nitroethane

[Chromic]

Last I checked, acetone peroxide is not dimethyldioxirane (DMDO). DMDO is like acetone, but instead of (CH₃)₂C=O you have (CH₃)₂C=(O-O).

Acetone peroxide is a cyclic species that likes to explode.

[lugh]

The alcohol nitration procedure referred to is on Rhodium's page at:

http://rhodium.lycaeum.org/chemistry/alcohol2nitro.html

  it's much superior to the ester route, since it starts directly with the alcohol. Yields are low so far, but only one bee has attempted it and reported results. As far as the vapor phase nitration process, it was done in a lab, it's not only industrial scale, basically it would involve two tanks of gas (propane/methane and nitrogen dioxide), suitable valves, and a reactor made from small diameter conduit of sufficient length heated with electrical heating tape (they used molten salt) and then insulated. A condenser and reciever would also be required. Obviously, this is suitable only for those with the McGyver impetus. I can post a reference if anyone has serious interest. Also, chloroacetic acid is generally produced by chlorinating acetic acid in the presence of acetic anhydride, phosphorus or sulfur.

[terbium]

Last I checked, acetone peroxide is not dimethyldioxirane (DMDO). DMDO is like acetone, but instead of (CH3)2C=O you have (CH3)2C=(O-O).

Acetone peroxide is a cyclic species that likes to explode.

True that DMDO is different from cyclic acteone peroxide. DMDO is cyclic though - one carbon and two oxygens for a ring isn't it? In any event, I thought that DMDO also liked to explode too. Acetone and methyl ethyl ketone hydroperoxides will certainly explode, they just aren't quite as shock sensitive as the cyclic forms.

[blue]

for what it is worth the synth from sodium ethyl sulfate and NaNO2 runs fine, it uses a fair bit of NaNO2 for the amount nitroethane produced

100g NaNO2 + 160g NaHEtSO4 + (catalytic amount)KHCO3 + heat =yeilded 25g nitroethane and a similar amount of what is assumed to be ethyl nitrite, that disappears in the water wash.
yeild ca 30% (yeilds could be improved by mixing reagents better than was done for this experiment)
rxn goes quik, 1/2 hour. its making the sodium ethyl sulfate that is tedious.

i'll warn ya though you need a shitload of headroom cuz the rxn foams ALOT! like a 2l flask for the above size rxn.

that other route via ethanol and NaNO2 also runs (triied nanonscale), but uses HUGE amounts of DCM that has to be stripped off, so it is volumetrically problematic. if i remember its like 250mls DCM to get a couple mls nitroproduct.

methods that scales better would sure be nice.

btw - how were they planning on oxidizing the ethylamine?


as in cobalt

[Osmium]

Nobody interested in the ethyl nitrite conversion?
Pfffffft.  

[blue]

I'm all ears Os, just have to take a day off work to get to the library before i'm in any position to comment.

it's similar to whats going on the sodium ethyl sulfate synth as well isn't it (minus the nitration)?

as in cobalt

[obituary]

can't remember exactly , but the sodium nitrite and ethanol does work at the either 50 or 500x scale to what's on Rhodium's site.  (try without the DCM- didn't want to mess with the solvent volume, so left it out-worked just fine)  just filter, wash, distill- however you want to purify.

[Rhodium]

Obit: I am very interested in a detailed writeup on that scale-up, including yields and stuff like that.

http://rhodium.lycaeum.org

[halfapint]

Yes, Obit: please clarify. Are you implying that you put sodium nitrite in ethanol, added acetic acid then hydrochloric acid, and casually distilled off a whole bunch of nitroethane? Because that would bee big news around here! TIA...

Half a pint's a half a pound, a half the world around, around.

[obituary]

sorry for the long wait but obit has been out of town for a while and will re-run the rxn and post the results, it's been to long for this short-memory bee to remember the details.  get back with ya- hopefully with good news.