RU2445311C1 - Method of producing 2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3,3,0]octane - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to organic chemistry and specifically to a method of producing 2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3,3,0]octane, involving nitration of a salt of 2,4,6,8-tetraazabicyclo[3,3,0]octane-2,4,6,8-tetrasulphonic acid, characterised by that nitration is carried out with a mixture of nitric acid and nitric anhydride or a mineral acid and/or anhydride thereof or an organic acid or anhydride thereof.

EFFECT: novel method of producing 2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3,3,0]octane, characterised by high output of the end product.

1 tbl, 2 ex

Description

The invention relates to organic chemistry, and specifically to a method for producing 2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo [3.3.0] octane (BCO), which is used as a heat-resistant powerful explosive.

A known method of obtaining BCO (US Pat. 5659032 "Process for synthesis of 2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo [3,3,0] octane" G.Eck, M.Piteau, Societe nationale des poudres et explosives, Paris, France, 08.19.1997.), Adopted for the prototype, including nitration of the original product.

In this case, 2,4,6,8-tetraacetyl-2,4,6,8-tetraazabicyclo [3.3.0] octane is used as the starting product, which is nitrated with nitronium boron fluoride in aprotic solvents (acetonitrile, nitromethane, chlorinated hydrocarbons) :

The output of the BCO obtained by this method is 20%. The nitronium salt used is an inaccessible and expensive agent.

The objective of the invention is the creation of an effective method for producing BCO, which allows to increase the yield of the target product while using a classic nitrating agent, which increases the economic attractiveness of the method.

The problem is solved by the proposed method for obtaining BCO, including nitration of the salt of 2,4,6,8-tetraazabicyclo [3.3.0] octane-2,4,6,8-tetrasulfonic acid. The peculiarity lies in the fact that the nitration is carried out with a mixture of nitric acid with nitric anhydride or with mineral acid and / or its anhydride or with organic acid or its anhydride.

The yield of the target product is up to 75%:

It is not known the technical solution to the problem in which the proposed combination of features would take place. The proposed method differs from the prior art method for producing BCO by another nitrating agent.

In turn, the 2,4,6,8-tetraazabicyclo [3.3.0] octane-2,4,6,8-tetrasulfonic acid salt is readily available by condensation of the corresponding sulfamic acid salt with formaldehyde and glyoxal.

Information confirming the possibility of implementing the method

Example 1-21

In a three-necked flask with a capacity of 50 ml, equipped with a stirrer and a thermometer, a nitrating agent is placed and cooled to the required temperature. At this temperature, a salt of 2,4,6,8-tetraazabicyclo [3.3.0] octane-2,4,6,8-tetrasulfonic acid (for example, potassium, or lithium, or sodium, or rubidium, or cesium, or ammonium, or methylammonium, or trimethylammonium, or triethylammonium, or calcium, or barium, or strontium), incubated for 30 minutes and diluted with a mixture of water and ice. The resulting BCO is filtered, washed on the filter with water until acidic, and dried. Additional parameters of the process of obtaining BCO are presented in the table.

¹³ C NMR spectrum (acetone d ₆ ) :( δ, ppm): 5.65 and 6.65 (two d, 4H, CH ₂ ), 7.86 (s, 2H, CH).

¹³ C NMR spectrum (acetone d ₆ ) :( δ, ppm): 64.91 (CH ₂ ); 78.14 (CH).

Example 22

To a solution of 100 g, for example, the potassium salt of sulfamic acid in 180 ml of water at a pH of 2.5-2.8 and a temperature of 45 ° C, 25 g of 40% formalin and 25 g of 40% glyoxal were added over 45 minutes. Maintained at this temperature for 30 minutes, cooled to 5 ° C. After the precipitation of the potassium salt of 2,4,6,8-tetraazabicyclo [3.3.0] octane-2,4,6,8-tetrasulfonic acid is complete, it is filtered off, washed with a small amount of chilled water and dried to constant weight. Obtain 80 g of salt in 80% yield.

¹ H NMR Spectrum (D ₂ O): (δ, from DSS, ppm): 4.38 and 4.88 (two d, 4H, CH ₂ ); 5.67 (s, 2H, CH).

¹³ C NMR Spectrum (D ₂ O): (δ, ppm): 67.0 (CH ₂ ); 81.1 (CH).

Other salts are similarly prepared - lithium, sodium, rubidium, cesium, ammonium, methylammonium, trimethylammonium, triethylammonium, calcium, barium, strontium.

No. p / p Nitrating agent T, ° С Module Exit, % one HNO ₃ (concentration - 100%) -thirty 10 68 2 HNO ₃ (concentration - 100%) -fifteen 10 58 3 HNO ₃ (concentration - 100%) 0 10 40 four HNO ₃ (concentration - 97%) -thirty 10 56 5 HNO ₃ (concentration - 97%) -fifteen 10 37 6 HNO ₃ (concentration - 97%) 0 10 8 7 12% N ₂ O ₅ in HNO ₃ -thirty 8 75 8 12% N ₂ O ₅ in HNO ₃ 0 8 56 9 12% N ₂ O ₅ in HNO ₃ -thirty 4,5 69 10 6% N ₂ O ₅ in HNO ₃ -thirty 4,5 66 eleven A mixture of H ₂ SO ₄ and HNO ₃ (10:90) -thirty four 58 12 A mixture of H ₂ SO ₄ and HNO ₃ (30:70) -thirty 10 52 13 A mixture of H ₂ SO ₄ and HNO ₃ (30:70) 0 10 31 fourteen A mixture of 20% oleum with HNO ₃ (30:70) -thirty 10 fifty fifteen A mixture of 20% oleum with HNO ₃ (50:50) -thirty 10 fifty 16 A mixture of 20% oleum with HNO ₃ (30:70) 0 10 34 17 A mixture of acetic anhydride with HNO ₃ (10:90) 0 6 45 eighteen A mixture of acetic anhydride with HNO ₃ (20:80) 0 6 47 19 A mixture of acetic anhydride with HNO ₃ (30:70) 0 6 49 twenty A mixture of acetic anhydride with HNO ₃ (30:70) -thirty 6 56 21 A mixture of acetic acid with HNO ₃ (10:90) -thirty 6 52

The implementation of the proposed technical solution will satisfy the existing need for an effective and economically attractive way to obtain BCO.

Claims (1)

A method for producing 2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo [3.3.0] octane, comprising nitration of a salt of 2,4,6,8-tetraazabicyclo [3.3.0] octane -2,4,6,8-tetrasulfonic acid, characterized in that the nitration is carried out with a mixture of nitric acid with nitric anhydride, or with mineral acid and / or its anhydride, or with an organic acid or its anhydride.