USH447H - Synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane - Google Patents
Synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane Download PDFInfo
- Publication number
- USH447H USH447H US07/024,437 US2443787A USH447H US H447 H USH447 H US H447H US 2443787 A US2443787 A US 2443787A US H447 H USH447 H US H447H
- Authority
- US
- United States
- Prior art keywords
- trinitro
- triazacyclohexane
- hexamethylenetetramine
- nitrating
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/04—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D251/06—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to ring nitrogen atoms
Definitions
- This invention relates to a method of preparing pure 1,3,5-trinitro-1,3,5-triazacyclohexane by the direct liquid phase nitration of hexamethylenetetramine.
- 1,3,5-trinitro-1,3,5-triazacyclohexane is currently prepared by a two-step procedure known in the art as the Bachman process.
- a mixture of ammonium nitrate and hexamine nitrate is added to a solution of nitric acid in acetic anhydride. While the product yield is about 70%, the intermediates and the final product contain about 10% of the contaminant 1,3,5,7-tetraaza-1,3,5,7-tetranitrocyclooctane.
- Further purification steps are required to reduce the presence of the contaminant to acceptable levels. These purification steps diminish the final yield of 1,3,5-trinitro-1,3,5-triazacyclohexane.
- nitration of hexamethylenetetramine to produce 1,3,5-trinitro-1,3,5-triazacyclohexane has also been achieved using concentrated nitric acid and small amounts of ammonium salts such as NH4NO3 and (NH4)2SO4 to prevent runaway reaction and reduce the decomposition of the 1,3,5-trinitro-1,3,5-triazacyclohexane to undesirable by-products.
- concentrated nitric acid and small amounts of ammonium salts such as NH4NO3 and (NH4)2SO4
- One object of this invention is an improved and more economical synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane.
- a further object of this invention is an economical synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane of high technical purity for use an important constituent in solid propellant and explosive formulations.
- 1,3,5-trinitro-1,3,5-triazacyclohexane of high technical purity is synthesized by the reaction of hexamethylenetetramine with dinitrogen pentoxide in 100% nitric acid under a separate organic phase.
- the method of the present invention for preparing 1,3,5trinitro-1,3,5-triazacyclohexane of high technical purity provides particular advantages over existing methods.
- the nitrating agent N2O5 in 100% HNO3 is stable indefinitely when kept at low temperatures near 0° C. under a separate chlorinated hydrocarbon phase. Additionally, the method produces pure 1,3,5trinitro-1,3,5triazacyclohexane with no trace of 1,3,5,7-tetraaza-1,3,5,7tetranitrocyclooctane contaminent requiring removal with additional steps. Both features provide for easy and economical scale-up.
- the improved synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane proceeds via nitrolysis of hexamethylenetetramine.
- the nitrating agent is a solution of about 20% to about 30% by weight N2O5 in 100% HNO3.
- the hexamethylenetetramine is then added slowly to the nitrating solution kept at -20° C. under a separate chlorinated hydrocarbon phase.
- the reagent are mixed for a sufficient time for the nitrolysis reaction to go to completion. After that time, the 1,3,5-trinitro-1,3,5-triazacyclohexane formed is extracted from this solution into ethyl acetate. After drying and solvent removal, the pure product is isolated under vacuum.
- Hexamethylenetetramine (0.5 g, 3.6 mmol) was added in portions over 5 minutes to a stirred solution of 25% N2O5/HNO3 (36 mL, 142 mmol N2O2) under CCl4 (20 ML) kept at -20° C. After 30 minutes, the yellow mixture was carefully poured onto ice (50 g), neutralized with NaHCO3 and extracted into ethyl acetate. After drying with MgSO4 and solvent removal under vacuum, 0.46 g of a white solid was isolated. This solid was shown to be pure 1,3,5-trinitro-1,3,5-triazacyclohexane by comparison with an authentic sample. The yield of this procedure was 57%. No trace of 1,3,5,7-tetraaza-1,3,5,7-tetranitrocyclooctane was found upon analysis by 200 MHz 1H NMR.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process of preparing 1,3,5-trinitro-1,3,5-triazacyclohexane of high teccal purity by a one-step direct liquid nitrolysis of hexamethylenetetramine with dinitrogen pentoxide in 100% nitric acid under a separate chlorinated hydrocarbon phase.
Description
1. Field of the Invention
This invention relates to a method of preparing pure 1,3,5-trinitro-1,3,5-triazacyclohexane by the direct liquid phase nitration of hexamethylenetetramine.
2. Description of the Prior Art
1,3,5-trinitro-1,3,5-triazacyclohexane is currently prepared by a two-step procedure known in the art as the Bachman process. In this process, a mixture of ammonium nitrate and hexamine nitrate is added to a solution of nitric acid in acetic anhydride. While the product yield is about 70%, the intermediates and the final product contain about 10% of the contaminant 1,3,5,7-tetraaza-1,3,5,7-tetranitrocyclooctane. Further purification steps are required to reduce the presence of the contaminant to acceptable levels. These purification steps diminish the final yield of 1,3,5-trinitro-1,3,5-triazacyclohexane.
It is also known to prepare 1,3,5-trinitro-1,3,5-triazacyclohexane by direct liquid nitration using dinitrogen pentoxide dissolved in a non-aqueous neutral solvent such as a hydrocarbon or halogenated hydrocarbon. Although the process has been described as producing relatively pure 1,3,5-trinitro-1,3,5-triazacyclohexane, the use of a hydrocarbon or halogenated hydrocarbon solvent results in impurities which must be removed by additional processing. Additionally, scale-up problems are caused by the limited half-life of didinitrogen pentoxide in hydrocarbon or halogenated hydrocarbon solvents.
The nitration of hexamethylenetetramine to produce 1,3,5-trinitro-1,3,5-triazacyclohexane has also been achieved using concentrated nitric acid and small amounts of ammonium salts such as NH4NO3 and (NH4)2SO4 to prevent runaway reaction and reduce the decomposition of the 1,3,5-trinitro-1,3,5-triazacyclohexane to undesirable by-products.
One object of this invention is an improved and more economical synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane.
A further object of this invention is an economical synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane of high technical purity for use an important constituent in solid propellant and explosive formulations.
According to the present invention, 1,3,5-trinitro-1,3,5-triazacyclohexane of high technical purity is synthesized by the reaction of hexamethylenetetramine with dinitrogen pentoxide in 100% nitric acid under a separate organic phase.
The method of the present invention for preparing 1,3,5trinitro-1,3,5-triazacyclohexane of high technical purity provides particular advantages over existing methods. The nitrating agent N2O5 in 100% HNO3 is stable indefinitely when kept at low temperatures near 0° C. under a separate chlorinated hydrocarbon phase. Additionally, the method produces pure 1,3,5trinitro-1,3,5triazacyclohexane with no trace of 1,3,5,7-tetraaza-1,3,5,7tetranitrocyclooctane contaminent requiring removal with additional steps. Both features provide for easy and economical scale-up.
The improved synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane proceeds via nitrolysis of hexamethylenetetramine. The nitrating agent is a solution of about 20% to about 30% by weight N2O5 in 100% HNO3. The hexamethylenetetramine is then added slowly to the nitrating solution kept at -20° C. under a separate chlorinated hydrocarbon phase. The reagent are mixed for a sufficient time for the nitrolysis reaction to go to completion. After that time, the 1,3,5-trinitro-1,3,5-triazacyclohexane formed is extracted from this solution into ethyl acetate. After drying and solvent removal, the pure product is isolated under vacuum.
The following example is given to illustrate but not limit the invention.
Hexamethylenetetramine (0.5 g, 3.6 mmol) was added in portions over 5 minutes to a stirred solution of 25% N2O5/HNO3 (36 mL, 142 mmol N2O2) under CCl4 (20 ML) kept at -20° C. After 30 minutes, the yellow mixture was carefully poured onto ice (50 g), neutralized with NaHCO3 and extracted into ethyl acetate. After drying with MgSO4 and solvent removal under vacuum, 0.46 g of a white solid was isolated. This solid was shown to be pure 1,3,5-trinitro-1,3,5-triazacyclohexane by comparison with an authentic sample. The yield of this procedure was 57%. No trace of 1,3,5,7-tetraaza-1,3,5,7-tetranitrocyclooctane was found upon analysis by 200 MHz 1H NMR.
Modifications and variations of the present invention are possible. It should be understood that, within the scope of the appended calims, the invention may be practiced otherwise than as specifically described.
Claims (4)
1. A process of preparing pure 1,3,5-trinitro-1,3,5-triaza cyclohexane having the step of reacting hexamethylenetetramine with dinitrogen pentoxide as a primary nitrating agent, the improvement comprising the steps of:
dissolving dinitrogen pentoxide in 100% nitric acid to form a nitrating solution;
contacting said nitrating solution with hexamethylenetetramine under nitrating conditions;
neutralizing said mixture with sodium bicarbonate and extracting said product with a suitable solvent; and
removing said solvent and isolating pure 1,3,5-trinitro-1,3,5-triazacyclohexane.
2. A process as in claim 1 wherein said nitrating solution comprises about 25% by weight dinitrogen pentoxide in 100% nitric acid.
3. A process as in claim 1 wherein contacting of said nitrating solution with hexamethylenetetramine comprises stirring said hexamethylenetetramine into said nitrating solution kept at -20° C. under a separate CCl4 phase.
4. A process as in claim 1 wherein said solvent for extracting said product is ethyl acetate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/024,437 USH447H (en) | 1987-03-11 | 1987-03-11 | Synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/024,437 USH447H (en) | 1987-03-11 | 1987-03-11 | Synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane |
Publications (1)
Publication Number | Publication Date |
---|---|
USH447H true USH447H (en) | 1988-03-01 |
Family
ID=21820582
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/024,437 Abandoned USH447H (en) | 1987-03-11 | 1987-03-11 | Synthesis of 1,3,5-trinitro-1,3,5-triazacyclohexane |
Country Status (1)
Country | Link |
---|---|
US (1) | USH447H (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6177033B1 (en) | 1999-06-01 | 2001-01-23 | The United States Of America As Represented By The Secretary Of The Navy | Nitration of organics in carbon dioxide |
-
1987
- 1987-03-11 US US07/024,437 patent/USH447H/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6177033B1 (en) | 1999-06-01 | 2001-01-23 | The United States Of America As Represented By The Secretary Of The Navy | Nitration of organics in carbon dioxide |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GOVERNMENT OF THE UNITED STATES, REPRESENTED BY TH Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:FISCHER, JOHN W.;ATKINS, RONALD L.;REEL/FRAME:004676/0845;SIGNING DATES FROM 19870217 TO 19870223 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |