WO2017013206A1 - Process for preparing 3,3'-dinitro-5,5'-bis(1h-1,2,4-triazole) - Google Patents

Process for preparing 3,3'-dinitro-5,5'-bis(1h-1,2,4-triazole) Download PDF

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Publication number
WO2017013206A1
WO2017013206A1 PCT/EP2016/067410 EP2016067410W WO2017013206A1 WO 2017013206 A1 WO2017013206 A1 WO 2017013206A1 EP 2016067410 W EP2016067410 W EP 2016067410W WO 2017013206 A1 WO2017013206 A1 WO 2017013206A1
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Prior art keywords
triazole
process according
bis
suspension
dinitro
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Ceased
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PCT/EP2016/067410
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French (fr)
Inventor
Dennis Fischer
Thomas Klapötke
Jörg Stierstorfer
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Ludwig Maximilians Universitaet Muenchen LMU
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Ludwig Maximilians Universitaet Muenchen LMU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms

Definitions

  • the invention relates to a process for preparing 3,3'-dinitro-5,5'-bis(1 H-1 ,2,4- triazole) (DNBT) from 3,3'-diamino-5,5'-bis(1 H-1 ,2,4-triazole) (DABT) and a process for preparing 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)-1 ,1 '-diol.
  • DNBT 3,3'-dinitro-5,5'-bis(1 H-1 ,2,4- triazole)
  • DABT 3,3'-diamino-5,5'-bis(1 H-1 ,2,4-triazole)
  • WO 2014/086599 discloses a process for preparing 3,3'-dinitro-5,5'-bistriazole- 1 ,1 '-diol where in an intermediate step DNBT is oxidized to afford 3,3'-dinitro-5,5'- bis(1 H-1 ,2,4-triazole)- 1 ,1 '-diol.
  • the DNBT is obtained by diazotization of DABT in sulfuric acid in the presence of nitrite.
  • this has been shown that this can form the hazardous and highly explosive byproduct bisdiazo-bi-1 ,2,4-triazole.
  • the present invention has for its object to specify respective processes for preparing DNBT from DABT and for preparing 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)- 1 ,1 '-diol, where this hazardous byproduct is not formed.
  • the invention provides a process for preparing DNBT from DABT, wherein in the presence of nitrite sulfuric acid is added, in particular slowly, to a suspension of DABT in water.
  • This nitrite may be present in an excess of 10 equivalents.
  • the excess sulfuric acid to be added may be 3 equivalents for example.
  • the addition may be effected dropwise and/or continuously over several hours, for example over a period of 12 hours, for example at room temperature, with stirring.
  • the addition of the sulfuric acid may be effected sufficiently slowly to ensure that no nitrous fumes are formed. Formation of nitrous fumes can be observed since these are typically yellow to reddish-brown.
  • a long reaction time ensures that there is no accumulation of the hazardous bisdiazo-bi-1 ,2,4-triazole. It is an essential feature of the invention that the sulfuric acid be added to the nitrite solution with DABT suspended therein rather than the nitrite solution being added to a sulfuric-acid-containing DABT suspension as is the case in the prior art. After the addition of the sulfuric acid the suspension/the solution formed in the process may be heated in order to destroy any diazonium compound potentially still present. After the heating, it is possible to boil the suspension/the solution and add to it an excess of H 2 SO such that the entirety of the still present nitrite is decomposed to form nitrous fumes.
  • the end of this decomposition may be detected by the fact that no further yellow to reddish-brown fumes (nitrous fumes) are formed. Based on the nitrite the excess of sulfuric acid may be about 1 .5 equivalents.
  • the DNBT formed may be separated in the form of a precipitate from the suspension or a/the solution formed during the process. The formation of the precipitate may be brought about or at least promoted by cooling the suspension or the solution formed during the process.
  • the process according to the invention has the advantage that it affords DNBT in relatively high yield.
  • the invention further provides a process for preparing 3,3'-dinitro-5,5'-bis(1 ,2,4- triazole)-1 ,1 '-diol, wherein the DNBT produced by the process according to the invention is oxidized, in particular using 2KHSO 5 -KHSO 4 K 2 SO 4 or another inorganic or organic peroxyacid, perborate, hydrogen peroxide or hypofluorous acid or another oxygen transfer agent, to afford 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)- 1 ,1 '-diol.
  • a dihydroxylammonium salt, diguanidinium salt or ditriaminoguanidinium salt of the thus produced 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)-1 ,1 '-diol may be obtained by incubation of 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)-1 ,1 '-diol with hydroxylamine, hydroxylammonium ions, guanidinium carbonate, guanidinium ions, guanidine or triaminoguanidine in alcoholic solution and separation of the thus obtained precipitate.
  • Exemplary embodiment 1 .66 g (10 mmol) of finely ground DABT are suspended in 50 ml of H 2 O. 13.8 g (200 mmol) of NaNO 2 are added thereto. 20 ml of 1 M sulfuric acid are added to the suspension dropwise at a constant rate over a period of 12 hours at room temperature with stirring. The long reaction time ensures that there is no accumulation of the hazardous bisdiazo-bi-1 ,2,4-triazole. This dropwise addition of sulfuric acid is effected no faster than is required for the reaction and in particular sufficiently slowly to ensure that no nitrous fumes are formed. Faster addition can bring about accumulation of the hazardous bisdiazo-bi-1 ,2,4-triazole.
  • the resulting mixture is heated to 50° C for 1 hour to destroy any diazonium compound potentially still present.
  • the suspension/the solution formed is subsequently boiled and about 1 .5 equivalents, based on the originally employed nitrite, of a 50% sulfuric acid solution are added to decompose any nitrite that might still be present.
  • This sulfuric acid is added until no more yellow to reddish-brown fumes (nitrous fumes) are formed.
  • the entirety of the reaction mixture now has a volume of about 100 ml. It is allowed to cool slowly.
  • the thus formed acicular crystalline precipitate is separated by filtration. After drying in air DNBT dihydrate is obtained with a yield of about 90%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a process for preparing 3,3'-dinitro-5,5'-bis(1H-1,2,4-triazole) (DNBT) from 3,3'-diamino-5,5'-bis(1H-1,2,4-triazole) (DABT), wherein in the presence of nitrite H2SO4 is added to a suspension of DABT in H2O.

Description

Process for preparing 3,3'-dinitro-5,5'-bis(1 H-1 ,2,4-triazole)
The invention relates to a process for preparing 3,3'-dinitro-5,5'-bis(1 H-1 ,2,4- triazole) (DNBT) from 3,3'-diamino-5,5'-bis(1 H-1 ,2,4-triazole) (DABT) and a process for preparing 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)-1 ,1 '-diol.
WO 2014/086599 discloses a process for preparing 3,3'-dinitro-5,5'-bistriazole- 1 ,1 '-diol where in an intermediate step DNBT is oxidized to afford 3,3'-dinitro-5,5'- bis(1 H-1 ,2,4-triazole)- 1 ,1 '-diol. The DNBT is obtained by diazotization of DABT in sulfuric acid in the presence of nitrite. However it has been shown that this can form the hazardous and highly explosive byproduct bisdiazo-bi-1 ,2,4-triazole.
The present invention has for its object to specify respective processes for preparing DNBT from DABT and for preparing 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)- 1 ,1 '-diol, where this hazardous byproduct is not formed.
The object is achieved by the process according to Claim 1 and by the process according to Claim 10. Useful embodiments are apparent from the features of Claims 2 to 9.
The invention provides a process for preparing DNBT from DABT, wherein in the presence of nitrite sulfuric acid is added, in particular slowly, to a suspension of DABT in water. This nitrite may be present in an excess of 10 equivalents. The excess sulfuric acid to be added may be 3 equivalents for example. The addition may be effected dropwise and/or continuously over several hours, for example over a period of 12 hours, for example at room temperature, with stirring. The addition of the sulfuric acid may be effected sufficiently slowly to ensure that no nitrous fumes are formed. Formation of nitrous fumes can be observed since these are typically yellow to reddish-brown. A long reaction time ensures that there is no accumulation of the hazardous bisdiazo-bi-1 ,2,4-triazole. It is an essential feature of the invention that the sulfuric acid be added to the nitrite solution with DABT suspended therein rather than the nitrite solution being added to a sulfuric-acid-containing DABT suspension as is the case in the prior art. After the addition of the sulfuric acid the suspension/the solution formed in the process may be heated in order to destroy any diazonium compound potentially still present. After the heating, it is possible to boil the suspension/the solution and add to it an excess of H2SO such that the entirety of the still present nitrite is decomposed to form nitrous fumes. The end of this decomposition may be detected by the fact that no further yellow to reddish-brown fumes (nitrous fumes) are formed. Based on the nitrite the excess of sulfuric acid may be about 1 .5 equivalents. The DNBT formed may be separated in the form of a precipitate from the suspension or a/the solution formed during the process. The formation of the precipitate may be brought about or at least promoted by cooling the suspension or the solution formed during the process.
In addition to avoiding the formation of a hazardous byproduct the process according to the invention has the advantage that it affords DNBT in relatively high yield. The invention further provides a process for preparing 3,3'-dinitro-5,5'-bis(1 ,2,4- triazole)-1 ,1 '-diol, wherein the DNBT produced by the process according to the invention is oxidized, in particular using 2KHSO5-KHSO4 K2SO4 or another inorganic or organic peroxyacid, perborate, hydrogen peroxide or hypofluorous acid or another oxygen transfer agent, to afford 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)- 1 ,1 '-diol. A dihydroxylammonium salt, diguanidinium salt or ditriaminoguanidinium salt of the thus produced 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)-1 ,1 '-diol may be obtained by incubation of 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)-1 ,1 '-diol with hydroxylamine, hydroxylammonium ions, guanidinium carbonate, guanidinium ions, guanidine or triaminoguanidine in alcoholic solution and separation of the thus obtained precipitate.
Exemplary embodiment: 1 .66 g (10 mmol) of finely ground DABT are suspended in 50 ml of H2O. 13.8 g (200 mmol) of NaNO2 are added thereto. 20 ml of 1 M sulfuric acid are added to the suspension dropwise at a constant rate over a period of 12 hours at room temperature with stirring. The long reaction time ensures that there is no accumulation of the hazardous bisdiazo-bi-1 ,2,4-triazole. This dropwise addition of sulfuric acid is effected no faster than is required for the reaction and in particular sufficiently slowly to ensure that no nitrous fumes are formed. Faster addition can bring about accumulation of the hazardous bisdiazo-bi-1 ,2,4-triazole. After addition of the sulfuric acid the resulting mixture is heated to 50° C for 1 hour to destroy any diazonium compound potentially still present. The suspension/the solution formed is subsequently boiled and about 1 .5 equivalents, based on the originally employed nitrite, of a 50% sulfuric acid solution are added to decompose any nitrite that might still be present. This sulfuric acid is added until no more yellow to reddish-brown fumes (nitrous fumes) are formed. The entirety of the reaction mixture now has a volume of about 100 ml. It is allowed to cool slowly. The thus formed acicular crystalline precipitate is separated by filtration. After drying in air DNBT dihydrate is obtained with a yield of about 90%.

Claims

Claims
1 . Process for preparing 3,3'-dinitro-5,5'-bis(1 H-1 ,2,4-triazole) (DNBT) from 3,3'-diamino-5,5'-bis(1 /-/-1 ,2,4-triazole) (DABT), wherein in the presence of nitrite H2SO4 is added to a suspension of DABT in H2O.
2. Process according to Claim 1 , wherein the suspension of DABT is basic or by addition of a base is brought to a basic pH, in particular in the range from pH 7.2 to 8.2, in particular pH 7.5 to 8.0.
3. Process according to Claim 1 or 2, wherein the H2SO is added sufficiently slowly to ensure that no nitrous fumes are formed.
4. Process according to any of the preceding claims, wherein the H2SO4 is added in excess.
5. Process according to any of the preceding claims, wherein the H2SO4 is added gradually or continuously, in particular dropwise, in particular over several hours.
6. Process according to any of the preceding claims, wherein the nitrite is present in excess.
7. Process according to any of the preceding claims, wherein after the addition of H2SO4 the suspension or a solution formed during the process is heated to at least 45°C, in particular at least 50°C, for at least 40 minutes, in particular at least 60 minutes.
8. Process according to Claim 7, wherein after the heating the suspension or the solution formed during the process is brought to boiling and excess H2SO4 is added thereto.
9. Process according to any of the preceding claims, wherein the DNBT formed is separated in the form of a precipitate from the suspension or a/the solution formed during the process.
10. Process for preparing 3, 3'-dinitro-5,5'-bis(1 ,2,4-triazole)-1 ,1 '-diol, wherein the DNBT produced according to any of the preceding claims is oxidized, in particular using 2KHSO5 KHSO K2SO or another inorganic or organic peroxyacid, perborate, hydrogen peroxide or hypofluorous acid or another oxygen transfer agent, to afford 3,3'-dinitro-5,5'-bis(1 ,2,4-triazole)-1 ,1 '-diol.
PCT/EP2016/067410 2015-07-22 2016-07-21 Process for preparing 3,3'-dinitro-5,5'-bis(1h-1,2,4-triazole) Ceased WO2017013206A1 (en)

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DE102015009297.9A DE102015009297A1 (en) 2015-07-22 2015-07-22 Process for the preparation of 3,3'-dinitro-5,5'-bis (1H-1,2,4-triazole)
DE102015009297.9 2015-07-22

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2892473A1 (en) * 2012-12-03 2014-06-12 Ludwig-Maximilians-Universitat Munchen 3,3'-dinitro-5,5'-bis-triazole-1,1'-diol
CN103965125A (en) * 2014-05-06 2014-08-06 西安近代化学研究所 Synthetic method of 3,3'-binitro-5,5'-di-1,2,4-triazole

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2624119B1 (en) * 1987-12-08 1990-03-23 Commissariat Energie Atomique 4,6-DI-2 (5-NITRO-1,2,4-TRIAZOLE) -5-NITROPYRIMIDINE, PREPARATION METHOD THEREOF, AND EXPLOSIVE MATERIAL CONTAINING THE SAME
DE4115365A1 (en) * 1991-05-10 1992-11-12 Apogepha Arzneimittel Gmbh 3-Nitro-1,2,4-triazole prepn. for use in nucleoside chemistry - by dissolving 3-amino-1,2,4-triazole in mineral acid, adding soln. to aq. inorganic nitrate soln. and isolating prod. by filtration

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2892473A1 (en) * 2012-12-03 2014-06-12 Ludwig-Maximilians-Universitat Munchen 3,3'-dinitro-5,5'-bis-triazole-1,1'-diol
CN103965125A (en) * 2014-05-06 2014-08-06 西安近代化学研究所 Synthetic method of 3,3'-binitro-5,5'-di-1,2,4-triazole

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