nitroso-2-nitroguanidine. Yield 1.15 g
(63%), mp 216–217°C (isopropanol–water, 1:1).
Found, %: C 42.36; H 4.77; N 21.96. C12H17N5O6.
Calculated, %: C 42.10; H 4.70; N 22.3.
5(3)-(3-Hydroxypropyl)-3(5)-nitroamino-1,2,4-
triazole (X) was prepared similarly from 1.88 g of 4-
hydroxybutanoic acid N-(2-nitroguanidino)amide IV
and 0.4 g of sodium hydroxide. Yield 1.1 g (65%), mp
197–199°C (water). Found, %: H 4.74; N 37.34.
C5H10N5O3. Calculated, %: H 4.81; N 37.43.
5(3)-Methyl-3(5)-nitroamino-1,2,4-triazole (VII).
a. A solution of 0.4 g of sodium hydroxide in 5 ml of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 9 2013

1786
EFIMOVA et al.
Protection Against Diseases), Leningrad: VIZR, 1991,
3(5)-Nitroamino-5(3)-(3-bromophenyl)-1,2,4-tri-
p. 73.
azole (XI) was prepared similarly from 2.99 g of 3-
bromobenzoic acid N-(2-nitroguanidino)amide V and
0.4 g of sodium hydroxide. Yield 1.91 g (71%), mp
198–199°C (water).
5. Henry, R.A., J. Am. Chem. Soc., 1950, vol. 72, no. 11,
p. 5343.
6. Chipen, G.I., Grinshtein, V.Ya., and Preiman, R.P., Zh.
Obshch. Khim., 1962, vol. 32, no. 2, p. 454.
3(5)-Nitroamino-5(3)-(3,4,5-trimethoxyphenyl)-
1,2,4-triazole (XII) was prepared similarly from 3.09 g
of 3,4,5-trimethoxybenzoic acid N-(2-nitroguanidino)-
amide VI and 0.4 g of sodium hydroxide. Yield 2.56 g
(92%), mp 210–212°C (water). Found, %: C 44.76; H
4.55; N 23.64. C12H15N5O5. Calculated, %: C 44.74; H
4.40; N 23.72.
7. Novikova, T.A., Metelkina, E.L., Efimova, T.P., and
Berestovitskaya, V.M., Russ. J. Org. Chem., 2004,
vol. 40, no. 8 p. 1210.
8. Metelkina, E.L. and Novikova, T.A., Russ. J. Org.
Chem., 2004, vol. 40, no. 4, p. 593.
9. Metelkina, E.L. and Novikova, T.A., Zh. Org. Khim.,
1993, vol. 29, no. 1, p. 2390.
10. Sil’verstein, R., Webster, F., and Kiml, D., Spektro-
metricheskaya identifikatsiya organicheskikh soedinenii
(Spectrometric Identification of Organic Compounds),
2011, p. 557.
Physico-chemical studies were performed in the
Center for Collective Use in Herzen State Pedagogical
University of Russia.
11. Pretch, E., Bühlmann, P., and Affolter, C., Structure
Determination of Organic Compounds: Tables of
Spectral Data, Springer: Berlin, 2000.
12. Astakhov, A.M., Vasil’yev, A.D., Molokeev, M.S.,
Revenko, V.A., and Stepanov, R.S., Russ. J. Org.
Chem., 2005, vol. 41, no. 6, p. 910.
ACKNOWLEDGMENTS
This work was financially supported by the
Government of St. Petersburg (diplomas PSP
no. 11035, PSP no. 11036, 2011).
13. Morozova, N.S., Metelkina, E.L., Novikova, T.A.,
Shlyapochnikov, V.A., Sergienko, O.I., and Perekalin, V.V.,
Zh. Org. Khim., 1983, vol. 19, no. 6, p. 1228.
14. Kofman, T.P., Kartseva, G.Yu., and Shcherbinin, M.B.,
Russ. J. Org. Chem., 2002, vol. 38, no. 9, p. 1343.
15. Pevzner, M.S., Gladkova, N.V., and Kravchenko, T.A.,
REFERENCES
1. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
Moscow: RIA “Novaya Volna,” 2012.
2. Shilova, I.B., Gus’kova, T.A., and Glushkov, R.G.,
Pharm. Chem. J., 2004, vol. 38, no. 4, p. 175.
Zh. Org. Khim., 1996, vol. 32, no. 8, p. 1230.
3. Ivanskii, V.I., Khimiya geterotsiklicheskikh soedinenii
(Chemistry of Heterocyclic Compounds), Moscow:
Vysshaya Shkola, 1978, p. 202.
4. Zdrozhevskaya, S.D. and Nechiporenko, N.I., Nauchnye
osnovy khimicheskoi zashchity sel’skokhozyaistvennykh
kul’tur ot boleznei (Scientific Basis of Chemical Crop
16. Anastas, P.T. and Warner, J.C., Green Chemistry:
Theory and Practice, New York: Oxford University
Press, 1998, p. 30.
17. McKay, A.F. and Wright, G.F., J. Am. Chem. Soc.,
1947, vol. 69, p. 3028.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 9 2013