Complete Guide to Trinitromethane [Published]
AndersHoveland
Acolyte
Trinitromethane, sometimes alternatively called nitroform, has the structure HC(NO2)3.
This dangerous chemical can be used to make powerful propellents or advanced performance explosives.
Physical Properties
Trinitromethane melts at 15°C, and begins slowly decomposing above 25°C
At room temperature it is a colorless, or slightly yellow, oily liquid.
Trinitromethane can form salts with a base, such as methylamine or ammonia, or it can dissolve in hydrocarbons (although this can be very dangerous).
Chemical Properties
Trinitromethane can form salts with a base, such as methylamine or ammonia, or it can dissolve in hydrocarbons. It can be mixed with either nitro methane or nitro ethane, to form a powerful explosive binary mixture. The one with EtNO2 is somewhat more powerful, but it also requires a higher ratio of HC(NO2)3, so if nitromethane is easily available in large quantities it may be preferable. (the 'Et' means the --CH2CH3 group)
Salts of trinitromethane are more stable (and somewhat less energetic) than perchlorates, although trinitromethane itself is fairly sensitive. The C(NO2)3(-) anion is very stable because of the resonances, there being four additional electrons to resonate around the the six oxygen atoms. These salts are also known as nitroformates and are bright yellow in color. Trinitromethane oxidizes ferrous ions (Fe+2) to ferric (Fe+3). Dinitromethane can also oxidize the Fe+2 ion, but only if an alkaline solution of dinitromethane is added to an acidified solution of a ferrous salt. This is because the transient "aci-form" tautomer O2NCH=NO2H, which only exists for a few seconds, is more reactive.
WARNING: Toxicity and Explosion Hazard
Trinitromethane, while still giving off mildly poisonous fumes, is far less toxic than tetranitromethane. You would be well advised to avoid ever preparing tetranitromethane, which was once considered for use as a chemical weapon. Trinitromethane is somewhat poisonous: 800 mg/m3/2 hour Inhalation Mouse LC50, compare this with 1230ppm (for 36min, LC50) for tetranitromethane.
It can be seen that tetranitromethane is far more toxic (it is highly recommended that the synthesis of this compound never be attempted), but nitroform should still be assumed to give off toxic vapor, and so should be handled outdoors or behind a windowed fumehood. The boiling point is 175.1 °C so at least it is much less volatile than tetranitromethane. Moderately toxic by inhalation. Irritating to skin, eyes, and mucous membranes. Inhalation can cause headache and nausea. Causes mild narcosis.
A very dangerous explosion hazard; explodes when heated rapidly. Dissolution is exothermic and solutions of more than 50% can explode. Mixtures of 90% trinitromethane + 10% isopropyl alcohol in polyethylene bottles have exploded. Frozen mixtures with 2-propanol (10%) explode when thawed. Can explode during distillation. Mixtures with divinyl ketone can explode at 4°C. Trinitromethane itself is sensitive (about as much as picric acid), and mixtures of it and other hydrocarbons are more sensitive than the dangerous nitrate esters. Such mixtures are thermally unstable, quickly decomposing above 100degC, such decomposition can lead to detonation.
Salts of Dinitromethane
Ammonium nitroformate is much more stable than the sodium salt. Silver nitroformate slowly decomposes at room temperature, and is a very sensitive explosive. The potassium salt, KC(NO2)3 is a lemon yellow crystalline solid that decomposes slowly at room temperatures and explodes above 95 °C. Ammonium nitroformate deflagrates or explodes above 200 °C. Hydrazinium nitroformate is thermally stable to above 125 °C. Most salts of trinitromethane derive from the aci-form. However, the silver and mercuric salts exist in two forms: colourless and yellow. This may indicate that two forms of these salts - nitro and aci - can exist.
Dinitromethane forms salts which are generally unstable and decompose at temperatures not very much above 100°C.
Preparation
There are several routes to prepare trinitromethane.
By direct substitution
Tetranitromethane has been obtained from iodopicrin I3CNO2 and silver nitrite AgNO2. Hantzsh, Chemische Berichte, 39, p2478, (year 1906)
Such yields would be expected to be low, less than 11%, since nitrite substitution on secondary and tertiary haloalkanes gives successively lower yields than a primary haloalkane because a small proportion of nitrite gets substituted instead of nitro groups, which in this case would lead to degredation of the molecules with such undesirable substitutions. Bromopicrin could alternatively be used, but the reaction rate for the substitution of chloropicrin would be far too slow to be practical (although there do exist room temperature catalysts to speed up such substitutions). Even with iodopicrin, the reaction will likely take several days for completion. Both starting chemicals must be first dissolved in appropriate solvents, for example benzene. Use of propylene carbonate as a solvent might possibly enable sodium nitrite to be used instead of silver nitrite.
By reducing tetranitromethane
Hantzsch and Rinckenberger obtained the ammonium salt of trinitromethane by treating tetranitromethane with aqueous ammonia.
It is well known that tetranitromethane can be reduced to nitroformate salts using an alkaline solution of hydrogen peroxide. This is the most usual route for preparing trinitromethane. Prepare a solution of 168 g of potassium hydroxide in 350 mL of water in a round-bottomed 1000-mL Florence flask, and cool to 5 °C with a salt-ice bath. While stirring, add 108 mL of 30% hydrogen peroxide to the solution. Next, add 117 mL of tetranitromethane at a rate which keeps the temperature at 20-25 °C, add while stirring. The temperature is then allowed to rise to 30 °C over 15 minutes. The bright yellow solid, that should have formed, is filtered to collect it using glass filter paper because of its high acidity, washed with anhydrous methyl alcohol, then anhydrous ethyl ether, and finally air dried to give 100% of the potassium salt of trinitromethane. The salt is suspended in anhydrous ethyl ether and anhydrous hydrogen chloride gas is passed in until the yellow color disappears. The white precipitate of potassium chloride is filtered off and washed with anhydrous ethyl ether. The ethyl ether is evaporated from the filtrate and additional washings at reduced pressure give 85-90% of crude trinitromethane which can be purified by sublimation.
Although usually an oxidizer, in some reactions hydrogen peroxide can act as a reducing agent. For example, it reacts with hypochlorite to form chloride and oxygen gas. Similarly, an alkaline solution of H2O2 reduces Cl2 to Cl- ions.
From Trinitroacetonitrile
Trinitroacetonitrile can be synthesized by the nitration of cyanoacetic acid with a solution of sulfur dioxide and 98+% concentrated nitric acid in carbon tetrachloride, with 73-77% yields. The trinitroacetonitrile can be stored as a solution in the carbon tetrachloride, and need not be isolated for further use on other reactions.
NCCH2C(=O)OH + (3) HNO3 + (3)SO2 -- > NCC(NO2)3 + CO2 + (3) H2SO4
Trinitroacetonitrile is a colorless, camphor-like, crystalline compound melting at 41.5 °, and detonating violently at 220°. It hydrolyzes to carbon dioxide and the ammonium compound of nitroform by water or alcohol at ordinary temperatures.
"Nitroacetonitrile has been prepared by treating methazonic acid with thionyl chloride SOCl2 in ether. That the compound so obtained is nitroacetonitrile follows from the fact that it yields a-nitroethenylamino-oxime with hydroxylamine, and gives the nitrolic acid reaction. Its formation from methazonic acid proves the correctness of the formula. (methazonic acid has the formula HON=NCHCH2NO2, and is well discussed elsewhere on this forum). Nitroacetone, NCCH2NO2 ,is obtained as a fairly stable yellow oily liquid. Wen pure, it may be distilled under reduced pressure (boiling point 96 ° under 14mmHg reduced pressure). It does not seem to be explosive, neither is the ammonium salt, which crystallizes in slender, yellowish-white needles, decomposing at 130-135°. The silver salt, obtained as a brown precipitate, however, is a sensitive explosive. A-Nitroethenylamino-oxime (NO2)CH2C(NH2)=NOH, obtained by the action of hydroxylamine on nitroacetonitrile, forms yellow crystals and decomposes suddenly at 108°."
Journal of the Royal Society of Chemistry (Great Britain), Volume 94. p.327 (year 1908)
It is known that dinitroacetonitrile can be nitrated to trinitroacetonitrile, so nitroacetonitrile probably can be similarly nitrated.
Shishkov (and later Steiner) claimed to have obtained trinitroacetonitrile by treating the sodium salt of fulminuric acid with a mixture of nitric and sulphuric acid, but it was later shown that the compound which is obtained from this reaction is not identical to trinitroacetonitrile.
“Nitroform (Trinitromethane), CH(N03)3, is obtained in the form of its ammonium salt by the decomposition of trinitroacetonitrile with water.” (L. Schischkoff, Ann., 1857, 10 3, p. 364).
Direct nitration of acetonitrile?
I am unsure, but I think it may be possible that trinitroacetonitrile could be prepared by nitration of acetonitrile using nitronium tetrafluoroborate. Although acetonitrile is commonly used a solvent for the nitration of other reagents by nitronium tetrafluoroborate, apparently without significant reaction of the acetonitrile, it may likely be that the acetonitrile does in fact slowly react, but much less rapidly than the nitration of the other reagent being nitrated. There is a reaction, which was developed by Olah, in which alkanes, which are generally fairly inert at room temperature, can be nitrated using nitronium salts. Thus it seems probably that acetonitrile could be similarly nitrated.
From Nitric Acid and Isopropanol
A 250 ml three-necked flask was fitted with a mechanical stirrer, a thermometer and a dropping funnel. 140 ml (3.33 moles) of 98% nitric acid was introduced into the flask. The acid was warmed to about 60.degree. C. and 20 ml (0.26 mole) of isopropyl alcohol was added dropwise over a 10-minute interval. External cooling was used to maintain the temperature at 60°C. The solution was then heated to a temperature of about 70°C. and held at this temperature for 2 hours. Substantial quantities of brown gaseous fumes evolved during this nitration. The solution subsequently was cooled to ambient temperature and analyzed for nitroform content. The yield of nitroform was determined to be 9.8 gm (approximately a 25% yield).
To obtain significant yields of the desired trinitromethane it is essential that the isopropyl alcohol be introduced into an excess of nitric acid. Thus, the molar ratio of nitric acid to isopropyl alcohol will be in excess of about 8:1. Too great an excess of nitric acid will, of course, increase the cost of the method, and will require an unnecessary amount of nitric acid to be distilled and recycled to the process. Thus, the molar ratio of nitric acid to isopropyl alcohol generally is maintained within a range of from about 10 to 25, and preferably within a range of from about 15:1 to 20:1.
The reaction temperature is not particularly critical, provided, of course, that the temperature must be sufficiently high to maintain the mixture of reactants in a liquid phase. In addition, the temperature should not be too high, otherwise substantial gas evolution takes place with little or no formation of nitroform. Therefore, the temperature generally has been maintained within a range of from about 25° to 85°C. and preferably within a range of from about 40° to 70°C. The time required for the reaction will vary with temperature, pressure ratio of reactants, etc. Generally, a time of from about 1 to 5 hours is sufficient to react substantially all of the isopropyl alcohol to form the desired trinitromethane. Yields of up to 50-58% have been obtained from a modification of this procedure.
Other Possible Methods
A mixture of nitromethane and NaOH will form the salt of nitromethane, sodium 'nitromethanate'. Bubble in nitrogen dioxide into a solution of this salt, and trinitromethane can be obtained, because the intermediate aci- form of nitromethane, which is vulnerable to oxidation, is formed. The aci-form is probably CH2=NO2H. Alternatively, bubble mixed nitric oxides into a solution of sodium nitrite and nitromethane (which is sparingly soluble in water), then bubble in only nitrogen dioxide. Sodium nitrate and trinitromethane will form in solution.
B G Gowenlock and I Batt
'The isomerisation of nitrosomethane to formaldoxime', Theochem-Journal of Molecular Structure, 454 1998: 103-4.
B G Gowenlock, B King, J Pfab and M Witanowski
'Kinetic studies of the reaction of some nitrosoalkanes with nitrogen dioxide', Journal of the Chemical Society, Perkin Transactions 2, 1998: 483-5.
Excess treatment with nitrogen dioxide would likely result in trinitromethane, as NO2 oxidizes nitroso.
"The oxidation of nitrosobenzene by nitrogen dioxide in carbon tetrachloride has been re-examined"
" There is an early report 5 that a small quantity of nitrobenzene was formed when dry chloroform solutions of nitrogen dioxide and nitrosobenzene were allowed to stand at 22 8C for 39 h."
J. Chem. Soc., Perkin Trans. 2, 1997, 1793 - 1798, DOI: 10.1039/a700258k
Kinetics of the oxidation of aromatic C-nitroso compounds by nitrogen dioxide
Brian G. Gowenlock, Josef Pfab and Victor M. Young
"Hydroxylamine, an intermediate in ammonia oxidation, reacts with formaldehyde to form formaldoxime" Methanol and Formaldehyde Oxidation by an Autotrophic Nitrifying Bacterium by PA Voysey - 1987
This dangerous chemical can be used to make powerful propellents or advanced performance explosives.
Physical Properties
Trinitromethane melts at 15°C, and begins slowly decomposing above 25°C
At room temperature it is a colorless, or slightly yellow, oily liquid.
Trinitromethane can form salts with a base, such as methylamine or ammonia, or it can dissolve in hydrocarbons (although this can be very dangerous).
Chemical Properties
Trinitromethane can form salts with a base, such as methylamine or ammonia, or it can dissolve in hydrocarbons. It can be mixed with either nitro methane or nitro ethane, to form a powerful explosive binary mixture. The one with EtNO2 is somewhat more powerful, but it also requires a higher ratio of HC(NO2)3, so if nitromethane is easily available in large quantities it may be preferable. (the 'Et' means the --CH2CH3 group)
Salts of trinitromethane are more stable (and somewhat less energetic) than perchlorates, although trinitromethane itself is fairly sensitive. The C(NO2)3(-) anion is very stable because of the resonances, there being four additional electrons to resonate around the the six oxygen atoms. These salts are also known as nitroformates and are bright yellow in color. Trinitromethane oxidizes ferrous ions (Fe+2) to ferric (Fe+3). Dinitromethane can also oxidize the Fe+2 ion, but only if an alkaline solution of dinitromethane is added to an acidified solution of a ferrous salt. This is because the transient "aci-form" tautomer O2NCH=NO2H, which only exists for a few seconds, is more reactive.
WARNING: Toxicity and Explosion Hazard
Trinitromethane, while still giving off mildly poisonous fumes, is far less toxic than tetranitromethane. You would be well advised to avoid ever preparing tetranitromethane, which was once considered for use as a chemical weapon. Trinitromethane is somewhat poisonous: 800 mg/m3/2 hour Inhalation Mouse LC50, compare this with 1230ppm (for 36min, LC50) for tetranitromethane.
It can be seen that tetranitromethane is far more toxic (it is highly recommended that the synthesis of this compound never be attempted), but nitroform should still be assumed to give off toxic vapor, and so should be handled outdoors or behind a windowed fumehood. The boiling point is 175.1 °C so at least it is much less volatile than tetranitromethane. Moderately toxic by inhalation. Irritating to skin, eyes, and mucous membranes. Inhalation can cause headache and nausea. Causes mild narcosis.
A very dangerous explosion hazard; explodes when heated rapidly. Dissolution is exothermic and solutions of more than 50% can explode. Mixtures of 90% trinitromethane + 10% isopropyl alcohol in polyethylene bottles have exploded. Frozen mixtures with 2-propanol (10%) explode when thawed. Can explode during distillation. Mixtures with divinyl ketone can explode at 4°C. Trinitromethane itself is sensitive (about as much as picric acid), and mixtures of it and other hydrocarbons are more sensitive than the dangerous nitrate esters. Such mixtures are thermally unstable, quickly decomposing above 100degC, such decomposition can lead to detonation.
Salts of Dinitromethane
Ammonium nitroformate is much more stable than the sodium salt. Silver nitroformate slowly decomposes at room temperature, and is a very sensitive explosive. The potassium salt, KC(NO2)3 is a lemon yellow crystalline solid that decomposes slowly at room temperatures and explodes above 95 °C. Ammonium nitroformate deflagrates or explodes above 200 °C. Hydrazinium nitroformate is thermally stable to above 125 °C. Most salts of trinitromethane derive from the aci-form. However, the silver and mercuric salts exist in two forms: colourless and yellow. This may indicate that two forms of these salts - nitro and aci - can exist.
Dinitromethane forms salts which are generally unstable and decompose at temperatures not very much above 100°C.
Preparation
There are several routes to prepare trinitromethane.
By direct substitution
Tetranitromethane has been obtained from iodopicrin I3CNO2 and silver nitrite AgNO2. Hantzsh, Chemische Berichte, 39, p2478, (year 1906)
Such yields would be expected to be low, less than 11%, since nitrite substitution on secondary and tertiary haloalkanes gives successively lower yields than a primary haloalkane because a small proportion of nitrite gets substituted instead of nitro groups, which in this case would lead to degredation of the molecules with such undesirable substitutions. Bromopicrin could alternatively be used, but the reaction rate for the substitution of chloropicrin would be far too slow to be practical (although there do exist room temperature catalysts to speed up such substitutions). Even with iodopicrin, the reaction will likely take several days for completion. Both starting chemicals must be first dissolved in appropriate solvents, for example benzene. Use of propylene carbonate as a solvent might possibly enable sodium nitrite to be used instead of silver nitrite.
By reducing tetranitromethane
Hantzsch and Rinckenberger obtained the ammonium salt of trinitromethane by treating tetranitromethane with aqueous ammonia.
It is well known that tetranitromethane can be reduced to nitroformate salts using an alkaline solution of hydrogen peroxide. This is the most usual route for preparing trinitromethane. Prepare a solution of 168 g of potassium hydroxide in 350 mL of water in a round-bottomed 1000-mL Florence flask, and cool to 5 °C with a salt-ice bath. While stirring, add 108 mL of 30% hydrogen peroxide to the solution. Next, add 117 mL of tetranitromethane at a rate which keeps the temperature at 20-25 °C, add while stirring. The temperature is then allowed to rise to 30 °C over 15 minutes. The bright yellow solid, that should have formed, is filtered to collect it using glass filter paper because of its high acidity, washed with anhydrous methyl alcohol, then anhydrous ethyl ether, and finally air dried to give 100% of the potassium salt of trinitromethane. The salt is suspended in anhydrous ethyl ether and anhydrous hydrogen chloride gas is passed in until the yellow color disappears. The white precipitate of potassium chloride is filtered off and washed with anhydrous ethyl ether. The ethyl ether is evaporated from the filtrate and additional washings at reduced pressure give 85-90% of crude trinitromethane which can be purified by sublimation.
Although usually an oxidizer, in some reactions hydrogen peroxide can act as a reducing agent. For example, it reacts with hypochlorite to form chloride and oxygen gas. Similarly, an alkaline solution of H2O2 reduces Cl2 to Cl- ions.
From Trinitroacetonitrile
Trinitroacetonitrile can be synthesized by the nitration of cyanoacetic acid with a solution of sulfur dioxide and 98+% concentrated nitric acid in carbon tetrachloride, with 73-77% yields. The trinitroacetonitrile can be stored as a solution in the carbon tetrachloride, and need not be isolated for further use on other reactions.
NCCH2C(=O)OH + (3) HNO3 + (3)SO2 -- > NCC(NO2)3 + CO2 + (3) H2SO4
Trinitroacetonitrile is a colorless, camphor-like, crystalline compound melting at 41.5 °, and detonating violently at 220°. It hydrolyzes to carbon dioxide and the ammonium compound of nitroform by water or alcohol at ordinary temperatures.
"Nitroacetonitrile has been prepared by treating methazonic acid with thionyl chloride SOCl2 in ether. That the compound so obtained is nitroacetonitrile follows from the fact that it yields a-nitroethenylamino-oxime with hydroxylamine, and gives the nitrolic acid reaction. Its formation from methazonic acid proves the correctness of the formula. (methazonic acid has the formula HON=NCHCH2NO2, and is well discussed elsewhere on this forum). Nitroacetone, NCCH2NO2 ,is obtained as a fairly stable yellow oily liquid. Wen pure, it may be distilled under reduced pressure (boiling point 96 ° under 14mmHg reduced pressure). It does not seem to be explosive, neither is the ammonium salt, which crystallizes in slender, yellowish-white needles, decomposing at 130-135°. The silver salt, obtained as a brown precipitate, however, is a sensitive explosive. A-Nitroethenylamino-oxime (NO2)CH2C(NH2)=NOH, obtained by the action of hydroxylamine on nitroacetonitrile, forms yellow crystals and decomposes suddenly at 108°."
Journal of the Royal Society of Chemistry (Great Britain), Volume 94. p.327 (year 1908)
It is known that dinitroacetonitrile can be nitrated to trinitroacetonitrile, so nitroacetonitrile probably can be similarly nitrated.
Shishkov (and later Steiner) claimed to have obtained trinitroacetonitrile by treating the sodium salt of fulminuric acid with a mixture of nitric and sulphuric acid, but it was later shown that the compound which is obtained from this reaction is not identical to trinitroacetonitrile.
“Nitroform (Trinitromethane), CH(N03)3, is obtained in the form of its ammonium salt by the decomposition of trinitroacetonitrile with water.” (L. Schischkoff, Ann., 1857, 10 3, p. 364).
Direct nitration of acetonitrile?
I am unsure, but I think it may be possible that trinitroacetonitrile could be prepared by nitration of acetonitrile using nitronium tetrafluoroborate. Although acetonitrile is commonly used a solvent for the nitration of other reagents by nitronium tetrafluoroborate, apparently without significant reaction of the acetonitrile, it may likely be that the acetonitrile does in fact slowly react, but much less rapidly than the nitration of the other reagent being nitrated. There is a reaction, which was developed by Olah, in which alkanes, which are generally fairly inert at room temperature, can be nitrated using nitronium salts. Thus it seems probably that acetonitrile could be similarly nitrated.
From Nitric Acid and Isopropanol
A 250 ml three-necked flask was fitted with a mechanical stirrer, a thermometer and a dropping funnel. 140 ml (3.33 moles) of 98% nitric acid was introduced into the flask. The acid was warmed to about 60.degree. C. and 20 ml (0.26 mole) of isopropyl alcohol was added dropwise over a 10-minute interval. External cooling was used to maintain the temperature at 60°C. The solution was then heated to a temperature of about 70°C. and held at this temperature for 2 hours. Substantial quantities of brown gaseous fumes evolved during this nitration. The solution subsequently was cooled to ambient temperature and analyzed for nitroform content. The yield of nitroform was determined to be 9.8 gm (approximately a 25% yield).
To obtain significant yields of the desired trinitromethane it is essential that the isopropyl alcohol be introduced into an excess of nitric acid. Thus, the molar ratio of nitric acid to isopropyl alcohol will be in excess of about 8:1. Too great an excess of nitric acid will, of course, increase the cost of the method, and will require an unnecessary amount of nitric acid to be distilled and recycled to the process. Thus, the molar ratio of nitric acid to isopropyl alcohol generally is maintained within a range of from about 10 to 25, and preferably within a range of from about 15:1 to 20:1.
The reaction temperature is not particularly critical, provided, of course, that the temperature must be sufficiently high to maintain the mixture of reactants in a liquid phase. In addition, the temperature should not be too high, otherwise substantial gas evolution takes place with little or no formation of nitroform. Therefore, the temperature generally has been maintained within a range of from about 25° to 85°C. and preferably within a range of from about 40° to 70°C. The time required for the reaction will vary with temperature, pressure ratio of reactants, etc. Generally, a time of from about 1 to 5 hours is sufficient to react substantially all of the isopropyl alcohol to form the desired trinitromethane. Yields of up to 50-58% have been obtained from a modification of this procedure.
Other Possible Methods
A mixture of nitromethane and NaOH will form the salt of nitromethane, sodium 'nitromethanate'. Bubble in nitrogen dioxide into a solution of this salt, and trinitromethane can be obtained, because the intermediate aci- form of nitromethane, which is vulnerable to oxidation, is formed. The aci-form is probably CH2=NO2H. Alternatively, bubble mixed nitric oxides into a solution of sodium nitrite and nitromethane (which is sparingly soluble in water), then bubble in only nitrogen dioxide. Sodium nitrate and trinitromethane will form in solution.
B G Gowenlock and I Batt
'The isomerisation of nitrosomethane to formaldoxime', Theochem-Journal of Molecular Structure, 454 1998: 103-4.
B G Gowenlock, B King, J Pfab and M Witanowski
'Kinetic studies of the reaction of some nitrosoalkanes with nitrogen dioxide', Journal of the Chemical Society, Perkin Transactions 2, 1998: 483-5.
Excess treatment with nitrogen dioxide would likely result in trinitromethane, as NO2 oxidizes nitroso.
"The oxidation of nitrosobenzene by nitrogen dioxide in carbon tetrachloride has been re-examined"
" There is an early report 5 that a small quantity of nitrobenzene was formed when dry chloroform solutions of nitrogen dioxide and nitrosobenzene were allowed to stand at 22 8C for 39 h."
J. Chem. Soc., Perkin Trans. 2, 1997, 1793 - 1798, DOI: 10.1039/a700258k
Kinetics of the oxidation of aromatic C-nitroso compounds by nitrogen dioxide
Brian G. Gowenlock, Josef Pfab and Victor M. Young
"Hydroxylamine, an intermediate in ammonia oxidation, reacts with formaldehyde to form formaldoxime" Methanol and Formaldehyde Oxidation by an Autotrophic Nitrifying Bacterium by PA Voysey - 1987