Difference between revisions of "Trinitroaniline"
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Nitrating 4-nitroaniline with dry [[sodium nitrate]] and conc. [[sulfuric acid]], at 0-5 °C, for 3 hours will yield TNA, giving an yield of 58%.<ref>Rosevear, Judi; Wilshire, John F. K.; Australian Journal of Chemistry; vol. 38; nb. 5; (1985); p. 723 - 733</ref> If [[potassium nitrate]] is used instead, and the reaction time is doubled, while the reaction temperature is maintained between 50-110 °C, the yield of the reaction is 50%.<ref>Mahmood, Javeed; Kim, Dongwook; Jeon, In-Yup; Lah, Myoung Soo; Baek, Jong-Beom; Synlett; vol. 24; nb. 2; (2013); p. 246 - 248</ref> A mixture of [[nitrosylsulfuric acid]], [[nitric acid]] and [[acetone]] stirred at 30 °C will also give TNA.<ref>[https://pubs.acs.org/doi/10.1021/ja01678a020 Varma; Kulkarni; Journal of the American Chemical Society; vol. 47; (1925); p. 145]</ref> | Nitrating 4-nitroaniline with dry [[sodium nitrate]] and conc. [[sulfuric acid]], at 0-5 °C, for 3 hours will yield TNA, giving an yield of 58%.<ref>Rosevear, Judi; Wilshire, John F. K.; Australian Journal of Chemistry; vol. 38; nb. 5; (1985); p. 723 - 733</ref> If [[potassium nitrate]] is used instead, and the reaction time is doubled, while the reaction temperature is maintained between 50-110 °C, the yield of the reaction is 50%.<ref>Mahmood, Javeed; Kim, Dongwook; Jeon, In-Yup; Lah, Myoung Soo; Baek, Jong-Beom; Synlett; vol. 24; nb. 2; (2013); p. 246 - 248</ref> A mixture of [[nitrosylsulfuric acid]], [[nitric acid]] and [[acetone]] stirred at 30 °C will also give TNA.<ref>[https://pubs.acs.org/doi/10.1021/ja01678a020 Varma; Kulkarni; Journal of the American Chemical Society; vol. 47; (1925); p. 145]</ref> | ||
| − | Can also be prepared by heating a mixture of [[picric acid]] and [[diammonium hydrogen phosphate]], ammonium carbamate or [[urea]] in [[sulfolane]], at 25 - 175 °C for 22 hours, in an autoclave. Yield for this route is around 87-93%. [[Ammonium acetate]] and ammonium picrate can also be used instead, but the yield is lower, at 32%.<ref>US2005/38297</ref> | + | Can also be prepared by heating a mixture of [[picric acid]] and [[diammonium hydrogen phosphate]], ammonium carbamate or [[urea]] in [[sulfolane]], at 25 - 175 °C for 22 hours, in an autoclave. Yield for this route is around 87-93%. [[Ammonium acetate]] and ammonium picrate can also be used instead, but the yield is lower, at 32%.<ref>[https://patents.google.com/patent/US20050038297A1/ US2005/38297]</ref> |
Refluxing 2,4,6-trinitrochlorobenzene with [[ammonia]] in n-[[propanol]] for 3 hours at 100 °C will yield picramide, for an yield of 75%. <ref>Corona, Paola; Loriga, Mario; Costi, M. Paola; Ferrari, Stefania; Paglietti, Giuseppe; European Journal of Medicinal Chemistry; vol. 43; nb. 1; (2008); p. 189 - 203</ref> [[Ethanol]] and [[hydroxylammonium chloride]] can also be used instead.<ref>Nietzki; Dietschy; Chemische Berichte; vol. 34; (1901); p. 55</ref> Alternatively, a mixture of n-butylamine with tetra-n-butylammonium tetrafluoroborate in [[dimethylformamide]] can also be used, for an yield of 95%.<ref>Gallardo, Iluminada; Guirado, Gonzalo; Marquet, Jordi; Journal of Organic Chemistry; vol. 67; nb. 8; (2002); p. 2548 - 2555</ref> | Refluxing 2,4,6-trinitrochlorobenzene with [[ammonia]] in n-[[propanol]] for 3 hours at 100 °C will yield picramide, for an yield of 75%. <ref>Corona, Paola; Loriga, Mario; Costi, M. Paola; Ferrari, Stefania; Paglietti, Giuseppe; European Journal of Medicinal Chemistry; vol. 43; nb. 1; (2008); p. 189 - 203</ref> [[Ethanol]] and [[hydroxylammonium chloride]] can also be used instead.<ref>Nietzki; Dietschy; Chemische Berichte; vol. 34; (1901); p. 55</ref> Alternatively, a mixture of n-butylamine with tetra-n-butylammonium tetrafluoroborate in [[dimethylformamide]] can also be used, for an yield of 95%.<ref>Gallardo, Iluminada; Guirado, Gonzalo; Marquet, Jordi; Journal of Organic Chemistry; vol. 67; nb. 8; (2002); p. 2548 - 2555</ref> | ||
Latest revision as of 19:47, 11 October 2020
| Names | |
|---|---|
| IUPAC name
2,4,6-Trinitroaniline
| |
| Other names
2,4,6-Trinitrobenzenamine
2,4,6-Trinitroaniline Picramide TNA Type 97 bakuyaku | |
| Properties | |
| C6H4N4O6 | |
| Molar mass | 228.12 g/mol |
| Appearance | Yellow/orange/red solid |
| Odor | Odorless |
| Density | 1.762 g/cm3 (14 °C) 1.72 g/cm3 (20 °C) |
| Melting point | 188–193.5 °C (370.4–380.3 °F; 461.1–466.6 K) |
| Boiling point | Detonates |
| 0.106 g g/100 ml (20 °C)[1] | |
| Solubility | Slightly soluble in acetone |
| Solubility in acetone | 4.798 g/100 ml (20 °C) |
| Solubility in benzene | 0.907 g/100 ml (20 °C) |
| Solubility in carbon disulfide | 0.013 g/100 ml (17 °C) |
| Solubility in carbon tetrachloride | 0.003 g/100 ml (17 °C) |
| Solubility in chloroform | 0.322 g/100 ml (17 °C) |
| Vapor pressure | ~0 mmHg |
| Thermochemistry | |
| Hazards | |
| Safety data sheet | None |
| Related compounds | |
| Related compounds
|
Picric acid Trinitrotoluene |
| Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
| Infobox references | |
2,4,6-Trinitroaniline, abbreviated as TNA and also known as picramide, a nitrated aromatic amine with the chemical formula C6H4N4O6. It is a powerful high explosive.
Contents
Properties
Chemical
TNA will react with hydrogen peroxide and conc. sulfuric acid to yield 1,2,4,6-tetranitrobenzene. The yield of the reaction is given as 93%.[2] If ozone is used instead of hydrogen peroxide, and the reaction takes place at room temperature for 72 hours, the yield of the reaction is 49%.[3]
Diazotized picramide coupled with β-naphthol yields a reddish product, more soluble in common solvents.[4]
TNA will decompose releasing carbon dioxide/monoxide. water, soot and unburnt side products.
Physical
TNA is a yellow solid, that has also been described as being orange or red. It is insoluble in water, but more soluble in organic solvents. Is melting point has been determined to be between 188-194 °C.[5][6][7]
Explosive
TNA is a sensitive explosive with a detonation velocity of 7,300 m/s.
Availability
TNA is not sold to the public being a dangerous explosive material.
Preparation
Nitrating 4-nitroaniline with dry sodium nitrate and conc. sulfuric acid, at 0-5 °C, for 3 hours will yield TNA, giving an yield of 58%.[8] If potassium nitrate is used instead, and the reaction time is doubled, while the reaction temperature is maintained between 50-110 °C, the yield of the reaction is 50%.[9] A mixture of nitrosylsulfuric acid, nitric acid and acetone stirred at 30 °C will also give TNA.[10]
Can also be prepared by heating a mixture of picric acid and diammonium hydrogen phosphate, ammonium carbamate or urea in sulfolane, at 25 - 175 °C for 22 hours, in an autoclave. Yield for this route is around 87-93%. Ammonium acetate and ammonium picrate can also be used instead, but the yield is lower, at 32%.[11]
Refluxing 2,4,6-trinitrochlorobenzene with ammonia in n-propanol for 3 hours at 100 °C will yield picramide, for an yield of 75%. [12] Ethanol and hydroxylammonium chloride can also be used instead.[13] Alternatively, a mixture of n-butylamine with tetra-n-butylammonium tetrafluoroborate in dimethylformamide can also be used, for an yield of 95%.[14]
Projects
- Blasting caps
- Compound collecting
Handling
Safety
Trinitroaniline is a dangerous explosive. Symptoms of exposure to this compound may include skin and eye irritation, headache, cyanosis and respiratory distress.
Storage
Should be kept wet, away from heat and reducing agent.
Disposal
Strongly diluted then neutralized with a diluted sol. of a base, before oxidation into harmless products.
References
- ↑ Desvergnes; Rev.Chim.ind.; vol. 40; (1931); p. 35
- ↑ Nielsen, Arnold T.; Atkins, Ronald L.; Norris, William P.; Coon, Clifford L.; Sitzmann, Michael E.; Journal of Organic Chemistry; vol. 45; nb. 12; (1980); p. 2341 - 2347
- ↑ Atkins, Ronald L.; Nielsen, Arnold T.; Bergens, Cynthia; Wilson, William S.; Journal of Organic Chemistry; vol. 49; nb. 3; (1984); p. 503 - 507
- ↑ J. Am. Chem. Soc. 1938, 60, 3, 725–726
- ↑ Mahmood, Javeed; Kim, Dongwook; Jeon, In-Yup; Lah, Myoung Soo; Baek, Jong-Beom; Synlett; vol. 24; nb. 2; (2013); p. 246 - 248
- ↑ Corona, Paola; Loriga, Mario; Costi, M. Paola; Ferrari, Stefania; Paglietti, Giuseppe; European Journal of Medicinal Chemistry; vol. 43; nb. 1; (2008); p. 189 - 203
- ↑ Mehilal; Sikder; Salunke; New Journal of Chemistry; vol. 25; nb. 12; (2001); p. 1549 - 1552
- ↑ Rosevear, Judi; Wilshire, John F. K.; Australian Journal of Chemistry; vol. 38; nb. 5; (1985); p. 723 - 733
- ↑ Mahmood, Javeed; Kim, Dongwook; Jeon, In-Yup; Lah, Myoung Soo; Baek, Jong-Beom; Synlett; vol. 24; nb. 2; (2013); p. 246 - 248
- ↑ Varma; Kulkarni; Journal of the American Chemical Society; vol. 47; (1925); p. 145
- ↑ US2005/38297
- ↑ Corona, Paola; Loriga, Mario; Costi, M. Paola; Ferrari, Stefania; Paglietti, Giuseppe; European Journal of Medicinal Chemistry; vol. 43; nb. 1; (2008); p. 189 - 203
- ↑ Nietzki; Dietschy; Chemische Berichte; vol. 34; (1901); p. 55
- ↑ Gallardo, Iluminada; Guirado, Gonzalo; Marquet, Jordi; Journal of Organic Chemistry; vol. 67; nb. 8; (2002); p. 2548 - 2555
