urea1990
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Diazidodinitromethane synthesis route?
I've been thinking through a potential synthesis of diazido(dinitro)methane - ideally, starting from OTC materials (which is proving a problem). I
know any product will be frisky, to say the least, so I will likely only attempt a synthesis in sub-100mg quantities. Needless to say, I'm looking
for feedback on this synth route; will it work, and is it feasible?
First, the substitution of nitromethane with chlorine1, 2:
CH3NO2 + NaOH + Cl2 → ClCH2NO2 + NaCl + H2O
ClCH2NO2 + KNO2 + KOH → K+CH(NO2)2- + KCl + H2O
Then, the reaction of potassium dinitromethane and chlorine in the presence of excess potassium hydroxide3:
K+CH(NO2)2- + 2Cl2 + KOH → Cl2C(NO2)2 + 2KCl +
H2O
Next, the azidation of dichloro(dinitro)methane to diazido(dinitro)methane with aqueous sodium azide:
Cl2C(NO2)2 + 2NaN3 → C(NO2)2(N3)2 + 2NaCl
The final reaction mixture - considering I plan to decant the dichloro(dinitro)methane to another vessel (i.e. a plastic one) before the azidation -
should consist of sodium chloride solution and DDNM, which will separate into layers.
Are there any problems with this synth route, other than the obvious instability of the product?
1 - https://pubs.acs.org/doi/abs/10.1021/jo00412a014
2 - https://www.wiley.com/en-us/Organic+Chemistry+of+Explosives-... (Halide substitution, p11)
3 - https://link.springer.com/article/10.1007/BF00845909
Edit 1: removed first-draft version of final reaction step.
Edit 2: cleaned up chlorine substitution in an alkaline solution within the first step.
[Edited on 2-5-2018 by urea1990]
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SWIM
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the chlorine doesn't disappear during the azidation, does it?
Looks to me like your sodium will be salt from the chlorine reacting with it.
It's like an SN2, right?
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urea1990
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Quote: Originally posted by SWIM  | the chlorine doesn't disappear during the azidation, does it?
Looks to me like your sodium will be salt from the chlorine reacting with it.
It's like an SN2, right? |
You're absolutely right. Fixed it.
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unionised
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| Quote: Originally posted by urea1990 |
First, the substitution of nitromethane with chlorine1:
2CH3NO2 + Cl2 → 2ClCH2NO2 + H2
[Edited on 2-5-2018 by urea1990] |
You might want to take another look at that
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urea1990
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This looks slightly less incorrect. Should've spotted that, sorry.
CH3NO2 + NaOH + Cl2 → ClCH2NO2 + NaCl + H2O
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