CS206382B1 - Process for the preparation of 1,5-endemethylan-3,? -Dinol * 1,3,5,7-tetraa and cyclooctane - Google Patents

Abstract

The invention relates to a process for the production of 1, 5-dimethylan-3, 7-dinitro-1,3,5,7-tetraazacyl-hexane by nitration of hexamethylenetetraene in the presence of urea and/or urea-formaldehyde condensate. The use of the title substance is intended for the production of the thermostable explosive 1,3,5,7-tetraamitro-1,3,5,7-tetraazacyl-hexane (tetraazacyl-hexane).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the process of producing 1,5-adead-methylan-3,7-dinitro-1,3,5,7-tevraazaeyl-octane by nitrating the hexamethylanetetraethane in a mixture of urea and / or urea-formaldehyde kendensate. The use of this substance is of particular interest in the preparation of thermo-labile explosives of 1,3,5,7-tetramethyl-1,3,5,7-tetrasmaeylleectane (ectegan).

206 382

The present invention relates to the production of 1,5-indoethylene-3,7-dinitro-1,3,5, -tetraazaeyklooctaine by the control of hexamethylanototraiain in a weakly acidic medium, wherein the reaction conditions are selected such that they substantially increase the safety and economy of the process.

The 1,5-endoaethylene-3,7-dinitro-1,3,5> 7-totraazaeyfclooktane produced, also known as H, H * -difluoropentamatylantetramine (code-named DPT), is possible to obtain * Manniohove * in addition to the electrolysis of hexamethylantotramine in a weakly acidic environment. by condensation Structure of suitable reactants. In the case of the Mannioh condensation, it is started from ntramide or its dimethylderivative, from methylanoulamine or ammonia and forwaldehyde. Dimethylolnitramium (also called dimethylelnitramide) is formed as a byproduct of the electrolysis of hexamethylanthotramine to 1,3,5-trinitro-1,3,5-triazaeyklehexane (code number RDX) by the attentive neutralization of waste nitric acid from this prooeslane with ammonia synthetamine 4% -aem yield compared to theory (Hale GJtJ. Am. Chom. Soo. 1920, 4χ, 275OJ Chotě VJ and Tus .: Can.

J. Ros. 1949, 27B.218). Dlmotylolnitramium is also one of the major products of sulfonic acid to hexamethylanetetramine dinitrate, so that neutralization of the corresponding reaction mixture with ammonia may afford dinitropontaotyl alanetotramine in up to 35% yield compared to the theory (Can. J. Res. Et al., J. Res. 27B .218)

Tastes V.J. and Kel .: Can. J. Ree. 1949, 27B. 280). By the action of methylenediaain on dimethylolnitramine (obtained from ntramide and formaldehyde) bel dinitrepentwaethylantetremine prepared in 97% yield over theory (Tastes V. J, et al., Can. J. Ros. 1949, 27R.

218). Good results are also given by the condensola and with those of the tramalds with formaldohyd and ammonium (Lamberton A.H .: J. Chom. Soo. 1949, 1650).

The nitrolysis of hexamothylanetetramine from a series of intermediates and aqueous products by successive deeradation, including a complex of nitro-lysing, hydrolytic-and neutralizing-complexes, is parallel and consecutively involved, but is also particularly 1,5-endometylán-. -3,7-dimitro-1,3,5,7-tetraazaeycloptane in a moderate acid environment. It is known from the investigations that by treating 4 moles of aootanhydride per mole of hexamothylanetetramine dinitrate at room temperature for several days, it may be possible to obtain nitropentamethylanetetrasyl in up to 30% of the yield (see Jut et al. Ree 1949, 27B,

218) Ohute VJ et al., Can. <7th Ree. 1949, 27B. 280). Another method of electrolysis consists in the simultaneous proportional dosing of a solution of 1 mole of hexamethylanthotramine in 3.1 moles of oleic acid and a solution of 2 moles of nitric acid, at least 96 µm, in 2.6 moles of aootanhydride to the present and possibly 0.73 moles of oic acid. at a reaction temperature of 25 to 30 ° C and a mixing time of the reactants of 60 minutes, after a further 30 minutes of reaction, at 25 to 30 ° C by passing this process at hot temperatures yields of the product rapidly swell and eating dinitropenteaotylantotramine versus theory (Baehmaaa VB et al., J. Aa. Chea. Soo. 1951, 22, ^and 79). This preparation process has been improved so that together with β, 44 moles of oleic acid, pareformaldehyde is assumed in an amount of 0.417 moles of monomeric rormaldebyde and dosed. dinitropentamethylenetetramine in up to 59 µm yield compared to theory (Castorina TC et al. t J. Am. Chea. Soo. 196, 82, 1617). By increasing the amount of present ootonic acid to 23.2 moles, the amount of oxaldehyde paraffin present to 0.79 moles of monomeric formaldehyde and the amount of acetic anhydride to 4.35 moles, and adding nitric acid to the reaction mixture as a 1.5 moles ammonium nitrate solution in 2 moles of nitric acid 99 at a reaction temperature of 44 [deg.] C., yields dinitrepoataphthylenetetramine yield from theory (Castorina TC et al., J. km. Chea. Soo.

1960, 82, 1617). .

As can be seen from the published methods for the control of gylethylenetetramine casinos in the environment, the presence of parafomoaldehyde and / or ammonium nitrate in the reaction mixture can favorably affect the yields of 1,5-endemethylene-3,7-dinitro-1,3,5,7- tetraazaoyklooktan (bibliographla, Orlova B. Ju et al .: Oktogen-thermoatojkoe vzryvčatoe vežčestvo, Izdat. Nedra, Moscow, 1975). As well as constructing suitable additives, it is possible to influence the combination of the fragments towards the predominant formation of nitrile clusters.

Current views on the mechanism of ammonium and / or ammonium salts during electrolysis under Beekman's conditions are different. In short, it can be said that they cite satisfactorily the question of the actual mechanism and scope. As already mentioned, the presence of ammonium nitrate results in predominantly eycliocyni polyni trams, in the absence of linearly acacia. Its effect can be kinetic in effect, ammonium nitrate is applied to the ions and shifts the ionic equilibrium of nitric acid to the left, resulting in a reduction in the end of nitronium cations as a nitrafine agent. The presence of * nitrate oaions reduces the acidity of the environment and thus affects the reaction mechanism. The transonizafine equilibrium is a direct nitrogen exchange between the ammonium and / or the incompletely substituted ammonium βοϊ'οη and the given intenaediate.

In the case of additives, the formaldehyde units, such as e.g. in the case of paraformaldehyde, it can be envisaged that it degrades to lower fragments that promote cyclopolymerization in Salch.

and

Urea and urea-formaldehyde condensates can also be considered according to the most recent knowledge of a structure suitable for promoting the formation of acidic nitramines. Urea was applied in nitrolysis of 1,5-diaeotyl-3,7-endomethylene-1,3,5,7-tetraazaoyclooctane with nitric acid in sulfuric acid to 1,5-diaoethyl-3,7-dloitro-1,3, 5.7% tetraazaoyclooktin, where its presence reduces the exothermicity of the reacoia, as well as the annual time, and increases the process / US yield. U.S. Pat. 3 92ú 953 /.

The urea-formaldehyde condensates in the nitrolysis mixture enhance the safety and recovery of hexamethyltetramine to 1,3,5-trinitro-1,3,5-triazaoyllehexane.

According to the present invention, a process for the preparation of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane by nitration of bexamethylene tetramine in acidic environment is characterized in that the nitration etching is carried out in the presence of urea and / or urea-formaldehyde condensates. % in an amount of 0.001 to 20% by weight, and preferably 0.33 * 15.13% by weight. for the loading of hexamethylenetetremine.

The advantage of conducting the electrolysis process in the mind of the present invention is that it is possible in the presence of urea to know the electrolysis at a pure temperature and to a greater degree of coloration of 1,5-dimethylene-3,7-dinitro-1,3,5,7-tetraazaoyclooktane.

Preferred additives and, in water and in organic solvent, insoluble urea-omaldehyde condensates formed by the urea-formaldehyde and formaldehyde in acidic environment (e.g. VSI patent specifications no. No. 3,981,845 and 4,081,741 /.

Ammonium nitrate can also be present or in the form of a solution in nitric acid together with these additives. The presence of ¹ urea-formaldehyde condensate in the nitrolysis plant significantly increases the yield compared to the process conducted without the additive (i.e. also without para-ormaldehyde). In comparison to para-ormaldebyd, the effect on the 1,5-endemethylene-3,7-dlltro-1,3,5,7-tetraazaoyclooktol of urea-ormaldehyde condensate is positively affected. The product of the schism using urea-formaldehyde and condensate contains a certain amount of this additive. This contamination of dinltropentamothylene tetramine is not a defect in the case of its application in the manufacture of 1,3,5,7-tetranitro-1,3,5,7-tetraaaaeyeylooklookan. /

Urea, in comparison with parafortaaldehyde, is more effective in influencing the efficacy of 1,5-andomethylene-3,7-dlltro-1,3,5,7-tetraazaoyclooctane, since the same effect is achieved by the minor addition of urea, as is the case with para? formaldehyde. Maviao in the presence of urea nolysis is already possible at a remarkable discharge temperature

This reading of the effect has not been described so far in Utoratur, and it can be explained that the additives present in the acidic environment will degrade to fragments that both limit the N-methylolysed side chain eaterification during the electrolytic recombination process by promoting recyclization.

They remove the effect by following the examples.

Example 1

There were two solutions of masses. Dioxamethylenetetramine (9.99 µm) elutes are dissolved in 23 vol., o-oic acid, 96.8 µmol (50.86 moles);

8.8 volume. diols of nitric acid 99.05% (20.87 moles) were cooled to 25 ° C with vigorous addition and dissolved in 25 volumes. dielooh aoetanhydri. dn (34.05 mol).

Into the quenched &

96.8% of other acetic acid (22.11 mol) and proper dosing of the above-mentioned solutions of hexamethylenetetraine and nitric acid begins. The dosing time is 30 minutes and the temperature of the reaction mixture is maintained at 25-30 ° C.

After the aa solution is added, the reaction is carried out for 30 minutes at 25 to 27 ° C. The reactant mixture aa then turns 60 [mu] l of water to 70 [deg.] ^C. warm and after 5 minutes of inoculation aa precipitates the product isolated by filtration. After washing twice with 10 volumes of water, once with 30 volumes, with 50 volumes of aqueous ammonia and twice with 10 volumes of water and dried. This results in 5.7 parts by weight of 1,5-endomotylene-3,7'-diaitre -1,3,5,7-tetraazaeyphcleectan, which is 26.15% of theory. The product melted at 200-204 ° C and recrystallized from dimethylsulphoxide (1% methanol solution) and raised to 211-213 ° C with decomposition.

Example 2

Proceeding as in Example 1, only prettyamethylethyl tetraain contains 2.28 wt. of urea-lofonmildehyde condensate (molar ratio of formaldehyde to urea of 1.04), a proporional dosing time of the hexaaethylenethotramine and nitric acid solutions of 32 minutes and a roakeio temperature, including doroagation, of 28 to 31 ° C. 5.8 wt. Of diols of the product and 0.24 wt. diols of urea-formaldehyde condensate, i. M.p. 196 DEG-200 DEG C., recrystallized as in Example 1, 210 DEG-213 DEG.

* Example 3

Proceeding aa as in Example 1, only the solution nicely fits into the tram aa prepared by dissolving 13 masses. diols of aubatane (92.7 moles) in 21.5 volumes, a portion of oetoic acid of 96.8 µm (4.54 mol) and 10 µmol. parts by weight of Israel 96.8% and present 1 wt. Dissolved urea in ermaldehyde in the condensate (initial molar ratio of formaldehyde to urea of 1.04). Proportional dosing of the hexasaethylutotramine and nitric acid solutions takes 33 minutes, at a temperature of 33 to 35 ° 0. 18.7 wt. % of the crude product and containing 0.75 wt. diols of urea-fermaldehyde in the condensate, which is 49.18 # against the theory of pure 1,5-andomethyl-3,7-danitro-1,3,5,7-tetraazaepflooctane. Melting point: 204-206 DEG C., and the rekryČtalizáeii that in Example 1, 210-213 ^e H dec.

Example 4

Reakel and and besides as in example 1, lea and 10 volume. dlolad. ootic acid 96, 8 others and present! 0.5 wt. parts of modovinoformaldehyde condensate (starting molar ratio of fernaldehyde to non-product of 1.04); and metering of hexamethylanototramine and dueledioic acid was carried out for 11 minutes at 30 to 32 ° C. 7.3 wt. 0.4 parts by weight of the crude product. parts of the modovinofermaldahydic condonate, up to 31.61% of theory, is based on the dietary product. The melting point of the product is 201 to 206 ° C and after recrystallization as in Example 1, 210 and 213 ° C and as described above.

Example 5

It proceeds aa as in Example 1, but the amount of the present o aoic acid aa does not take into the reaction, but ea feeds hexamethylenetetramine (the whole amount) and add 2 wt. lengths of modovine formaldehyde codenaate (initial molar ratio of formaldehyde to modus 1.04). Up to this flow aa at a temperature of 46 ° C to 48 ° C, for 14 minutes it dosed with a mixture of dueledioic acid, and then a 15 minute dereaction was carried out at 44 ° C to 45 ° C. 3.9 wt. parts of the crude product, and containing 1.6 wt. parts of modovinoformaldehyde condonaate, up to 10.53% of theory; underlaid on distilled product.

Example 6

In addition to Example 1, flax ea provides 5 volumes of oic acid 96.8% (11.05 m) in which ea disperses 1.3 wt. parts of parafermaldehyde. The proporolonal inoculation of the hexamethylaatotramine and quaternary duodenum aa produces 13 ounces at a temperature of 33 ° ^{C to} 35 ° ^C , followed by a 15 minute delay at 33.5 ° ^C to 34.5 ° C. 9.6 wt. parts of the product, do 44.06% of theory. The melting point of the product is 201 to 205 ° C and after recrystallization as in Example 1 211 to 213 ° C.

Example 7

As in Example 6, only paraforaaldsfayd aa replaces 1.3 wt. % of formaldehyde-formaldehyde condensate (initial molar ratio of formaldehyde to binder 1.04). 11.5 faamt, parts of product and 1.5 wt. parts of moevinephenaldehyde condonate, i. j. $ 46.36 versus the dietary product theory. The temperature of the product is 198 to 203 ° C and recrystalline as in the example), 210 to 212 ° C, respectively.

&

*

Example 8

The reaction ® is in ® d ± ® as in Examples 6 and 7, only in place of parafermaldehyde resp. of urea-formaldehyde condensate is applied urea in an amount of 1 wt. The mixture was divided into 10 volumes of 96.8% oic acid. Proportional dávkováni® with hexane and Tylan Traminer and nitric ea performed 11 minutes at an internal temperature of 35 to 38 ° C, 20 minútový® post-reaction at 4 © C. to 43 ^g of the results of 9.6 wt. parts of the product, S0 is 44.6% compared to theory. Mp 205-209 ° C with decomposition and recrystallization as in Example 1,

210-212 ° C with decomposition.

Example 9

Vitrolysis is carried out in addition to Example 1, together only and 10 volumes, 1 ml of 96.8% acetic acid are introduced with 1 wt. % of the formaldehyde-free condensate (starting mol.% formaldehyde to urea 0.99) and 3 wt. ammonium nitrate solution and a solution of 8.5 volumes of 99.05 IU of nitric acid (20.16 moles in 28 volumes, dl of oetamhydride (38.13 moles)) is applied. Approximately half of the solutions of hexamethylan tetrsminine and nitric acid are allowed in the C and the remainder is dosed for 5 minutes at 4 to 42 C. The reaction is carried out for 25 minutes at 45 to 46 C. This results in 9.2 parts by weight. product and a content of 7 parts by weight of urea-formaldehyde contamination, i.e. 39.01 .mu.m compared to theory, calculated on the pure product.

Example 1 ©

The present mixture consisted of 65 volumes, parts by weight of oic acid 96.8% (1443.73 mole), 1.5 volumes, part by weight of acetic anhydride (2.04 mole), and 2.5% by weight. parts by volume of urea vinoformaldehyde condensate (initial molar ratio of formaldehyde to urea of 0.99) is dosed in a preperoneal manner with 35 volumes of parts of acetic anhydride (47.67 mol) of 14 wt. parts of hexane tylante tramin (9.99 mall) in 23 volume, longitude 96.8% by weight of acetic acid (50.86 mall), and a solution of 12.2 wt. parts of ammonium nitrate (14.35 mall) in 8.5 volume, longitudes of 99.05? -? ® nitric acid (20.16 mall). The temperature of the mixture at a dose is maintained at 43 to 45 and ^e © dosing period is 15 minutes. After 15 minutes post-reaction at 44 to 46 ^e G, the reaction was cooled to 12 ®C and the solid formed was filtered off. This results in 9.7 parts by weight of a crude product containing 1.2 parts by weight. parts of urea formaldehyde condensate, which is $ 39.01 compared to the tall, calculated on the pure product.

Claims (1)

The process for the preparation of 1,5-endoiaotylene-3,7-dinitro-1,3,5,7-tetraazaoyclooctane by filtering the hexamstylanetetramine under acidic conditions, is characterized in that the nitrating stiopsole is carried out in the presence of urea and / or urea formaldehyde condenser in an amount of % 0.001 to 20 wt.%, Preferably 0.35 to 15.15 wt. for the loading of hexamotylantotramine.