what did i do wrong w/amalgamation

[dynamicduorr]

everything seemed as if it was going good for spiderman in his laboraotry during the amalgamation, bubbles from champagne size to furiuos bubbling and then he began dripping his ketone/nitro/methanol solution, the bubbling stopped and the mixture turned greenish grey.  after 2 hrs of stirring the mixture was a dark grey and still had a significant amount of uneffected alumminum. what did spiderman do wrong?

[Protium]

No one can help you if you don't post your ratio's and give someone a vague clue as to your procedure.  I can tell you offhand that the green color is generally a good sign that you fucked up, but you knew that.
Pr(+)tium

[GOD]

did swiy smell MeAm?  Was there ice-cold water flowin through the condensor?
Problem with the name? call me swig

[dynamicduorr]

i followed MM's, M&P's to a tee and i fail to see the error of my ways. the help would be greatly appr.

[GOD]

Same question, different bee:

You have to give details if'n you want help, we arent mind readers here.

What route did you take to ketone?
Did you clean it up first?
Did you do a bisulfite test (to make sure you had ketone)?
When you distilled the tone, what temp did it come over at?
What temp did the saf come over?
How did swiy (and for how long) store the tone before amination?
What was the source of the nitro? (was it straight, or did swiy separate it from a mix?  If so, how?
Did swiy use lab grade reactants?
Did swiy take any shortcuts?
Did swiy let it run full term?
Did he add heat?
What was the Al source?

Theres a million and one possible reasons why shit went wrong, no way of knowing unless swiy explains himself.
If your too lazy to give a description of what happened, why do you think anyones gonna put the effort into helping swiy out.
Problem with the name? call me swig

[dynamicduorr]

from the beginning
i used benzo waker oxi to get the ketone
everything was cleaned and acetone rinsed
no bisulfate test. didnt know about it (novice)
distillation of tone was done under vacuum using an
     aspirator came over at 180 cel
i distilled all of saf without vac 232 cel
tone was stored for a day in the freezer
nitro was distilled from rc fuel 101 cel
lab grade benzo, pdcl2, hgcl2
no shortcuts very patient it has taken me weeks to
       get this far
reaction was allowed to stir after addition for 8hrs
no heat added
extra heavy duty reynold wrap used. groune w/coffee grinder

sorry about not gigving detail, its just that i am frustrated because i can see the light but i'm not there yet. thanX

[Protium]

99% of the time that you run the amalgam and it fails, the reason is that you didn't have ketone, or at least enough ketone to gain an observable quantity of amine in your extractions.  I've heard the Al/Hg described before as newbee-proof.  Get yourself some proper thermometer readings and learn to use a nomograph to estimate temperature and take proper fractions.  Measure the boiling point as you distill under vacuum and collect the fraction you have calculated to be in line with the boiling point of the ketone.  If you want an alternative to this, although I wouldn't reccomend it, a bisulfite verification would do. You don't just follow the procedure to a "T" and it fails, as if you had followed the procedure correctly it would not have.  There is no magic chem-fairy that determines the success of your reaction, you do, so you need to know precisely what you are doing and what you have done if you expect any answers.

The best advice I can give you is to make sure that you have quality reagents, properly distilled precursors, and try not to sniff the solvents too much, as that has ruined many-a-good reaction

It's good to take notes along the way, that way you can go back and remember what you did wrong, or in some cases what you did right, or, you know, just what the hell it was you were doing before you passed out.

Pr(+)tium

[terbium]

It's good to take notes along the way, that way you can go back and remember what you did wrong, or in some cases what you did right, or, you know, just what the hell it was you were doing before you passed out.
And if you ever get raided the police and prosecutor will thank you for this too.


Baseline Does Not Exist.

[lab_bitch]

What color was your ketone?
How viscous was it?
Was there any safrole pre-run?  If so, how much?

Do you have any idea what pressure your aspirator pulls?  Take the temperature of boiling safrole to determine the pressure.  Be warned, though, that vacuum tends to decrease with the volitility of the solution as well as the hotplate setting and oilbath temp; even the condenser water temp.  There is a chart on Rhodium's page that gives the boiling point of safrole at various pressures.  This will give you at least a range of vacuum you might be pulling in.

Did you observe the violent reflux that results while adding the reactants?  How long did it take you to add the reactants?

Did you smell methylamine?
How small did you grind your foil?
Over what b.p. range did you distill your nitromethane?
With what degree of precision did you weigh out the HgCl2?  How much did you add?
Where did your methanol come from?
How long did the amalgamation take?

[Protium]

And if you ever get raided the police and prosecutor will thank you for this too.

Well in the event that you get raided by the police, chances are you're fucked anyway.  I'm just talking about the kind of lab procedure they teach kids in schools, it really does help, and by taking good notes you can often optimize the reaction conditions without doing a shred of math. 

Plus I always write in shorthand, but I suppose you could also print a disclaimer at the top of your stationary that says:

Never use the following fictional information without having the theoretical background, the practical experience, the proper equipment, and a valid permission. Any person caught breaking the law is subject to prosecution to the fullest extent of the law. Any accidents or legal problems are not the responsibility of this author.


Pr(+)tium

[wyndowlicker]

Theres so many things that could have happened you should answer all questions above and maybee just maybee some bee can help.
You can tell the queen of diamonds,by the way that she shines.-GD

[ketone]

If you live in the U.S., just having the chems and equipment is enough to be fucked royally....so who cares if you keep lab notes in shorthand, longhand, or on frickin' microfiche.

To the original poster: what makes you think you had ketone from the Wacker? That's where I'd concentrate my investigation first. Unfortunately, it can be hard to be sure you've got our favourite friend at first....but once you know what it's like, it's relatively easy to differentiate in future.

-ketone

[dynamicduorr]

the ketone was a greenish lemonade color. what is a safrole pre-run? the aspirator is connected to the sink. i dont know how much pressure it pulls. i'll check it tonight. yes i did smell meth. i used a shredder to shred the aluminum, then used a coffee grinder to grind it. i have to look at my notes to find the temperature for the nitro. i used an electronic scale for the hg. i distill my meth from the rc fuel. the amag.started after 1 minute. i left it stirring for 3 hours. there still was some aluminum pieces in there. the was one concern though, the hg did not dissolve completely.

[Rhodium]

what is a safrole pre-run?

Waxker oxidation of safrole never goes to 100% completion, and your reaction mixture will always contain safrole and isosafrole in addition to MDP2P. As safrole/isosafrole boils at a lower temperature than MDP2P, it is usually referred to as a forerun (pre-run is incorrect terminology).

the was one concern though, the hg did not dissolve completely.

Then you should use more solvent or less HgCl2, alternatively stir the mixture for a longer time and/or at a higher temperature. Any HgCl2 which doesn't dissolve won't be a part of the reaction anyway.

[dynamicduorr]

first of all, i would like to thank anyone who offers advice or criticism. it all helps in the end. forerun was not done. will do that tonight. will any hg work? are there any that is not reccomended?

[Rhodium]

Any soluble Hg salt will work, the more soluble it is the better (faster amalgamation, less losses).

[dynamicduorr]

There is a chart on Rhodium's page that gives the boiling point of safrole at various pressures. [orange]
where can i find this?

[Rhodium]

Third link from the top, "Distillation of safrole". Did you even bother to check?

https://www.thevespiary.org/rhodium/Rhodium/chemistry/safrole.distillation.html

[dynamicduorr]

thank you for the reply. yes, i did look, however what i found did not seem to be the one. there was something similiar on the link to wacker oxidation of safrole. i did not think that was it. it was after that, i posted my request.

[lab_bitch]

You must answer every one of my questions for me to be able to give you any help.

[dynamicduorr]

the ketone was a lemonade bright neon yellow color
during the reflux was flowing down to the reaction flask  continuously
there was no safrole prerun after the dcm came over there was no safrole that came over in the recieving flask.(Im so stupid to not remember that)
nitro came over at 101cel with no vac
electronic scale measured the hg and 200mg was added i didnt have the 2l flask yet so i was working in half batches from what methyl man recommended

[ketone]

Are you being a bit aggressive in your distillation, per chance? Write up how long the process is taking you, please.

Your description of ketone sounds reasonable, although it's hard to say for sure without seeing and smelling it.

-ketone

[lab_bitch]

If the rxn got violent like you say it did, then you either have two problems.  Either you did not have ketone, or you fucked up on the workup.  Did you perform the workup EXACTLY as methylman details?  If not, what did you do differently.  You say that their was constant reflux while adding the reactants.  Was it a constant stream (no drops).  If it was not, how fast was it dripping.  How strong was the MeAm smell a/f the rxn?  Your ketone couldn't possibly have all come over at 180; what was the range?  Determine the pressure of your vacuum using the method I detailed.  More than likely, you did not have ketone, and your problem lies with the wacker.  How much distillate did you collect while distilling the wacker product?  How much safrole did you use in the wacker?  Most aspirator pumps, in my opinion, are not powerfull enough to distill ketone.  Did the distillate freeze when you stored it in the freezer?  If it did, then you maily had safrole.  If so, your pump only pulls about 180 torr, and your ketone wouldn't come over until 220C, at which it will rapidly polymerize.  How much crap was left in the flask after distillation?  I suggest that instead of following MM's workup procedure, you basify it with 300-400g of 25% NaOH.  The aluminum should coagulate and crash to the bottom and you can filter it.  Then, neutralize the pH and strip off the methanol under vacuum.  Take the water/freebase that is left in the distilling flask and bring the pH up to about 12.  Extract this 3 times with about 50 mL of toluene.  Then perform a typical A/B extraction and strip off whatever solvent you collected the freebase in after the A/B.  Distill the freebase (20-30C higher than safrole) under vacuum and gas it.  This way, you can weigh the freebase b/f you gas it and know exactly how much you got.  Also, try to replace your aspirator with a real vacuum pump - preferably a refridgerator evacuation pump.

[Bubbleplate]

I noticed that there was only a faint Methylamine smell during workup. Turns out what I thought was pure Nitromethane - I distilled in from fuel like you - was only 50% pure. What % Nitro was the fuel you used? Did you dump everything prior to hitting 101 C.?
SWIM went and bought 99.99% Nitro instead and next time workup smelled like girls lockeroom tampon can...
Do yourself a big favor and buy a Vacuum pump! You can get a belt drive pump for $100 on auction and it will pull 1 micron vacuum all day long! SWIM gets his Ketone to come over at 105 C.

[ketone]

Another good thing for first timers is to make the darn MeAm rather than trying to do it in situ. It's not hard to make, and you can make it fairly damn pure....and the reagents aren't hard to get at all, even for lab grade.

I wouldn't trust ANYTHING I get from a hobby supply store For all you know, R/C car fuels might have all sorts of minimal added agents that could help inhibit the reaction, or cause side products.

-ketone

[wyndowlicker]

Think bigger than RC you might bee OK!
You can tell the queen of diamonds,by the way that she shines.-GD

[dynamicduorr]

i finally went out and got everything i needed. i got myself the much needed vacuum pump. im attempting to distill for the ketone as we speak. however, im having a problem. first of all the dcm came over around 60c. the safrole is coming over at 120 degrees. but for some reason it seems that while the safrole is coming over, something is crystalyzing in the vig column. i have the vig insulated with glass wool, i dont have any leaks, and im doing this under vacuum. the crystals seem to be the color of the safrole. i dont know if im doing anything wrong. im going to continue, if ive fucked up at least i will know where i messed up at. the saf. is still coming over. got to play the waiting game for now.

[hCiLdOdUeDn]

DCM should come over at 40C at normal pressures (1 ATM) and under vacuum it should come over at less then room temps.
Sink or SWIM

[dynamicduorr]

i think the crystalation was caused by the lack of sufficient insulation. i will redo everything.

[hCiLdOdUeDn]

safrole doesnt crystalize when you distill it...PERIOD
Sink or SWIM

[dynamicduorr]

do yo have any idea what it might be?

[hCiLdOdUeDn]

Ive never seen anything crystalize when heating it up e.g. distillin it. Because when you heat a substance it shouldnt crystalize. There are only a few compounds that have lower solubility in higher temps.

Its probably some kind of polymerized thing. most likely bunk sassy...
Sink or SWIM

[GOD]

quinone?
Loriel... because Im worth it!

[dynamicduorr]

well, im doing it over again. the dcm is coming over at about 42 degrees. well see.

[dynamicduorr]

well, i started doing Reductive Amination of MDP2P with Al/Hg + Nitromethane by Methyl Man. im using the recomended aluminum, the right amount of meth and everything else. last time i did this i had no problem with the aluminum dissolving. however this time, i must have done something wrong. the aluminum is not even bubbling up. the only differnce between this time and last time is the methenol. last time i distilled it from rc fuel while i was distilling nitromethane. this time i used methenol i bought from a company. also the hg that im using is not disolving completely. if that makes a diffierence i added more methenol as recomended by rhodium. however it is not dissolving completely. im using HgNH2Cl, i dont know if that makes a difference. maybe i need to crack a thermometer. if thats is the problem.