Post by Anders Hoveland on Feb 2, 2011 19:38:38 GMT -8
1-nitrimino,2-[oxytetrazolyl]-tetrazole
O{N4HC}{N4H}C=NNO2
The molecular structure can be seen in the picture at the bottom of the page at the following link :
sites.google.com/site/energeticscribble/nitrimino-tetrazoles
This compound would almost certainly be more powerful than HMX, and might possibly be less sensitive to impact. Nitraminotetrazole compounds have conflictingly been described in literature as either highly thermally and physically stable, or as dangerously sensitive to shock.
Aminoguanidine can be reacted with nitrous acid to form guanylazide, which can then be cyclized to form
1-amino-tetrazole. This can then react with cyanogen azide
to form 2-tetrazolyl-tetrazole. This could then be nitrated, and then reacted with ammonium persulfate using an activator containing cyano (--CN) groups.
While the synthesis would be fairly straight forward,
the bromocyanogen used to generate the cyanogen azide in solution would make production dangerous.
Produced on an industrial scale, the regents are all relatively cheap, and the process simple, but there would be a significant danger of explosion if the cyanogen azide became generated faster than it reacted.
Mainly because of the required bromocyanogen (BrCN), this synthesis would not be very suitable to the home experimenter, although this precursor could potentially be produced without much difficulty.
One thought I had was to fuse formamide, HC(=O)NH2, with lime (CaO). This might form Ca(CN)2, also forming Ca(OH)2 byproduct.
Formamide could be prepared by heating formic acid and a solution of ammonia in a sealed tube over flame, although there are several other ways to make it.
HCN can also be produced by the dry distillation of ammonium formate. (cyanides can give off deadly fumes)
A note about the structure, the hydrogen is preferably bonded onto the tetrazole ring, rather than on the nitrogen connected to the nitro group. Thus this molecule has a nitrimino group, not a nitramino group. The tetrazole ring is more electron- withdrawing than the nitro group. Furthermore, the NH group in the ring can nevertheless be electron donating to the nitro group because of the aromaticity of the conjugated bonds between the two groups.
I am also thinking about using the Ammonium persulfate oxidation on 5,5'-diazoaminotetrazole, which has the structure:
(HN4C)NHN=N(CN4H). The NH in the bridge might need to have a protecting group on it before the oxidation. This could potentially add three oxygen atoms to the molecule. (perhaps H2O2 with O3, known as "Peroxone" could be used?)
Nitrous acid (HONO) oxidizes aminoguanidine nitrate H2NC(=NH)NH2 into guanyl azide N=N=NC(=NH)NH2, which cyclizes into aminotetrazole {HN4C}NH2 when boiled under alkaline conditions. This takes several hours and gives 70-85% yield.
from sciencemadness :
5,5’-Diazoaminotetrazole H(N4C)-N=N-NH-(CN4)H*H2O. This substance is the product of condensation of diazotetrazole with 5-aminotetrazole. In its pure form it is almost colorless, lustrous plates with double raytrayce, and crystallizes with one molecule of water. The substances contain three acidic hydrogen atoms, which can be replaced by metal ions. There are some patents, proposing salts of diazoaminotetrazole as components of electro-igniter mixtures, and as sensitizers for conventional primary explosives. Monosodium salt of diazoaminotetrazole NaC2N11H2 exists as yellow needles, readily soluble in water. Copper salt Cu3(C2N11)2 – amorphous precipitate with an olive-green color, almost insoluble in water, insoluble in organic solvents. Sensitive to impact and friction, on strong grinding in mortar, only part of product is exploded (which was directly below the pestle), explodes from fire, flash point 195-220°C. Copper-ammonium salt Cu3(C2N11)2 * 2NH3 – dark green plates, expoding from friction, impact or heating, more sensitive then simple copper salt, flash point 220-230°C, mixture with potasium chlorate, has more initiation power then same mixture with mercury fulminate. Silver salt Ag2C2HN11*H2O – white amorphous powder, exploding on heating or strong friction. Barium salt Ba3(C2N11)2*8H2O - yellow plates, explodes on moderate heating.
Another quick though is 1-oxytetrazolo,-5-nitrotetrazole, which would probably be much more stable. It could likely be made by a modication of the Sandemeyer reaction between aminotetrazole and a mixture of copprous nitrite, then reacting the resulting nitrotetrazole with a copprous base (CuOH) to form a salt, then react the copper(1) nitroetrazolate salt with more aminotetrazole in another Sandemeyer-type reaction.
O{N4HC}{N4H}C=NNO2
The molecular structure can be seen in the picture at the bottom of the page at the following link :
sites.google.com/site/energeticscribble/nitrimino-tetrazoles
This compound would almost certainly be more powerful than HMX, and might possibly be less sensitive to impact. Nitraminotetrazole compounds have conflictingly been described in literature as either highly thermally and physically stable, or as dangerously sensitive to shock.
Aminoguanidine can be reacted with nitrous acid to form guanylazide, which can then be cyclized to form
1-amino-tetrazole. This can then react with cyanogen azide
to form 2-tetrazolyl-tetrazole. This could then be nitrated, and then reacted with ammonium persulfate using an activator containing cyano (--CN) groups.
While the synthesis would be fairly straight forward,
the bromocyanogen used to generate the cyanogen azide in solution would make production dangerous.
Produced on an industrial scale, the regents are all relatively cheap, and the process simple, but there would be a significant danger of explosion if the cyanogen azide became generated faster than it reacted.
Mainly because of the required bromocyanogen (BrCN), this synthesis would not be very suitable to the home experimenter, although this precursor could potentially be produced without much difficulty.
One thought I had was to fuse formamide, HC(=O)NH2, with lime (CaO). This might form Ca(CN)2, also forming Ca(OH)2 byproduct.
Formamide could be prepared by heating formic acid and a solution of ammonia in a sealed tube over flame, although there are several other ways to make it.
HCN can also be produced by the dry distillation of ammonium formate. (cyanides can give off deadly fumes)
A note about the structure, the hydrogen is preferably bonded onto the tetrazole ring, rather than on the nitrogen connected to the nitro group. Thus this molecule has a nitrimino group, not a nitramino group. The tetrazole ring is more electron- withdrawing than the nitro group. Furthermore, the NH group in the ring can nevertheless be electron donating to the nitro group because of the aromaticity of the conjugated bonds between the two groups.
I am also thinking about using the Ammonium persulfate oxidation on 5,5'-diazoaminotetrazole, which has the structure:
(HN4C)NHN=N(CN4H). The NH in the bridge might need to have a protecting group on it before the oxidation. This could potentially add three oxygen atoms to the molecule. (perhaps H2O2 with O3, known as "Peroxone" could be used?)
Nitrous acid (HONO) oxidizes aminoguanidine nitrate H2NC(=NH)NH2 into guanyl azide N=N=NC(=NH)NH2, which cyclizes into aminotetrazole {HN4C}NH2 when boiled under alkaline conditions. This takes several hours and gives 70-85% yield.
from sciencemadness :
5,5’-Diazoaminotetrazole H(N4C)-N=N-NH-(CN4)H*H2O. This substance is the product of condensation of diazotetrazole with 5-aminotetrazole. In its pure form it is almost colorless, lustrous plates with double raytrayce, and crystallizes with one molecule of water. The substances contain three acidic hydrogen atoms, which can be replaced by metal ions. There are some patents, proposing salts of diazoaminotetrazole as components of electro-igniter mixtures, and as sensitizers for conventional primary explosives. Monosodium salt of diazoaminotetrazole NaC2N11H2 exists as yellow needles, readily soluble in water. Copper salt Cu3(C2N11)2 – amorphous precipitate with an olive-green color, almost insoluble in water, insoluble in organic solvents. Sensitive to impact and friction, on strong grinding in mortar, only part of product is exploded (which was directly below the pestle), explodes from fire, flash point 195-220°C. Copper-ammonium salt Cu3(C2N11)2 * 2NH3 – dark green plates, expoding from friction, impact or heating, more sensitive then simple copper salt, flash point 220-230°C, mixture with potasium chlorate, has more initiation power then same mixture with mercury fulminate. Silver salt Ag2C2HN11*H2O – white amorphous powder, exploding on heating or strong friction. Barium salt Ba3(C2N11)2*8H2O - yellow plates, explodes on moderate heating.
Another quick though is 1-oxytetrazolo,-5-nitrotetrazole, which would probably be much more stable. It could likely be made by a modication of the Sandemeyer reaction between aminotetrazole and a mixture of copprous nitrite, then reacting the resulting nitrotetrazole with a copprous base (CuOH) to form a salt, then react the copper(1) nitroetrazolate salt with more aminotetrazole in another Sandemeyer-type reaction.