Nitrimines: VII. Reaction of S,S′-Dimethyl-N-nitroimidodithiocarbonate with Alkali. Synthesis of S-Methyl-N-nitrothiocarbamate and Its Salts

Article abstract of DOI:10.1134/S1070428018110039

Reaction of S,S′-dimethyl-N-nitroimidodithiocarbonate with alkali in aqueous-alcoholic solution results in salts of S-methyl-N-nitrothiocarbamate. In anhydrous ethanol a salt of nitrouretane is obtained. By the reaction of S-methyl-N-nitrothiocarbamate salts with hydrazine 4-nitrosemicarbazide salts were prepared.

Full text of DOI:10.1134/S1070428018110039

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2018, Vol. 54, No. 11, pp. 1638–1642. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © A.M. Astakhov, D.V. Antishin, А.А. Nefedov, G.E. Salnikov, E.S. Buka, 2018, published in Zhurnal Organicheskoi Khimii, 2018,
Vol. 54, No. 11, pp. 1629–1633.
Nitrimines:
VII.1 Reaction of S,S'-Dimethyl-N-nitroimidodithiocarbonate
with Alkali. Synthesis of S-Methyl-N-nitrothiocarbamate and Its
Salts
A. M. Astakhova,* D. V. Antishina, А. А. Nefedovb, G. E. Salnikovb, and E. S. Bukaa
a Reshetnev Siberian State University of Science and Technology,
pr. im. gazety “Krasnoyarskii rabochii” 31, Krasnoyarsk, 660037 Russia
*e-mail: alexastachov@mail.ru
b Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090, Russia
Received April 20, 2018
Revised April 20, 2018
Accepted April 20, 2018
Abstract—Reaction of S,S'-dimethyl-N-nitroimidodithiocarbonate with alkali in aqueous-alcoholic solution
results in salts of S-methyl-N-nitrothiocarbamate. In anhydrous ethanol a salt of nitrouretane is obtained. By the
reaction of S-methyl-N-nitrothiocarbamate salts with hydrazine 4-nitrosemicarbazide salts were prepared.
DOI: 10.1134/S1070428018110039
Nitrimines are interesting as energy rich [2–4] and
biologically active compounds [5–8]. A classic method
of such compounds preparation is N-nitration of the
corresponding imino derivatives [2, 9]. However, a
number of compounds that may be obtained by this
method is limited. Another path of synthesis of target
nitrimines is to use the substitution reaction of
compounds that already possess nitrimine function
and, besides that, group easily leaving under the action
of nucleophilic agents (Scheme 1).
the expected nitrourea salts, but in salts of
nitrocyanamide [14] (Scheme 2).
In this connection in was interesting to investigate
the reaction with alkali of compound 2. Due to the
insolubility of the latter in water we applied aqueous-
alcoholic solutions as the reaction medium. To a
solution of compound 2 in ethanol aqueous solution
was added with calculated amount of NaOH and the
reaction solution was heated till reflux.
One of the reaction products is sodium carbonate
whose yield depends on the ratio compound 2–sodium
Such compounds, convenient for the preparation of
nitrimines of different structure are, for example, S-
methyl-N-nitroisothiourea
nitroimidodithiocarbonate 2, whose molecules contain
one or two methylsulfanyl groups respectively.
1
and S,S'-dimethyl-N-
Scheme 1.
NNO2
Y
NNO2
Nu
NuH
_YH
Published data exist on reactions of compounds 1
and 2 with different mono- and diamines [10, 11],
hydrazine [4, 12], and hydroxylamine [13].
Y = SR, OR, NHNO2.
Scheme 2.
_
[N CNNO2]
80_90%
Previously we demonstrated that although the
reaction of compound 1 with alkali occurred with the
substitution of methylsulfanyl group it resulted not in
NNO2
NH2
_
HO
_MeSH
_
MeS
NNO2
1
1
O
NH2
For communication VI, see [1].
1638

NITRIMINES. VII. REACTION OF S,S'-DIMETHYL-N-NITROIMIDODITHIOCARBONATE
1639
Scheme 3.
NNO2
OH
HCl
MeS
3
_
_
2
2
NNO2
_
NNO2
SMe
NNO2
O
H2O
_NH2NO2
NaOH
_MeSH
NaOH
_MeSH
MeS
O
MeS
O
OH
2Na+
O
O
Na+
3a
2Na+
2
N2O + H2O
HCl
NHNO2
NNO2
EtO_
_MeSH
_
EtO
O
EtO
O
Na+
4a
4
hydroxide. Increasing the alkali concentration and the
reaction time leads to an increased yield of sodium
carbonate. For instance, at the molar ratio of
components 1 : 2 the yield of sodium carbonate is
~90% after 2 h from the beginning of the reaction. At
the molar ratio of components in the range from 1 : 1
to 1 : 2 a compound was isolated possessing an
absorption maximum in the UV spectrum at 280 nm
that turned out to be a previously unknown sodium salt
of S-methyl-N-nitrothiocarbamate 3a. Also along with
compound 3a and sodium carbonate we isolated from
the reaction mixture the unreacted initial compound 2.
The optimization of reaction conditions allowed
increasing the yield of compound 3a to 65%.
hydrolytically unstable salt of nitrocarbamic acid
whose hydrolysis eventually leads to carbonate.
In anhydrous ethanol the reaction with alkali also
probably occurs with the primary formation of
compound
3 salt. The subsequent nucleophilic
substitution of the second methylsulfanyl group by
ethoxide anion explains the formation of nitrouretane
salt 4a (Scheme 3).
The composition and structure of previously
unknown compound 3 were confirmed by elemental
analysis, high resolution mass-spectrometry, IR, UV,
and NMR spectra.
Essentially there are two possible structures of
compound 3: nitrimine and primary nitramine,
distinguished by the place of localization of the
hydrogen atom (Scheme 4).
Free S-methyl-N-nitrothiocarbamate 3 is easily
isolated quantitatively from its salts by treating with
HCl (Scheme 3).
At replacing 95% ethanol with anhydrous ethanol
compound 3a was not obtained, however besides
sodium carbonate from reaction mixture a compound
was isolated possessing an absorption maximum in the
UV spectrum at 260 nm. It was identified as a sodium
salt of nitrocarbamic acid ethyl ether 4a, which at
treating with HCl provided nitrouretane 4 in a 60%
yield. Similary from compound 2 and KOH we
obtained a potassium salt of S-methyl-N-nitrothio-
carbamate 3b.
Scheme 4.
NNO2
NHNO2
NNO2
_
MeS
OH
MeS
O
MeS
anion
O
nitrimine
nitramine
We believe that compound 3 possesses a nitrimine
structure. Particularly it is evidenced by the lack of a
typical for a carbonyl group strong absorption band in
the range 1700 cm–1 (for example, for nitrouretane
1739 cm–1) in the IR spectrum. The probable attribution
of IR spectra is described in the experimental part, it is
made by comparison with the other nitrimines and
nitramines [15]. Thus, the strong band at 1632 cm–1 is
assigned to the stretching vibrations of the СN bond,
and bands at 1408 and 1316 cm–1, to the stretching
The formation of salts 3a and 3b evidences that
alkaline hydrolysis of nitrimine 2 occurs through
nucleophilic substitution of methylsulfanyl group with
the hydroxide anion. The formation of carbonates is
due to the substitution of the second methylsulfanyl
group, probably, with the intermediate formation of a
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 11 2018

ASTAKHOV et al.
1640
Scheme 5.
NHNO2
O
NHNH2
5
N2H4
3
NNO2
NNO2
_
_
N2H5+
N2H5+
N2H4
O
_MeSH
O
SMe
NHNH2
5a
vibrations of nitro group (νas and νs respectively),
which is close to the data on IR spectra of
nitroguanidine [16]. In alkali salts 3a, 3b the
absorption bands at 1311–1301 and 918–927 cm–1 are
attributed to vibrations of nitro group (νas and νs). Such
a shift of vibration frequencies of nitro group at
ionization is typical of N-nitrocompounds [15].
substances for the synthesis of other compounds [17–
22] previously were obtained in the reaction of
hydrazine with N,N'-dinitrourea [17].
In the reaction of equimolar amounts of compound
3 and hydrazine only hydrazinium salt forms
quantitively, while the substitution of methylsulfanyl
group does not occur. At the same time at the action of
2 mol of hydrazine on compound 3 mercaptan is
liberated and hydrazinium salt 5a forms. It allows an
assumption that in the reaction with hydrazine the
anion of compound 3 takes part (Scheme 5).
The coincidence of UV spectra of compound 3 with the
spectra of its salts 3a and 3b evidences that compound
3 in aqueous solution also exists as an anion. Meanwhile
regardless of the initial structure of compound 3 its
anion should have a similar structure in both cases
with a general delocalization of electron density.
This assumption was confirmed at investigation of
reaction with hydrazine of salts 3a and 3b. In both
cases for the formation of the corresponding salts of
nitrosemicarbazide it was enough to add 1 mol of
hydrazine (Scheme 6).
1Н, 13С, and 15N NMR spectra do not allow
distinguishing between nitramine and nitrimine
structures, moreover that also in DMSO the formation
of anion and fast proton exchange are possible. Yet the
NMR spectra confirm the formation of compound 3. In
Scheme 6.
1
NNO2
the H NMR spectrum two signals are present: the
_
N2H4
_MeSH
M+
singlet of the methyl group at 2.30 ppm and a
broadened signal at 10.76 ppm of the OH proton. In
the 13С NMR spectrum the signal of the methyl atom
appears at 12.0 ppm, and of the second carbon atom, at
167.3 ppm. The chemical shift value of the latter is
typical of nitrimine carbon atom C=NNO2, however the
signal of carbonyl atom C=O may appear in the same
range. In 15N NMR spectrum the signal at –39.7 ppm
corresponds to nitrogen atom of nitro group, the
second nitrogen atom appears at –164.3 ppm. In this
case it is also difficult to determine the localization
place of the hydrogen atom.
3a, 3b
O
NHNH2
5b, 5c
M = Na (b), K (c).
The ammonium salt 5d was obtained from salt 3b
at treating with ammonium chloride and hydrazine
without isolation of intermediate ammonium salt
(Scheme 7).
Scheme 7.
1. NH4Cl
2. N2H4
NNO2
NH4+
_
The methylsulfanyl group in compound 3 and its
salts can be substituted as well with other nucleophiles,
in particular, in reaction of compounds 3 and 3a and
3b with hydrazine we have obtained salts of 4-
nitrosemicarbazide.
3b
_MeSH
O
NHNH2
5d
At increasing the excess of hydrazine the rate of
reaction of compound 3 with salts increases, however
at the same time increases the yield of the side product,
4-Nitrosemicarbazide
5
and its derivatives,
promising as energy rich compounds and as initial
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 11 2018

NITRIMINES. VII. REACTION OF S,S'-DIMETHYL-N-NITROIMIDODITHIOCARBONATE
1641
1,3-diaminourea, the formation of which from
compound 5 has been demonstrated previously [22].
The side product is well soluble in ethanol, unlike salts
of nitrosemicarbazide, which in course of reaction
precipitate from the reaction mixture.
Sodium salt of S-methyl-N-nitrothiocarbamate
(3a). To solution of 0.50 g (3 mmol) of S,S'-dimethyl-
N-nitroimidodithiocarbonate 2 in 5 mL of ethanol was
added 5 mL of aqueous solution containing 0.12 g
(3 mmol) of NaOH, the mixture was heated till reflux
in a round bottom flask equipped with a reflux condenser
and was maintained for 2 h. After that the reaction
mixture was evaporated till dryness and extracted with
acetone (3 × 15 mL). The extract was evaporated, the
residue was recrystallized from acetone. Yield 0.31 g
(65%), mp 149–150°С. UV spectrum: λmax 280 nm, logε
4.10. IR spectrum, ν, cm–1: 2983, 2924, 2852, 1650, 1391,
1311, 1203, 1099, 1066, 960, 927, 784, 735, 710, 662.
Found, %: C 15.96; H 2.199; N 17.52. C2H3N2NaO3S.
Calculated, %: C 15.19; H 1.91; N 17.72.
The method we have developed for the preparation
of nitrosemicarbazide salts has a number of benefits
comparing to the method of obtaining them from N,N'-
dinitrourea [17]. In particular, the process occurs in
ethanol where final target products are insoluble, but
the initial and side substances are well soluble. Nitro-
semicarbazide salts 5a–5d formed in course of reaction
crystallize directly from the reaction solution and may
be used in further reactions without additional puri-
fication. Yet the preparation of salts of nitrosemicar-
bazide by the method [17] is performed in aqueous
solution because at application of alcohols N,N'-di-
nitrourea quickly enough reacts with them even at low
temperatures with the formation of nitrouretanes [17].
Potassium salt of S-methyl-N-nitrothiocarbamate
(3b) was obtained similarly from compound 2 and
0.17 g of KOH. Yield 0.32 g (62%), mp 112°С. UV spec-
trum: λmax 280 nm, logε 4.10. IR spectrum, ν, cm–1: 2972,
2927, 2849, 1631, 1405, 1301, 1197, 918, 780, 732, 710,
661. Found, %: C 14.05; H 1.88; N 16.54. C2H3KN2O3S.
Calculated, %: C 13.79; H 1.74; N 16.08.
EXPERIMENTAL
UV spectra were recorded on a spectrophotometer
Shimadzu UV-1601 from aqueous solutions. Vibration
spectra were taken on a spectrometer Nicolet
AVATAR 380 from tablets with KBr. Elemental
analysis was carried out on an automatic CHN-
Ethyl ether of carbamic acid (nitrouretane) (4).
To a solution of 0.50 g (3 mmol) of compound 2 in
5 mL of anhydrous ethanol was added 5 mL of ethanol
solution containing 0.24 g (6 mmol) of NaOH. The
reaction mixture was heated till reflux in a round
bottom flask equipped with a reflux condenser and was
maintained for 1 h, after that it was evaporated till
dryness and extracted with acetone (3 × 15 mL). To
the extract 0.25 mL of 30% HCl was added. The
precipitate was filtered off, the filtrate was evaporated
till dryness, the residue was recrystallized from
benzene. Yield 0.28 g (60%), mp. 62–63°С (64°С
[23]). UV spectrum: λmax 260 nm, logε 4.01. IR
spectrum, ν, cm–1: 3235, 3006, 2989, 1739, 1605,
1456, 1393, 1368, 1331, 1240, 1117, 1018, 998, 879,
799, 769, 730, 605 (full coincidence of spectrum with
the spectrum of an authentic sample).
1
analyzer Vario EL III. H, 13С, and 15N NMR spectra
are recorded on a spectrometer Bruker AV-600 (600,
150, and 60 МHz respectively) at room temperature in
DMSO-d6, internal reference TMS (for 15N chemical
shifts δ are reported in CH3NO2 scale). Mass spectrum
was measured on a high resolution spectrometer
Thermo Electron DFS with direct input of sample
(ionization energy 70 eV).
S-Methyl-N-nitrothiocarbamate (3). To solution
of 0.50 g (2.8 mmol) of salt 3b in 10 mL of acetone
was added 0.6 mL of 30% HCl, the precipitate was
filtered off, the filtrate was evaporated till dryness, the
residue was recrystallized from benzene. Yield 0.36 g
(94%), mp 93–95°С. UV spectrum: λmax 280 nm, logε
4.10. IR spectrum, ν, cm–1: 3121, 2980, 2799, 1632,
1605, 1408, 1337, 1316, 1276, 1192, 1039, 971, 785,
Hydrazinium salt of 4-nitrosemicarbazide (5a).
To a solution of 0.25 g (1.8 mmol) of compound 3 in
5 mL of ethanol was added 0.16 mL (3.6 mmol) of
75% hydrazine hydrate. The reaction mixture was
heated till reflux in a round bottom flask equipped with
a reflux condenser and was maintained for 2 h. The
precipitated crystals were filtered off, washed with a
small amount of ethanol and dried in open air. Yield
0.23 g (82%), mp 130°C (130°С [17]). UV spectrum:
λmax 256 nm, logε 3.91. IR spectrum, ν, cm–1: 3325,
1
731, 697, 637, 573, 446. H NMR spectrum, δ, ppm:
2.30 s (3H, CH3), 10.76 br.s (1H, OH). 13С NMR
spectrum, δ, ppm: 12.0 (SCH3), 167.3 (C=NNO2). 15N
NMR spectrum, δ, ppm: –164.3 (NNO2), –39.7
(NNO2). Mass spectrum: m/z 135.9938. Found, %: C
17.81; H 3.01; N 20.16. C2H4N2O3S. Calculated, %: C
17.65; H 2.96; N 20.58. M 135.9937.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 11 2018

ASTAKHOV et al.
1642
(NTREM)”, University of Pardubice, Pardubice, Czech
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3229, 3001, 2924, 2845, 2801, 2644, 1667, 1619,
1548, 1513, 1382, 1349, 1271, 1182, 1107, 971, 849,
776, 759. Found, %: C 8.07; H 5.11; N 55.62.
CH8N6O3. Calculated, %: C 7.90; H 5.30; N 55.25.
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Sodium salt of 4-nitrosemicarbazide (5b). To a
solution of 0.30 g (1.9 mmol) of salt 3a in 5 mL of ethanol
was added 0.10 mL (2.25 mmol) of 75% hydrazine
hydrate and the mixture was stirred for 2 h at reflux
with a reflux condenser. The precipitated crystals were
filtered off, washed with a small amount of ethanol,
and dried in open air. Yield 0.20 g (73%), mp 151°C
(with decomposition). UV spectrum: λmax 255 nm, logε
3.91. IR spectrum, ν, cm–1: 3314, 3253, 3207, 2923,
2856, 1661, 1606, 1502, 1376, 1320, 1158, 1032, 929,
786, 686. Found, %: C 8.40; H 2.35; N 38.44.
CH3N4O3Na. Calculated, %: C 8.46; H 2.13; N 39.44.
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Potassium salt of 4-nitrosemicarbazide (5c) was
obtained similarly from salt 3b. Yield 0.23 g (76%),
mp 139–140°C (with decomposition) {130°С (with de-
composition) [17]}. UV spectrum: λmax 255.5 nm, logε
3.91. IR spectrum, ν, cm–1: 3325, 3228, 3018, 2925, 2852,
1667, 1619, 1535, 1359, 1263, 1187, 1048, 1029, 957,
825, 781, 689. Found, %: C 7.38; H 1.86; N 35.48.
CH3KN4O3. Calculated, %: C 7.59; H 1.91; N 35.42.
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Ammonium salt of 4-nitrosemicarbazide (5d). To
a solution of 0.50 g (2.9 mmol) of salt 3b in 10 mL of
water was added 0.19 g (3.45 mmol) of ammonium
chloride. After a full dissolution 0.13 mL (2.9 mmol)
of 75% hydrazine-hydrate was added and the reaction
mixture was stirred for 30 min at 30°С. Then 10 mL of
ethanol was added, the reaction mixture was cooled to
–15°С, the precipitate was filtered off, washed with a
small amount of ethanol, and dried in open air. Yield
0.27 g (70%), mp 145°С (with decomposition). UV
spectrum: λmax 255 nm, logε 3.91. IR spectrum, ν, cm–1:
3318, 3260, 3017, 1778, 1656, 1615, 1545, 1405,
1351, 1315, 1257, 1180, 1114, 1028, 950, 867, 822,
781, 732. Found, %: C 9.12; H 5.17; N 51.44.
CH7N5O3. Calculated, %: C 8.76; H 5.15; N 51.08.
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