Reactions of amidosulfuric acid salts with formaldehyde

Article abstract of DOI:10.1023/A:1012443003868

Potassium amidosulfate reacts with formaldehyde at pH 7-12 to afford a mixture of dipotassium 4-hydroxy-1,3-diazabutane-1,3-disulfonate hydrate and tripotassium 6-hydroxy-1,3,5-triazahexane-1,3,5-trisulfonate HO(CH₂NSO₃K)_n·H₂O (n = 2, 3). The reaction of the same compounds at pH 1-3 gives diammonium 1,3,5,7-tetraazabicyclo[3.3.1]nonane-3,7-disulfonic acid sulfate dihydrate.

Full text of DOI:10.1023/A:1012443003868

Russian Journal of Organic Chemistry, Vol. 37, No. 7, 2001, pp. 1030 1033. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 7, 2001,
pp. 1080 1082.
Original Russian Text Copyright
2001 by Lyushnina, Bryukhanov, Turkina, Malakhov, Golod.
Reactions of Amidosulfuric Acid Salts with Formaldehyde
G. A. Lyushnina, A. Yu. Bryukhanov, M. Turkina,
K. V. Malakhov, and E. L. Golod
St. Petersburg State Institute of Technology, Moskovskii pr. 26, St. Petersburg, 198013 Russia
fax: (812)1127791
Received December 14, 1999
Abstract Potassium amidosulfate reacts with formaldehyde at pH 7-12 to afford a mixture of dipotassium
4
-hydroxy-1,3-diazabutane-1,3-disulfonate hydrate and tripotassium 6-hydroxy-1,3,5-triazahexane-1,3,5-tri-
sulfonate HO(CH NSO K) H O (n = 2, 3). The reaction of the same compounds at pH 1 3 gives diammo-
2
3
n
2
nium 1,3,5,7-tetraazabicyclo[3.3.1]nonane-3,7-disulfonic acid sulfate dihydrate.
Condensation of potassium amidosulfate with
formaldehyde at pH 5 leads to formation of tripotas-
sium 1,3,5-triazacyclohexane-1,3,5-trisulfonate (I) [1].
There are no published data on the effect of pH on
the process. The goal of the present work was to study
the condensation of amidosulfuric acid with formalde-
hyde over a wide range of pH values. First of all, we
examined the reaction in the pH range from 7 to 12.
Insofar as the reaction is reversible (in dilute solution
the equilibrium is displaced toward initial com-
pounds), the condensation was carried out using high
reactant concentrations. Potassium amidosulfate was
dissolved in 30% formaldehyde solution at 20 and
concluded that the above method is applicable to
potassium salts II.
In the mass spectrum of product II we observed
negative ion peaks with m/z values of 291 and 438,
which correspond to anions derived from 4-hydroxy-
1,3-diazabutane-1,3-disulfonic acid monopotassium
4
0 C. The concentration of potassium amidosulfate
salt hydrate (IIIa, n = 2) and 6-hydroxy-1,3,5-triaza-
hexane-1,3,5-trisulfonic acid dipotassium salt hydrate
was 30 and 57% to ensure equimolar reactant ratio.
Throughout the examined pH range the same products
were formed (according to the IR spectra and ele-
mental analyses), which were insoluble in organic
solvents. In keeping with their elemental composition
and results of determination of formaldehyde and
amidosulfate ion, the products were assigned the
structure of hydroxypoly(N-sulfomethyleneamine)
potassium salt hydrate HO[CH N(SO K)] H H O
(IIIb, n = 3).
2
3
n
2
(II). The molecular weight of II was determined by
mass spectrometry using secondary ion ion emission
technique, which is based on generation of secondary
+
ions like [M H] or [M H] by the action of cesium
ion beam [2, 3]. Taking into account that this tech-
nique was not applied previously to potassium-con-
taining derivatives of amidosulfuric acid, we initially
tested it with tripotassium salt I as an example. The
resulting spectrum contained a peak with m/z 402,
corresponding to quasimolecular ion Ia; we thus
Hence the reaction of formaldehyde with potassium
amidosulfate gave a mixture of compounds IIa (n = 2,
M 330) and IIb (n = 3, M 377). Judging by the IR
spectra, analogous products were formed with other
+
2+
2+
amidosulfuric acid salts with Na , Ca , and Ba
as cations.
1
070-4280/01/3707-1030$25.00 2001 MAIK Nauka/Interperiodica

REACTIONS OF AMIDOSULFURIC ACID SALTS WITH FORMALDEHYDE
1031
In the reaction of potassium amidosulfate with
formaldehyde at pH 3 5, the mixture also contained
product I. Ammonium amidosulfate behaved dif-
1,3,5,7-tetraazabicyclo[3.3.1]nonanes (V). Soon-Ben
Teo and Siang-Guan Tech [8] recently proposed
a template procedure for synthesis of bicyclononanes
ferently. It is known that hydrolysis of amidosulfuric V, which is based on the reaction of amino acids
acid is a very slow process [4]. However, on addition
of formaldehyde solution to a solution of ammonium
amidosulfate at 0 C the pH of the medium jumps
from 3.0 to 1.0 1.5, and diammonium 1,3,5,7-tetra-
azabicyclo[3.3.1]nonane-3,7-disulfonate sulfate di-
hydrate (IV) is formed in high yield.
with formaldehyde and ammonia in the presence of
nickel, zinc, or copper salts. The reaction of ammo-
nium amidosulfate with formaldehyde reperesents
the second known (in addition to the synthesis of
3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane [6])
case of noncatalytic cyclization with formation of
bicyclononane V.
The structure of compound IV was confirmed by
its transformations in reactions with some electro-
philic reagents. Treatment of IV with sodium nitrite
in aqueous acetic acid gave 1,3,5-trinitroso-1,3,5-tri-
azacyclohexane (VI), and with nitric acid, 1,3,5-tri-
nitro-1,3,5-triazacyclohexane (VII, hexogen) was
formed. When the nitration was carried out in a mix-
ture of acetic acid with acetic anhydride in the pres-
ence of ammonium nitrate, we obtained a mixture of
compound VII and 1,3,5,7-tetranitro-1,3,5,7-tetraaza-
cyclooctane (VIII, octogen) (Scheme 1), i.e., com-
pound IV reacted like 3,7-dinitro-1,3,5,7-tetraazabi-
cyclo[3.3.1]nonane [6]. The structure of IV was also
proved by its reaction with acetic anhydride. Com-
pound IV decomposes in acetic anhydride, but addi-
tion of acetic anhydride to a solution of IV in acetic
acid, preliminarily treated with ammonium acetate to
neutralize sulfuric acid, leads to formation of a mix-
ture of 1,3,5-triacetyl-1,3,5-triazacyclohexane (IX,
yield 18%), 1,3,5,7-tetraacetyl-1,3,5,7-tetraazacyclo-
octane (X, 12%), and 3,7-diacetyl-1,3,5,7-tetraazabi-
cyclo[3.3.1]nonane (XI, 8%) (Scheme 2).
The IR spectrum of IV contains absorption bands
1
due to the NSO group (1230 1200, 1020 cm ),
3
1
+
4
sulfate ion (1130 cm ), and NH ion (1430, 3200
300 cm ). In the H NMR spectrum we observed
1
1
3
three groups of signals from CH groups at , ppm:
2
5
.1 s, 4.6 d, 4.35 d (intensity ratio 2:2:1). Potentio-
metric titration showed the presence of two acid
equivalents in IV. Treatment of IV with an alcoholic
solution of picric acid gives urotropine picrate.
Until recently, heterolysis of urotropine [5 7] was
the only method for preparation of N-substituted
Scheme 1.
EXPERIMENTAL
The IR spectra were recorded on a UR-20 spec-
1
trometer in KBr. The H NMR spectra were obtained
on a Bruker AM-300 (300 MHz) instrument in
DMSO-d using HMDS as internal reference. Values
6
of pH were measured with the aid of a pH-673
pH-meter voltmeter. The elemental compositions
were determined on a Hewlett Packard 185 analyzer.
The mass spectra were run on an MI-1201 instrument
adapted for the secondary ion ion emission technique
[3]. Silicagel L 100/200 m (Chemapol) was used for
column chromatography.
Dipotassium 4-hydroxy-1,3-diazabutane-1,3-di-
sulfonate hydrate (IIIa) and tripotassium 6-hy-
droxy-1,3,5-triazahexane-1,3,5-trisulfonate hydrate
(
IIIb). To a solution of 15 g (0.11 mol) of potassium
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

1
032
LYUSHNINA et al.
Scheme 2.
amidosulfate in 25 ml of water we added with stirring
1.3 g (0.11 mol) of a 30% formaldehyde solution.
The mixture was adjusted to pH 7 12 by adding
a 10% solution of potassium hydroxide and was kept
for 3 h at 25 or 40 C. The precipitate was filtered
off, washed with ethanol, and dried in a vacuum
1,3,5,7-Tetranitro-1,3,5,7-tetraazacyclooctane
(VIII) [9]. To a suspension of 9.2 g (0.02 mol) of
compound IV in 25 ml of acetic acid, stirred at 50 C,
we added over a period of 30 min simultaneously
from two dropping funnels a solution of 0.8 g
1
(
0.01 mol) of ammonium nitrate in 6.02 g (0.02 mol)
of 98% nitric acid and 10 g (0.035 mol) of acetic
anhydride. The mixture was kept for 20 min at 70 C
and poured into 100 ml of ice water. The product was
filtered off, treated with hot water for 2 h at 100 C,
and repeatedly washed with cold water. The isolated
material, 1.33 g (40%), was a mixture of compound
VII (0.93 g, 70%) and 1,3,5,7-tetranitro-1,3,5,7-tetra-
azacyclooctane (VIII) (40 g, 30%). The composition
of the mixture was determined by the procedure
described in [10].
desiccator over phosphoric anhydride. Yield 12.6 g
1
(69%). IR spectrum, , cm : 960, 1000 1070, 1200
(
NHSO ), 650, 1245 (H O), 3290 (NH), 3380 (H O),
3
2
2
3
480 (OH). Found, %: C 7.67; H 2.10; N 8.71.
C H K N O S . Calculated for n = 2, %: C 7.29;
2
8
2
2
8 2
H 2.43; N 8.51. C H K N O S . Calculated for n =
3
10
3
3
11 3
3
, %: C 7.55; H 2.10; N 8.88.
Diammonium 1,3,5,7-tetraazabicyclo[3.3.1]-
nonane-3,7-disulfonate sulfate dihydrate (IV). Am-
monium amidosulfate, 27.3 g (0.24 mol), was added
at 0 5 C to 48 ml (0.48 mol) of a 30% formaldehyde
solution. The mixture was kept for 4 h at 0 5 C. The
original pH value (3) changed to 1 (by the end of
addition of ammonium amidosulfate) and then to 0.8
Acetylation of diammonium 1,3,5,7-tetraazabi-
cyclo[3.3.1]nonane-3,7-disulfonate (IV). To a solu-
tion of 1.9 g (0.024 mol) of ammonium acetate in
1
5 ml of acetic acid we added 5.5 g (0.012 mol) of
compound IV. The mixture was kept for 30 min,
the precipitate was filtered off, the filtrate was cooled
to 10 C, 3 ml (0.03 mol) of acetic anhydride was
added, and the mixture was evaporated to dryness in
a stream of air. The residue (0.7 g) was subjected to
column chromatography. We isolated 0.3 g (16%) of
1,3,5-triacetyl-1,3,5-triazacyclohexane (IX), mp 94 C
[11], 0.25 g (9%) of 1,3,5,7-tetraacetyl-1,3,5,7-tetra-
azacyclooctane (X), mp 160 C [12], and 0.18 g (8%)
of 3,7-diacetyl-1,3,5,7-tetraazabicyclo[3.3.1]nonane
(by the end of the process). The mixture was poured
with vigorous stirring into a 10-fold amount of
acetone cooled to 0 C, and the mixture was stirred
until complete crystallization. The precipitate was fil-
tered off, washed with acetone, and dried in a vacuum
desiccator over sulfuric acid. Yield 37.3 g (95%).
Found, %: C 12.78, 12.79; H 5.52, 5.55; N 18.69,
1
8.61; S 20.45, 20.11. C H N O S . Calculated, %:
5 24 6 12 3
C 13.16; H 4.82; N 18.42; S 21.05.
,3,5-Trinitroso-1,3,5-triazacyclohexane (VI). To
a solution of 3 g (0.0065 mol) of compound IV in
5 ml of 50% acetic acid we added at 0 C 1 g
0.014 mol) of sodium nitrite. The mixture was kept
(XI), mp 195 C [8].
1
REFERENCES
Binnie, W.P., Cohen, H.L., and Wright, G.F., J. Am.
Chem. Soc., 1950, vol. 72, no. 10, pp. 4457 4461.
Gall, L.I. and Turkina, M.Ya., Usp. Khim., 1985,
2
(
1
2
.
.
for 1 h at 0 C and poured into 50 ml of acetone, and
the precipitate was filtered off. Yield 0.2 g (18%),
mp 105 C (from ethanol) [6].
vol. 54, no. 5, pp. 741 746.
1
,3,5-Trinitro-1,3,5-triazacyclohexane (VII).
Compound IV, 1 g (0.0062 mol), was added to
0 ml of 98% nitric acid cooled to 40 C. The
3. Chapman, J.R., Practical Organic Mass Spectro-
metry, Chichester: Wiley, 1985.
4. Benson, G.A. and Sillane, W.J., Chem. Rev., 1980,
1
mixture was kept for 1.5 h at that temperature and
poured into water. Yield 0.19 g (38%), mp 205 C
vol. 80, no. 2, pp. 151 186.
5. Warman, M., Siele, V.J., and Gilbert, E.E., J. Hetero-
cycl. Chem., 1973, vol. 10, no. 1, pp. 97 98.
(from acetone) [6].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

REACTIONS OF AMIDOSULFURIC ACID SALTS WITH FORMALDEHYDE
1033
6
.
Orlova, E.Yu., Khimiya i tekhnologiya brizantnykh
vzryvchatykh veshchestv (Chemistry and Technology
of High Explosives), Leningrad: Khimiya, 1973,
pp. 502, 520, 550.
10. Scullion, H., Coibett, J., Lewis, J., and Mc-
Comack, J., Chem. Ind., 1963, vol. 35, no. 11,
pp. 1463 1465.
1
1. Warman, M., Siele, V.J., and Gilbert, E.E.,
J. Heterocycl. Chem., 1973, vol. 10, no. 1,
pp. 97 98.
7
8
9
.
.
.
Ju, Ch., Shaofang, W., and Fuping, L.R., Propell.
Explos. Pyrotechn., 1990, vol. 15, no. 2, pp. 54 57.
Soon-Ben Teo and Siang-Guan Tech, Inorg. Chim.
Acta, 1985, vol. 107, no. 1, pp. 35 38.
1
2. Siele, V.J., Warman, M., Laccacorvi, J., Hutchu-
son, R.W., Motto, R., Gilbert, E.E., Benziger, T.M.,
Coburn, M.D., Rohwer, R.K., and Davey, R.K.,
Propell. Explos., 1981, vol. 6, no. 1, pp. 67 71.
Fischer, H., Chem. Ber., 1949, vol. 82, no. 1,
pp. 190 194.
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