Nitration of styrenes using 2-methyl-5-trinitromethyltetrazole

Full text of DOI:10.1007/s10593-012-1107-y

Chemistry of Heterocyclic Compounds, Vol. 48, No. 7, October, 2012 (Russian Original Vol. 48, No. 7, July, 2012)
NITRATION OF STYRENES USING
2-METHYL-5-TRINITROMETHYLTETRAZOLE
1
1
M. A. Abdel'rakhim and A. G. Tyrkov *
Keywords: 2-methyl-5-dinitromethyltetrazole, 2-methyl-5-trinitromethyltetrazole, -nitro ketone,
nitroalcohol, nitromethane oxime, styrene.
Details of the methods of synthesis, chemical properties, and practical importance of tetrazoles have
been reported in the studies [1, 2] and in a series of reviews [3-5]. At the same time, the chemical
transformations of 5-trinitromethyltetrazoles have been investigated to a lesser degree. It is only known that
5
-trinitromethyl-1H-tetrazole is denitrated in the presence of an alkaline solution of hydroxylamine to give the
potassium salt of 5-dinitromethyltetrazole, while its reaction with excess diazomethane results in the formation
of a mixture of the isomeric 5-(1-methyltetrazolyl)- and 5-(2-methyltetrazolyl)trinitromethanes [6].
We have found that 2-methyl-5-trinitromethyltetrazole (1) reacts with the styrenes 2a-d as a nitrating
agent. The reaction of tetrazole 1 with the ethenes 2a-d in a neutral medium results in the denitration of
compound 1 to give the -nitro ketones 3a-c (from the alkenes 2a-c) or the 1-methyl-2-nitro-1-phenyl-1-ethanol
3
d (from alkene 2d). In addition, the degradation products of compound 1 (the nitromethanone oxime 4 from
the reactions with compounds 2a-c or the 5-dinitromethyltetrazole 5 from the reaction with compound 2d) are
formed in low yields.
HON
NO2
O
(
from 2a–c)
N
NO2
2
R
+
Ph
N
N
1
Me
R
N
4
C(NO2)
3
R
3
a–c
N
1
Et O
2
R
+
Ph
N
N
O N
2
0
–5°C
Me
2
N
R
NO2
1
2
a–d
Me OH
Ph
(from 2d)
N
+
NO2
N
N
Me
N
5
3
d
1
2
1
2
1
2
1
2
a R = R = R = H; b R = R = H, R = Me; c R = H, R = R = Me; d R = Me, R = R = H
_
*
______
To whom correspondence should be addressed, e-mail: tyrkov@rambler.ru.
1
Astrakhan State University, 1 Shaumyana Sq., Astrakhan 414000, Russia.
_
________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1192-1194, July, 2012. Original
article submitted February 28, 2012.
009-3122/12/4807-1111©2012 Springer Science+Business Media New York
0
1111

The nature of the reaction products allows us to propose that the reaction of compound 1 with alkenes
a-d occurs by a known scheme [7, 8] through a stage of charge-transfer complex formation from nitroalkyl
2
ether of aci-dinitrotetrazolylmethane, which dissociates via an intramolecular oxidation-reduction to the -nitro
ketones 3a-c or nitroalcohol 3d.
1
13
IR spectra were recorded on an Infralum FT-02 spectrophotometer in KBr pellets. H NMR and
C
NMR spectra were recorded on a Bruker Avance II 300 SF spectrometer (300 and 75 MHz, respectively) in
DMSO-d with HMDS as internal standard. Elemental analysis was carried out on a EuroVector Euro EA 3000
6
CHNS analyzer. The tetrazole 1 was prepared by the method reported in the study [6]. Compounds 2a-d were
synthesized from the corresponding carbonyl compounds and alkylmagnesium halides to yield alcohols which
were then dehydrated [9].
Reaction of 2-Methyl-5-trinitromethyltetrazole (1) with Alkenes 2a-d (General Method).
Compound 1 (1.17 g, 5 mmol) in absolute diethyl ether (30 ml) was added to a solution of compound 2a-d
(
5 mmol) in the same solvent (20 ml) at 0-5ºC. The reaction mixture was maintained at 25ºC for 140 h, solvent
was evaporated under reduced pressure, and the residue was chromatographed on an activated Silicagel
1
4
00/400 grade column (10×250 mm). The eluent for compounds 3a-d was benzene, while for the compounds
, 5 it was diethyl ether.
2
-Nitro-1-phenyl-1-ethanone (3a). Yield 0.48 g (58%). Colorless crystals, mp 105-107ºC (mp 105-107ºC
1
[
10]). The H NMR spectrum agreed with that given in the literature [11]. Found, %: C 58.25; H 4.15; N 8.37.
C H NO . Calculated, %: C 58.18; H 4.24; N 8.48.
8
7
3
2
0
20
2
-Methyl-2-nitro-1-phenyl-1-ethanone (3b). Yield 0.58 g (65%). Oily liquid, ηD 1.5465 (ηD 1.5465
1
[
12]). The H NMR spectrum agreed with that given in the literature [11]. Found, %: C 60.45; H 4.94; N 7.71.
C H NO . Calculated, %: C 60.34; H 5.03; N 7.82.
9
9
3
2
0
20
2
,2-Dimethyl-2-nitro-1-phenyl-1-ethanone (3c). Yield 0.49 g (55%). Oily liquid, ηD 1.5280 (ηD
1
1
.5280 [12]). The H NMR spectrum agreed with that given in the literature [11]. Found, %: C 62.27; H 5.58;
N 7.13. C H NO . Calculated, %: C 62.18; H 5.70; N 7.25.
1
0
11
3
2
0
20
1
-Methyl-2-nitro-1-phenyl-1-ethanol (3d). Yield 0.47 g (52%). Oily liquid, ηD 1.5190 (ηD 1.5190
1
[
10]). The H NMR spectrum agreed with that given in the literature [13]. Found, %: C 59.74; H 5.97; N 7.63.
C H NO . Calculated, %: C 59.67; H 6.08; N 7.73.
9
11
3
(
2-methyltetrazol-5-yl)nitromethanone Oxime (4). Yield 0.13 g (15%), Colorless crystals, mp
-
1
1
1
1
85-187ºC. IR spectrum, , cm : 1555, 1380 (NO ). H NMR spectrum, , ppm (J, Hz): 4.53 (3H, s, CH );
3.75 (1H, br. s, OH). C NMR spectrum, , ppm: 39.6 (СН ); 65.2 (C); 146.9 (C-5). Found, %: С 21.02;
2
3
13
3
H 2.26; N 48.91. С H N O . Calculated, %: С 20.94; H 2.34; N 48.83.
3
4
6
3
2
-Methyl-5-dinitromethyltetrazole (5). Yield 0.09 g (10%). Colorless crystals, mp 37-38ºC (Et O–
2
1
hexane, 1:1) (mp 37-38ºC [6]). The H NMR spectrum agreed with that given in the literature [6]. Found, %:
C 19.22; H 2.03; N 44.58. C H N O . Calculated, %: C 19.15; H 2.13; N 44.68.
3
4
6
4
This work was carried out with the financial support of the program "Development of Innovative
Infrastructure in Russian Universities" (grant No. 13.637.31.0038) using the Collective Use Center science
systems "Biotechnologies to Obtain Original Pharmaceutical Substances".
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