US3000953A - Tetranitramines - Google Patents

Tetranitramines Download PDF

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US3000953A
US3000953A US666271A US66627157A US3000953A US 3000953 A US3000953 A US 3000953A US 666271 A US666271 A US 666271A US 66627157 A US66627157 A US 66627157A US 3000953 A US3000953 A US 3000953A
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tetraazaheptadecane
formula
acid
nitric acid
radical
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US666271A
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Milton B Frankel
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Aerojet Rocketdyne Inc
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Aerojet General Corp
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine

Definitions

  • the high energy tetranitramines of this invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge.
  • An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949.
  • One way of using the high explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed.
  • a charge thus prepared is sufliciently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impact or timefuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.
  • the high energy tetranitramines of my invention are prepared by reacting a dinitramine with nitric acid in accordance with the general reaction scheme set forth below:
  • Example I Preparation of 2,5 ,9,1 2-tezraaza-2,5 ,7,7 ,9,1 2- hexanitrotridecane
  • a mixture of 200 ml. of 99% nitric acid, 200 ml. of concentrated sulfuric acid and 25 g. of 2,5,9,l2-tetraaza- 2,7,7,IZ-tetranitrotridecane was maintained within the temperature range of 50-55 C. for thirty minutes and then cooled and poured on ice.
  • the product was obtained as white solid, washed with water, and dried; 13.19 g. of a material having an MP. of 94-96 C. was obtained.
  • reaction temperature is not critical in the practice of this invention, the only eliect of temperature variation being a corresponding increase or decrease in reaction rate.
  • a dehydrating agent such as sulfuric acid.
  • the dehydrating agent takes up the water of reaction thereby shifting the reaction equilibrium so as to increase the product yield.
  • My invention is not limited to the use of sulfuric acid as a dehydrating agent.
  • Other conventional dehydrating agents such as acetic anhydride, phosphoric acid, phosphoric anhydride, lower organic acid anhydrides such as butyric acid, propionic acid, etc, anhydrides, trifluoroacetic anhydride, or their equivalents can be used in the practice of my invention.
  • the dinitramines used as starting materials for the preparation of the high energy tetranitramines of this invention are obtained by condensing nitraza amines, such as 3nitraza-1-buty1amine, with 2,2-dinitro-l,3-propanediol, as more fully disclosed in my oopending U.S. patent application Serial No. 666,275, filed concurrently with the present application.
  • nitraza amines In condensing the nitraza amines with the 2,2-dinitm-l,3-propanediol, it is preferred to generate the nitraza amines from strong mineral acid salts-thereof in situ, preferably by neutralizing the salts with inorganic basic salts of alkali or alkaline earth metals such as hydroxide, lithium carbonate, calcium bicarbonate, etc, or with weak organic acid salts of alkali or alkaline. earthmetals such as potassium acetate, magnesium butyrate, etc.
  • the strong mineral acid salts of nitraza amines from which the freenitraza amines generated in situ, as described above, are prepared by reacting corresponding nitraza isocyanates, such as 3-nitraza-l-butyl isocyanate, with aqueous solutions of strong mineral acids, for example, hydrochloric acid, nitric acid, etc., as more fully described in my copending U.S. patent application Serial No. 666,273, filed concurrently with the present application.
  • the dinitramine starting materials of the present invention can be those which have been prepared from mixtures of nitraza amines as well as those prepared from individual nitraza amines.
  • unsymmetrical dinitramines such as those in which the two Rs and/or the two A's as shown in the general formula are not identical can be nitrated by the method of my invention to form corresponding unsymmetrical tetranitrarnines.
  • tetranitramine compounds within the scope of my invention can be prepared by the method of this invention.
  • 3,1,11,15 ztelraaza 3,9,9,l5 tetrauitroheptadecane; 2,2,4,9,9, 14,1 6, l6-octanitro4,7, l 1,14-tetraazaheptadecane; and 2,2,4,9,9,l5-hexanitro-4,7,11,15-tetraazaheptadecane can be nitrated to yield 3,7,9,9,l1,l5 hexa- Intro-3,7,11,15-tetraazaheptadecanel; 2,2,4,7,9,9,1 1,14,16, l6-decanitro-4,7,l l,14-tetraazaheptadecane; and 2,2,4,7,9', 9,1 l,l5-octanitro-4,7
  • a tetranitramine having the formula:
  • R is a radical selected from the group consisting of hydrogen, lower alkyl and lower nitroalkyl radicals and A is a lower alkylene radical.
  • R is a lower alkyl radical and A is a lower alkylene radical.
  • a tetranitramine hav- 1T0, 17701 ITTO N N0 R-CHrN-A-CHrN-CHrC-GHrN-CHz-A-N-CHt-R wherein R is a lower nitroalkyl radical and A is a lower alkylene radical.
  • R is a radical selected from the group consisting of hydrogen, lower alkyl and lower nitroalkyl radicals and A is a lower alkylene radical.
  • R is a lower alkyl radical and A is a lower alkylene radical.
  • R is a lower nitroalkyl radical and A is a lower alkylene radical.

Description

United States Patent Ofiice 3,000,953 Patented Sept. 19, 1961 INES Milton B. Frankel, Pasadena, Calif., assignur to Aerojetglelireral Corporation, Aznsa, Califl, a corporation of No Drawing. Filed June 13, 1957, Ser. No. 666,271 16 Claims. (Cl. 260-583) wherein R is a hydrogen, alkyl or nitroalkyl radical and A is an alkylene radical.
The high energy tetranitramines of this invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162, is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufliciently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impact or timefuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.
The high energy tetranitramines of my invention are prepared by reacting a dinitramine with nitric acid in accordance with the general reaction scheme set forth below:
No, NO:
wherein R and A are as defined above.
To more clearly illustrate my invention, the following example is presented. It should be understood that this example is presented merelyas a means of illustration and is not intended to limit the scope of the invention to the particular conditions set forth therein.
Example I.Preparation of 2,5 ,9,1 2-tezraaza-2,5 ,7,7 ,9,1 2- hexanitrotridecane A mixture of 200 ml. of 99% nitric acid, 200 ml. of concentrated sulfuric acid and 25 g. of 2,5,9,l2-tetraaza- 2,7,7,IZ-tetranitrotridecane was maintained within the temperature range of 50-55 C. for thirty minutes and then cooled and poured on ice. The product was obtained as white solid, washed with water, and dried; 13.19 g. of a material having an MP. of 94-96 C. was obtained. The product, 2,5,9,12-tetraaza-2,5,7,7,9,12- hexanitrotridecane, was recrystallized from concentrated nitric acid and then from ethylene dichloride to produce a final material having an MP. of ll5-117 C.
AHHIYSZ Sr-CflCI-IlfitBd for C H N O Percent C, 23.58; percent H, 3.96; percent N, 30.56. Found: Percent C, 21.65; percent H, 3.66; percent N, 28.92.
The reaction temperature is not critical in the practice of this invention, the only eliect of temperature variation being a corresponding increase or decrease in reaction rate.
It is preferred to carry out the nitration reaction of the present invention in the presence of a dehydrating agent such as sulfuric acid. The dehydrating agent takes up the water of reaction thereby shifting the reaction equilibrium so as to increase the product yield. My invention is not limited to the use of sulfuric acid as a dehydrating agent. Other conventional dehydrating agents such as acetic anhydride, phosphoric acid, phosphoric anhydride, lower organic acid anhydrides such as butyric acid, propionic acid, etc, anhydrides, trifluoroacetic anhydride, or their equivalents can be used in the practice of my invention.
The dinitramines used as starting materials for the preparation of the high energy tetranitramines of this invention are obtained by condensing nitraza amines, such as 3nitraza-1-buty1amine, with 2,2-dinitro-l,3-propanediol, as more fully disclosed in my oopending U.S. patent application Serial No. 666,275, filed concurrently with the present application. In condensing the nitraza amines with the 2,2-dinitm-l,3-propanediol, it is preferred to generate the nitraza amines from strong mineral acid salts-thereof in situ, preferably by neutralizing the salts with inorganic basic salts of alkali or alkaline earth metals such as hydroxide, lithium carbonate, calcium bicarbonate, etc, or with weak organic acid salts of alkali or alkaline. earthmetals such as potassium acetate, magnesium butyrate, etc.
The strong mineral acid salts of nitraza amines from which the freenitraza amines generated in situ, as described above, are prepared by reacting corresponding nitraza isocyanates, such as 3-nitraza-l-butyl isocyanate, with aqueous solutions of strong mineral acids, for example, hydrochloric acid, nitric acid, etc., as more fully described in my copending U.S. patent application Serial No. 666,273, filed concurrently with the present application.
It should be noted-that the dinitramine starting materials of the present invention can be those which have been prepared from mixtures of nitraza amines as well as those prepared from individual nitraza amines. Thus, unsymmetrical dinitramines, such as those in which the two Rs and/or the two A's as shown in the general formula are not identical can be nitrated by the method of my invention to form corresponding unsymmetrical tetranitrarnines.
It will be appreciated that a wide variety of tetranitramine compounds within the scope of my invention can be prepared by the method of this invention. For example, 3,1,11,15 ztelraaza 3,9,9,l5 tetrauitroheptadecane; 2,2,4,9,9, 14,1 6, l6-octanitro4,7, l 1,14-tetraazaheptadecane; and 2,2,4,9,9,l5-hexanitro-4,7,11,15-tetraazaheptadecane can be nitrated to yield 3,7,9,9,l1,l5 hexa- Intro-3,7,11,15-tetraazaheptadecanel; 2,2,4,7,9,9,1 1,14,16, l6-decanitro-4,7,l l,14-tetraazaheptadecane; and 2,2,4,7,9', 9,1 l,l5-octanitro-4,7,l1,15-tetraazaheptadecane, respec tively. Other members of this new series of compounds are prepared simply by reacting appropriate starting materials according to the teachings of this invention.
I claim:
1. As a composition of matter, a tetranitramine having the formula:
wherein R is a radical selected from the group consisting of hydrogen, lower alkyl and lower nitroalkyl radicals and A is a lower alkylene radical.
ing the formula:
wherein R is a lower alkyl radical and A is a lower alkylene radical.
3. As a composition of matter, a tetranitramine hav- 1T0, 17701 ITTO N N0: R-CHrN-A-CHrN-CHrC-GHrN-CHz-A-N-CHt-R wherein R is a lower nitroalkyl radical and A is a lower alkylene radical.
4. As a composition of matter, 2,5,9,12-tetraaza-2,5, 7,7,9,l2-hcxanitrotridecane having the structural formula:
5. As a composition of matter, 3,7,9,9,11,15-hexanitro- 3,7,11,15-tetraazaheptadecane having the structural formula:
6. As a composition of matter, 2,2,4,7,9,9,11,14,16,16- decanitro-4,7,11,14-tetraazaheptadecane having the structural formula:
7. As a composition of matter, 2,2,4,7,9,9,11,15-octanitro-4,7,l1,l5-tetraazaheptadecane having the structural formula:
D50: 1110, NO: NO: NO: Nos CH| U HrN-CHg CH|CHrN-CHs--CHrNCHaCHrN-CHg--CH l N O i N 0 i 8. The method of preparing tetranih'amines having the formula:
1110 a 1110 s N 0: N0: N0: R-O HrN-A-CHg-N-CHr +43 Hr-N-OHa-A-N-C HrB.
which comprises reacting a dinitramine having the formula:
with nitric acid; wherein R is a radical selected from the group consisting of hydrogen, lower alkyl and lower nitroalkyl radicals and A is a lower alkylene radical.
9. The method of claim 8 wherein the nitration reaction is conducted in the presence of sulfuric acid.
10. The method of preparing 2,5,9,l2tetraaza-2,5,7, 7,9,12-hexanitrotridecane which comprises reacting 2,5,9, l2-tetraaza-2,7,7,IZ-tetranitrotridecane with nitric acid.
11. The method of preparing 3,7,9,9,11,15-1hexanitro- 3,7,11,15-tetraazaheptadecane which comprises reacting 3,7,11,15 tetraaza. 3,9,9,15 tetranitroheptadecane with nitric acid.
12. The method of preparing 2,2,4,7,9,9,l1,14,16,16- decanitro-4,7,11,14-tetraazaheptadecane which comprises reacting 2,2,4,9,9,14,16,16 octanitro 4,7,11,14-tetraazaheptadecane with nitric acid.
13. The method of preparing tetranil i mines having the formula:
which comprises reacting a dinitramine having the formula:
with nitric acid; wherein R is a lower alkyl radical and A is a lower alkylene radical.
14. The method of preparing tetranitramines having the formula:
which comprises reacting a dinitramine having the formula:
with nitric acid; wherein R is a lower nitroalkyl radical and A is a lower alkylene radical.
15. The method of claim 10 wherein the reaction is conducted in the presence of sulfuric acid.
1-6. The method of preparing 2,2,4,7,9,9,11,15-octanitro-4,7,11,15-tetraazaheptadecane which comprises reacting 2,2,4,9,9,15 hexanitro 4,7,11,15 tetraazaheptadecane with nitric acid.
No references cited.

Claims (1)

1. AS A COMPOSITION OF MATTER, A TETRANITRAMINE HAVING THE FORMULA:
US666271A 1957-06-13 1957-06-13 Tetranitramines Expired - Lifetime US3000953A (en)

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