Nitration of triazolyl-substituted ketones

Article abstract of DOI:10.1007/s11178-005-0239-2

By nitration of 3-R-1,2,4-triazol-1-ylalkanones with a mixture of concentrated sulfuric and nitric acids a series of compounds was obtained containing a trinitromethyl fragment at the nitrogen of the ring. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11178-005-0239-2

Russian Journal of Organic Chemistry, Vol. 41, No. 5, 2005, pp. 753-757. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005,
pp. 767-771.
Original Russian Text Copyright Ó 2005 by Kofman, Kartseva, Glazkova, Krasnov.
.
Nitration of Triazolyl-substituted Ketones
T.P. Kofman, G.Yu. Kartseva, E.Yu. Glazkova, and K.N. Krasnov
St. Petersburg State Technological Institute, St. Petersburg, 198013 Russia (812)112 779
Received August 16, 2004
Abstract—By nitration of 3-R-1,2,4-triazol-1-ylalkanones with a mixture of concentrated sulfuric and nitric acids
a series of compounds was obtained containing a trinitromethyl fragment at the nitrogen of the ring.
The reaction of destructive nitration of aliphatic
ketones was thoroughly investigated by an example of
1,1,1-trinitro-4-pentanone nitration into hexanitroethane
[5, 6]. It was established that the use of concentrated
nitric acid alone did not result in nitration, but the mixtures
of sulfuric and nitric acids at the optimum components
ratio [HNO3:H2SO4 = (1–2):1 (by weight), low water
content (up to 3%), and high liquor ratio of the acid bath
(acids mixture: ketone = 15–20:1)] afforded the hexa-
nitroethane in a high yield. The presence of nitrogen oxides
did not affect the process. The kinetic data on this reaction
were published in [6], and based thereon the mechanism
of ketones destructive nitration was suggested. In keeping
with the data the reaction was represented as a multistage
sequential-parallel process whose kinetics were plausibly
described by an equation of a double-stage reaction. In
both rate-determining stages the nitronium cation is
involved, and the non-protonated form of the ketone
enters into the reaction.
The nitration of compounds possessing a methylene
fragment activated by a carbonyl group may be regarded
as a fairly general synthetic procedure for preparation of
aliphatic mono-, di-, and trinitromethyl compounds [1–6].
Treating simple aliphatic ketones with nitric acid is
known [1] to result in the rupture of the chain and in
formation of 1,1-dinitroalkanes that were however obtain-
ed in a low yield. The nitration of ketones possessing
a methylene group activated by additional acceptor (ethyl
acetoacetate, acetylacetone) under mild conditions (with
a mixture of sulfuric and nitric acids in chloroform at low
temperature) afforded the corresponding mononitrocom-
pounds [2], and treating polynitroalkyl-sunstituted ketones
of the general formula R(CH2)nCOCH3 with mixtures of
concentrated sulfuric and nitric acids resulted in the
synthesis of the corresponding R-dinitro and R-trinitro
derivatives [R = CH(NO2)2, RC(NO2)3] [3–6].
Mononitro-substituted ketones as well as 1-aryl-1,1-
dinitro-4-pentanones were not involved into the reaction
[4]. In no case Golod et al. [3–6] succeeded in isolation
of compounds with the terminal dinitromethyl group.
The short survey of the above studies suggested that
the nitration of N-oxoalkyl-1,2,4-triazole with mixtures of
sulfuric and nitric acids would provide nitro derivatives
with a polynitroalkyl fragment attached to the nitrogen
atom of the ring.
Alongside the nitration of polynitroalkyl-substituted
ketones an example was described of a successful nitra-
tion carried out with N-heteryl-substituted propanones [7]:
At treating the N-methylated N-(2-oxopropyl)azoles with
a diluted mixture of sulfuric and nitric acids ylides were
obtained with a dinitromethyl fragment at the nitrogen of
the five-membered ring.
We selected for the study a series of ketones mono-
substituted in the ring, both previously synthesized by us
[8, 9] and newly prepared: 3-R-1,2,4-triazol-1-ylbutan-3-
ones R = H (Ia), N3 (IIa) [9], Cl (IIIa), NO2(IVa) [8],
5
5
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1+ 2+ꢀꢀꢀ+&O
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R = H (I), N3 (II), Cl (III), NO2 (IV). Z = O (Ia–IVa), NOH (Ib).
1070-4280/05/4105-0753Ó2005 Pleiades Publishing, Inc.

KOFMAN et al.
754
5
1
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compound IVa furnished a negligible amount (less than
1%) of 1-trinitromethyl-3-nitro-1,2,4-triazole (IVc).
and 3-R-1,2,4-triazol-1-ylpropan-2-ones: R = N3 (IIb) [9],
NO2 (IVb) [8].
In nitration with mixtures of concentrated sulfuric and
nitric acid we varied the liquor ratio of the acid bath:
acids mixture: ketone = 20–40:1 (by weight), the ratio of
acids in the mixture HNO3:H2SO4 = 1:1–1:4 (by weight),
temperature 0–20°C, reaction time from several hours
to 5–7 days. The reaction progress was monitored by
weight of the accumulating final product that was isolated
by diluting an aliquot of the nitrating mixture under
standard conditions.
Compounds IIa–IVa were obtained by condensation
of 3-R-1,2,4-triazoles I–IV with methyl vinyl ketone. The
isolation and identification of triazol-1-ylbutanone (Ia) was
performed by conversion of the crude product into oxime
Ib.
3-R-1,2,4-Triazol-1-ylpropan-2-ones IIb and IVb were
prepared as described in [8, 9] by alkylation of triazole II
and IV with bromoacetone or propylene oxide followed
by oxidation of the alcohols obtained with Jones’ reagent.
Some regular trends in the reaction and also the effect
of substarate structure on the process were investigated
by varying the nitration conditions by the example of
triazol-1-ylbutanones IIa, IVa, R = N3, NO2 and 3-nitro-
1,2,4-triazol-1-ylpropanone (IVb, R = NO2) (Fig. 1–3).
Nitration conditions for 3-R-1,2,4-triazol-1-ylalkanones
were taken at the beginning as described in [5].
We established that under the chosen conditions the
destructive nitration of triazolyl-substituted ketones, like
that of polynitroalkylbutanones, afforded trinitromethyl
derivatives Ic–IVc, but in contrast to the polynitro-
substituted ketones the nitration of ketone Ia gave rise
also to dinitromethyl compound Id, the natural precursor
of 1-trinitromethyl-1,2,4-triazole (Ic). Nitration to
trinitromethyl compounds is a very slow process with the
3-R-1,2,4-triazol-1-ylalkanones.
It was established that ketones nitration into the
trinitromethyl compounds is accompanied by decomposi-
tion of the target product in the nitrating mixture: the ac-
cumulation curves reached a maximum, and then the yield
of the target product notably decreased (Figs. 1–3) with
the greatest speed for the most active ketone (Fig. 1,
curves 1, 2, 4). Therefore the workup of the reaction
mixture should be done at a proper time. Therewith for
each ketone a certain exposure time exists where the
yield remains sufficiently stable under the given conditions.
For instance, the exposure intervals in the nitrating mixture
may be regarded as optimum for the following ketones :
36–48 h for triazolylpropanone IVb, 70–96 h for
triazolylbutanone IVa, and 120 h for triazolylbutanone IIa
(HNO3:H2SO4 = 1:1, liquor ratio 20).
The nitration products of the first compound in this
series, 1,2,4-triazol-1-ylbutanone (Ia) or its oxime Ib were
isolated only in small overall yield, up to 10% (extraction
from the diluted nitrating mixture) and after long exposure
time (1–7 days); therewith the yield did not grow at
prolonging the exposure to 20 days.
The introduction of an electron-acceptor substituent
into the triazole ring (compounds IIa–IVa) significantly
accelerated the process and increased the yield of the
corresponding 1-trinitromethyl-1,2,4-triazoles IIc–IVc.
The latter precipitated in a virtually pure state on diluting
the nitrating mixture and did not contain the corresponding
1-dinitromethyl-1,2,4-triazoles. The extraction of diluted
In the general case the maximum yield of the product
and the time required to obtain it is governed by the ketone
structure and the reaction temperature and also depends
on the liquor ratio of the acid bath and the proportion of
nitrating mixture with ethyl acetate after nitration of the acids in the nitrating mixture. Triazolylpropanone IVb
RUSSIAN JOURNALOF ORGANIC CHEMISTRYVol. 41 No. 5 2005

NITRATION OFTRIAZOLYL-SUBSTITUTED KETONES
755
<LHOGꢀꢁꢂꢁ
is nitrated faster than homologous IVa (Fig. 1, curves 1,
2) in good agreement with the ease of destruction of
a shorter chain, and in the butanone series the activity
grows with the increasing electron-acceptor effect of the
substituent in the ring: nitro-substituted triazolylbutanone
IVa is notably more reactive than the corresponding
azidoanalog IIa and affords the trinitromethyl compound
in a higher yield (Fig. 1, curves 2, 4). The reaction rate
considerably decreased at lower temperature (Fig. 1,
curves 2, 3) and although the stability of the trinitromethyl
compound grew under these conditions, carrying out the
nitratione at 0°C is unfeasible due to the long duration of
the process and low yield of the target product.
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Fig. 1. Yield of trinitromethyl compounds at nitration of
compounds IVb (1), IVa (2, 3) , IIa (4). Liquor ratio 20.
HNO3:H2SO4 = 1:1; 20OC (1, 2, 4); 3–0°C (3).
The yield and reaction time can be adjusted by varying
the liquor ratio of the acid bath and the acids proportion
(Fig. 2, 3). For compounds IVa and IIa the maximum
yield of trinitromethyl compounds (63 and 45%
respectively) was attained at sufficiently stringent
conditions [HNO3:H2SO4 = 1:2, liquor ratio = 30, 20°C
(sulfuric acid content in the mixture 64%, water content
up to 3%)]. With the growing proportion of sulfuric acid
in the nitrating mixture (HNO3:H2SO4 = 1:1, 1:2) (Fig. 2,
curves 2, 1; Fig. 3, curves 1, 3) at the constant liquor
ratio (20) the process notably accelerated, but the yield
increased only for the azido derivative. Raising of the
liquor ratio at the high content of the sulfuric acid in the
mixture (liquor ratio = 20–30, HNO3:H2SO4 = 1:2)
resulted both in a faster process and a greater yield (Fig.
2, curves 1, 3; Fig. 3, curves 3, 4) and it is especially
pronounced with the nitro derivative. The attempt to
increase the yield of azido compound IIc by applying
even higher liquor ratio (40) was not successful: The
process accelerated but the yield was decreased (Fig. 3,
curve 2).
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Fig. 2. Nitration of triazolylbutanone IVa at variable liquor
ratio and the ratio of acids in the nitrating mixture, 20°C:
(1) liquor ratio = 20, HNO3:H2SO4 = 1:2; (2) liquor ratio = 20,
HNO3:H2SO4 = 1:1; (3) liquor ratio = 1:30, HNO3:H2SO4 = 1:2.
ꢁ
7LPHꢀꢁK
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Just these conditions of the destructive nitration (liquor
ratio = 30, HNO3:H2SO4 = 1:2, 20°C) we believe to be
optimum for the N-azolyl-substituted ketones, and we
have carried out under these conditions the nitration of
the chlorine-substituted ketone IIIa.
ꢊꢄꢁ
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The structure of all compounds obtained was confirmed
by their analyses and spectral data. Their IR spectra are
characterized by a certain shift of the absorption bands
from the asymmetrical stretching vibrations of the
trinitromethyl fragment to the high-frequency region
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–1
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(1600–1640 cm ) with respect to the spectra of the other
–1
Fig. 3. Nitration of butanone IIa at variable liquor ratio and
the ratio of acids in the nitrating mixture, 20°C: (1) liquor
ratio = 20, HNO3:H2SO4 = 1:1; (2) liquor ratio = 40,
HNO3:H2SO4=1:2; (3) liquor ratio = 1:20, HNO3:H2SO4 =
1:2; (4) liquor ratio = 30, HNO3:H2SO4 = 1:2.
aliphatic polynitro derivatives (1597–1603 cm ) [10].
This phenomenon was previously observed for
pentanitroethyl compounds and hexanitroethane (1595–
–1
1636 cm ) [6]: therewith in the latter spectra a strong
RUSSIAN JOURNALOF ORGANIC CHEMISTRYVol. 41 No. 5 2005

KOFMAN et al.
756
dublet was observed in this region. In our case similarly
for trinitromethyl compounds IIIc–IVc possessing
electron-acceptor substituents 2–3 very strong bands
were observed in this region. This fact evidences most
likely the spatial nonequivalence of the nitro groups in
the trinitromethyl fragment.
3-Azido-1,2,4-triazol-1-ylbutan-3-one (IIa). Yield
65%, mp 34–35°C (freezing out from ether) [9].
3-Chloro-1,2,4-triazol-1-ylbutan-3-one (IIIa). Oily
substance, yield 60%, isomers 9:1 (reprecipitation from
–1
ether with petroleum ether). IR spectrum, n, cm : 1180
1
(C=O), 1515 (cycle), 1730 (C=O). H NMR spectrum,
In the 1H NMR spectra the signal from C5H proton is
located typically in a very weak field (d 9.30–9.98 ppm)
as compared to the initial triazoles (d 8.0–8.6 ppm) due
to introduction of a very strond electron-acceptor into
the position 1 of the triazole ring. The characteristic
feature of the UV spectra is the presence of a single
maximum of high intensity: lmax, nm, (log e): 231 (4.1)
(IIc), 212 (4.17) (IVc).
d, ppm: 8.42 s (1H, H5), 7.95 s (1H, H3), 4.48 t (2H,
CH2), 4.40 t (2H, CH2), 3.15 t (2H, CH2), 2.18 s (3H,
CH3). Found, %: C 41.33; H 4.66; N 24.55. C6H8ClN3O.
Calculated, %: C 41.5; H 4.6; N 24.2.
3-Nitro-1,2,4-triazol-1-ylbutan-3-one (IVa). Yield
82%, mp 60–61°C (from aqueous methanol) [8].
3-Azido-1,2,4-triazol-1-ylpropan-2-one (IIb).Yield
75%, nD20 1.577 (reprecipitation from ether with petroleum
ether) [9].
It should be remarked that all trinitromethyl compounds
of this series are exceedingly sensitive to heating and
mechanical effects and therefore they should be handled
with special care and the syntheses and purification
should be performed with small charges.
3-Nitro-1,2,4-triazol-1-ylpropan-2-one (IVb).
Yield 70%, mp 100–101°C (from chloroform) [8].
1-Dinitromethyl- and 1-trinitromethyl-1,2,4-
triazoles (Id and Ic). General procedure. To a mixture
of 13 ml of nitric (d 1.51 g/cm3) and 12 ml of sulfuric
acid (d 1.84 g/cm3) at 0–5°C was added while stirring by
portions a solution of 2 g of ketone Ia (oxime Ib) in 10 ml
of concn. H2SO4. The reaction mixture was stirred at 0–
5°C for 1 h, then the temperature was raised to ambient,
and the mixture was kept for 1–20 days. Then the nitrating
mixture was poured into a 4-fold amount of finely crushed
ice with water, extracted with dichloromethane (4´25 ml)
(compound Id) and then with ethyl acetate (4´25 ml)
(a mixture of compounds Ic and Id). Both extracts were
washed with water (2´50 ml). The ethyl acetate from
the second extract was evaporated, the residue was
treated with hot dichloromethane (2´25 ml) to extract
compound Id, and this solution was combined with the
first extract containing the main portion of the compound.
The residue after extraction was crystallized from
chloroform. From the combined dichloromethane solutions
the solvent was evaporated, and the product obtained
was crystallized from chloroform.
EXPERIMENTAL
1H NMR spectra were registered on a spectrometer
Perkin Elmer R-12 (60 MHz) in acetone-d6, internal
reference HMDS. IR spectra were recorded on a spectro-
photometer Specord 75IR (from films), UV spectra were
measured on SF-4A device from solutions in ethanol of
–4
concentration about 10 mol/l, cell thickness 1 cm.
3-R-1,2,4-Triazol-1-ylbutan-3-ones Ia–IVa. To a
solution of 0.044 mol of substituted triazole I–IV was
added 1 ml of triethylamine and 4.5 ml (0.054 mol) of
methyl vinyl ketone, the mixture was kept for 48 h at
room temperature, the solvent was removed, and the
residue was crystallized.
1,2,4-Triazol-1-ylbutan-3-one oxime (Ib). To a
solution of 10 g (0.145 mol) of 1,2,4-triazole Ia in 50 ml
of ethanol was added 18 ml (0.22 mol) of methyl vinyl
ketone and 3 ml of triethylamine. The mixture was kept
at room temperature for 3 days, the solvent was
evaporated, and to the residue was added hydroxylamine
solution prepared in methanol from 10 g (0.145 mol) of
hydroxylamine hydrochloride and 8.1 g (0.145 mol) of
KOH. The mixture was kept at room temperature for
24 h, the solvent was evaporated, and the residue was
crystallized from 1-pentanol. Yield 11.2 g (50%), mp 113–
1-Dinitromethyl-1,2,4-triazole (Id). Yield 5–7%,
–1
mp 106–107°C (CHCl3). IR spectrum, n, cm : 1500
(cycle), 1610 s [C(NO2)2]. 1H NMR spectrum, d, ppm:
9.25 s (1H, H5), 8.50 s (1H, H3), 8.40 s [1H, C(NO2)2H],
exchange in D2O. Found, %: C 20.95; H 1.86; N 40.89.
C3H3N5O4. Calculated, %: C 20.8; H 1.73; N 40.5.
–1
114°C, IR spectrum, n, cm : 1480 (cycle), 1520 (C=N).
1H NMR spectrum, d, ppm: 8.52 s (1H, H5), 8.0 s (1H,
H3), 4.50 t (2H, CH2), 2.75 t (2H, CH2), 1.80 s (3H,
CH3). Found, %: C 46.18; H 6.44; N 36.69. C6H10N4O.
Calculated, %: C 46.7; H 6.5; N 36.4.
1-Trinitromethyl-1,2,4-triazole (Ic). Yield 7%, mp
–1
101–102°C (CHCl3). IR spectrum, n, cm : 1480 s (cycle),
1560 s, 1630 s [C(NO2)3]. 1H NMR spectrum, d, ppm:
9.30 s (1H, H5), 8.50 s (1H, H3). Found, %: C 16.58;
RUSSIAN JOURNALOF ORGANIC CHEMISTRYVol. 41 No. 5 2005

NITRATION OFTRIAZOLYL-SUBSTITUTED KETONES
757
H 0.99; N 38.77. C3H2N6O6. Calculated, %: C 16.50;
H 0.92; N 38.50.
triazolylpropanone IVb), mp 99–100°C (CHCl3). IR
–1
spectrum, n, cm : 1520 sc (cycle), 1570 v.s (NO2),
1
1610 v.s, 1620 v.s, 1625 v.s [(C(NO2)3]. H NMR
1-Trinitromethyl-1,2,4-triazoles
IIc–IVc.
spectrum, d, ppm: 9.98 s (C5H). Found, %: C 13.63;
H 0.37; N 37.22. C3HN7O8. Calculated, %: C 13.7;
H 0.4; N 37.3.
General procedure. To a mixture of 13 ml of nitric (d
1.51 g/cm3) and 12 ml of sulfuric acid (d 1.84 g/cm3) at
0–5°C was added while stirring by portions a solution of
2 g of ketone IIa–IVa, IIb, and IVb. The reaction mixture
was stirred at 0–5°C for 1 h, then the tempera-ture was
raised to ambient and the reaction mixture was kept at
intermittent stirring. The reaction progress was monitored
by weight of the accumulating final product that was
isolated by sampling an aliquot of the nitrating mixture (5
ml). The aliquot of the nitrating mixture was poured into
a 4-fold amount of finely crushed ice with water, the
precipitated product was filtered off through a teflon
nutsch filter and fiber-glass and washed with ice water
(2´5 ml), dried in air, and weighed. A fair yield was
obtained by keeping the nitrating mixture for 1.5 or 3
days (ketones IVb and IVa respectively) or 5 days
(ketones IIa, IIb, and IIIa). Recrystallization of products
was performed with the use of a water bath.
The study was carried out under financial spport of
the ISTC (project no. 2468).
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leev Commun., 1993, p. 58.
1-Trinitromethyl-3-azido-1,2,4-triazole (IIc).Yield
45%, mp 58–59°C (from petroleum ether). IR spectrum,
–1
n, cm : 1540 s (cycle), 1600 s, 1630 v.s [C(NO2)3],
2155 s (N3). 1H NMR spectrum, d, ppm: 9.50 s (C5H).
Found, %: C 14.09; H 0.38; N 48.72. C3HN9O6. Calculat-
ed, %: C 13.9; H 0.4; N 48.7.
1-Trinitromethyl-3-chloro-1,2,4-triazole (IIIc).
–1
Yield 45%, mp 37–38°C (CHCl3). IR spectrum, n, cm :
1
1520 m (cycle), 1615 s, 1645 s [C(NO2)3]. H NMR
8. Kofman, T.P., Uspenskaya, T.L., Medvedeva, N.Yu., and
Pevzner, M.S., Kh. Geterotsikl. Soed., 1976, p. 991.
9. Kofman, T.P. and Krasnov, K.K., Zh. Org. Khim., 2004,
vol. 40, p. 1699.
spectrum, d, ppm: 9.85 s (C5H). Found, %: C 14.32;
H 0.43; N 32.94. C3ClHN6O9. Calculated, %: C 14.25;
H 0.39; N 33.3.
1-Trinitromethyl-3-nitro-1,2,4-triazole (IVc).
Yield 63% (from triazolylbutanone IVa), 90% (from
10. Noble, R., Borgardt, F., and Reed, W.L., Chem. Rev., 1964,
vol. 64, p. 19.
RUSSIAN JOURNALOF ORGANIC CHEMISTRYVol. 41 No. 5 2005