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Author: Subject: Diazidodinitromethane synthesis route?
urea1990
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[*] posted on 2-5-2018 at 09:08
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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[*] posted on 2-5-2018 at 10:11


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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[*] posted on 2-5-2018 at 10:21


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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[*] posted on 2-5-2018 at 10:51


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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[*] posted on 2-5-2018 at 11:10


Quote: Originally posted by unionised  
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


This looks slightly less incorrect. Should've spotted that, sorry.

CH3NO2 + NaOH + Cl2 → ClCH2NO2 + NaCl + H2O
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