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Author: Subject: Reduction of Phenyl-2-nitropropene with Al/Hg failed. Why??
nimgoldman
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sad.gif posted on 26-5-2019 at 02:22
Reduction of Phenyl-2-nitropropene with Al/Hg failed. Why??


Today I tried to perform the aluminium amalgam reduction of phenyl-2-nitropropene. Although this reaction is described in several writeups and seems fairly simple to do, it failed miserably in my case and I have absolutely no clue why.

Three writeups I found used the same reagents, only in different proportions, so I adjusted the amounts to fit the scale I wanted, which starts with 10 g of nitropropene.

I cut thick Al foil (3 sheets at a time) and crumbled it in into small balls weighing little over 16 grams total:

[file]75666[/file]

Now to make the amalgam, I dissolved 0.2 g of my mercuric chloride (made by the procedure I posted here) in 200 mL water and then dumped in the Al balls.

To my suprise, the reaction was very vigorous and the solution almost boiled with lots of bubbling and sizzling (why???):

[file]75668[/file]

From the videos and images I seen, this should be a fairly calm reaction where the aluminium simply obtains a grayish coating.

I tried to filter the suspension, but there was a heavy amount of gray powder which clogged the filter (elemental Al?) ... So I poured everything through a sieve, washing the amalgamated balls 3 times with water and keeping them.

[file]75670[/file]

I loaded a 500 mL RBF with the amalgamated Al, followed by 150 mL 75% acetic acid and 100 mL isopropanol containing phenyl-2-nitropropene. Here is everything in the flask:

[file]75672[/file]

According to the writeup, this should start reacting spontaneously, but nothing happens at all. The phenyl-2-nitropropene even started crashing out of solution. There were only tiny bubbles appearing around the Al here and there. I heated everything a bit to jump start the reaction but it did not seem to help.

So I refluxed the reaction mixture for 90 minutes, it went very smoothly, no frothing or anything:

[file]75674[/file]

Here is the whole reflux setup. Notice the H2 vent on top leading to a fume hood:

[file]75676[/file]

After the reaction, the flask contained milky liquid - but it should be purple according to other writeups:

[file]75678[/file]

There also seems to be a powdery sediment on the bottom:

[file]75680[/file]

I went ahead and basified the mixture with 25% NaOH and bit of 50% NaOH to obtain strongly basic solution (pH paper was deep blue).

The mixture became transparent, the Al started reacting and there was a strong amine smell (umistakably smelled of amphetamine):

[file]75682[/file]

I tried to filter the mixture with little success as the aluminium mush clogged the filter. Meanwhile, I noticed layer separation and there is the brown oily layer on top:

[file]75684[/file]

Again, I had to remove the Al balls manually and washed them with isopropanol to keep the oil:

[file]75686[/file]

I then extracted the filtrate with 2 x 50 mL of diethyl ether and here is the ethereal extract:

[file]75688[/file]

I dried the extract with magnesium sulfate, filtered and put into rotary evaporator:

[file]75690[/file]

To my suprise, nothing came over even at 50 °C. Ether should distill much more easily... I haven't used vacuum as I wanted to recoved all of the ether, but it haven't condensed anyway :( ... So I just cranked the heat up to 70-80 °C and waited until no more liquid comes over.

There was very little ether recovered (20 mL or so), I don't know why... Anyway, here is the lefover oily liquid:

[file]75692[/file]

I found a small powdery residue on bottom and don't know what that is...

[file]75694[/file]

I immediately tried a few test tube experiments, mixing the oily liquid with isopropanol and adding sulfuric acid, hoping to obtain amine sulfate, but there was no precipitation:

[file]75696[/file]

I even added 98% sulfuric acid directly to the oily liquid and it only turned reddish and there was kind of layer separation (the rightmost tube).

So I made this post and then fell into immense frustration. Why is it that every damn cook can make this substance in a kitchen by kilograms and me who just want to study simple amines, even with all the effort put into it, can't even make a single milligram... What am I doing wrong?

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nimgoldman
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[*] posted on 26-5-2019 at 02:43


...because the only writeups I found used exclusively Hg/Cl and from all the googling I haven't found a single one using tin, except one thread here on SM where a guy tried it and it didn't work - I guess he got something called oxime - an intermediate product, not an amine.

Here even Wikipedia talks about mercury(II) chloride in WATER, not a word about methanol... The description of the reaction on the wiki page shows there is water needed in the process. Hence I though it would be safer to use water than experimenting with methanol, especially if there are several writeups using water with success.

Even Vogel uses aqueous mercuric chloride!!

People (incl. you) so far provided me with only more and more suggestions of different procedures but no explanation of why this haven't worked. I really want to understand this.

Sorry but why no one has ever made a clear and easy to follow writeup of the working procedure for this? I made virtually all the mistakes possible just because there is no solid information on the net. And those who know how to perform this keep it a secret for some reason. I really don't get this... and when someone does not understand a thing, they send him stupid smileys... oh thank you very much. That really helps.

BTW the aluminium foil is the thickest I could find.

I used the apparatus mostly for various plant alkaloid extractions which I did for years. I am new to chemistry and syntheses, still learning the basics in spare time - but it's freaking 800 pages of chemistry textbooks before I get to the interesting stuff so I spend more time in the home lab - it's more fun...

[Edited on 26-5-2019 by nimgoldman]
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[*] posted on 26-5-2019 at 03:08


Okay that makes sense. I will try methanol then. It's really interesting the sludge does not happen for other people using foil though.

It's really nitropropene, I made it using Henry reaction from benzaldehyde and nitroethane, so I am pretty sure it's nitroalkene with double bond, not nitroalkane.

Here is one of the writeups I used. It even comes from SM. Somehow it works and mine does not.

[Edited on 26-5-2019 by nimgoldman]
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JJay
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[*] posted on 26-5-2019 at 03:19


Hi,

I've been lurking here for quite a while, and I've seen some pretty provocative posts, but this thread really goes beyond what is acceptable. This is not a photo of something that happened in the past or a discussion of theoretical chemistry. This is a thread regarding an ongoing synthesis of an illegal drug. It is illegal to assist.

I don't personally care what anyone does in his or her own lab, but I don't want to see the board go away. Please put a stop to this.

I'm not saying that everyone who has spoken or may yet speak on this thread is a bad person or is breaking the law, but please desist in offering any aid. Very few members can legally perform the reactions discussed here.

nimgoldman, if I misjudged the circumstances and what you're doing here is legal, please speak up. I don't care what you do, but don't drag the board into any felony conspiracies.




I'm no longer involved in this forum.
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nimgoldman
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[*] posted on 26-5-2019 at 03:38


I am sorry I am not a professional. I should have just mentioned a possioble problem with aluminium amalgam formation, not mentioning the nitropropene (stupid me) as it pops up red flags. I understand then why this is frowned upon. Maybe it would be best to delete this thread and I will continue self-studying instead of seeking support here as it is on the edge for such a forum (unfortunately my curiosity and pursuit of freedom of experimentation is way beyond what law allows).

The problem has been resolved anyway. It's the water used as solvent for the amalgam. I just imagine how many kilograms of mercury is wasted every week by amateur chemists trying to make aluminium amalgam in water, just because that exact advice pops up in top searches every time, even on Wikipedia and even in Vogel.

I would delete this thread myself but I haven't found a way to do it.

[Edited on 26-5-2019 by nimgoldman]
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draculic acid69
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[*] posted on 26-5-2019 at 05:17


I understand jjay's concern for the board and I understand nimgoldman's desire to synth a compound to study be it legal or not.(I don't give a shit) but I just want to point out that this is the problem with america.; Felony conspiracy just for giving someone information.drug laws so over the top that they do more damage than the drugs do.but let's face one thing.methylamine threads(meth), phosphorus synthesis threads(war gasses,drugs), toluene to benzaldehyde sticky(meth/P2P), and acetic anhydride (heroin/P2P) sticky threads which happen to be the most popular on this board are all precursors that are illegal to make without a DEA permit.(3letter agencies can go fuck themselves for all I care) point I'm making is like gunpowder,bombs and explosives drugs are an integrated part of the amatuer/hobby/non professional chemistry world that isn't going away.you don't have to like it but we shouldn't despise people who have an interest in something some government that forces it's ways on the rest of the world says we can't have.
But yeah nimgoldman's ongoing and current project which he was silly enough to photograph is a bit too blatant and right in everyone's face for this board.funny thing is if he re-worded it and left out the intended end compound ppl would be unafraid and glad to help.(knowing full well what nitropropene is being reduced with what amalgum). Maybe it's best if this thread is deleted
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monolithic
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[*] posted on 26-5-2019 at 07:02


It's probably not a good idea to take pictures of this. And if you are foolish enough to provide photographic evidence, it would be smart(er) to mask the background -- not a blur filter, as these can sometimes be reversed.

[Edited on 26-5-2019 by monolithic]
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S.C. Wack
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[*] posted on 26-5-2019 at 07:38


Conspiracy eh. One would think all the explosives talk here would be more interesting to the authorities. Did you know that there is a synthesis of amphetamine in the Journal of Chemical Education? Using P2P, ethanol, NH4OH, and Al/Hg? That sounds like a fun class.



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monolithic
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[*] posted on 26-5-2019 at 07:50


Quote: Originally posted by S.C. Wack  
Conspiracy eh. One would think all the explosives talk here would be more interesting to the authorities. Did you know that there is a synthesis of amphetamine in the Journal of Chemical Education? Using P2P, ethanol, NH4OH, and Al/Hg? That sounds like a fun class.


I believe you can legally make explosives (without a license or permit) if you use them immediately and do not transport or store them. That's not the case with scheduled drugs.
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S.C. Wack
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[*] posted on 26-5-2019 at 08:01


No one was killing US soldiers with amphetamine in Iraq. No terrorists are using meth in their bombs. Chlorate, on the other hand, I could tell exactly how to make 50 pounds of KClO3 for less than a dollar a pound in less than 6 hours, but would rather not.



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monolithic
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[*] posted on 26-5-2019 at 08:23


Quote: Originally posted by S.C. Wack  
No one was killing US soldiers with amphetamine in Iraq. No terrorists are using meth in their bombs. Chlorate, on the other hand, I could tell exactly how to make 50 pounds of KClO3 for less than a dollar a pound in less than 6 hours, but would rather not.


I agree with what you're saying, that we should be free to do whatever we want as long as it's not harming others. And like draculic acid69 mentioned, plenty of illegal shit goes on behind closed doors if you look at the most popular posts on this message board. Still, it's not a good idea to be so blunt about what you're doing, especially with pictures.
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[*] posted on 26-5-2019 at 13:42


And off to detritus. This is done now at the request of teh OP.
We aren't doing explicit drug cookery here. We do discuss chemistry. But this steps over the line.




If you are interested, take a look at the latest offering from sum_lab:
A primer on metals and non-metals with at least one novel experiment.
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[*] posted on 28-5-2019 at 23:49


Let me add one thing.

Some compounds have no general use in home chemistry or other hobby applications, and are specifically used to make illegal drugs (e.g. P2NP, as mentioned in this thread, or APAAN). Discussing the synthesis and use of that kind of compounds is not allowed on sciencemadness.

Other compounds, like red P, I2, acetic anhydride, methylamine, are quite basic compounds and in many countries there is no issue in obtaining them. These basic compounds have many other legit interesting uses in home chemistry and possibly in other hobbies as well. Discussing the synthesis and use of these compounds is allowed on sciencemadness.

[Edited on 29-5-19 by woelen]




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