WO2003018514A1 - Method of preparing nitroform - Google Patents

Method of preparing nitroform Download PDF

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Publication number
WO2003018514A1
WO2003018514A1 PCT/SE2002/001551 SE0201551W WO03018514A1 WO 2003018514 A1 WO2003018514 A1 WO 2003018514A1 SE 0201551 W SE0201551 W SE 0201551W WO 03018514 A1 WO03018514 A1 WO 03018514A1
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Prior art keywords
gem
nitroform
nitration
group
eller
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PCT/SE2002/001551
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French (fr)
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WO2003018514A9 (en
Inventor
Abraham Langlet
Nikolai Latypov
Ulf Wellmar
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Totalförsvarets Forskningsinstitut
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Publication of WO2003018514A1 publication Critical patent/WO2003018514A1/en
Publication of WO2003018514A9 publication Critical patent/WO2003018514A9/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups

Definitions

  • the invention relates to a method of preparing trinitromethane or nitroform which is the common name of the compound.
  • Nitroform is a valuable compound for producing propellants and explosive components by its high oxygen content and an unstable hydrogen atom, which facilitates its forming of derivatives.
  • Nitroform is used, for example, for preparing hydrazinium nitroformat (HNF) which is a salt between hydrazine and nitroform and is used as oxidiser in, inter alia, rocket propellants.
  • the oxidiser is chlorine-free, which is increasingly desired in propellant compositions.
  • Nitroform is also used as a starting material for producing energetic plasticisers.
  • the most well-known method for preparing nitroform is nitration of acetylene with nitric acid, using a mercury catalyst.
  • An industrial process for preparing nitroform according to this method is described by A. Wetterholm: Tetrahedron, 1963, Vol. 19, pp 155-163.
  • the use of acetylene gas as starting material requires specific measures of precaution in the process, and the use of a mercury catalyst has obvious drawbacks from the environmental point of view.
  • An object of the present invention is to provide a simple and safe method for preparing nitroform.
  • a starting material dissolved or suspended in sulphuric acid is nitrated.
  • the starting material is selected from a group consisting of 1) a gem-dinitroacetyl urea with the general formula
  • nitrating agent consisting of nitric acid, nitrate salts or nitrogen pentoxide is added to the sulphuric acid solution/suspension. It will thus be easy to control the nitration. Further nitro groups are added to the starting material in nitration, forming a gem-trinitro compound which by hydrolysis splits off nitroform.
  • the nitration is carried out at a temperature from -10°C to +80°C, preferably from +10°C to +60°C.
  • the sulphuric acid may have a concentration of 70-100%, preferably about 95%.
  • the nitric acid which is the preferred nitrating agent, is added as a concentrated acid, especially with a concentration of 85-100%.
  • the molar ratio between nitrating agent and substrate may be 2.0-6.0:1 , and is preferably 3.0-4.0:1. Good yields have been obtained with such a low molar ratio as 3.0:1, which in combination with reuse of the sulphuric acid, as will be mentioned below, makes the method economically attractive.
  • the nitration can be carried out in an ordinary stain- less steel reactor without any special arrangements.
  • the product (the gem-trinitro compound) is hydro- lysed for splitting off nitroform by mixing the reaction mixture with an aqueous medium, for instance pouring it onto crushed ice, diluting it with water or the like.
  • the nitroform prepared can be extracted from the reaction mixture using a polar extracting agent which is stable in the environment at issue, for instance methylene chloride or diethyl ether.
  • a neutralising agent can then be added to precipitate the corresponding salt of nitroform.
  • the sulphuric acid may then be used several times.
  • the starting material according to a) above can be produced by nitration of barbituric acid to gem-5,5-dinitrobarbituric acid which is then hydrolysed with water to form gem-dinitroacetyl urea or is treated with a ring-opening nucleophile, for instance ammonia, methanol, ethanol, isopropanol or an amine, to form substituted gem-dinitroacetyl urea.
  • a ring-opening nucleophile for instance ammonia, methanol, ethanol, isopropanol or an amine
  • the starting material according to b) above can correspondingly be produced by nitration of 2-amino-4,6-dihydroxypyrirnidine followed by hydrolysis with water, as described in Latypov et al: A new convenient route to gem-dinitroalifatic compounds, Conference Proceedings, 31st International Conference of ICT: 2000.
  • the starting material according to c) is a commercially available product.
  • Potassium dinitroacetyl urea (6.8 g) was dissolved in sulphuric acid (20 ml, 95% concentration). Concentrated nitric acid (1.4 ml) was added by drops. The temperature was increased to about 40°C for one hour. The reaction mixture was poured onto 60 g crushed ice and then extracted with 2x50 ml diethyl ether. The ether phase was dried with sodium sulphate. Potassium hydroxide dissolved in ethanol was added. A yellow precipitate of potassium nitroform (4.6 g; 68% yield) was obtained.
  • 4,6-dihydroxypyrimidine (4 g) was dissolved in sulphuric acid (20 ml, 95% concentration). Fuming nitric acid was added (6 ml) during cooling with ice and was then kept at room temperature for 12 hours. The reaction mixture was poured onto crushed ice and extracted with methylene chloride. Yield of nitroform 60%, measured by UV spectroscopy in methylene chloride.
  • Dinitroacetyl urea (3 g) was dissolved in sulphuric acid (20 ml, 95% concentration). Concentrated nitric acid (0.57 ml) was added. The reaction mixture was stirred for one hour at 20°C. Then it was poured onto 77 g crushed ice, heated to 50°C for 10 minutes and extracted with 2 x 125 ml methylene chloride. Yield of nitroform 62%.
  • Example 4 Dinitroacetyl urea (3 g) was dissolved in sulphuric acid (20 ml, 95% concentration). Concentrated nitric acid (0.57 ml) was added. The reaction mixture was stirred for one hour at 20°C with a cover (covering layer) consisting of 30 ml methylene chloride. The methylene chloride was separated from the reaction mixture and mixed with 30 ml n-heptane. The mixture was evaporated to 20 ml and then trinitroacetyl urea precipitated. The trinitroactyl urea could now easily be hydrolysed with potassium hydroxide for splitting off potassium nitroform.

Abstract

A method of preparing nitroform (trinitromethane) by nitrating a starting material which is dissolved or suspended in sulphuric acid. A nitrating agent consisting of nitric acid, nitrate salts or nitrogen pentoxide is added to the sulphuric acid solution/suspension at a temperature from -10°C to +80°C. The starting material is selected from a group consisting of a) a gem-dinitroacetyl urea with the general formula wherein Y is H or a group, wherein Y is an alkoxy or amino group, and salts thereof; b) gem-dinitroacetyl guanidine, and c) 4,6-hydroxypyrimidine. In nitration, a gem-trinitro compound is formed which in hydrolysis splits off nitroform.

Description

Method of Preparing Nitroform
The invention relates to a method of preparing trinitromethane or nitroform which is the common name of the compound.
Nitroform is a valuable compound for producing propellants and explosive components by its high oxygen content and an unstable hydrogen atom, which facilitates its forming of derivatives. Nitroform is used, for example, for preparing hydrazinium nitroformat (HNF) which is a salt between hydrazine and nitroform and is used as oxidiser in, inter alia, rocket propellants. The oxidiser is chlorine-free, which is increasingly desired in propellant compositions. Nitroform is also used as a starting material for producing energetic plasticisers.
The most well-known method for preparing nitroform is nitration of acetylene with nitric acid, using a mercury catalyst. An industrial process for preparing nitroform according to this method is described by A. Wetterholm: Tetrahedron, 1963, Vol. 19, pp 155-163. The use of acetylene gas as starting material requires specific measures of precaution in the process, and the use of a mercury catalyst has obvious drawbacks from the environmental point of view.
An object of the present invention is to provide a simple and safe method for preparing nitroform. According to the invention, a starting material dissolved or suspended in sulphuric acid is nitrated. The starting material is selected from a group consisting of 1) a gem-dinitroacetyl urea with the general formula
Figure imgf000002_0001
wherein X is H or a group '"^L^ > wherein Y is an alkoxy or amino group, M
and salts thereof; 2) gem-dinitroacetyl guanidine, and
3) 4,6-hydroxypyrimidine.
In nitration, a nitrating agent consisting of nitric acid, nitrate salts or nitrogen pentoxide is added to the sulphuric acid solution/suspension. It will thus be easy to control the nitration. Further nitro groups are added to the starting material in nitration, forming a gem-trinitro compound which by hydrolysis splits off nitroform. The nitration is carried out at a temperature from -10°C to +80°C, preferably from +10°C to +60°C. The sulphuric acid may have a concentration of 70-100%, preferably about 95%. The nitric acid, which is the preferred nitrating agent, is added as a concentrated acid, especially with a concentration of 85-100%. The molar ratio between nitrating agent and substrate may be 2.0-6.0:1 , and is preferably 3.0-4.0:1. Good yields have been obtained with such a low molar ratio as 3.0:1, which in combination with reuse of the sulphuric acid, as will be mentioned below, makes the method economically attractive. The nitration can be carried out in an ordinary stain- less steel reactor without any special arrangements.
After completion of the nitration, the product (the gem-trinitro compound) is hydro- lysed for splitting off nitroform by mixing the reaction mixture with an aqueous medium, for instance pouring it onto crushed ice, diluting it with water or the like. The nitroform prepared can be extracted from the reaction mixture using a polar extracting agent which is stable in the environment at issue, for instance methylene chloride or diethyl ether. A neutralising agent can then be added to precipitate the corresponding salt of nitroform. It is also possible to extract directly from the nitration mixture the primarily prepared gem-trinitro compound and subsequently hydrolyse the same for splitting off nitroform, for instance by adding a base. The sulphuric acid may then be used several times.
The starting material according to a) above can be produced by nitration of barbituric acid to gem-5,5-dinitrobarbituric acid which is then hydrolysed with water to form gem-dinitroacetyl urea or is treated with a ring-opening nucleophile, for instance ammonia, methanol, ethanol, isopropanol or an amine, to form substituted gem-dinitroacetyl urea. This is described in Langlet et al: Synthesis and reactions of 5,5-dinitrobarbituric acid, Conference Proceedings, XIX:th European Colloquium on Heterocyclic Chemistry, Aveiro Portugal, July 19-22, 2000, p. A-70. The starting material according to b) above can correspondingly be produced by nitration of 2-amino-4,6-dihydroxypyrirnidine followed by hydrolysis with water, as described in Latypov et al: A new convenient route to gem-dinitroalifatic compounds, Conference Proceedings, 31st International Conference of ICT: 2000. The starting material according to c) is a commercially available product.
The invention will be described below by way of Examples.
Example 1
Potassium dinitroacetyl urea (6.8 g) was dissolved in sulphuric acid (20 ml, 95% concentration). Concentrated nitric acid (1.4 ml) was added by drops. The temperature was increased to about 40°C for one hour. The reaction mixture was poured onto 60 g crushed ice and then extracted with 2x50 ml diethyl ether. The ether phase was dried with sodium sulphate. Potassium hydroxide dissolved in ethanol was added. A yellow precipitate of potassium nitroform (4.6 g; 68% yield) was obtained.
Example 2
4,6-dihydroxypyrimidine (4 g) was dissolved in sulphuric acid (20 ml, 95% concentration). Fuming nitric acid was added (6 ml) during cooling with ice and was then kept at room temperature for 12 hours. The reaction mixture was poured onto crushed ice and extracted with methylene chloride. Yield of nitroform 60%, measured by UV spectroscopy in methylene chloride.
Example 3
Dinitroacetyl urea (3 g) was dissolved in sulphuric acid (20 ml, 95% concentration). Concentrated nitric acid (0.57 ml) was added. The reaction mixture was stirred for one hour at 20°C. Then it was poured onto 77 g crushed ice, heated to 50°C for 10 minutes and extracted with 2 x 125 ml methylene chloride. Yield of nitroform 62%.
Example 4 Dinitroacetyl urea (3 g) was dissolved in sulphuric acid (20 ml, 95% concentration). Concentrated nitric acid (0.57 ml) was added. The reaction mixture was stirred for one hour at 20°C with a cover (covering layer) consisting of 30 ml methylene chloride. The methylene chloride was separated from the reaction mixture and mixed with 30 ml n-heptane. The mixture was evaporated to 20 ml and then trinitroacetyl urea precipitated. The trinitroactyl urea could now easily be hydrolysed with potassium hydroxide for splitting off potassium nitroform.

Claims

Claims
1. A method of preparing nitroform, characterised by dissolving a starting material selected from a group consisting of a gem-dinitroacetyl urea with the general formula
Figure imgf000005_0001
wherein X is H or a group • wherein Y is an alkoxy or amino group,
Figure imgf000005_0002
and salts thereof; b) gem-dinitroacetyl guanidine, and c) 4,6-hydroxypyrimidine, or suspending the same in sulphuric acid; nitrating the starting material in said sulphuric acid solution/suspension by adding a nitrating agent selected from the group nitric acid, nitrate salts and nitrogen pentoxide, for forming a gem-trinitro compound and hydrolysing the gem-trinitro compound for splitting off nitroform.
2. A method as claimed in claim 1, characterised in that Y is NH2, methoxy, ethoxy or isopropoxy.
3. A method as claimed in claim 1 , characterised in that the nitration is carried out at a temperature from -10°C to +80°C.
4. A method as claimed in claim 1 , characterised in that the nitration is carried out at a temperature from +10°C to +60°C.
5. A method as claimed in claim 1 , characterised by hydrolysing the gem-trinitro compound by mixing the reaction mixture obtained in nitration with an aqueous medium, and extracting split-off nitroform from the thus resulting mixture.
6. A method as claimed in claim 1 , characterised by extracting the gem-trinitro compound from the reaction mixture obtained in nitration and subsequently hydrolysing the gem-trinitro compound for splitting off nitroform.
Sammandrag. .
Satt att framstalla nitroform (trinitrometan) genom nitrering av ett startmaterial som ar lost eller suspenderat i svavelsyra. Ett nitrermedel bestaende av salpetersyra, nitratsalter eller kvavepentoxid tillsatts svavelsysalόsningen/suspensionen vid en temperatur av fran -10°C till +80°C. Startmaterialet ar valt fran en grupp bestaende av a) en gem-dinitroacetylurea med den allmanna formeln
Figure imgf000007_0001
dar X ar H eller en grupp , dar Y ar en alkoxy- eller amino-grupp,
Figure imgf000007_0002
och salter darav; b) gem-dinitroacetylguanidin, och c) 4,6-hydroxypyrimidin.
Vid nitreringen bildas en gem-trinitrofδrening som vid hydrolys avspjalkar nitroform.
PCT/SE2002/001551 2001-08-31 2002-08-30 Method of preparing nitroform WO2003018514A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105111087A (en) * 2015-08-19 2015-12-02 南京理工大学 Trinitroethanol preparation method with improved process safety

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3007960A (en) * 1958-11-10 1961-11-07 Purdue Research Foundation N-trinitroalkyl-n-nitroaminoalkyl acids and derivatives thereof
US3125606A (en) * 1964-03-17 Process for the manufacture of
US3491160A (en) * 1968-02-05 1970-01-20 Escambia Chem Corp Process for producing nitroform
US4122124A (en) * 1977-12-05 1978-10-24 Rockwell International Corporation Production of trinitromethane
WO1997038967A1 (en) * 1996-04-16 1997-10-23 Arco Chemical Technology, L.P. Reducing tetranitromethane in compositions containing nitroaromatic compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3125606A (en) * 1964-03-17 Process for the manufacture of
US3007960A (en) * 1958-11-10 1961-11-07 Purdue Research Foundation N-trinitroalkyl-n-nitroaminoalkyl acids and derivatives thereof
US3491160A (en) * 1968-02-05 1970-01-20 Escambia Chem Corp Process for producing nitroform
US4122124A (en) * 1977-12-05 1978-10-24 Rockwell International Corporation Production of trinitromethane
WO1997038967A1 (en) * 1996-04-16 1997-10-23 Arco Chemical Technology, L.P. Reducing tetranitromethane in compositions containing nitroaromatic compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105111087A (en) * 2015-08-19 2015-12-02 南京理工大学 Trinitroethanol preparation method with improved process safety

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SE519778C2 (en) 2003-04-08
WO2003018514A9 (en) 2004-04-22
SE0102908D0 (en) 2001-08-31
SE0102908L (en) 2003-03-01

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