Author Topic: 3-base distillation temperatures  (Read 907 times)

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raffike

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3-base distillation temperatures
« on: June 09, 2003, 01:46:00 PM »
Raf thought he should start distilling his freebases.He does 50-60 grams of ketone in a run and has 10 mm pump MDP2P coming over 155 C or so.If post-rx mix is basified and alcohol layer sepped off,he thought he should evap alcohol and distill without ab'ing.Is there any problems with decomposition of freebase or freebase reacting with impurities in distilling flask at 160 C or so.Distillation sounds like a good idea,raf just wants to make sure.


LaBTop

  • Guest
Always A/B
« Reply #1 on: June 09, 2003, 03:43:00 PM »
The Acid/Base wash procedure should be standard procedure. Yes, I know I had some minor misunderstandings in the past with Osmium, wether or not you need to A/B, but some strange experiences in the past let me step in his camp.
If sometime raw MDMA freebase was directly distilled by non-chemists and not A/B'ed, the consumer felt a very nasty feeling in his legs for several hours, as if one couldn't stand.
When the raw freebase was A/B'ed first, then distilled by them, no side effects anymore!
(prolly caused by greed, no 5% distillate forerun and 5% postrun discarding)

SO A/B !!!  LT/


Rhodium

  • Guest
Wise desicion, if just everybody thought like you
« Reply #2 on: June 09, 2003, 03:50:00 PM »
You should definitely A/B before distilling the freebase, not only to avoid the risk of the freebase reacting with the byproducts at elevated temperatures, but also to increase the purity of your freebase - for example, the bp of MDP2Pol is not far from that of MDMA.

Also collect your non-polar washes from that A/B extraction, after recycling the solvent you can vacuum distill the MDP2Pol (the major component in that mix), oxidize that to MDP2P and re-use it.

raffike

  • Guest
Ok,new plan for post Al/Hg: 1)Basifiying 2)Sep
« Reply #3 on: June 10, 2003, 12:20:00 AM »
Ok,new plan for post Al/Hg:
1)Basifiying
2)Sep off alcohol layer and dump aqueous(Ritter said there no product locked up there)
3)Add xylene to water layer and then some water to get 2 layers(alcohol/water layer and xylene/FB)
4)Sep of xylene layer and dump alcoholic layer(guess it's not worth washing either,i can't see how there can be some FB "locked up")
5)Wash xylene layer twice with 200 mls of 5% HCl solution.
6)Pour reddish water washes to sep funnel and add some strong NaOH solution so that pH of mix is 12 or so.
7)Freebase floats on water(is water layer worth washing with some NP?maybe now there's some FB locked up as there's a lot of water and only about 40 grams of freebase)and is sepped of and distilled once at 10 mm.
8)Freebase is soluted in alcohol and titrated to pH 6 with HCl acid.
PS Raf isn't afraid of distilling small amounts,he once decided to redistill his once distilled ketone that weighed 44 grams.Distillation gave 36,5 grams of purer MDP2P and there was some fluid left in distillation so we could safely say that one doesn't lose more than 2-3 grams of product but he sure loses impurities.Raf used 1 liter RB as distillation flask and 1 liter RB for receiving flask.


Rhodium

  • Guest
advice
« Reply #4 on: June 10, 2003, 05:43:00 AM »
2)Sep off alcohol layer and dump aqueous(Ritter said there no product locked up there)

Where did he say that, and which alcohol did he refer to?

3)Add xylene to water layer and then some water to get 2 layers(alcohol/water layer and xylene/FB)

Didn't you dump that layer? And if you suggest to extract alcohol with xylene, I'm not sure that will work good, add lots of water or even better - evaporate most alcohol under vacuum.

4)Sep of xylene layer and dump alcoholic layer(guess it's not worth washing either,i can't see how there can be some FB "locked up")

Most definitely extract at least once more with xylene.

7)Freebase floats on water(is water layer worth washing with some NP?

Most definitely extract 1-2 times with xylene here, then dry the solution over magnesium sulfate or equivalent before distilling.

8)Freebase is soluted in alcohol and titrated to pH 6 with HCl acid.

How do you suggest to isolate the MDMA.HCl from this alcoholic solution? If you are just going to evaporate it, then you need to recrystalize it before you are done to remove impurities.

raffike

  • Guest
Where did he say that, and which alcohol did...
« Reply #5 on: June 10, 2003, 06:51:00 AM »
Where did he say that, and which alcohol did he refer to?

https://www.thevespiary.org/rhodium/Rhodium/chemistry/ritter-alhg.html


"Mix up about 1.5 or 2 liters of 35% NaOH solution and allow to cool. Slowly add the gray aluminum gook produced in the first reaction to the NaOH solution and pour into a large separatory funnel. Two distinct layers will appear after sitting for maybe an hour, the top being a reddish alcoholic solution of product and the bottom garbage NaOH/Al(OH)3. Simply separate off the garbage bottom layer and discard. Don’t worry, there’s no product tied up in it...
Didn't you dump that layer? And if you suggest to extract alcohol with xylene, I'm not sure that will work good, add lots of water or even better - evaporate most alcohol under vacuum.
Yup,didn't notice that mistake.It should have read "add xylene to alcohol layer and add some water.
I'm not sure that will work good
In raf experience it does,alcohol and water form their own layer.
How do you suggest to isolate the MDMA.HCl from this alcoholic solution? If you are just going to evaporate it, then you need to recrystalize it before you are done to remove impurities.
Raf thinks distillation and following acetone wash removes most of em.Raf will probably try gassing or titrating freebase in acetone.With impure freebase gassing was difficult as it oiled out,maybe with purer freebase it works.
Most definitely extract 1-2 times with xylene here, then dry the solution over magnesium sulfate or equivalent before distilling
Why dry?BP difference between water and freebase is nearly 200 C,i don't think it will interfere with distillation procedure.


Rhodium

  • Guest
More advice, just trust uncle Rhodium
« Reply #6 on: June 10, 2003, 05:03:00 PM »
First, Ritter is referring to the solid grey sludge not holding any product, any water/alcohol above it should be processed.

In raf experience it does,alcohol and water form their own layer.

But you did not mention any water added, just alcohol (and you didn't specify *which* alcohol).

Raf thinks distillation and following acetone wash removes most of em.

Yes, but new ones form as you are treating the freebase with acid, just watch the colors - if it isn't water-white and clear, you have impurities which should be removed. Take pride in the purest possible product!

With impure freebase gassing was difficult as it oiled out,maybe with purer freebase it works.

Most certainly, make sure you have dry solvents and use 10x the volume of solvent to freebase (madmax has written good posts on this).

Why dry?BP difference between water and freebase is nearly 200 C,i don't think it will interfere with distillation procedure.

Post 439125

(hypo: "because water sucks", Newbee Forum)

raffike

  • Guest
Mhh...raf never had any problems distiling wet
« Reply #7 on: June 10, 2003, 10:33:00 PM »
Mhh...raf never had any problems distiling wet stuff.Try to dry post hydrolysis MDP2P/polymer goop :) .
But you did not mention any water added, just alcohol (and you didn't specify *which* alcohol).
We are still talking about that upper alcoholic layer that forms when base is added to post rxmix.
First, Ritter is referring to the solid grey sludge not holding any product, any water/alcohol above it should be processed.
Aluminium sludge stays suspended in water layer making it uniformly grey,i doesn't form sediment in sep funnel at least in my experience.


Rhodium

  • Guest
You confuse me... Which merits has your procedure?
« Reply #8 on: June 16, 2003, 06:12:00 PM »
Mhh...raf never had any problems distiling wet stuff.Try to dry post hydrolysis MDP2P/polymer goop

Works if you dilute it with a np solvent, then dry. But in the case of that goop, water is less of an issue, as MDP2P and its impurities does not steam distill, as opposed to MDMA freebase, and if that happens there are usually no "problems" occurring, as in small catastrophes happening, but you get a less pure product as you will get less fraction separation...

But you did not mention any water added, just alcohol (and you didn't specify *which* alcohol).
We are still talking about that upper alcoholic layer that forms when base is added to post rxmix.

That happens without any base added if you use IPA, and it happens with difficulty if you use methanol. The specific alcohol matters. If you add as much NaOH as to dissolve the aluminum hydroxide/oxides in the aqueous layer, then you are close to pH 14, and the MDMA becomes very labile and easily begin to decompose, especially if it gets hotter than room temp (no heat when removing the alcohol, only vacuum!).

Aluminium sludge stays suspended in water layer making it uniformly grey,i doesn't form sediment in sep funnel at least in my experience.

Why are you pouring it into your sep funnel? When the reductive amination is over, the best way is to filter off the aluminum over celite or similar, then evaporate the alcohol (alternatively distill it and recover the excess methylamine which co-distills), dissolve the residue in acidic water, wash with np, basify, extract with np, wash the np with brine (to pre-dry), then dry over MgSO4 or similar, evaporate the solvent and finally vacuum distill the freebase.

runne

  • Guest
Basifying question?
« Reply #9 on: June 16, 2003, 06:24:00 PM »
Rhodium,

"That happens without any base added if you use IPA, and it happens with difficulty if you use methanol. The specific alcohol matters. If you add as much NaOH as to dissolve the aluminum hydroxide/oxides in the aqueous layer, then you are close to pH 14, and the MDMA becomes very labile and easily begin to decompose, especially if it gets hotter than room temp (no heat when removing the alcohol, only vacuum!). "

This is the first I've read that we must be careful to not go that high in PH. What is a "safe" range then? It's great not to deal with the aluminum, but SWIM would rather deal with it than have a reduction in quality/yield.

And to clarify:
1) The end reaction should be basic in a standard MM Al/Hg?
2) The added base is to help separate the layers and reduce the "aluminum crud" in the solution?

Therefore - Bee's should only add as much NaOH solution as needed to separate layers in workup? The MDMA is already an oil so the NaOH is not doing anything to the product we want, just adjusting other things in the solution?

Runne

Rhodium

  • Guest
pH 14 at room temp for short periods is okay...
« Reply #10 on: June 16, 2003, 06:54:00 PM »
pH 14 at room temp for short periods is okay if necessary, but you WILL see decomposition if you heat it (as in trying to boil off any alcohol), red tars forming and your yield drops like a countdown timer...

I'd say that pH 11 is always safe with our most common compounds, but I wouldn't be scared of pH 12 either - but why go higher than required for the MDMA to become a freebase and/or the Al/Hg reaction running at a reasonable speed (as in a gentle reflux at most, forced wild boiling is unnecessary and stupid).

1) The end reaction should be basic in a standard MM Al/Hg?

Yes, It's basic as is, because of the rxn: Al + 3 H2O => Al3+ + 3 OH- + 3 H2

2) The added base is to help separate the layers and reduce the "aluminum crud" in the solution?

Yes, to decompose all traces of residual Al metal, to turn any formed Al2O3 to Al(OH)3 (more granular, easier to filter) and increasing the ionic strength of the aqueous solution (making the alcohol separate).

Therefore - Bee's should only add as much NaOH solution as needed to separate layers in workup?

Yes, pretty much so in my opinion. There are a lot of people doing other things, but their strategy is more based on a desire to skip steps and take short-cuts than to increase the purity and yield of the product.

The MDMA is already an oil so the NaOH is not doing anything to the product we want, just adjusting other things in the solution?

Yes, exactly. Addition of more than 2 mL of 25% NaOH to the reaction mixture for every gram MDP2P you begun with is really unnecessary.

The Al/Hg procedures on my page for making Meth from P2P

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p-meth.html) are identical to what would be used if making MDMA, just use 1.35 times the weight of MDP2P than P2P in those examples (to compensate for the higher molecular weight of MDP2P) - other than that change nothing. Note that the procedures differ pretty much when it comes to small details, but all the important things are kept the same - illustrating that you can be flexible in SOME places, but not in others, you need to know what is critical or not.