Chemistry of urea nitro derivatives: III. Reactions of N,N′ -dinitrourea with bases

Article abstract of DOI:10.1023/A:1022503310689

N,N′-Dinitrourea reacts with bases to form the corresponding acid or neutral salts. Its reaction with hydrazine yields 4-nitrosemicarbazide, and the reaction with hydroxylamine leads to N-hydroxy-N′-nitrourea.

Full text of DOI:10.1023/A:1022503310689

Russian Journal of Organic Chemistry, Vol. 38, No. 12, 2002, pp. 1731 1738. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 12, 2002,
pp. 1793 1799.
Original Russian Text Copyright
2002 by Il’yasov, Lobanova, Popov, Sataev.
Dedicated to Full Member of the Russian Academy of Sciences
V.A. Tartakovskii on the 70th Anniversary of His Birth
Chemistry of Urea Nitro Derivatives:
III. Reactions of N,N -Dinitrourea with Bases
*
S. G. Il’yasov, A. A. Lobanova, N. I. Popov, and R. R. Sataev
Altai Federal Research-and-Production Center, ul. Sotsialisticheskaya 1, Biisk, Altai Region, 659322 Russia
e-mail: post@frpc.secna.ru
Received May 15, 2000
Abstract N,N -Dinitrourea reacts with bases to form the corresponding acid or neutral salts. Its reaction with
hydrazine yields 4-nitrosemicarbazide, and the reaction with hydroxylamine leads to N-hydroxy-N -nitrourea.
The development of a simple procedure for pre-
paration of N,N -dinitrourea has opened a new way
to N-nitroamines starting from urea [1, 2]. The avail-
ability of N,N -dinitrourea salts makes it possible to
synthesize new compounds on their basis. Symmetric
N,N -dinitrourea is a fairly strong dibasic acid which
is capable of undergoing stepwise ionization with
formation of acid and neutral salts [2]:
explosion; therefore, they should be handled with
special precautions.
While studying reactions of acid dinitrourea salts
with alkalies, salts containing various cations were
obtained. Treatment of an aqueous solution of dinitro-
urea monoammonium salt with aqueous KOH and
subsequent precipitation with ethyl alcohol gave a salt
whose melting point (194 C) clearly differed from
that of the initial monoammonium salt (105 107 C):
M = Na, K, Cs.
This reaction could give rise to both dipotassium
(
mp 182 186 C) (Table 1) and diammonium dinitro-
+
The existence of acid salts Ia was proved by
physical methods, as well as by the transformations
Ib. Neutral salts Ib are formed on
prolonged heating of aqueous solutions of salts Ia:
urea salt (mp 135 C). The concentrations of K and
+
4
NH cations in the salt, determined by potentiometric
Ia
I and Ia
titration, are consistent with the binary salt structure.
However, this does not mean that it is not a mixture
of two or three substances. On the other hand, a mix-
ture of substances usually has a lower melting point
than those of the pure components.
A distinct proof for the existence of binary dinitro-
urea salts was obtained by quantitative preparation of
of potassium silver salt III. The same product was
synthesized from dinitrourea dipotassium salt IV by
exchange reaction with silver nitrate:
In the presence of excess alkali, these salts undergo
complete decomposition:
All dinitrourea salts, especially acid, are very sen-
sitive to impact and are capable of decomposing with
_
*
___________
For communication II, see [1].
1
070-4280/02/3812-1731$27.00 2002 MAIK Nauka/Interperiodica

1
732
IL’YASOV et al.
corresponding to the CuSO :IV ratios 1:1, 1:2, 1:3,
4
and 1:4; these data suggest formation of four kinds
of complexes according to the following equations
(which are typical of stepwise complex formation [3]):
When dinitrourea was taken as initial compound,
the reaction followed the standard scheme to give
the silver salt.
Treatment of dinitrourea or its salts with bases or
the corresponding bivalent metal salts gives dinitro-
urea salts containing either similar or different cations,
depending on the conditions:
M = Mg; Ca; Ba.
Among the assumed products, we isolated and
identified compounds V and VI. Insofar as complexes
A and B were not isolated, we believe that they exist
In the reaction with copper(II) hydroxide, the
exchange process can be accompanied by complex
formation where dinitrourea anion acts as ligand:
in solution at spectrophotometric concentrations of
3
to 10 4 M.
10
Wide prospects of the application of dinitrourea
anion in the chemistry of coordination compounds are
demonstrated by the synthesis of salts VII and VIII
(Table 1).
The reaction of dinitrourea dipotassium salt IV
with copper(II) sulfate in solution was studied by
spectrophotometry using the molar ratios technique
which makes it possible to determine the composition
of the resulting complexes. The smooth trend of curve
2
in Fig. 1 indicates dissociation in water of the com-
plexes formed. Curve 1 in Fig. 1 has four plateaux
Acid and neutral dintrourea salts are also obtained
with the use of ammonia and amines as bases.
Diammonium salts of dinitrourea undergo decom-
position to give nitrourea monoammonium salts by
the action of excess amonia or amine.
Fig. 1. Plots of optical density at = 800 nm of solutions
versus molar ratio of N,N -dinitrourea dipotassium salt (IV)
3
and CuSO : (1) water, l = 2 cm, [CuSO ] = 5 10 M;
4
4
(
[
2) 0.05 N potassium hydrogen phthalate, l = 5 cm,
CuSO ] = 0.01 M.
XI, R = H; XII, R = Me.
4
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

CHEMISTRY OF UREA NITRO DERIVATIVES: III.
Table 1. Melting points, colors, and densities of dinitrourea salts
1733
Salt
Na [O NNCONHNO ]
Color
mp,
140
126 128
136 137
140
C
Density, g/cm3
+
Colorless
Colorless
Colorless
Colorless
Colorless
Colorless
Colorless
Colorless
Greenish
Blue
1.99
2.11
2.12
2.78
2.97
1.75
1.70
2
2
+
2
+
Na [CO(NNO ) ] Na
2
2
+
K [O NNCONHNO ]
Cs [O NNCONHNO ]
2
2
+
2
2
+
2
+
Cs [CO(NNO ) ] Cs
200
2
2
+
NH [O NNCONHNO ]
105 107
135 138
143
186 187
171
4
2
2
+
2
+
NH [CO(NNO ) ] NH
4
4
2 2
+
2
+
K [CO(NNO ) ] Ag (III)
2
2
+
2
+
K [CO(NNO ) ]
K
(IV)
2.20
2.10
2.25
2.19
2.28
2
2
2
+
2
Cu [CO(NNO ) ] 3H O (V)
K Cu[CO(NNO ) ] (VI)
K Cu(NH ) [CO(NNO ) ] (VII)
2
2
2
+
2
Lilac
Dark blue
Lilac
182
238
179
2
2 2 2
+
2
2
3 2
2 2 2
+
2
K CuCO(NH ) [CO(NNO ) ] (VIII)
2
2 2
2 2 2
O NHNCONHNO C H N HNO3 (XVI)
Colorless
Colorless
Colorless
Colorless
98
202
212
198
2
2
6 12 4
2
+
2
Mg [CO(NNO ) ] 3H O
1.75
1.85
2
2
2
2
+
2
Ca [CO(NNO ) ] 3H O
2
2
2
2
+
2
Ba [CO(NNO ) ] 3H O
2
2
2
Table 2. Reactions of N,N -dinitrourea dipotassium salt (IV) with amines at 30 C
Amine
IV: amine, mol/mol Time, min
Product
K[O NNCONH ]
Yield, %
Decomp. point, C
NH3
MeNH2
BuNH2
1: 4
1: 1
1: 1
1: 1
1: 1
60
60
60
40
30
90
90
70
70
40
126
156
190
130
133
2
2
K[O NNCONHMe]
2
K[O NNCONHBu]
2
NH NH2
K[O NNCONHNH ]
2
2 2
NH ON
K[O NNCONHOH]
2
2
By treatment of dinitrourea with 1 2 equiv of
hydrazine we obtained 4-nitrosemicarbazide (XIII).
In the presence of excess hydrazine, 4-nitrosemicarba-
zide hydrazinium salt (XIIIa) was formed.
soluble in water. It exists in crystal as a mixture of
neutral and zwitterionic forms XIII and XIII which
are very difficult to separate.
Neutral form XIII is formed as the corresponding
monohydrate at an equimolar ratio of dinitrourea and
hydrazine, whereas zwitterionic form XIII is the
major product at a reactant ratio of 1:(2 2.5) in the
presence of sulfuric acid. Presumably, zwitterionic
form XIII gives rise to associates, for its IR spectrum
Neither 4-nitrosemicarbazide nor its salts were
reported previously. Direct nitration of semicarbazide
with mixtures of sulfuric and nitric acids is known
lacks absorption bands typical of free NH and NH
2
groups of the hydrazinium and N-nitroamino frag-
[
4] to give carbamic azide. 4-Nitrosemicarbazide is
ments but contains bands assignable to stretching
+
a colorless crystalline substance, which is sparingly
vibrations of ammonium group like RNH (3010,
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

1
734
IL’YASOV et al.
salt (IV) readily reacts in water with ammonia,
methylamine, butylamine, hydrazine, and hydroxyl-
amine. In the UV spectra of the reaction mixtures
we observed fast displacement of the absorption
maximum at 274 nm, which is tipical of dinitrourea,
to the region 250 260 nm. These data indicate decom-
position of the dinitrourea anion (Fig. 2) with forma-
tion of the corresponding potassium salts (Table 2).
The amine basicity is the most important factor
affecting the reactions of amines with dinitrourea
salts; on the other hand, steric factor should also be
taken into account. For example, no products were
obtained in reactions of dinitrourea salts with secon-
dary amines. Using dinitrourea monopotassium salt
as starting compound, we isolated fairly pure samples
of the target products which required no additional
purification.
Fig. 2. Kinetic curves for decomposition of N,N -dinitro-
urea dipotassium salt (IV) by the action of amines; IV-to-
amine molar ratio 1:1, 30 C: (1) Et NH (pK 11.09),
2
a
(
(
2) NH (pK 9.25), (3) BuNH (pK 10.78), (4) MeNH
3 a 2 a 2
pK 10.66), (5) NH OH (pK 5.95), (6) H NNH (pK 6.5).
a
2
a
2
2
a
1
585, and 1500 cm ). In the region of 3400 cm 1 we
1
observed a weak diffuse band, and a strong band at
180 cm 1 was present; however, we failed to assign
3
It is not recommended to carry out reactions with
dinitrourea in alcohols as solvents. N,N -Dinitrourea
these bands. By contrast, neutral form XIII clearly
shows in the IR spectrum absorption bands due to
(
I) readily reacts with alcohols even at low tempera-
stretching vibrations of free NH group (strong bands
2
1
ture to give the corresponding N-nitrocarbamates.
On the other hand, this reaction povides a very simple
and convenient procedure for preparation of N-nitro-
carbamates.
at 3460 and 3400 cm ).
4
-Nitrosemicarbazide melts in the temperature
range from 227 to 235 C (Boetius device). On re-
peated heating (after solidification), the sample melts
at a higher temperature, 260 263 C. Derivatographic
study of neutral form XIII revealed an endo effect
at 60 100 C, which indicates the presence of crystal-
lization water. The structure of 4-nitrosemicarbazide
R = Me (a), Et (b), Pr (c).
(
XIII) was also confirmed by its conversion into
potassium and nickel salts XIIIb and XIIIc:
Dinitrourea reacts with urotropin in the presence
of nitric acid, yielding hexamethylenetetraaminium
dintrourea nitrate (XVI); treatment of the latter with
potassium hydroxide leads to decomposition with
formation of uroptropin, N,N -dinitrourea dipotassium
salt, and potassium nitrate.
The reaction of dinitrourea with hydroxylamine
leads to formation of hitherto unknown N-hydroxy-
N -nitrourea (XIV) which attracts interest from the
viewpoint of synthesis of new high-energy com-
pounds. While studying reactions of dinitrourea with
bases, we have found that dinitrourea salts can also
be used as substrates. N,N -Dinitrourea dipotassium
It is interesting that product XVI has structural
fragments favoring formation of cyclic compounds.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

CHEMISTRY OF UREA NITRO DERIVATIVES: III.
1735
Dissolution of XVI in concentrated nitric acid or its
weighed with an accuracy of 0.0001 g, the solution
was adjusted to a required volume by adding distilled
mixture with H SO results in formation of 1,3,5-tri-
2
4
nitrohexahydro-1,3,5-triazin-2-one (XVII). The syn-
thesis of compound XVII will be discussed in more
detail in our next communication.
water, and the optical density at
measured. The concentration of IV in the reaction
mixture g (g) was calculated by the formula
= 274 nm was
g = (M V a D)/( a0 1000),
where M is the molecular weight of dinitrourea (226);
V is the volume of the flask (200 ml); a is the weight
0
of the reaction mixture, g; D is the optical density;
is the molar absorption coefficient of salt IV in
water, 12 400 l mol 1 cm ; and a is the sample
weight, g.
N,N -Dinitrourea calcium salt (Ic, M = Ca).
To a solution of 5.52 g (0.03 mol) of dinitrourea
diammonium salt in 20 ml of water we added at
1
EXPERIMENTAL
The IR spectra were recorded on a Specord M-80
spectrometer in KBr. The UV spectra of aqueous
solutions were measured on Specord UV-Vis and
Specord M-40 spectrophotometers. The concentration
of crystallization water in crystal hydrates was deter-
mined by the thermogravimetric method on a Paulik
Paulik Erdey derivatograph. Determination of metal
2
0 2 C under continuous stirring a solution of 7.08 g
(0.03 mol) of Ca(NO ) 4H O in 15 ml of water,
3
2
2
the mixture was kept for 30 min at 0 2 C, and the
precipitate was filtered off, washed with water, ethyl
alcohol, and ether, and dried at room temperature.
Yield 1.69 g (30%). Decomposes at 212 C with ex-
plosion. Found, %: Ca2 15.3. Ca[CO(NNO ) ]
+
+
2+
2+
+
cations (K , Na , Ba , Cu ) in dinitrourea salts
was performed by potentiometric titration in glacial
acetic acid with a 0.1 N solution of perchloric acid in
2
2
2
+
3
H O. Calculated, %: Ca 16.53.
2
N,N -Dinitrourea potassium ammonium salt (II).
To a solution of 1.67 g (0.01 mol) of N,N -dinitrourea
monoammonium salt in 5 ml of water we added at
+
dioxane. Determination of Ag in III was performed
by indicator titration with a 0.1 N solution of ammo-
nium thiocyanate in water. Potassium and silver
cations in compound III were determined by potentio-
metric titration of its solution in AcOH with a 0.1 N
solution of perchloric acid in dioxane (both K and
Ag cations were titrated simultaneously within
a single wave), followed by titration of a solution
of III in water with 0.1 N ammonium thiocyanate
only Ag was thus determined). The concentration
of K was determined from the difference between the
experimental volume of 0.1 N perchloric acid (found
in the titration in AcOH) and that calculated from the
already known amount of silver. Nickel and copper
cations were determined by complexometric titration
with Trilon B.
N,N -Dinitrourea (I), N,N -dinitrourea monopotas-
sium salt, and N,N -dinitrourea dipotassium salt were
prepared by the procedure described in [2].
Spectrophotometric study of reactions of N,N -
dinitrourea dipotassium salt (IV) with amines.
To a solution of 2.26 g (0.01 mol) of dipotassium salt
IV in 100 ml of water we added at 30 1 C under
continuous stirring 0.01 mol of appropriate amine.
Samples were withdrawn immediately after mixing
the reactants and then every 5 min. A 0.1-ml portion
was placed in a 200-ml volumetric flask and was
2
0 C under continuous stirring a solution of 0.56 g
(0.01 mol) of potassium hydroxide in 5 ml of water.
Ethyl alcohol, 10 ml, was then added, and the precip-
itate was filtered off, washed with ethyl alcohol and
ether, and dried at room temperature. Yield 2.05 g
+
+
(
%
100%). Decomposes at 194 C with explosion. Found,
+
+
: K 19.0; NH 8.5. CH KN O . Calculated, %:
4 4 5 5
+
+
+
4
(
K 19.02; NH 8.78.
+
N,N -Dinitrourea potassium silver salt (III).
To a solution of 1.88 g (0.01 mol) of N,N -dinitrourea
monopotassium salt in 50 ml of water we added at
2
0 C under continuous stirring a solution of 1.7 g
(0.01 mol) of silver nitrate in 50 ml of water. The
precipitate was filtered off, washed with water, ethyl
alcohol, and ether, and dried at room temperature.
Yield 3.31 g (100%). Decomposes at 143 C with ex-
+
+
plosion. Found, %: Ag 31.5; K 10.7. CAgKN O
4
5
+
+
2
H O. Calculated, %: Ag 32.63; K 11.78.
2
N,N -Dinitrourea copper(II) salt (V). To a sus-
pension of 1.105 g (5 mmol) of CuCO Cu(OH) in
3
2
10 ml of water we added at 20 C under continuous
stirring 1.5 g (0.01 mol) of dinitrourea. The mixture
was stirred for 30 min, diluted with 40 ml of acetone,
and filtered, and the filtrate was evaporated to dryness.
Yield of salt V (trihydrate) 2.0 g (75%), blue crystals,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

1
736
IL’YASOV et al.
1
decomp. point 171 C. IR spectrum, , cm : 3440
Found, %: C 20.0; H 4.8; N 29.0. C H N O . Calcu-
2
5
3
3
(
H O); 1688 (C O); 1608, 1600 (NNO ); 1525, 1495,
lated, %: C 20.17; H 4.20; N 30.25.
2
2
1
9
425, 1382, 1335, 1295 (NNO ); 1185, 1075, 1025,
2
N-Methyl-N -nitrourea potassium salt (XIIa).
Compound I, 15 g (0.1 mol), was added at a temera-
ture not exceeding 20 C to 37.2 g (0.3 mol) of 25%
aqueous methylamine under continuous stirring. The
mixture was stirred for 120 min at 30 C and cooled
to 20 C, and 300 ml of ethyl alcohol was added. The
mixture was allowed to settle down, and the layers
were separated. A 30% aqueous solution of KOH
60, 880, 830, 790, 775, 750, 685. Found, %:
2
+
+
Cu 23.9; K 10.7. Cu[CO(NNO ) ] 3H O. Calcu-
lated, %: Cu 24.1.
2
2
2
2
+
Potassium bis(N,N -dinitrocarbamido)cuprate(II)
VI). To a solution of 2.26 g (0.01 mol) of salt IV
(
in 25 ml we added at 20 C under continuous stirring
a solution of 1.25 g (5 mmol) of CuSO 5H O in
4
2
(
5.6 g) was added to the organic phase, the resulting
5
ml of water. The precipitate was filtered off, washed
with water, ethyl alcohol, and ether, and dried at 50
0 C under reduced pressure. Yield 2.1 g (95%).
solution was evaporated under reduced pressure, and
the solid residue was washed with ethyl alcohol and
ether and dried at room temperature. Yield 15.2 g
(97%), mp 156 C (decomp.); published data [6]: mp
145 C (decomp.). Found, %: K 24.5. C H KN O .
Calculated, %: K 24.68.
6
Decomposes at 182 C with explosion. IR spectrum, ,
cm : 1645 (C O), 1420, 1310, 1180, 970, 905, 775,
7
C CuK N O . Calculated, %: C 5.48; Cu 14.61;
K 17.81; N 25.57.
Potassium bis(N,N -dinitrocarbamido)diammine-
cuprate(II) (VII) was synthesized in a similar way
from salt IV and 1 ml (0.01 mol) of 26.7% aqueous
ammonia. Yield 1.9 g (80%). Decomposes at 238 C
1
+
2
+
+
40. Found, %: C 5.3; Cu 14.6; K 17.25; N 24.9.
2
3
3
3
+
2
+
2
2
8
10
+
4-Nitrosemicarbazide (XIII , neutral). A 1.5-g
0.01-mol) portion of compound I (prepared by
(
passing hydrogen chloride through a suspension of
dinitrourea monopotassium salt in ether; method a in
[
2]) was dissolved in 5 ml of water under continuous
stirring, maintaining the temperature below 20 C.
Hydrazine hydrate, 0.5 g (0.01 mol), was added to
the solution at a temperature not exceeding 30 C.
The mixture was kept for 60 min at 30 C and cooled
to 5 C, and the precipitate was filtered off, washed
with cold water, and dried at room temperature. Yield
of 4-nitrosemicarbazide monohydrate 0.62 g (45%),
1
with explosion. IR spectrum, , cm : 3300 3160
(NH ), 1650 (C O), 1400, 1310, 1170, 970, 775,
3
2
+
+
7
35. Found, %: C 4.6; H 1.8; Cu 12.5; K 16.0;
N 29.3; (NH ) 7.0. C H CuK N O . Calculated, %:
3
2
6
2
10 10
2
+
+
C 5.08; H 1.27; Cu 13.56; K 16.52; N 29.66;
(NH ) 7.20.
3
1
Potassium bis(N,N -dinitrocarbamido)(urea)-
mp 227 235 C (decomp.). IR spectrum, , cm :
cuprate(II) (VIII) was synthesized in a similar way
with the difference that 0.6 g (0.01 mol) of urea in
3460 s, 3400 s, 3110 br.s, 3000, 2760 br.s, 2700,
1660 (C O), 1620 m, 1570 s, 1540 s (NNO ), 1500,
2
5
ml of water was additionally added to a solution of
1400 s, 1330 s, 1290 s (NNO ), 1200 s, 1155 s,
2
salt IV. Yield 1.9 g (76%). Decomposes at 179 C
with explosion. Found, %: C 7.2; H 1.0; Cu 11.5;
K 14.9; N 26.0. C H CuK N O . Calculated, %:
C 7.22; H 0.80; Cu 12.85; K 15.66; N 28.11.
1035 m, 970, 790, 750, 610, 500, 365. Found, %:
C 8.1; H 4.2; N 45.6. CH N O H O. Calculated, %:
2
+
4
4
3
2
+
C 8.70; H 4.35; N 40.10.
3
4
2
10 11
2
+
+
4
-Nitrosemicarbazide (XIII , zwitterionic).
N-Nitrourea ammonium salt (XI). Compound I,
g (0.02 mol), was added at 20 25 C to 25 ml of
6% aqueous ammonia under continuous stirring. The
mixture was kept for 24 h and was evaporated under
reduced pressure. Yield 0.9 g (73%), mp 120 121 C
A 1.88-g portion of compound I, prepared by nitration
of urea in a mixture of nitric and sulfuric acids
(method b in [2]), was dissoled in 5 ml of water under
continuous stirring, maintaining the temperature
below 20 C. Hydrazine hydrate, 1.25 g (0.025 mol),
was added at a temperature not exceeding 30 C, the
mixture was kept for 60 min at 30 C and cooled to
5 C, and the precipitate was filtered off, washed with
cold water, and dried at room temperature. Yield 0.3 g
3
2
(
decomp.). UV spectrum (H O):
260 nm,
2
max
1
1
9
700 l mol cm . Found, %: C 9.68; H 5.00;
+
N 44.90; NH4 13.55. CH N O . Calculated, %:
6
4
3
+
C 9.84; H 4.92; N 45.90; NH 14.75.
4
N-Methyl-N -nitrourea (XII). Compound I, 1.5 g
0.01 mol), was added at a temperature not exceeding
0 C to 12.4 g (0.1 mol) of 25% aqueous methyl-
amine under continuous stirring. The mixture was
kept for 16 h at 20 C and extracted with ethyl acetate
(27%), mp 230 231 C (decomp.). IR spectrum,
cm : 3400 br.w, 3180 s, 3100 s, 3010, 2920 br.s,
2680, 1660 (C O), 1585 m, 1540, 1500, 1410 s,
,
1
(
2
1320 m, 1260 s (NNO ), 1190 w, 1140 s, 1025 s, 975,
2
820, 790, 765, 750, 675, 580, 505, 440, 365. Found,
%: C 10.5; H 2.9; N 46.1. CH N O . Calculated, %:
(
3 20 ml), and the extract was evaporated under
4
4
3
reduced pressure. Yield 0.95 g (80%), mp 162 C [5].
C 10.00; H 3.33; N 46.67.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

CHEMISTRY OF UREA NITRO DERIVATIVES: III.
1737
4-Nitrosemicarbazide hydrazinium salt (XIIIa).
2810, 1705, 1685 (C O), 1630, 1490, 1460, 1420,
Compound I, 1.5 g (0.01 mol), was dissolved in 5 ml
of water under continuous stirring, maintaining the
temperature below 20 C. Hydrazine hydrate, 5.0 g
1340, 1275 (NNO ), 1125, 1065, 960, 805, 760, 735,
2
715, 575, 475, 455, 435, 340, 300. Found, %: C 10.0;
H 2.5; N 34.5. CH N O . Calculated, %: C 9.91;
3
3
4
(0.1 mol), was added to the solution at a temperature
H 2.48; N 34.71.
not exceeding 30 C, the mixture was kept for 30 min
at 30 1 C and cooled to 5 C, 50 ml of ethyl alcohol
was added, and the precipitate was filtered off,
washed with alcohol and ether, and dried at room
temperature. Yield 1.2 g (80%), mp 130 C (DSC).
N-Hydroxy-N -nitrourea hydroxylammonium
salt (XIVa). Compound I, 15 g (0.1 mol), was dis-
solved in 20 ml of water under continuous stirring,
maintaining the temperature below 20 C, and 9.9 g
(
0.3 mol) of hydroxylamine in 20 ml of water was
added to the solution at a temperature not exceeding
0 C. The mixture was kept for 30 min at 30 C,
1
IR spectrum, , cm : 3310, 3180, 3000, 2640, 1660
(
C O), 1615, 1540, 1515, 1380, 1350, 1330, 1260
3
(NNO ), 1190, 1110, 975, 960, 775, 765, 745, 675,
2
cooled to 5 C, and diluted with 50 ml of ethyl al-
cohol. The precipitate was filtered off, washed with
alcohol and ether, and dried at room temperature.
Yield 12.3 g, mp 155 C (decomp.). Found, %: C 7.8;
H 3.9; N 36.3. CH N O . Calculated, %: C 7.79;
6
10, 510, 450, 419, 395, 385. Found, %: C 7.3;
H 4.8; N 55.0. CH N O . Calculated, %: C 7.89;
8
6
3
H 5.26; N 55.26.
-Nitrosemicarbazide potassium salt (XIIIb).
Compound XIII, 1.19 g (0.01 mol), was dissolved in
4
6
4
5
H 4.00; N 36.36.
2
0
0 ml of water at 20 C under continuous stirring, and
.56 g (0.01 mol) of potassium hydroxide in 5 ml of
Methyl nitrocarbamate (XVa). A solution of 3 g
0.02 mol) of compound I in 50 ml of methyl alcohol
(
water was added. The mixture was diluted with 50 ml
of ethyl alcohol, and the precipitate was filtered off,
washed with ethyl alcohol and ether, and dried at
room temperature. Yield 1.5 g (95%), mp 130 C
was heated to the boiling point, kept for 30 min under
reflux, cooled to 20 C, and evaporated under reduced
pressure. The residue was recrystallized from ether
hexane. Yield 0.6 g (85%), mp 86 88 C [7].
Ethyl nitrocarbamate (XVb) was synthesized in
a similar way using ethyl alcohol. Yield 2.68 g
(
decomp.). UV spectrum (H O):
258 nm,
2
max
1
1
+
8
100 l mol cm . Found, %: K 23.8. CH KN O .
3 4 3
+
Calculated, %: K 24.68.
-Nitrosemicarbazide nickel salt (XIIIc). Com-
pound XIIIa, 1.58 g (0.01 mol), was dissolved in
(100%), mp 62 63 C [8].
4
Propyl nitrocarbamate (XVc) was synthesized in
a similar way using 1-propanol. Yield 0.49 g (100%),
2
1
0 ml of water at 20 C under continuous stirring, and
.45 g (0.005 mol) of Ni(NO ) 6H O was added.
oily substance, n2 1.447.
0
D
3
2
2
The mixture was stirred for 10 min, and the precip-
itate was filtered off, washed with water, alcohol, and
ether, and dried at room temperature. Yield 1.55 g
Hexamethylenetetraaminium N,N -dinitrourea
nitrate (XVI). To 21 g of nitric acid (d = 1.5 g/cm )
3
we added 21 g of oleum (20% SO ), and 6 g (0.1 mol)
3
(
(
99% on Ni[O NNCONHNH ] H O), mp 254 C
decomp., DSC). IR spectrum, , cm : 3400, 3345,
of urea was added in portions to the resulting mixture
at 5 to 0 C under continuous stirring. The mixture
was kept for 30 min at that temperature and was
poured into 54 g of an aqueous solution of urotropin
2
2 2
2
1
3
1
5
320, 1660 (C O), 1445, 1375, 1310, 1285 (NNO2),
165, 1110, 1085, 985, 785, 755, 665, 615, 590,
10. Found, %: Ni 17.8. CH N NiO . Calculated, %:
(
14 g, 0.1 mol) at such a rate that the temperature
3
4
3
did not exceed 20 C. The precipitate was filtered off,
washed with alcohol and ether, and dried at room
temperature. Yield 19.8 g (56%), mp 98 C. Found, %:
C 24.8; H 4.4; N 34.9. C H N O . Calculated, %:
Ni 18.6.
N-Hydroxy-N -nitrourea (XIV). Compound I,
5 g (0.1 mol), was dissolved in 20 ml of water under
1
7
15
9
8
continuous stirring, maintaining the temperature
below 20 C, and 9.9 g (0.3 mol) of hydroxylamine
in 20 ml of water was added at a temperature not
exceeding 30 C. The mixture was kept for 30 min
at 30 C and cooled to 5 C, and 70 ml of concentrated
sulfuric acid was added at a temperature not exceeding
C 23.80; H 4.25; N 35.69.
General procedure for preparation of nitrourea
derivatives from N,N -dinitrourea dipotassium
salt (IV) and amines (Table 2). Salt IV, 2.26 g
(0.01 mol), and appropriate amine, 0.01 mol, were
added at 20 C to 10 20 ml of water under continuous
stirring. The mixture was kept for 40 60 min at 30 C,
cooled to 15 20 C, and diluted with 40 100 ml of
ethyl alcohol. The precipitate was filtered off, washed
with alcohol and ether, and dried at room temperature.
1
0 C. The precipitate was filtered off, washed with
glacial acetic acid, and dried at room temperature.
Yield 8.4 g (69%), mp 189 C (decomp.); after recrys-
tallization from water, mp 151 C (decomp.). IR
1
spectrum, , cm : 3320 (NH), 3220, 3100, 2980,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

1
738
IL’YASOV et al.
General procedure for preparation of nitrourea
(NH), 3080, 1630 (C O), 1580, 1550, 1520, 1450,
1370, 1340, 1210 s, 1120, 1060, 950, 850, 790, 610,
derivatives from N,N -dinitrourea monopotassium
salt and amines. The procedure is the same as above
with the difference that 0.01 mol of N,N -dinitrourea
monopotassium salt and 0.02 mol of amine are used.
+
510, 455, 380. Found, %: K 24.88. CH KN O . Cal-
2
3
3
+
culated, %: K 24.53.
Nitrourea potassium salt. Decomposition point
REFERENCES
1
26 C (decomposes on heating [8]). IR spectrum, ,
1
cm : 3384, 3300 (NH ), 3192, 1676 (C O), 1640
1. Lobanova, A.A., Il’yasov, S.G., Popov, N.I., and
Sataev, R.R., Russ. J. Org. Chem., 2002, vol. 38,
no. 1, pp. 1 6.
2
(
3
NH ), 1540, 1372, 1300, 1108, 800, 688, 592, 472,
2
+
12. Found, %: K 27.8. CH KN O . Calculated, %:
2
3
3
+
K 27.27.
2
.
Lobanova, A.A., Sataev, R.R., Popov, N.I., and
Il’yasov, S.G., Russ. J. Org. Chem., 2000, vol. 36,
no. 2, pp. 164 167.
N-Butyl-N -nitrourea potassium salt. Decomposi-
+
tion point 190 C. Found, %: K 20.08. C H KN O .
Calculated, %: K 19.60.
5
10
3
3
+
3
.
Schlafer, H.L., Komplexbildung in Losung; Methoden
zur Bestimmung der Zusammensetzung und der Stabili-
tatskonstanten geloster Komplexverbindungen, Berlin:
Springer, 1961.
N-Butyl-N -nitrourea. A suspension of 1.99 g
0.01 mol) of N-butyl-N -nitrourea in 100 ml of dry
(
ether was saturated at 0 C with gaseous hydrogen
chloride. The mixture was kept for 2 4 h, the precip-
itate of potassium chloride was filtered off, and the
filtrate was evaporated to dryness under reduced pres-
sure. Yield 1.34 g (83%), mp 74 76 C [9]. IR spec-
4
5
6
7
.
.
.
.
Urbanski, T., Chemie und Technologie der Explosiv-
stoffe, Leipzig: Grundstoffindustrie, 1964, p. 527.
Backer, H.J., Recl. Trav. Chim. Pays Bas, 1915,
vol. 34, pp. 187 203.
1
trum, , cm : 3420 (NH), 3120, 3040, 2940, 2860,
Degner, O. and Pechmann, H., Ber., 1897, vol. 30,
2
1
(
800, 1695 (C O), 1600, 1550 (NNO ), 1490, 1470,
2
p. 652.
460, 1440, 1420, 1360, 1350, 1320, 1300, 1250
Beilsteins Handbuch der organischen Chemie, H,
NNO ), 1200, 1160, 1140, 1040, 1000, 920, 900,
2
vol. 3, p. 125.
8
05, 780, 760, 750, 735, 720, 600, 520, 460, 430.
Found, %: C 37.0; H 6.5; N 24.5. C N N O . Cal-
culated, %: C 37.27; H 6.83; N 26.09.
8. Thiele, J. and Lachman, A., Justus Liebigs Ann.
Chem., 1895, vol. 288, p. 287.
5
11
3
4
N-Hydroxy-N -nitrourea potassium salt. Decom-
position point 133 C. IR spectrum, , cm : 3300
9. Nec, R., Chem. Prum., 1979, vol. 29, no. 11, pp. 589
592; Ref. Zh., Khim., 1980, no. 23Zh104.
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002