symboom
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Mood: Doing science while it is still legal since 2010
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Nitrotetrazolate 2N-oxide
Thought I would share this article
https://blogs.sciencemag.org/pipeline/archives/2010/11/15/th...
Excerpt.
Nitro groups are just the kind of bad company I mean, since they both bring their own oxygens to the party and pull electrons around in delightfully
destabilizing ways. So nitrotetrazole is already not something I’d feel good about handling (its metal salts are primary explosives), but today’s
paper goes a step further and makes an N-oxide out of a nitrogen on a nitrotetrazole ring. This both adds more oxygen and tends to make the crystal
packing tighter, which raises the all-important kapow/gram ratio. (There is, of course, little reason to do this unless you feel that life is empty
without sudden loud noises). The paper mentions that “Introducing N-oxides onto the tetrazole ring may . . . push the limits of well-explored
tetrazole chemistry into a new, unexplored, dimension.”, but (of more immediate importance) it may also push pieces of your lab equipment into
unexplored parts of the far wall.
Turns out that you can make the N-oxides through pretty mild chemistry (oxone at room temp)
Synthysis
http://pubs.acs.org/doi/abs/10.1021/ja106892a
12.5g of the sodium salt of 5-nitrotetrazole is dissolved in 50mL water, then reacted with 45g of potassium peroxy-monosulfate ("Oxone") and 20g of
potassium acetate, which acts as a buffer. The solution is stirred for 24 hours at 50 degC.
A solution containing 0.09 moles of tertiary amine sulfate, such as Et3NH(+), Na(+), SO4(-2), dissolved in 200mL of water, is added. Then the 5-nitro
tetrazole-2N-oxide is extracted using 300mL of ethyl acetate. The yellow product moves into the ethyl acetate layer. The 5-nitro tetrazole-2N-oxide
product may be purified by crystallization from EtOAc or toluene, resulting in thin yellow crystals. The yield is 70%.
The calculated density for the hydroxylamine salt of 5-nitro tetrazole-2N-oxide is 1.87 g/cm3. The salt has a formula of CN6O4H4. Several salts of the
nitrotetrazole oxide anion decomposed at between 153 and 211 degC
[Edited on 22-10-2020 by symboom]
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DBX Labs
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What might be the purpose of the tertiary amine sulfate in the proposed oxidation? Is it really all that necessary considering that oxidation of the
Ammonium salt is achieved and followed by the immediate extraction of the free acid in ether?
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Microtek
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I've been wondering about this too. Maybe its used as a phase transfer catalyst for getting the product more cleanly extracted?
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