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PHILOU Zrealone
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Maybe you could work with dilluted HNO3 instead.The use of conc HNO3 induces more oxydation products.
IIRC cyclohexane coboiling and heating below 200°C (150°C or so) afwords easily nitrocyclohexane.
I guess hexane will do aswel.
See US Patent 3066173
[Edited on 16-4-2016 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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Pumukli
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PHILOU Zrealone may be right.
Here's how Konovalov summarized his diverse findings regarding nitration of aliphatic hydrocarbons:
"Tertiary hydrogen atoms react most readily in nitration, and primary least readily. The secondary hydrogen atoms assume an intermediate position.
Nitration takes place before oxidation. Oxidation takes place at the carbon atom at which the nitro group is located. The velocity of the nitration
increases with the concentration of nitric acid, but the oxidation also increases, and more rapidly. (emphasis mine) At higher temperatures,
primary substitution is preferred."
Btw. Konovalov preferred to use 13% nitric acid (density: 1.075) in his experiments.
Jimmymajesty, you should definitely consult the following book (available at least for preview online):
Paraffins: Chemistry and technology by F. Asinger.
I've been reading/browsing this book for a few minutes now and it has a good 50 pages devoted to nitration in the gas phase of C1 - C5 (or so)
paraffins, either at elevated or normal pressure, in (glass) tube reactors similar to yours. I think it would be a goldmine for you. :-)
[Edited on 17-4-2016 by Pumukli]
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clearly_not_atara
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Is alpha-nitration of carbonyl compounds a possibility? You could use acetic anhydride or phenyl thioacetate etc followed by decarboxylation (the free
acid should decarboxylate spontaneously).
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Melgar
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As the one who started this thread years ago, the process has still been in the back of my mind. Now, I'm wondering if independently heating the two
gases before combining them might be a better way to go. That way, you could optimize their radicalization temperatures separately, and cool them
more quickly after they recombine, thus reducing the chances of runaway oxidation.
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Pumukli
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Melgar,
Dr. Hass and his students in 1930 or so who first run this process succesfully only heated the nitric acid (not too hot) and bubbled the hydrocarbon
through it. This way the hydrocarbon stream got enriched with nitric acid vapors and then was this mixture led to the (much hotter) tube-reactor part
of the arrangement to carry out the nitration.
The runaway was controlled (prevented) by immersing the tube reactor into molten salt mixture to stabilize its temperature and by adjusting the rate
of hydrocarbon flow. Too slow flow leads to too long contact time and NO2 appears in the out gas because of oxidation prevails. On the
other hand if the contact time in the hot tube-reactor part is only 0.1 - 0.2 sec then the nitration won't end up in oxidation and the outgasses are
not brown but colorless. The color of NO2 tells the experimenter how the process is going. Aim for just a little brown in the outgass at
the start and then increase the hydrocarbon flow rate until the brown disappears. (And it also means that there won't be runaway as I understood.)
But I warmly recommend you to read that book what I referenced yesterday. It goes into details of the process I just can't summarize (better) from
memory.
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Corrosive Joeseph
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Quote: Originally posted by Pumukli  |
Paraffins: Chemistry and technology by F. Asinger.
I've been reading/browsing this book for a few minutes now and it has a good 50 pages devoted to nitration in the gas phase of C1 - C5 (or so)
paraffins, either at elevated or normal pressure, in (glass) tube reactors similar to yours. I think it would be a goldmine for you. :-)
[Edited on 17-4-2016 by Pumukli] |
""Paraffins - Chemistry and Technology" - F. Asinger (1968)
Chapter 4 - The Nitration and Nitration Products of the Parafffins - Pages 365-482
http://libgen.io/book/index.php?md5=B458DD22F6BED7EFFD08F296...
/CJ
Being well adjusted to a sick society is no measure of one's mental health
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Corrosive Joeseph
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More nitropaffifin gold........... Stuffed full of information
'Process of nitrating paraffin hydro' - US 1967667 A
https://www.google.com/patents/US1967667
Henry Hass and them ole boys from the Purdue Research Foundation come to the rescue yet again..........
Also.......... Nitroalkane Info Dump........ Attached
/CJ
Attachment: Revised organic compounds containing Nitrogen.pdf (1.9MB)
This file has been downloaded 689 times
Being well adjusted to a sick society is no measure of one's mental health
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Melgar
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I'm embarrassed by me eight years ago, and my transparently obvious Shulgin-wannabe scheming. And my piss-poor diagrams.
I guess I'm not that much better these days, only more self-aware.
Setting up the reactor was an interesting learning experience though. And I got about 3 mL of mixed nitroparaffins, so it wasn't a total failure.
[Edited on 6/11/18 by Melgar]
The first step in the process of learning something is admitting that you don't know it already.
I'm givin' the spam shields max power at full warp, but they just dinna have the power! We're gonna have to evacuate to new forum software!
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Corrosive Joeseph
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/CJ
Attachment: The Nitroparaffins - Henry Hass and Elizabeth Riley (1941).pdf (3.5MB)
This file has been downloaded 723 times
Being well adjusted to a sick society is no measure of one's mental health
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wiglaf
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melgar,
I have some cursory experience in doing what you've attempted. Just wanted to write to say that I'm impressed with your work. I'm glad you didn't
get hurt AND that you were able to make a few mL of material.
Be safe out there.
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wiglaf
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jimmymajesty,
I want to congratulate you, too. Nice work. scary but good. also, I think you fine using propane. it will crack to nitroethane as the reaction
goes. not much, but some. Mostly nitropropane. higher temps crack a bit more but shouldn't be a big difference. remember the reaction generates a
lot of heat so you don't need to supply it all yourself. pre-heating the propane is the industrial way to do this.
Be safe.
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