Roads to Nitroethane

[Hansje]

provided that DCM and nitroethane doesn't form an azeotrope

This came from some azeotrope didicated webpage:
Binary azeotropes of:
(substance/bp/comp.wt%-wt%)
Nitroethane:
1-butanol/107.7/55-45
toluene/106.2/25-75
DCM:
glycol/168.7/86-14

They don't claim to list all existing azeotropes, but they list so many that I don't think DCM/nitroethane will form one.

Hansje Pansje Kevertje.....

[Rhodium]

See

https://www.thevespiary.org/rhodium/Rhodium/pdf/nitroalcohol.pdf

- this method is history...

[otto]

hi ab2,

don't bee angry on otto, but it seems that all your effort was useless. check out Synlett; 07, 2001, pp 1121-1122 the article "Can Nitroalkanes be Obtained Directly from Alcohols and Sodium Nitrite in Acetic Acid - Hydrochloric Acid Mixture?" says that it isnt possible, instead of nitroalkanes they always got the corresponding nitrite esters. you can get the .pdf from www.thieme-connect.com, when you sign a trial-account.

otto

[Rhodium]

Otto: Uh? I have uploaded exactly that PDF to my website above.

[Aurelius]

Hey Rhodium, "this method is history..."  are you saying that it doesn't work?

[Rhodium]

Yes, and why it is so is detailed in the PDF file I linked to (it is the PDF version of the article otto refereced).

[Aurelius]

So, if we can in good yeild produce ethyl nitrite- why not?  It is easy enough to convert to nitroethane by isomerization, right?

https://www.thevespiary.org/rhodium/Rhodium/chemistry/nitrite2nitro.html

didn't read the whole thing, so if there is a reason that this is hard to do, please state. 

[Rhodium]

It is much easier to produce ethyl nitrite than using the method described in the article, just look at my page - ethanol, NaNO2 and H2SO4 - no need for DCM/HOAc.

The isomerization method is indeed theoretically easy, but not suitable on a small scale.

[Aurelius]

So what do you think the minimal size would be?  and how to make it "safe".

[Aurelius]

Rhodium, as is the usual case, is correct.  the percent yeild really isn't that bad (10% of nitroethane by volume) considering the recycling for repeated attempts for converting the rest of the nitrite.  However, the article stated that it took 4-5 HOURS to pass a relatively small (less than a liter) of nitrite through.  if one had a continuous still (dangerous) aurelius could see the benifit.  But as Rhodium stated- not for small scale.

[Aurelius]

Just thought it was appropriate

Post 238118

(Aurelius: "Re: What can be done to improve the performance of clandestine nitroethane synth?", Chemistry Discourse)

[ChemicalSolution]

SWIM did 3 batches of this stuff...  All of her distilled products had a density of around 2g/ml.. She vac distilled, distilled @ 1ATM, and lastly, distilled with water..  Any other bees (that bothered to mass the distillate) have this problem??

[otto]

hi rhodium,

before otto started to type your post wasnt there. then some people came in drawing otto off the computer for a talk and otto of course didnt check again the forum before finishing the post.

otto