Post by Anders Hoveland on Jun 27, 2011 11:57:48 GMT -8
4-nitro,5,6-triazolo-1,2,3-triazine-2,7-N-dioxide
Molecular Formula C3N7HO4
NTTO is a hypothetical target molecule which is extremely likely to be significantly more powerful than HMX, with less sensitivity. Although HMX consists of bigger molecules, NTTO is likely to have closer molecular packing because the molecule is much more polar, and because of hydrogen bonding. The aromaticity and electron-donation from the NH group to all four oxygen atoms would be expected to provide molecular stability and reduce sensitivity.
NTTO may possibly even approach the calculated power of DTTO, meaning it could exceed the power of octonitrocubane. There are structural similarities between NTTO and DTTO, and the molecular formulas, C3N7HO4 and C2N8O4 respectively, are also somewhat similar. The structure of NTTO may also be compared with LLM-116 (4-amino-3,5-dinitropyrazole), which has been calculated to be 90% as powerful as HMX, and has the formula C3N5H3O4, with two less nitrogen atoms and two more hydrogen than NTTO.
NTTO may hold promise as an excellent new high-performance energetic compound.
expected decomposition
C3N7HO4 --> (2½)CO + (½)CO2 + (½)H2O + (3½)N2
Possible Preparation
Glyoxal is condensed, under alkaline solution, with a limited quantity of nitromethane to form
O=CHCH(OH)CH2NO2.
This is then oxidized to
O=CHCH(=O)CH2NO2. A molar excess of the resulting product is then reacted with sodium hypochlorite solution to obtain
O=CHCH(=O)CH2ClNO2, with a chlorine atom added to carbon atom with the nitro group.
The O=CHCH(=O)CH2ClNO2 is reacted first with sodium azide, then with an alcoholic solution of ammonia (without water), and simultaneously cyclized in a "one-pot" reaction.
NH=CHC(NH2)=C(NO2)(N3) forms as an intermediate before transforming into 4,5-amino-6-nitro-1,2,3-triazine through a Michael-type cyclization reaction. Shevelev obtained 4-methyl,5-nitro-1,2,3-triazole in a similar reaction from the condensation of acetaldehyde with ethyl-2,2-dinitroacetate in the presence of sodium azide. (Shevelev used this as the precursor to 4,5-dinitro-1,2,3-triazole).
The one of the two vicinal amino groups of the 4,5-amino-6-nitro-1,2,3-triazine can be diazotized, with acidified sodium nitrite, and then cylized to form the adjoining triazolo ring. The 4-nitro,5,6-triazolo-1,2,3-triazine thus prepared may then be oxidized by potassium persulfate to form the final product, 4-nitro,5,6-triazolo-1,2,3-triazine-2,7-N-dioxide. This is not actually a technical name, as there is not really a "7-position" unless the compound were described as "bicyclo-hexaazo-nonane-tetraene", the N-oxide in the triazolo add-on ring not being on the nitrogen viscinal [adjacent] to the nitro group.
Molecular Formula C3N7HO4
NTTO is a hypothetical target molecule which is extremely likely to be significantly more powerful than HMX, with less sensitivity. Although HMX consists of bigger molecules, NTTO is likely to have closer molecular packing because the molecule is much more polar, and because of hydrogen bonding. The aromaticity and electron-donation from the NH group to all four oxygen atoms would be expected to provide molecular stability and reduce sensitivity.
NTTO may possibly even approach the calculated power of DTTO, meaning it could exceed the power of octonitrocubane. There are structural similarities between NTTO and DTTO, and the molecular formulas, C3N7HO4 and C2N8O4 respectively, are also somewhat similar. The structure of NTTO may also be compared with LLM-116 (4-amino-3,5-dinitropyrazole), which has been calculated to be 90% as powerful as HMX, and has the formula C3N5H3O4, with two less nitrogen atoms and two more hydrogen than NTTO.
NTTO may hold promise as an excellent new high-performance energetic compound.
expected decomposition
C3N7HO4 --> (2½)CO + (½)CO2 + (½)H2O + (3½)N2
Possible Preparation
Glyoxal is condensed, under alkaline solution, with a limited quantity of nitromethane to form
O=CHCH(OH)CH2NO2.
This is then oxidized to
O=CHCH(=O)CH2NO2. A molar excess of the resulting product is then reacted with sodium hypochlorite solution to obtain
O=CHCH(=O)CH2ClNO2, with a chlorine atom added to carbon atom with the nitro group.
The O=CHCH(=O)CH2ClNO2 is reacted first with sodium azide, then with an alcoholic solution of ammonia (without water), and simultaneously cyclized in a "one-pot" reaction.
NH=CHC(NH2)=C(NO2)(N3) forms as an intermediate before transforming into 4,5-amino-6-nitro-1,2,3-triazine through a Michael-type cyclization reaction. Shevelev obtained 4-methyl,5-nitro-1,2,3-triazole in a similar reaction from the condensation of acetaldehyde with ethyl-2,2-dinitroacetate in the presence of sodium azide. (Shevelev used this as the precursor to 4,5-dinitro-1,2,3-triazole).
The one of the two vicinal amino groups of the 4,5-amino-6-nitro-1,2,3-triazine can be diazotized, with acidified sodium nitrite, and then cylized to form the adjoining triazolo ring. The 4-nitro,5,6-triazolo-1,2,3-triazine thus prepared may then be oxidized by potassium persulfate to form the final product, 4-nitro,5,6-triazolo-1,2,3-triazine-2,7-N-dioxide. This is not actually a technical name, as there is not really a "7-position" unless the compound were described as "bicyclo-hexaazo-nonane-tetraene", the N-oxide in the triazolo add-on ring not being on the nitrogen viscinal [adjacent] to the nitro group.
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