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SuperOxide
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Quote: Originally posted by Tsjerk  | | I believe the salts of toluidine are stable, so you could form for example the HCl salt and store it as a water solution. Before use you then freebase
it, extract with a solvent, dry with sodium sulfate and evaporate the solvent. |
Ahh, ok. Good tip!
@Benignium - I have two questions:
1) What was your yield? You said you started with 14.19g of anthranilic acid and 9.63g of the o-toluidine. How much of the end product did you get on
the other end? (Sorry if you mentioned this in an above post, I didn't see it though).
2) You said you started from OTC chemicals, does that mean the toluene you got was just a paint thinner/solvent? (Like the Klean Strip Toluene?) If so, did you nitrate it as it was, or did you do anything to clean it up or dry it first? I have some and I wasn't sure if
I should go through the trouble of distilling it then trying to pull as much water out as possible, or if I could nitrate it as it is.
[Edited on 18-1-2021 by SuperOxide]
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zed
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Question about Toluidine degradation.
Freshly opened bottles of Aniline and Phenyl Hydrazine, contain a product that is colorless to yellowish, this product discolors quickly once the
bottle has been opened.
Exposure to oxygen, I suppose.
When you revisit this bottle a few weeks later, the contents will be reddish, or reddish brown (though still clear). I can imagine a small amount of
Toluidine in a fairly large bottle (lots of oxygen) could develop a molasses-like appearance pretty quickly.
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Tsjerk
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Yes, it is indeed oxygen which causes the coloring.
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SuperOxide
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| Quote: Originally posted by zed | Question about Toluidine degradation.
Freshly opened bottles of Aniline and Phenyl Hydrazine, contain a product that is colorless to yellowish, this product discolors quickly once the
bottle has been opened.
Exposure to oxygen, I suppose.
When you revisit this bottle a few weeks later, the contents will be reddish, or reddish brown (though still clear). I can imagine a small amount of
Toluidine in a fairly large bottle (lots of oxygen) could develop a molasses-like appearance pretty quickly. |
I figured it was either O2 or UV causing the degradation. I have some N2 gas left in a container, perhaps when I create the o-toluidine I'll put it in
the smallest possible bottle, then try to fill the dead space with the N2.
I plan on creating some phenol as well, so I may do the same thing to that.
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Tsjerk
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Phenol isn't air sensitive is it? Phenolates are though.
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njl
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I though phenol was air/uv sensitive with respect to polymerization?
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Benignium
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SuperOxide, I have no accurate yield to report. I started out with 9.63 grams of the crude. Beside impurities, a lot of the material ended up being
tossed while investigating solubility and different methods of purification. Right now I have well over two grams of completely colorless material
that I'm trying to get to form nice crystals.
The toluene is from a hardware store thinner. Fortunately for me it is quite pure - I have even made tosylic acid without much discoloration in the
final product. I would highly recommend distillation as well as drying or separating any azeotrope, even if the MSDS states toluene as the only
ingredient. However, some water isn't going to affect this particular nitration.
Thanks to zed, I figured out how to remove the remaining coloration. Treating the solution of methaqualone base in toluene seems to be the ticket
here. It does not remove everything straight off the bat, however, and forming the hydrobromide salt after an A/B treatment using oxalic acid and
recrystallizing it from methanol seems to be the most reliable way to get there.
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mackolol
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| Quote: Originally posted by Benignium |
Thanks to zed, I figured out how to remove the remaining coloration. Treating the solution of methaqualone base in toluene seems to be the ticket
here. It does not remove everything straight off the bat, however, and forming the hydrobromide salt after an A/B treatment using oxalic acid and
recrystallizing it from methanol seems to be the most reliable way to get there.
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This reminded me of purification of anthranillic acid thread. I don't really know the solubility of methaqualone freebase in hydrocarbons such as
heptane, nor can I find it, but this can be solution for removing the remaining coloration: https://www.sciencemadness.org/whisper/viewthread.php?tid=15...
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Benignium
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I did actually try something like that. As the amount I was working with was too small for my only soxhlet apparatus, I folded a basket out of coffee
filter, loaded it with a paste of methaqualone paste mixed with some sodium carbonate and suspended it over boiling 60-90 petroleum ether, under
reflux. I let it go for 24 hours or so. The methaqualone did indeed accumulate on the bottom of the boiling vessel, but so did some of the brown
color. The extracted material was a clear, exceedingly tough gel with a brown tinge. The filter paper was- Actually, I believe I have pictures...
[Edited on 19-1-2021 by Benignium]
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SuperOxide
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| Quote: Originally posted by Benignium | | The toluene is from a hardware store thinner. Fortunately for me it is quite pure - I have even made tosylic acid without much discoloration in the
final product. I would highly recommend distillation as well as drying or separating any azeotrope, even if the MSDS states toluene as the only
ingredient. However, some water isn't going to affect this particular nitration. |
Right, I figured I should perhaps purify it using sulfuric acid to get rid of the thiophene contamination that's common with toluene, then distill it
to get rid of as much water as possible.
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Tsjerk
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I was still wondering about this and had a quick search, I'm pretty sure it is only sensitive to light, maybe it oxidizes in air under the influence
of light.
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SuperOxide
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I know in your PPA synth thread you mentioned that it etched away at the glass. Did that happen here as well in any step? You said you added the hot
PPA (hot hot?), did the reaction vessel get etched away at all?
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Benignium
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No, not at all. The etching is only significant at temperatures exceeding 200 deg. C, possibly even 250.
On an unrelated note, I neglected to mention that the way I got rid of the last bit of color was by treating in toluene with activated
carcoal. I should really learn to proofread my stuff properly.
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SuperOxide
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| Quote: Originally posted by Benignium | | I neglected to mention that the way I got rid of the last bit of color was by treating in toluene with activated carcoal. I should
really learn to proofread my stuff properly. |
I wonder if that would be enough to purify it without having to go through some of the various purification steps you mentioned you tried, some of
which seem tedious or repetitive. Perhaps just treat it with activated charcoal in toluene, then recrystallize it using methanol.
I hope to get to try this in the near future. I have everything needed for it now, except for time and space 
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Benignium
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It wasn't quite that easy for me at least. A couple of methanol-acetone cycles, A/B using oxalic acid and finally charcoal is the minimum amount of
workup you're looking at. That is unless you start with less impurities or figure out a better method. There's also no shame in settling for a
slightly impure product as long as you're happy. Just don't consume it.
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Amos
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Benignium, thank you so much for keeping up with the thread and addressing all of the comments with such thoroughness. There are some qualities that
have been lacking on forum posts of late and it looks like some of us are happy to see them freshly embodied here.
If you want to answer yet another question: When you say solvent/water was removed by evaporation, do you mean simply leaving a solution out to
naturally concentrate, or are you assisting the process with a vacuum or other means?
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Benignium
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I appreciate the kind words, Amos! 
Whenever there is the possibility of speeding up the process without the risk of losing product, I tend to go for it. I haven't utilized vacuum all
that much thus far because my equipment lacks the necessary protection. Mostly I just heat the mixture near, or all the way to, its boiling point
using either an oven, a water/oil bath or just a hotplate. I've also used PC fans to further encourage evaporation but lately that has fallen out of
favor for no particular reason.
With all that said, I suspect the methaqualone may actually slowly break down into something yellow. The best indication of this was when converting
colorless methaqualone base in toluene into the hydrochloride salt using hydrochloric acid while also applying heat. Of course, given that melting
point tests are generally the most advanced analytical method in my arsenal, I cannot reasonably rule out the possibility of remaining impurities
being the culprit.
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SuperOxide
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It definitely does degrade. Though apparently adding small amounts of HCl will help slow that down by a factor of 100 (approx).
https://lclane.net/text/phenol2.html
Wonder if that would work with o-toluidine...
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njl
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The salt is probably more stable than the freebase.
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SuperOxide
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@Benignium - in your initial post here, you said:
| Quote: Originally posted by Benignium | [...]
9.63 grams of o-toluidine, 14.19 grams of anthranilic acid and 9.00 grams of glacial acetic acid were combined in a 250 mL Erlenmeyer. With strong
stirring, 90 grams of hot polyphosphoric acid was added in 10-20 gram portions using a glass syringe. The mixture was heated to and kept at
185 degrees Celsius for three hours.
[...] |
However, in the Rhodium article you referenced, in the From Anthranilic Acid (Klosa) section you've used, it states:
| Quote: | | [...] After this, the mixture was heated to 180°C for 10 minutes, then cooled and poured in 150-200ml water, [...]
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Which leaves me with a few questions:
Is there any reason you went for 3 hours when the article says only 10 minutes is needed?
Was there a noticeable change in the reaction flask that signaled the end point?
Is there any risk of going for such a long time? (eg: more side products being created, leaving to an overly contaminated product)
Sorry if I'm hassling you with so many questions, hope it's not too much trouble.
As always, thanks for keeping up with the replies to the thread.
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SuperOxide
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| Quote: Originally posted by karlos³ | [...]
Also, a personal opinion, I consider the product rather boring and would always prefer thalidomide to which I grew a certain fondness over time [...] |
You prefer thalidomide? As in recreationally? Interesting... I didn't know it had any desirable effects.
Edit: I guess there is some market for it, very surprising. Found this thread on it's synthesis here.
[Edited on 29-3-2021 by SuperOxide]
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SuperOxide
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Thought I'd add some input to this suggestion:
| Quote: Originally posted by Pumukli | [...]
- How thoroughly could you check the properties of the target compound? Do you know its solubility in various solvents? Could it be e.g. steam
distilled? Sublimated? (You mentioned people used to smoke it. Well, it may be a good candidate for sublimation.)
[...] |
I was able to get this MQ synthesis a go as well (worked a treat thanks to OP's detailed post. So much in there that's not detailed anywhere else).
I decided to try the sublimation that was suggested by Pumukli. I took some photos of the process
Note: This was my first vacuum sublimation, so it's a rather sketchy setup, be gentle in your critiques, lol.
Summary: It does work ok. The crystals weren't nice and white like I was hoping, but they were definitely better than the crude product. Probably
would have worked better with a higher vacuum and a better distributed heat source (eg: heating mantle instead of flame that needed to be moved
around).
Here's a few of the photos of the crystals that sublimated onto the test tube:
[Edited on 3-5-2021 by SuperOxide]
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Benignium
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Thank you for trying the sublimation, SuperOxide! Very nice to see that it works.
For resizing the embedded image, I recommend augmenting the BBCode: [img] -> [img=16x9] -- so width x height given in pixels.
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SuperOxide
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| Quote: Originally posted by Benignium | Thank you for trying the sublimation, SuperOxide! Very nice to see that it works.
For resizing the embedded image, I recommend augmenting the BBCode: [img] -> [img=16x9] -- so width x height given in pixels.
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Thanks! I modified the previous post to show a few of the pictures.
Perhaps sublimation of the base then using A/C in toluene is the way to go. Sublimation clearly gets rid of a lot of black residue (assuming carbon),
but the crystals are still colored, hence the A/C.
[Edited on 4-5-2021 by SuperOxide]
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SuperOxide
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| Quote: Originally posted by Benignium | Thanks to zed, I figured out how to remove the remaining coloration. Treating the solution of methaqualone base in toluene seems to be the ticket
here. It does not remove everything straight off the bat, however, and forming the hydrobromide salt after an A/B treatment using oxalic acid and
recrystallizing it from methanol seems to be the most reliable way to get there.
|
Also thanks to Zed, I tried the same thing, and it seemed to work out perfectly.
It's not 100% white, it has a very small hint of yellow if you look at it at the right angle or under the right light, but it's by far the best I've
done yet.
[Edited on 5-5-2021 by SuperOxide]
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