Chromogenic Reaction of 1,1-Dimethylhydrazine with Aryltetrazolium Salts

Article abstract of DOI:10.1134/S107036321807006X

The reactions of 1,1-dimethylhydrazine with 2,3,5-triphenyl-2Н-tetrazolium and 2,5-diphenyl-3-(4-nitrophenyl)-2Н-tetrazolium chlorides in a solution and on a cellulose carrier have been studied by means of spectrophotometry and chromato–mass spectrometry to develop new chromogenic indicators for detection of 1,1-dimethylhydrazine. 1,3,5-Triphenylformazan and 1,3-diphenyl-5-(4-nitrophenyl)formazan are formed in these reactions, respectively; deep red shifts have been observed. Other products of these reactions result from oligomerization and addition of short-living 1,1-dimethylhydrazyl and tetrazolium radicals.

Full text of DOI:10.1134/S107036321807006X

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 7, pp. 1385–1389. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © V.M. Ostrovskaya, D.O. Shchepilov, E.A. Kletter, 2018, published in Zhurnal Obshchei Khimii, 2018, Vol. 88, No. 7, pp. 1092–
1
097.
Chromogenic Reaction of 1,1-Dimethylhydrazine
with Aryltetrazolium Salts
a,b
b
b
V. M. Ostrovskaya *, D. O. Shchepilov , and E. A. Kletter
a
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
*
e-mail: ostr@igic.ras.ru
b
The 25th State Research Institute of Chemmotology, Ministry of Defense of the Russian Federation, Moscow, Russia
Received February 15, 2018
Abstract―The reactions of 1,1-dimethylhydrazine with 2,3,5-triphenyl-2Н-tetrazolium and 2,5-diphenyl-3-(4-
nitrophenyl)-2Н-tetrazolium chlorides in a solution and on a cellulose carrier have been studied by means of
spectrophotometry and chromato–mass spectrometry to develop new chromogenic indicators for detection of
1
,1-dimethylhydrazine. 1,3,5-Triphenylformazan and 1,3-diphenyl-5-(4-nitrophenyl)formazan are formed in
these reactions, respectively; deep red shifts have been observed. Other products of these reactions result from
oligomerization and addition of short-living 1,1-dimethylhydrazyl and tetrazolium radicals.
Keywords: tetrazolium, formazan, 1,1-dimethylhydrazine, chromogenic reaction
DOI: 10.1134/S107036321807006X
1
,1-Dimethylhydrazine is widely used as fuel in
space-rocket technology and in chemical industry [1].
,1-Dimethylhydrazine is a toxic compound of the first
for new chromogenic reactions for detection of 1,1-
dimehylhydrazine in therefore a topical issue.
1
In view of the chemical properties of 1,1-di-
methylhydrazine 1, we turned to a class of widely utilized
oxygen-free reduction indicators, almost colorless 2Н-
tetrazolium salts which can be reduced into strongly
colored formazans. There are many compounds which
react with tetrazolium salts depending on their electron
acceptor properties; therefore, tetrazolium salts are
used in organic, inorganic, and biochemical analysis
[15]. Available 2,3,5-triphenyl-2Н-tetrazolium chloride
2 produced in many countries on industrial scale can
be reduced to 1,3,5-triphenylformazane 3 via inter-
class of hazard; it is a superecotoxicant [2] exhibiting
high fugitiveness which can be adsorbed on different
surfaces including metals, easily evaporated and de-
sorbed, and is miscible with water in almost any ratio.
Express test methods of 1,1-dimethylhydrazine
detection on solid surfaces, in air, and in water have
been developed over recent decades. Such chromo-
genic indicators as piperidine-4-carbaldehyde [3], bromo-
thymol blue and silver salts [4, 5], 12-molibdosilicon
acid [6], 4-(dimethylamino)cinnamic aldehyde [7],
indicator powder based on phosphotungstate, Safranin
T, malachite green, and sulfate barium [8], 5,7-dinitro-
·
mediate formation of tetrazolium radical (T ). The re-
versible redox reaction tetrazolium 2 D formazan 3
4
-chlorbenzofurazane [9, 10], 4-(dimethylamino)
benzaldehyde [11], phosphomolybdic heteropoly acids
12], and cobalt salts [13] have been used. The listed
occurs as given in Scheme 1 [16–18].
The reduction of tetrazolium salt 2 may not stop at
the formation of formazan 3 but rather proceeds further
to afford hydrazidine, amidrazone, and aniline, depend-
ing on the nature of the substituents in the tetrazole salt
molecule and the reductant type [15].
[
indicators have some disadvantages like toxicity,
limited shelf life, limited red shift in the color test
reaction, sophisticated specimen preparation, high
detection limit (above maximum permissible concentra-
tion). The reactions of oxygen-containing indicators
with 1,1-dimethylhydrazine lead to the formation of
cancerogenic nitrosodimethylamine [14]. The search
We have investigated the chromogenic properties
of the products of 1,1-dimethylhydrazine 1 reactions
with two aryltetrazolium salts: 2,3,5-triphenyl-2Н-
1
385

1
386
OSTROVSKAYA et al.
F
А, rel. units
IP-3
IP-5
λ, nm
Fig. 1. Electronic diffuse reflection spectra of strips (1, 3)
IP-3 and (2, 4) IP-5 formed upon reactions of IP-2 and IP-
λ, nm
Fig. 2. Histograms of optical density of IP-3 and IP-5
4
strips with 1,1-dimethylhydrazine in (1, 2) aqueous
strips.
medium and (3, 4) in air.
Scheme 1.
marked as IP-5, Figs. 1, curve 2). The strip became
colorless after several days due to deeper reduction of
the formed compound 5.
_
Cl
N
Ph
Ph
Ph
Ph
+
_
e
N
N
N
N
Indicator strips IP-2 and IP-4 were tested as chromo-
genic chemical reagents using an exposition in a
Ph
_
e
Ph
_
N
N
N
T
Tishchenko flask. Air with concentration of compound
3
1
1200 mg/m was pumped through the flask at flow
Ph
H
2
3
rate 5–6 cm /min. The strips color was changed from
white to dark-red after 17 min (dark-red strips marked
as IP-3 and IP-5, Figure 1, 3, 4; 2).
_
e
N
N
N
N
_
e
Ph
_
A dark-red suspension was formed as a result of the
reaction of 1,1-dimethylhydrazine with salt 2 in
ethanol; the formation of dark-red precipitate was then
observed. Mass spectrum of that precipitate cor-
responded to that of 1,3,5-triphenylformazan 3 (ac-
cording to the NIST 05 mass spectra database). The
Ph
3
tetrazolium chloride 2 and 3-(4-nitrophenyl)-2,5-di-
phenyl-2H-tetrazolium chloride 4 which are signify-
cantly different in the reduction potentials . The pro-
ducts were identified using chromato–mass spectro-
metry and spectrophotometry.
1
+
observed signals corresponded to the [M] peaks of
1
compound 3, products of dimerization of radicals R
2
and R into dimers 6 and 7, cyclic hexamerization of
2
Indicator paper strips impregnated with salts 2 or 4
IP-2 and IP-4, respectively) upon contact with
radical R into compound 8 (Scheme 2).
(
·
3
Intermediate formation of tetrazolium radical T
aqueous solution of 1,1-dimethylhydrazine (1 mg/cm )
demonstrated different chemical and chromogenic
properties. The strip IP-2 turned dark-red (this color is
typical of compound 3), and the coloration was stable
during keeping; the final state is marked as IP-3,
Fig. 1, curve 1). The strip IP-4 significantly faster
colored dark-red, in the color typical of 5-(4-nitro-
phenyl)-1,3-diphenylformazan 5; the final state is
was indicated by the peaks with m/z corresponding to
1
the products of its addition to Ph and R radicals
(
Scheme 3).
Mass spectrometry data for the products of 1,1-di-
methylhydrazine 1 reaction with salt 4 evidenced the
formation of compound 5, products of di- and oligo-
merization 6–8, products of addition (11, 12) of nitro-
1
1
tetrazolium radical to Рh and R radicals, and products
Polarography half-wave reduction potentials relative to saturated
calomel electrode at 25°С (pH 7.2): Е1/2 –0.80 (2) and –0.43 (4) V
of deeper reduction of salt 4 into C-phenyl-N-(4-
+
[
19].
nitrophenyl)amidrazone 13 (m/z 256 [М] , M 256.27)
calc
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 7 2018

CHROMOGENIC REACTION OF 1,1-DIMETHYLHYDRAZINE
1387
Scheme 2.
_
Ph
Cl
N
Ph
Ph
Me
Me
+
N
N
N
N
N
N
Me
Me
Me
Me
Ph +
H
Ph
+
N
+
N
N
NH2
N
NH
R1
N
Ph
2
1
3
R2
Me
Me
Me
Me
Me
Me
Me
N
HCl
N
N
Me
Me
N
N
N
N
N
N
N
N
NH
NH
N
Me
Me
Me
Me
N
N
N
N
+
+
N
N
8
Me
Me
Me
Me
Me
Me
Me
6
7
+
m/z 118 [M]+
m/z 348 [M]+
m/z 116 [M]
Scheme 3.
Me
Me
Ph
N
Ph
N
N
Ph
Ph
N
N
9
N
N
T
N
N
N
NH
Ph
Me
Ph
Ph
Ph
N
N
N
Ph
Ph
Ph
N
N
H
Me
R1
10
m/z 358 [M]+
+
m/z 299 [M]+
m/z 376 [M]
and aniline (Scheme 4). In contrast to the behavior of
salt 4, salt 2 with lower reduction potential was not
reduced into diphenylamidrazone and aniline and was
more stable to the action of 1,1-dimethyl-hydrazine.
phenyl-2Н-tetrazolium and 3-(4-nitrophenyl)-2,5-di-
phenyl-2H-tetrazolium chlorides in a solution and on a
cellulose paper carrier revealed the formation of the
corresponding formazan (via the tetrazolium radical),
cyclohexamer of 1,1-dimethylhydrazyl biradical,
product of 1,1-dimethylhydrazyl radical addition to the
tetrazolium radical, and dimers of both radicals.
Aryltetrazolium salts are promising sensitive chromo-
genic reagents for detection of 1,1-dimethylhydrazine.
The mass spectra of ethanol extracts from strips IP-
2
and IP-4 the peaks of salts 2 and 4, respectively,
were revealed. The peaks of compounds 3 and 5 and
products of the 1,1-dimethylhydrazine transformations
6
–8 appeared in the spectra upon the strips treatment
with 1,1-dimethylhydrazine.
EXPERIMENTAL
Development of the absorbance of strips IP-3 and
IP-5 during their reduction in air containing 0.4 mg/m
Diffuse reflection spectra of indicator strips were
recorded using an ilPro (Gretag Mackbet, Switzerland)
minispectrophotometer and processed using Kubelka–
3
of 1,1-dimethylhydrazine (with the formation of
formazans 3 and 5, respectively) was monitored using
a LED with λ 505 nm (Fig. 3). The experiment
revealed that the reduction of salt 4 was significantly
faster compared to salt 2.
2
Munk function [F = (1 – R) /2R, R being reflection
coefficient]. Absorbance of indicator strips was
measured with an EKOTEST 20-40 reflectometer
equipped with 8 LEDs and outboard exchangeable
cartridges [20] (EKONIKS). Mass spectra were regis-
tered using a Khromatek-Kristall 5000 (Khromatek)
In summary, spectral study of the chromogenic
reactions of 1,1-dimethylhydrazine with 2,3,5-tri-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 7 2018

1
388
OSTROVSKAYA et al.
Scheme 4.
O N
2
Ph
O N
2
Me MMee
Me
N N
N N
N
N
-
Ph
H
Cl
NH
2
2
+
NH
N
N
N
N
N
N
Ph
Ph
N
N
Ph
Ph
•
4
1
NO
2
T
O N
2
5
.
Me
Me NMeMe
N
·
Ph
Ph
NH
.
NH
H N
2
O N
2
O N
2
Ph
H
H
N
N N
NH2
Ph
Ph
N
N
N
N
N
N
Ph
N
N
Ph
Ph
O N
2
1
1
12
13
+
+
+
m/z 421 [M]
m/z 403 [M]
m/z 256 [M]
gas-liquid chromatograph equipped with a mass
spectroscopic detector and direct injection system
Concentration of 1,1-dimethylhydrazine in air was
determined using an ITM-8 indicator tube (Servek).
(
electron ionization, frequency 50 Hz, carrier gas
The used chemicals and solvents were of “pure” or
chemically pure” grade.
helium; resolution R = M/ΔM = 300). The components
were identified using NIST 05 mass-spectra database.
“
Indicator strips IP-2 and IP-4 were obtained by
soaking the express test paper strips (TU OP 13-
310005-20-83) in a solution of tetrazolium salt 2 or 4
19] (0.1% in a DMF–ethanol mixture, 1 : 1 by volume),
7
[
respectively. The obtained pieces were dried and cut
using a precise cutter [21]. White 9.5×50 mm indicator
strips were thus prepared.
Products of the reaction of 1,1-dimethylhyd-
razine 1 with 2,3,5-triphenyl-2Н-tetrazolium chlo-
ride 2 in liquid medium. 0.33 g (5.5 mmol) of 1,1-
dimethylhydrazine was added to a solution of 1.50 g
(
5 mmol) of compound 2 in 50 mL of ethanol. The
reaction mixture was kept for 2 days until the
formation of a dark-red suspension. The precipitate
Exposure time, days
Fig. 3. Developing of absorbance (λ 505 nm) of (1) IP-2
and (2) IP-4 strips during exposure in air with 1,1-di-
(
0.9 g) was filtered off and dried. Triphenyl formazan
3
methylhydrazine concentration 0.40±0.05 mg/m .
(3), t 0.40 min. Mass spectrum, m/z (I , %): 300 (43)
R
rel
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 7 2018

CHROMOGENIC REACTION OF 1,1-DIMETHYLHYDRAZINE
1389
+
[
М] (calculated for С Н N : 300.37). Mass spectrum
2. Sittig’s Handbook of Toxic and Hazardous Chemicals
and Carcinogens, Pohanish, R.P., Ed., Amsterdam;
Sydney; Tokyo: Elsevier, 2012, p. 1057.
3. Kolesnikov, S.V., Stepanov, N.D., Boldakova, I.P., and
Stukolova, E.V., RF Patent 2305835, 2007; Byull.
Izobret., 2007, no. 25.
19
16
4
+
of the filtrate, m/z (I , %): 300 (40) [М] , 376 (12)
Т + Ph] , 358 (2) [Т + Me N H ] , 348 (2) [Me N ] ,
23 (15) [М – Рh] , 195 (90) [PhC=NNHPh] , 116 (7)
rel
·
+
·
· +
+
[
2
[
(
2 2 12 12
+
+
+
+
+
Me N ] , 118 (12) [Me N H ] , 92 (98) [HNPh] , 77
4 4 4 4 2
20) [Ph].
Products of the reaction of 1,1-dimethylhyd-
4
. Litvinenko, A.N, Avzalov, A.F., Litvinenko, A.A., and
Litvinenko, N.A., RF Patent 2084872, 1997.
razine 1 with 3-(4-nitrophenyl)-2,5-diphenyl-2H-
tetrazolium chloride 2 in liquid medium. 0.33 g
5. Drager-Tubes & CMS Handbook Soil, Water, and Air
Investigations as Well as Technical Gas Analysis,
Lubeck: KGaA, 2011, p. 173.
(
5.5 mmol) of 1,1-dimethylhydrazine was added to a
6
. Ostrovskaya, V.M., Vinogradov, Yu.V., and Korolev, Yu.S.,
RF Patent 2088916, 1997; Byull. Izobret., 1997, no. 24.
. Chernova, R.K., Kozlova, L.M., Shestopalova, N.B.,
and R’yanova, Yu.O., Izv. Saratovsk. Univ., Ser. Khim.,
Biol., Ekol., 2008, vol. 8, no. 2, p. 15.
solution of 1.60 g (5 mmol) of salt 4 in 50 mL of
ethanol. The obtained dark-red suspension was filtered.
7
0
.8 g of formazan 5 was obtained, t 0.64 min. Mass
R
+
spectrum, m/z (I , %): 345 (50) [М] (calculated for
rel
C H N O : 345.36). Mass spectrum of the solution,
1
9
15
5
2
8
9
. Farmakovskaya, T.A., Veksler, K.V., and Kalinin, D.S.,
RF Patent 2562990, 2015; Byull. Izobret., 2015, no. 22.
. Evgen’ev, M.I., Goryunova, S.M., and Evgen’eva I.I.,
Vestn. Kazan. Tekhnol. Univ., 2015, vol. 18, no. 21,
p. 27.
+
·
+
m/z (I , %): 345 (16) [М] , 421 (6) [NO Т + Ph] , 403
1) [NO Т + Me N H ] , 348 (2) [Me N ] , 268 (6)
М – Рh] , 256 (2) [Ph(NH)NNHС Н NO ] , 223 (3)
М – РhNO ] , 195 (62) [PhC=NNHPh] , 240 (19)
PhC=NNHNO ] 137 (10) [HNPhNO ] , 116 (4)
Me N ] , 118 (4) [Me N H ] , 92 (58) [HNPh] , 77
55) [Ph].
Products of the reactions of 1,1-dimethylhyd-
razine 1 with 2,3,5-triphenyl-2Н-tetrazolium chloride
and 3-(4-nitrophenyl)-2,5-diphenyl-2H-tetrazo-
rel
2
·
· +
+
(
[
[
[
[
(
2 2 2 12 12
+
+
6
4
2
+
+
2
+
+
2
2
10. Evgen’ev, M.I. and Levinson, F.S., Khim. Geterotsikl.
Soedin, 1991, no. 11, p. 1565.
11. Khamrakulov, T.K. and Kondrat’ev, O.T., Zav. Lab.
Diagnost. Mater., 2002, vol. 68, no. 10, p. 24.
+
+
+
4
4
4
4
2
1
2. Morosanova, E.I., Talanta, 2012, no. 102, p. 114. doi
0.1016/j.talanta.2012.07.043
1
2
1
3. Posokhov, N.N., Pashinin, V.A., Kosyrev, P.N., Se-
min, A.A., and Khalimova A.S., RF Patent 2563839,
lium chloride 2 immobilized on a cellulose carrier.
Colorless strips IP-2 and IP-4 were placed into an air
2
015; Byull. Izobret., 2015, no. 26.
chamber with 1,1-dimethylhydrazine 1 concentration
14. Ostrovskaya, V.M., Man’shev, D.A., Lyamina, O.I.,
Popov, O.V., and Kupriyanova, T.A., Membrany. Ser.
Krit. Tekhnol., 2002, no. 15, p. 29.
3
1
200 mg/m and kept until appearance of strong
coloration. The obtained dark-red strips were marked
IP-3 and IP-5. Their absorbance (A) was measured
1
5. Buzykin, B.I., Lipunova, G.N., Pervova, I.G.,
Ostrovskaya, V.M., Lipunov, I.N., Maslakova, T.I.,
Stozhko, N.Yu., Barachevskii, V.A., and Sigeikin, G.I.,
Progress v khimii formazanov. Sintez–svoistva–prime-
nenie (Advanced in Chemistry of Farmazones. Syn-
thesis, Properties, and Application), Moscow: Nauchnyi
Mir, 2009.
(
Fig. 2).
Extracts of tetrazolium salts and formazans
from indicator strips. Indicator strip (1×1 cm) was
placed into a test tube; 0.5 mL of ethanol was added,
and the mixture was kept for 15 min. 1 µL of the
ethanol extract was tested using a chromatograph.
1
1
1
6. Rapta, P., Brezova, V., Ceppan, M., Melnik, M., Bustin, D.,
and Stasko, A., Free Rad. Res., 1994, vol. 20, no. 2,
p. 71.
Mass spectrum, m/z (I , %): before reaction, 299 (38)
rel
(
(
salt 2), 344 (10) (salt 4); after reaction, 300 (98)
formazan 3), 345 (40) (formazan 5).
7. Pikaev, A.K. and Kriminskaya, Z.K., Russ. Chem. Rev.,
1
998, vol. 67, no. 8, p. 671. doi 10.1070/
RC1998v067n08ABEH000392
CONFLICT OF INTERESTS
No conflict of interest was declared by the authors.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 7 2018