SYNTHESIS OF POLYCYCLIC NITRAMINES BY NITRATION OF CONDENSATION PRODUCTS OF GLYOXAL AND FORMALDEHYDE WITH SULFAMIC ACID SALTS S.V.

Sysolyatin1, G.V. Sakovich1, Y.T. Chernikova1,V.N. Surmachev1, A.A. Lobanova2

1 2

Institute for Problems of Chemical and Energetic Technologies SB RAS FGUP FR&PCALTAI

1, Sozialisticheskaya, Biysk, Altai Region, 659322, Russian Federation

Abstract
This paper describes methods of synthesis of polycyclic nitramines by nitration of condensation products of glyoxal and formaldehyde with sulfamic acid salts. The course of the reaction of glyoxal and formaldehyde with sulfamic acid salts is dependent on molar ratio and reaction conditions such as temperature, medium acidity and reacting substances concentration. Nitrolysis of obtained iminosulfonates by nitric acid-based mixtures proceeds under relatively soft conditions and results in the corresponding polycyclic nitramines.

Polycyclic nitramines are high-dense and energy-rich explosives. Synthesis of polycyclic amines usually includes two stages: formation of a cage and nitrolysis. It is possible to obtain polycyclic amides by condensation of amides with aldehydes. In this turn initial polycyclic amides should have the easily leaving acyl group. We believe that the sulfamic group can serve as such group. It is known that RDX is prepared by nitration of the condensation product of formaldehyde with sulfamic acid salts [1]:
H NH2SO3M
+

MO3S

N N

SO3M NO2

O2N

N N

NO2

H2C

O SO3M NO2

The nitrolysis of 1,3,5-triazacyclogehanetrisulfonate salts (white salt) proceeds only under action of acidic nitration mixtures and interactions with nitronium

salts are not observed. Fig.1 shows dependence of the RDX yield on temperature at nitration by concentrated nitric acid:
80

60
Yield, %

40

20

0 -40 -20 0 20 40 60
Temperature, 0C

Fig. 1 Dependence of an RDX yield on temperature 1,2 - nitric acid (99 %) with module 4,5 and 2,5 3,4 - nitric acid (96 %) with module 4,5 and 2,5.

Such a form of the curve speaks on the change of the nitrolysis mechanism. Replacement of the sulfogroup by nitro group dominates in a range of temperatures 35-250C. And in a range of temperatures 25450C there is an area of resynthesis of nitamines fragments. Thus, nitrolysis of cyclic iminosulfonates includes the following stages [2]:
R N R R N R R R NH NO2 + H R C OH R R R C R N H NO2 C H SO3M SO3M R R NH SO3M + H R C OH R R N NO2 + HO SO3M

Decrease of the yield depends on hydrolysis of the N-C bond proceeding in the whole range of temperatures. The course of each of these reactions is promoted by its range of acidity (H0), temperatures and concentration of iminosulfonates salt. Synthesis of polycyclic cages by condensation is possible only with the use of glyoxal. Condensation of glyoxal with sulfamic acid salts in 1:1 molar ratio results in preparation of 2,3,5,6-tetrahydroxypiperazine-1,4-disulfonates salts (THP):

H NH2SO3M

HO

OH

SO3M HO N OH

+
O H HO NHSO3M HO N SO3M OH

Reaction at the basic catalysis has the yield of 31% [3]. cid catalysed reaction of glyoxal with sulfamic acid salts gave THP in 95 % yield [4]. Optimum acidity will be 3,5-4,5, at which formation of proceeds fuller and time of the reaction is shorter. At higher acidity there is a hydrolysis of sulfamic acid salts, and at lower acidity the speed of the condensation process is lower. Rise in temperature accelerates proceeding of the processes. The optimal temperature is 35-450C. Increase in concentration of sulfaminate salts leads to an increase in the yield. It is known [3] that nitration of with mixture of nitric acid and acetic anhydride results in yield of 2,3,5,6-tetraacetoxy-1,4-dinitropiperazine and 2,5diacetoxy-3,6-dinitrato-1,4-dinitropiperazine:
O O CH3 SO3M HO N OH O O CH3 NO2 N O O CH3 N O2N CH3 O O

HO

N SO3M

OH

NO2 O CH3 O O

NO2 N O O CH3 N NO2 O NO2

Using concentrated nitric acid under optimal conditions for resynthesis of nitamines fragments results in synthesis of the polycyclic nitramine 4,10-dinitro2,6,8,12-tetraoxa-4,10-diazatetracyclo[5, 5, 0, 03,11 ,05,9]dodecane [5].
SO3M HO N OH NO2+ HO N SO3M OH O2N N O2N N O O O O

Fig. 2 and 3 show dependences of the TEX yield on temperature and the module of nitration.

Yield, % 30 25 20 15 10 5 0 -30 -20 -10 0 10 20 30 40

Yield, % 30 25 20 15 10 5 0 0 2 4 6 8 10
Module

Tem perature, C

Fig. 2. Dependence of the TEX yield on nitration temperature

Fig. 3. Dependence of the TEX yield on nitration module

Increase in concentration of nitric acid from 94,0% up to 99,8% results in increase in yield from about 0% up to 31% (the module - 2,5, temperature 0-50). Nitration at the increased module of nitric acid (concentration of 94,0%) up to 10 and at temperatures up to 5-100 gives 13 % TEX yield. Maintenance of the constant nitration module with synchronous dosage of all components also results in some increase in yield. Undoubtedly, that each reaction (replacement of the sulfogroup by nitro group, fragmentation and resynthesis) needs a specified acidity and temperature of reaction mixture. Table 1 shows dependence of the TEX yield on cation. Table 1. Dependence of the TEX yield on cation of 2,3,5,6-tetrahydroxypiperazine1,4-disulfonates salts. Cation Yield,% Lithium 16 Sodium 23 Potassium 31 Cesium 13 Ammonium 22

cid catalysed reaction of glyoxal and formaldehyde with sulfamic acid salts gave 2,4,6,8-tetraazabicyclo[3, 3, 0]octane-2,4,6,8-tetrasulfonates salts [2, 6]:
KO 3S H H2N SO3K O N N SO 3K

H2 C

+
N O H KO 3S SO 3K N

Nitrolysis of 2,4,6,8-tetraazabicyclo[3, 3, 0]octane-2,4,6,8-tetrasulfonates salts with concentrated nitric acid at -35-300C results in 2,4,6,8-tetranitro-2,4,6,8tetraazabicyclo[3, 3, 0]octane in 60% yield:

KO 3S N N

SO 3K NO 2
+

O 2N N

NO 2 N

N KO 3S

N SO 3K O 2N

N NO 2

Realization of nitration under resynthesis conditions results in the formation of 2,4,6-trinitro-8-oxa-2,4,6-triazabicyclo[3, 3, 0]octane, RDX and N-sulfoimidazole:
KO3S N N SO3K NO2
+

O2N

N N

NO2

O 2N N

NO2 N

+
N O 2N O

SO3M

N KO3S

N SO3K

NO2

RDX formation occurs owing to resynthesis of nitramine fragments. Formation of 2,4,6-trinitro-8-oxa-2,4,6-triazabicyclo[3, 3, 0]octane should occur through hydrolysis, disclosing of a cycle, and the subsequent cyclization. Formation of Nsulfoimidazole occurs easier in less concentrated nitric acid owing to hydrolysis of a cycle and the lack of nitronium cation. The most interesting for synthesis of polycyclic nitramines is condensation of glyoxal with sulfamic acid salts in a molar ratio different in 1:1. cid catalysed reaction of glyoxal with sulfamic acid salts in the molar ratio 3:4 gave 2,6-dioxa-4,8,10,12tetraazatetracyclo[5, 5, 0, 03,11 ,05,9]decane-4,8,10,12-tetrasulfonates salts (SAA)[2, 6].
SO3M H H2N SO3M + O C C H HO NHSO3M HO N SO3M OH O HO OH HO N OH

MO3SHN HO

OH NHSO3M MO3S N MO3S N SO3M N O

SO3M + HCOOH MO3S

However the basic direction of the condensation reaction is formation of Nsulfoimidazole. The fact of that easier rupture of the - bond at =2,8 and below

was unexpected. Nevertheless, decrease, temperature rise in 1:2 molar ratio of glyoxal with sulfamic acid salts serve as the reason of the N-sulfoimidazole formation in very high yield. The absence of an exchange of protons of a ring in the N- sulfoimidazole and the proton in a molecule of formic acid in deuterium oxide allows one put to forward the mechanism of its formation:
SO3M HO N N SO3M N CH HO N SO3M H+ - H2O OH H+ - HOSO3M HO OH HO N N SO3M N + HCOOH N SO3M

OH H2O - HCOOH

OH

Nitrolysis of 2,6-dioxa-4,8,10,12-tetraazatetracyclo[5, 5, 0, 03,11 , 05,9]decane4,8,10,12-tetrasulfonates salts (SAA) with concentrated nitric acid results in 4,8,10,12-tetranitro-2,6-dioxa-4,8,10,12-tetraazatetracyclo[5, 5, 0, 03,11 ,05,9]decane (AA) [7, 8]:
MO3S N MO3S N N MO3S O SO3M N O O2N NO2+ N O2N N O2N N O NO2 N O

The process of nitrolysis of SAA with nitric acid has a time dependence of an yield (fig. 3), whereas the maximal RDX yield and biHMX yield (2,4,6,8-tetranitro2,4,6,8-tetraazabicyclo[3, 3, 0]octane) are reached at once upon finishing a dosage of initial iminosulfonates. Decomposition of AA in acid mixture is not observed at increase in nitration temperature from -30 up to 40. The further temperature rise results in deacrease in AA yield. So, at 50 the AA yield reaches 89 % that is connected with hydrolysis of the N- bond in initial and intermediate nitration products. The yield remains constant while using nitric acid with the concentration 90-100%. The further decrease in the concentration of nitric acid leads to decrease in yield: 80% 89%; 85% 40%; 80% 2 % AA, that is also connected with the N- bond rupture.

Yield, %

100 80 60 40 20 0 0 50 100 150 200

Time, min

1- nitration module 30 2- nitration module 10 3- nitration module 5 4- nitration module 3 Fig. 3 Dependence of the AA yield on nitration time in nitric acid (99 %) at -30

Nitration of tetrasodium salts of 2,6-dioxa-4,8,10,12-tetraazatetracyclo[5, 5, 0, 0

3,11

,0 ]decane-4,8,10,12-tetrasulfonates (KSAA) by nitric acid of various concen-

5,9

tration at the fixed temperatures has been investigated. The yield of AA and sulfate ion formed in the reaction were determined. Fig. 4 and 5 show results of experiments.
Yield, %

100
Yield, % 100 80 60 40

80 60 40 20

20 0 0 10 20 30 40 50 60 70 8

0 0 50 100 150 200 250 300

Time, min.

Time, min

Fig. 4. Dependence of the yield of AA and sulfate - ion on the reaction time. Nitric acid (99 %), the module - 30, temperature -30. 1 - curve of AA yield, 2 - curve of sulfate - ion yield.

Fig. 5. Dependence of the yield of AA and sulfate - ion on the reaction time. 1 and 3 curves of allocation of the sulfate - ion and AA respectively, at nitration by nitric acid (90 %), the module -30, temperature-20 2 and 4 curves of allocation of the sulfate - ion and AA respectively, at nitration by nitric acid (95 %), the module - 30, temperature -30.

The observed non-simultaneous formations of the sulfate - ion and AA are not connected with hydrolysis of N-S bond of intermediate products at the quench by pouring into ice, and show the presence of the intermediate substance containing NH fragment in the mixture. Occurrence of AA (from fig. 5) is observed in 30 minutes after the ending of dosage of KSAA, whereas the yield of the sulfate - ion is 69%. Rise in temperature of nitration (nitric acid of 99 %, the module - 30, the temperature 10) results in merge of both curves; the AA yield reaches maximal point upon ending of the KSAA dosage. Such a kind of curves is similar to observed curves during the study of nitration of cyclic iminosulfonates till biHMX and RDX and shows strong influence of temperature on the speed of KSAA nitration. The indirect confirmation of existence of the intermediate substances containing the NH fragment indicates the formation of N-nitrosamines at interaction of the reactionary mixture with a water solution of sodium nitrite. Direct nitrosation of iminosulfonates does not result in formation of N-nitrosamines.
MO3S N MO3S N N MO3S ON N + N O2N NO2 N + O ON N O2N N NO2 N + O O2N N O SO3M N O O2N O2N N NO2 N O NO2+ HNO2 N O2N N O2N N O NO N + O

O2N N O

O2N N O

O2N N O

The compound containing the NH fragment synthesized by nitration of KSAA solution in sulfuric acid with stoichiometric quantity of nitrating agent:
MO3S N MO3S N N MO3S O SO3M N O HNO3 H2SO4 N O2N O2N N O2N N O H N O

Hence, it is shown that nitrolysis of cyclic iminosulfonates proceeds in steps with formation as intermediate products, containing the NH fragment, which are exposed to the further N-nitration:

R N R R N R H SO3M

H2O

R N R R N R NO2 H + HO SO3M

NO2+

The first stage represents the process of return sulfonation. Such a course of the nitrolysis reaction is probably connected with a steric obstacle for formations of transitive conditions (S2) in polycyclic cages:

O2N

SO3H

This mechanism, apparently, is not related to nitrolysis iminosulfonates of the linear structure, where the S2 mechanism can be easily realized. Nitration of SAA salts (temperature 0-5, concentration of nitric acid 98 %, module 10) resulted in the formation of AA (table 2). Table 2 - Dependence of the yield of 4,8,10,12-tetranitro-2,6-dioxa-4,8,10,12tetraazatetracyclo[5, 5, 0, 03,11 ,05,9]decane (AA) on cation of 2,6-dioxa-4,8,10,12tetraazatetracyclo[5, 5, 0, 03,11 ,05,9]decane-4,8,10,12-tetrasulfonates (SAA) salts Cation Yield,% Lithium 89 Sodium 95 Potassium 97 Cesium 93 Ammonium 97

Nitration of SAA salts by other nitrating agents (mixtures on the basis of nitric acid and anhydrides of mineral and organic acids) does not result in increase in yield. The maximal yield is reached after the end of dosing the SAA salt into nitrating mixture. Long keeping of the SAA salt solution in sulfuric acid with the subsequent nitration results in the formation of AA structural isomer 4,6,10,12-tetranitro-2,8dioxa-4,6,10,12-tetraazatetracyclo[5, 5, 0, 03,11 ,05,9]decane:
MO3S N MO3S N N MO3S O SO3M N O 1. H2SO4 2. NO2+ N O2N O2N N O2N N O O N NO2

Apparently, formation of this substance includes two stages: resynthesis and nitration. Formation of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5, 5, 0, 03,11 ,05,9]decane is observed at nitration of a condensation product of gluoxal with sulfaminate salts in the molar ratio 1:21:2,2:
KO3S H 3 O C C H KO3S O + 6 H2N SO3K N N KO3S N N KO3S SO3K N N SO3K O2N O2N N O2N N N N O2N NO2 N N NO2

In these conditions the mix of various condensation products is formed. The nitolysis of mixes was carried out without division. The greatest yield of condensation products is formed at realization of the process in the range of =3,4 3,8. However, the greatest yield of nitrocompounds is formed at nitration of the condensation products obtained at =3,0-3,4. When the temperature decreased, the yield of condensation products increased, but the respective yield of the nitration products lowered. The maximal yield of hexanitrazaisowurzitane was reached by condensation of gluoxal with potassium sulfaminate in the molar ratio 1:2,1, at = 3,2-3,4 and the temperature of 60-650. Thus, nitration of condensation products of gluoxal with sulfaminate salts results in the broad set of polycyclic nitramines. Course of these reactions depends not only on a ratio of reacting substances: gluoxale and salts of sulfamic acid, but also on conditions of the condensation reaction: concentration, acidities, temperatures and reaction time, and on conditions of the realization nitrolysis of formed cyclic iminosulfonates.

References
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