Post by Anders Hoveland on Feb 7, 2011 15:44:24 GMT -8
amino-DPNA
(3-nitro,4-amino-benzene diazonium perchlorate)
fairly sensitive to mechanical shock
explodes on contact with flame
capable of easily initiating a less sensitive booster charge
moderate stability, darkens on exposure to sunlight
amino-DPNA (as I will refer to it) would make a good candidate for the imaginary explosive (which was supposedly made from mothballs and ammonia) used in the first "Terminator" film. (the pipebombs were thrown toward Schwarzenegger as he chased Linda Hamilton and Michael Biehn)
Required Precursors:
Mothballs (the type with paradichlorobenzene)
Ammonia (typical 15% concentrated commercial cleaning solution)
Sulfuric Acid (boiled down to at least 65% concentration)
Sodium Nitrate
Sodium Nitrite (meat preservative)
Sodium Perchlorate
Hydrochloric Acid (25-30% concentrated)
Summary of Reactions:
(1) NaClO4 and HCl mixed. NaCl separates from solution as solid. The HCl solution, which now also contains HClO4, is separated off. The HCl is boiled out, leaving only dilute HClO4 in solution.
(2) Limited nitration of paradichlorobenzene gives nitroparadichlorobenzene.
(3) Nitroparadichlorobenzene condenses with ammonium salt
(4) 2-nitrobenzene-1,4-diamine thus formed is diazotized with sodium nitrite using dilute perchloric acid
Discussion of Chemical Reactions:
Paradichlorobenzene mothballs are still widely available, despite most of the mothballs having converted to using naptha instead. Limited nitration of paradichlorobenzene gives nitroparadichlorobenzene. This could then react with ammonium sulfate to form 2-nitro, 4-chloro-analine. (hydrazine sulfate is known to condense with dinitroparadichlorobenzene in a similar reaction). That last chlorine will not easily be substituted with an amine, since there is no nitro group either adjacent or directly opposite it on the ring. The reaction with anhydrous ammonia would be extremely slow (several months).
Instead, utilize the Finkelstein reaction. NaI or KI dissolved in an acetone solvent. The NaCl that forms precipitates out, being insoluble. This by itself would take about 9 months, however to speed up the reaction a small ammount of copper(1) iodide catalyst and ethylene diamine could be added. (CuI is easily formed by simply mixing a Cu+2 salt with iodide ions, this also forms free elemental I2 as a byproduct). Note that CH3NHCH2CH2NHCH3 works even better than ethylene diamine. (the fact that the chlorine is on an aromatic ring also helps increase the reaction rate). Such a reaction will still take several days, but this is considered fast for organic chlorine substitution. I think that only a very small ammount of ethylene diamine should be used, since it probably eats up some of the alkyl iodide that forms (unsure such reaction would affect its catalytic ability). Finally the 2-nitro, 4-iodo-analine which forms is reacted with anhydrous ammonia to form nitro-paradiaminobenzene. --- Alternatively tetrahexylammonium Bromide (or iodide) with dry calcium bromide can serve as a catalyst, directly reacting chloro-hydrocarbons with anhydrous ammonia within 24 hours (the yields for single chloro- substitution are over 90%, substituting two chlorines on the same molecule will give yields below 30%)
The nitroparadiaminobenzene thus obtained could then be reacted with dilute perchloric acid and sodium nitrite to form 3-nitro,4-amino-benzene diazonium perchlorate. Note that this is the same thing as DPNA, except there is an extra amino group opposite the diazonium on the ring. This will bring some added stability to the compound, without taking away from its power.
For example, adding three amino groups to trinitrobenzene (TATNB), makes it much more resistant to impact, and actually a little more powerful in addition.
A small ammount of added stability would be desirable for DPNA, since it is so sensitive. The main advantage, however, is that paradichlorobenzene is far easier to obtain than either making or obtaining 3-nitroanaline.
It should be noted, however, that dinitroparadichlorobenzene (and likely the mono-nitro derivitive as well) gives off poisonous fumes (with toxicity similar to carbon monoxide) and the compound causes a severe rash if it comes in contact with skin.
Another advantage of this is that the nitration would be comparatively easy. Since only one nitro group is being added to the ring, concentrations as low as 65% nitric acid could be used (nitration conducted at 95 degC). The later diazotization does not require concentrated acid; even 5% concentrated solutions of perchloric acid would be satisfactory.
Procedures for Preparation
details of the procedure are under construction...
(3-nitro,4-amino-benzene diazonium perchlorate)
fairly sensitive to mechanical shock
explodes on contact with flame
capable of easily initiating a less sensitive booster charge
moderate stability, darkens on exposure to sunlight
amino-DPNA (as I will refer to it) would make a good candidate for the imaginary explosive (which was supposedly made from mothballs and ammonia) used in the first "Terminator" film. (the pipebombs were thrown toward Schwarzenegger as he chased Linda Hamilton and Michael Biehn)
Required Precursors:
Mothballs (the type with paradichlorobenzene)
Ammonia (typical 15% concentrated commercial cleaning solution)
Sulfuric Acid (boiled down to at least 65% concentration)
Sodium Nitrate
Sodium Nitrite (meat preservative)
Sodium Perchlorate
Hydrochloric Acid (25-30% concentrated)
Summary of Reactions:
(1) NaClO4 and HCl mixed. NaCl separates from solution as solid. The HCl solution, which now also contains HClO4, is separated off. The HCl is boiled out, leaving only dilute HClO4 in solution.
(2) Limited nitration of paradichlorobenzene gives nitroparadichlorobenzene.
(3) Nitroparadichlorobenzene condenses with ammonium salt
(4) 2-nitrobenzene-1,4-diamine thus formed is diazotized with sodium nitrite using dilute perchloric acid
Discussion of Chemical Reactions:
Paradichlorobenzene mothballs are still widely available, despite most of the mothballs having converted to using naptha instead. Limited nitration of paradichlorobenzene gives nitroparadichlorobenzene. This could then react with ammonium sulfate to form 2-nitro, 4-chloro-analine. (hydrazine sulfate is known to condense with dinitroparadichlorobenzene in a similar reaction). That last chlorine will not easily be substituted with an amine, since there is no nitro group either adjacent or directly opposite it on the ring. The reaction with anhydrous ammonia would be extremely slow (several months).
Instead, utilize the Finkelstein reaction. NaI or KI dissolved in an acetone solvent. The NaCl that forms precipitates out, being insoluble. This by itself would take about 9 months, however to speed up the reaction a small ammount of copper(1) iodide catalyst and ethylene diamine could be added. (CuI is easily formed by simply mixing a Cu+2 salt with iodide ions, this also forms free elemental I2 as a byproduct). Note that CH3NHCH2CH2NHCH3 works even better than ethylene diamine. (the fact that the chlorine is on an aromatic ring also helps increase the reaction rate). Such a reaction will still take several days, but this is considered fast for organic chlorine substitution. I think that only a very small ammount of ethylene diamine should be used, since it probably eats up some of the alkyl iodide that forms (unsure such reaction would affect its catalytic ability). Finally the 2-nitro, 4-iodo-analine which forms is reacted with anhydrous ammonia to form nitro-paradiaminobenzene. --- Alternatively tetrahexylammonium Bromide (or iodide) with dry calcium bromide can serve as a catalyst, directly reacting chloro-hydrocarbons with anhydrous ammonia within 24 hours (the yields for single chloro- substitution are over 90%, substituting two chlorines on the same molecule will give yields below 30%)
The nitroparadiaminobenzene thus obtained could then be reacted with dilute perchloric acid and sodium nitrite to form 3-nitro,4-amino-benzene diazonium perchlorate. Note that this is the same thing as DPNA, except there is an extra amino group opposite the diazonium on the ring. This will bring some added stability to the compound, without taking away from its power.
For example, adding three amino groups to trinitrobenzene (TATNB), makes it much more resistant to impact, and actually a little more powerful in addition.
A small ammount of added stability would be desirable for DPNA, since it is so sensitive. The main advantage, however, is that paradichlorobenzene is far easier to obtain than either making or obtaining 3-nitroanaline.
It should be noted, however, that dinitroparadichlorobenzene (and likely the mono-nitro derivitive as well) gives off poisonous fumes (with toxicity similar to carbon monoxide) and the compound causes a severe rash if it comes in contact with skin.
Another advantage of this is that the nitration would be comparatively easy. Since only one nitro group is being added to the ring, concentrations as low as 65% nitric acid could be used (nitration conducted at 95 degC). The later diazotization does not require concentrated acid; even 5% concentrated solutions of perchloric acid would be satisfactory.
Procedures for Preparation
details of the procedure are under construction...