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Publication numberUS3873579 A
Publication typeGrant
Publication dateMar 25, 1975
Filing dateAug 20, 1969
Priority dateAug 20, 1969
Publication numberUS 3873579 A, US 3873579A, US-A-3873579, US3873579 A, US3873579A
InventorsRonald Rosher
Original AssigneeUs Navy
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Organic azides and method of preparation thereof
US 3873579 A
Abstract
Compounds of the formula WHERE R represents H, and alkyl group of 1 to 6 carbon atoms or an alkyl group of 1 to 6 carbon atoms where at least one hydrogen atom has been replaced by the group TO FORM A GROUP OF THE FORMULA ARE PREPARED BY REACTING AN AMINE OF THE FORMULA WHERE R' represents H, -NH-NO2, alkyl of 1 to 6 carbon atoms or alkyl of 1 to 6 carbon atoms where at least one hydrogen atom has been replaced by -NH-NO2 to form the group -CH2-NH-NO2 with formaldehyde and HCl to effect a chloromethylation and thereafter reacting an ionic azide with the chloromethylated product.
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United States Patent 1 Rosher l l ORGANIC AZIDES AND METHOD OF PREPARATION THEREOF [751 Inventor: Ronald Rosher, Cumberland, Md.

{73] Assignee: The United States of America as represented by the Secretary of the Navy, Washington DC.

[22] Filed; Aug. 20. 1969 [Il] Appl, No.: 851,765

[52] US. Cl 260/349, 149/88, 149/92 lnt. (L C07c 117/00 Field of Search 260/349; 149/92, 88

[56] References Cited LNlTED STATES PATENTS 347mb}! lI/Wh Menke et al. 149/88 Prumlr [iiairliner-Stephen .l. Lechert, Jr. Mmnu'r Agent, or FirmR. S. Sciascia; J. A Cooke [5H ABSTRACT ('ompounds of the formula W2 R- CH -N-CH -N here R represents H,

[ Mar. 25, I975 and alkyl group of l to 6 carbon atoms or an alkyl group of l to 6 carbon atoms where at least one hydrogen atom has been replaced by the group to form a group of the formula 2 -CH2- IiI-CH N3 are prepared by reacting an amine of the formula R cu -h-No 8 Claims, N0 Drawings ORGANIC AZIDES AND METHOD OF PREPARATION THEREOF BACKGROUND OF THE INVENTION This invention generally relates to the preparation and use of organic nitrogen containing compounds and more specifically to the preparation and use of organic azides.

Double-base propellants, which have become widely used in recent years, have two principle ingredientsnitrocellulose and nitroglycerine. In addition various other materials have been added to the above propellant to modify the properties thereof. Thus, plasticizers such as phthalates, triacetin or other well known plasticizers can be added to the principle ingredients. Stabilizers such as 2-nitrodiphenylamine, tert-butyl catechol, resorcinol or any other art recognized stabilizer can be added to the basic propellant as well. It has also been the practice to add burning-rate modifiers such as, for example, lead salts to the basic propellant as well as extrusion lubricants such as stearates and soaps. Flash supporters such as potassium salts have also been added to these propellants. More recently additional oxidizers have been added such as ammonium perchlorate, potassium perchlorate, lithium perchlorate, potassium nitrate as well as a host of others known in the art. Finally, a fuel, such as aluminum may also be added.

Thus, the basic composition can be modified as desired merely by adding any one or combination of the known additives for their known effect.

Recently attempts have been made to modify the double-base propellants not only by the addition of specific modifying agents but by the replacement, either partially or totally, of one of the principle ingredients, the nitroglycerin in order to increase the specific impulse and the burning rate of the propellant.

SUMMARY OF THE INVENTION Accordingly, one object of this invention is to provide materials which can successfully replace all or part of the nitrogylcerine in double-base propellants.

Another object of this invention is to provide compositions of double-base propellants in which all or part of the nitroglycerin has been replaced without a loss of the desired properties of the composition.

Another object of this invention is to effect an increase in both specific impulse and burning rate of double-base propellant compositions.

A still further object of this invention is to provide organic azides compounds.

A further object of this invention is to provide a method for the production of organic azides from amines.

These and other objects of this invention are accomplished by providing organic azides of the formula wherein R is selected from the group consisting of H, alkyl of l to 6 carbon atoms,

and alkyl of l to 6 carbon atoms wherein at least one of the hydrogen atoms has been replaced by the I CH N radical. These organic azides, and all similar azides which contain the group -N-No l CH2- N can be prepared from amines containing the radical NI-INO by reacting said amine with HCl and formaldehyde to obtain the chloromethylation product and thereafter reacting said chloromethylated product with an ionic azide.

DESCRIPTION OF PREFERRED EMBODIMENT The compounds of this invention are readily prepared by reacting a nitramine with formaldehyde and HCl, thus forming a nitramine chloride. This intermediate is then converted to the desired product by reacting it with an ionic azide. This general method is applicable to produce azides from any amine of Formula 1 hereinafter defined, as long as the starting materials do not contain groups that will react with the other reagents present in the reaction.

Thus, the process itself can be looked on generally as a process for converting a compound containing the radical CI-I NH--NO (I) to a compound containing the radical au a-m (II) CH N by means of reacting (I) with formaldehyde and HCl to obtain the chloromethylated product and thereafter reacting said chloromethylated product with an ionic azide to obtain (II). The only limit on this reaction is that the groups attached to the carbon atom of Formula I must not react with any of the reagents that are being used to bring about the desired transformation. Thus, any amine as in Formula (I) can be converted so long as the above limitation with respect to the other functional groups in the molecule is kept in mind.

The primary nitramines which are used as starting materials can contain cyclic, acyclic or aromatic radicals as well as various other substituents as long as these substituents do not react with the other reagents which will be used in this reaction as hereinbefore disclosed. Some typical nitramines that can be used in the instant process are H R- CH2-N-m2 111 wherein R represents H, an aliphatic radical, an aromatic radical, a cyclic radical, NI-I--NO or an aliphatic, aromatic or cyclic radical wherein at least one of the hydrogen atoms is replaced by the --NI-I-NO group to form the radical CH Nl-INO The preferred starting materials are those wherein R represents H, alkyl of 1 to 6 carbon atoms, -NHNO and alkyl of l to 6 carbon atoms wherein at least one of the hydrogen atoms has been replaced by the NHNO radical to form the radical CH NHNO (i.e. R represents -CH NHNO CH -CH -N- HNO etc).

The formaldehyde used in this reaction can be from any of the known sources of formaldehyde and may be generated in situ using any the the conventional techniques.

The reaction temperature at which the chloromethylation takes place is not critical but is preferably kept below about 60 C although other temperatures can be used.

The final reaction needed to obtain the products of this invention consists of reacting the chloromethylation product obtained above with an ionic azide, such as for example sodium azide or other alkali metal azides at a temperature below about C and preferably under a dry nitrogen atmosphere.

The compositions contemplated by this invention include the known compositions of all double base propellants where some or all of the nitroglycerin has been replaced by the compounds of this invention.

The simplest composition comtemplated by this invention is merely a mixture of an organic azide of this invention and nitrocellulose. A composition such as this when used as a gun propellant serves to increase impetus without increasing the flame temperature significantly by virtue of the fact that this composition produces more gas per unit weight on decomposition than does the nitrocellulose nitroglycerin propellant.

To the basic ingredients, nitrocellulose and nitroglycerin which is totally or partially replaced by the azides defined by Formula (ill) may be added various other ingredients such as plasticizers, stabilizers, burning-rate modifiers, extrusion lubricants, flash supporters as well as additional oxidizers and fuels. Thus. any double-base propellant can be converted merely by the substitution with the azides of Formula III for either all or part of the nitroglycerin.

The instant compositions can be processed in any of the art recognized manners. For example one can prepare a composition by the slurry process and then cure it to obtain the final composition or one can produce a product by means ofthe well known cast powder process.

The general nature of the invention having been set forth, the following examples are presented as specific illustrations thereof. it will be understood that the invention is not limited to these specific examples but is susceptible to various modifications that will be recog nized by one of ordinary skill in the art.

EXAMPLE 1 Preparation of l,6-Diazido-2,5-Dinitrazahexane Five hundred ml. of glacial acetic acid and 150 g of trioxymethylene were placed in a flask equipped with a gas inlet tube, a mechanical stirrer and a reflux condenser fitted with a drying tube. Dry HCl gas was passed through the suspension until only a slight turbidity remained.

The HCl treatment was interrupted while 150 g of dry powdered ethylene dinitramine was added over a period of several minutes. Treatment with HCl was then resumed and the temperature rose slowly to 40 C.

After approximately two hours a white preipitate began to form and the addition of HCl was continued for two hours. Then the mixture was stirred for 16 hours after which the product was separated by filtration. It was washed first with cold glacial acetic acid and was then slurried with benzene prior to drying in a desiccator at ambient temperature. A yield of -85% was obtained.

Twenty grams of the chloromethylated product was dissolved in ml of acetone. The solution was stirred while nitrogen was passed over its surface and it was cooled by immersion in an ice-salt bath. A solution of 21 g of sodium azide in 100 ml of water was added at such a rate that the temperature did not exceed 10 C. The crystalline product was allowed to stand in contact with the mother liquor for 16 hours prior to filtration after which it was washed with water and air dried for two hours.

The product was recrystallized from hot benzene, separated and slurried with ether. After drying a yield of 75% was obtained.

EXAMPLE 2 Preparation of l,5-DiaZido-2,4-Dinitrazapentane The above procedure was repeated except that 136 g of methylene dinitramine was chloromethylated instead of g ethylene dinitramine. Occasionally, it was necessary to cool the flask to initiate crystallization of the chloromethylated product which was obtained in 75% yield. The yield of the diazide was 60%.

EXAMPLE 3 Preparation of Z-Nitrazapropyl Azide Two hundred and fifty ml. of redistilled dioxane and 62.4g. of trioxylmethylene were placed in a 1 liter three necked flask having a gas inlet tube, a mechanical stirrer, a thermometer and a drying tube. Dry HCl gas was passed into the mixture until it was almost clear.

The addition of HCl was stopped and the temperature of the reaction mixture was allowed to drop to 35 C before 396 g. of dry, powdered methyl nitramine has added. The rate of addition was such that the temperature did not rise above 40 C. After the addition was complete, the passage of HCl was resumed and continued for 3 hours. The reaction mixture was allowed to stand for 18 hours at ambient temperature. The solvent was then removed on a rotary evaporator. The product was a greenish-yellow oil.

15.7 g. of the oil was dissolved in 100 ml of acetone in a beaker and the beaker was immersed in an ice-salt bath. A solution of 25.2 g. of sodium azide in 75 ml of water was added with mechanical stirring. The reaction mixture was blanketed with dry nitrogen during this operation and the temperature was maintained below 10 C.

After standing 64 hours the reaction mixture was extracted with ether and the extract was dried over MgSO, The ether was evaporated leaving a greenishyellow product in an amount equivalent to an 80% yield. Distillation under reduced pressure gave a clear liquid n,, 1.4828.

EXAMPLE 4 Typical Compositions s A composite made up of the following materials was mixed by conventional slurry techniques and cured in the conventional manner.

Nitrocellulose l2 Nitroglycerine 25. l,6-diazido-2,5- 8 dinitrazahexane Ammonium Perchlorate 34. Aluminum 1 6 Z-Nitrodiphenylamine l Resorcinol l Triacetin l A casting powdered was also prepared by the conventional methods. It was cast with 90% casting solvent giving a product of the following composition:

Nitrocellulose Nitroglycerine l ,G-ClIQZidO-LS dinitrazahexane Ammonium Perchlorate Aluminum I-Nitrodiphenylamine Resorcinol Triacetin EXAMPLE 5 Compositions containing l,5-diazido-2,4- dinitrazapentane (DADZP) were also prepared. Column A lists the percentage of each material in the slurry that was prepared as in example 4 above and column B lists the percentage of each material in the casting power process prepared as in Example 4 above.

What is claimed and desired to be secured by Letters Patent of the United States is:

1. Compounds of the formula wherein R is selected from the group consisting of H, alkyl of l to 6 carbon atoms,

CHE-N.)

and alkyl of l to 6 carbon atoms wherein at least one of the hydrogen atoms has been replaced by the N- NO 2 CH N radical to form the radical 2. A compound of claim 1 wherein R is hydrogen. 3. A compound of claim 1 wherein R is -N-NO 4. A compound of claim 1 wherein R is -C1-1 1:1- NO CH N 5. A method of converting compounds containing the radical CH NH N0 to a compound containing the radical I-cn u N02 [111- Q cs N3 which comprises reacting a compound with the radical CH NH N0 with formaldehyde and HCl to obtain the chloromethylated product and thereafter reacting said chloromethylated product with an ionic azide to obtain a compound with the radical 6. A method of producing the azides of the formula .3 CH2: N 0

CH N

wherein R is selected from the group consisting of H, alkyl of l to 6 carbon atoms,

and alkyl of l to 6 carbon atoms wherein at least one of the hydrogen atoms has been replaced by the radical to form the radical CH N which comprises reacting amines of the formula R CH NHNO wherein R" is selected from the group consisting of H, alkyl of l to 6 carbon atoms, N- H-NO and alkyl of l to 6 carbon atoms wherein at least one hydrogen atom has been replaced by the N-

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3476623 *Apr 9, 1968Nov 4, 1969Dynamit Nobel AgMetal azide electrically conductive priming composition and manufacture thereof
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4085123 *Oct 21, 1976Apr 18, 1978Rockwell International Corporation1,3-Diazido-2-nitrazapropane
US4141910 *Aug 15, 1977Feb 27, 1979Rockwell International CorporationPlasticizers, oxidizers
US4362583 *Apr 21, 1981Dec 7, 1982The United States Of America As Represented By The Secretary Of The NavyExplosives, propellants; high energy
US4406718 *Jul 16, 1981Sep 27, 1983The United States Of America As Represented By The Secretary Of The NavyPropellants; firearms; rockets; esterification of a diacid chloride with a diazido alkanol
US4419285 *Feb 19, 1982Dec 6, 1983The United States Of America As Represented By The Secretary Of The Air ForceAzido fluorodinitro amines
US4419286 *Apr 21, 1982Dec 6, 1983The United States Of America As Represented By The Secretary Of The Air ForceAzido esters
US4440687 *Apr 8, 1982Apr 3, 1984The United States Of America As Represented By The Secretary Of The Air ForcePlasticizers for solid propellants
US4450110 *Mar 24, 1983May 22, 1984Hercules IncorporatedPlasticizing firearm and rocket propellants; low reaction heat; high combustion rate
US4482404 *Dec 6, 1983Nov 13, 1984The United States Of America As Represented By The Secretary Of The Air ForceCuts down flames in exhaust gases
US5013856 *Jun 4, 1981May 7, 1991Rockwell International CorporationPlasticizer for solid propellant
EP0445357A2 *Sep 25, 1990Sep 11, 1991Rockwell International CorporationUltra high-energy azide containing gun propellants
EP0608488A1 *Oct 20, 1993Aug 3, 1994Rockwell International CorporationUltra-high burn rate gun propellants
WO1998034891A1 *Feb 6, 1998Aug 13, 1998Diehl Stiftung & CoPropellant powder for barrelled weapons
WO2008048146A2Oct 12, 2007Apr 24, 2008Obshestvo S Ogranichennoy OtveModifier for explosives
Classifications
U.S. Classification552/11, 149/92, 149/88
International ClassificationC06B25/34
Cooperative ClassificationC07C247/00, C06B25/34
European ClassificationC07C247/00, C06B25/34