Author Topic: 1st time mdma success, kind of  (Read 3248 times)

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homeslice

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1st time mdma success, kind of
« on: January 04, 2004, 09:14:00 PM »
Swim yielded between 7-10 grams of salt from 25 grams of honey. Now to everyone else that looks bad but swims ecstatic  :)

But onto to the reason why... When swim was performing the amalgum, he used 900 mg's of Hg in a bottle of tincture. Many bees said this would work. Most said between 500-1000 mg's of hg and i guess it did work. But a strange thing happened... After the foil  hgi2 and meoh had been stirring about 5 minutes, there was no sign of bubbling. So swim let it stir off an on about another 5 minutes and let it sit about 3 more minutes. After 3 more he saw tiny bubbles and started his addition. Now MM calls for 5 minutes stir off and on, and when you see bubbles to start addition. Swim believes he may have waited too long to start the addition and that is why this happened... 30 minutes after the start of the addition there was no more reflux. 20  Minutes after the start he was done adding. Swim read many posts on the hive, especially by baalchemist, about the al/hg and learned that it should run really hot and drip at a rate of 2-3 drops per sec. And he did that... But why did the reflux stop at 30 minutes? Meoh was pouring out of the condenser at about 25 minutes and at 27 it was 1 drop a sec at 30 it was done and swim sat there and stared at the condenser like what the fuck?! Swim just let it stir then for 3 hours and the solution never really got thick. it never had a problem stirring and was water-like. It was grey with blue overtones, no green.

Swims thinking that maybe the 900mg of hg in the tincture was too much. He shook the bottle every day for 7 days. Oh by the way swim used 15 Ml's of the tincture, not the whole bottle. Maybe the excess of HgI2, dissolved the foil too much? Swim doesnt know?

Swims going to attempt it again maybe tomorrow or the next if swim gets some positive advice about this one.

EDIT: Total yield after drying 11.85 grams of the best roll swim ever ate.


Bond_DoubleBond

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swim has no experience with this reaction, but
« Reply #1 on: January 05, 2004, 02:38:00 AM »
swim has no experience with this reaction, but perhaps you should try charging the reaction mixture at the beginning with a few mls of meno2 and allow it to reduce a bit before the ketone/meno2 addition.  that way there is methylamine available to react as soon as ketone is introduced.  otherwise, if there is no methylamine avaible, the ketone will reduce instead of the desired imine, leaving you with an alcohol instead of amine.

Bond_DoubleBond

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one thing you might consider trying (if you...
« Reply #2 on: January 05, 2004, 03:43:00 AM »
one thing you might consider trying (if you have a three necked flask, claisen adapter, and two addition funnels) is adding the ketone/meoh separately from the meno2.  actually you wouldn't even need a claisen adapter if you didn't care about the reaction temperature and controlled the additions by visually juding the vigorousness of the reaction.  since it is desired that the meno2 be reduced first, begin the meno2 addition first and wait a period of time before starting the ketone addition.  this way, the meno2 can reduce to methylamine and will stay dissolved in the system.  you also might want to add a few mls meno2 extra to the actual amount called for in this method.  swim can see from rhodium's site that at least a 10% concentration of methylamine is attainable in methanol.  you could even add a little dh20 to increase the solubility of methylamine in the meoh/water azeotrope.  one would need to calculate in advance the desired drip rates (or at least be watching the exhaustion of the ketone,meno2 reagents to make sure the ketone finishs up just after the meno2 does).

the way swim sees it, if you make sure that there is always a good concentration of methylamine freebase in the reaction matrix (750mls of meoh can hold over 50g of meam), then your ketone molecules have a better chance of being aminated to an imine before being reduced by the aluminum, which is the desired reaction sequence.  in fact, now that swim thinks about it, he thinks that it might be desirable to allow as much as half of the the nitromethane to be introduced quickly into the reaction so that it may be reduced and the meam dissolved and trapped in the methanol.   

even if all of the nitromethane was reduced to methylamine and the entire supply of meam available for every drop of ketone addition, there would be 20ml meno2 x 1.13g/ml = 22.6g methylamine.  that's 22.6g meam per 25g ketone.  when swim does the osmium/brightstar al/hg (swim should say 'did', as he will no longer be using this method) there was 66.9g meam per 55.2g ketone.  that's a ratio of .904 mean/ketone (g/g) vs. a ratio of 1.21.  and, not only that, swim's reation took place in almost half of the amount of alcohol solvent.  this leads swim to believe that while the amount of nitromethane used in this reaction stoichiometricly leads to an excess of methylamine, it is not sufficient for the practical conditions of the reaction.  nitromethane is not a financially limiting reagent, and is safe when handled correctly.

swim plans to try the following reaction the next time he's fucking around.  this will be swim's first try at a nitromethane method and will be his last al/hg as well (for the purposes of honey at least).

swim will follow the methylman al/hg procedure (loosely) and will use all the same solvent/reagent amounts, but will use 2.5x more nitromethane and an arbitrarily greater amount of aluminum to account for the new multi-stepped reaction and the increase in reagents needing reducing.  swim will use the exact same reaction setup as methylman, will allow all of the of the nitromethane to be reduced first before adding ketone/meoh to the addition funnel and then start to drip ketone.  in fact, he might not even drip it, he might just let it flow straight through the addition funnel during a temporary high speed stirring of the reaction contents.  we'll see.  swim will probably also add about 100mls of water to increase methylamine solubility.  swim thinks what with a few little procedural tweaks, yield could be increased greatly, and at this scale, it would mean a big deal.

will post the results in a week or two.  :)

cublium

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even if all of the nitromethane was reduced to
« Reply #3 on: January 05, 2004, 10:34:00 AM »
even if all of the nitromethane was reduced to methylamine and the entire supply of meam available for every drop of ketone addition, there would be 20ml meno2 x 1.13g/ml = 22.6g methylamine.  that's 22.6g meam per 25g ketone.  when swim does the osmium/brightstar al/hg (swim should say 'did', as he will no longer be using this method) there was 66.9g meam per 55.2g ketone.  that's a ratio of .904 mean/ketone (g/g) vs. a ratio of 1.21.  and, not only that, swim's reation took place in almost half of the amount of alcohol solvent.  this leads swim to believe that while the amount of nitromethane used in this reaction stoichiometricly leads to an excess of methylamine, it is not sufficient for the practical conditions of the reaction.  nitromethane is not a financially limiting reagent, and is safe when handled correctly.
I don't think you got that right.22.6 grams of MeNO2 doesn't mean 22.6 grams of MeNH2 cuz some oxygens get lost which means it's less than 20 grams of MeNH2.That 66.9 grams to 55.2 ketone is of freebase methylamine but salt which has almost twice MW of freebase.Cub's thinks that red. amination with nitro also produces some amount of dimer of MDMA or whatever you call reduced intermediate of MDMA and ketone(PMK) because there's always little methylamine to take care of ketone and definitely not 3x excess.

Bond_DoubleBond

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cublium: you are right.
« Reply #4 on: January 05, 2004, 11:10:00 AM »
cublium:  you are right.  swim miscalculated the meam/ketone ratios.  the first total meam amount is 20ml x 1.13g/ml x (33g MeNH2 /63g MeNO2) = 11g.  the ratio would then be 11g meam per 25g ketone = 0.44.  the second total meam would be 66.9g salt x (33g MeNH2 fb / 70g MeNH2 salt) = 31.5g MeNH2 fb.  the second ratio would be 31.5g meam per 55.2g ketone = 0.57.

The first still trails the second by nearly the same percentage and the fact the nitro method takes place in twice the amount of alcohol still makes swim believe that the methylamine freebase concentration during this reaction could be improved upon.

homeslice

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HgI2 is the issue
« Reply #5 on: January 06, 2004, 01:48:00 AM »
First, search for baal's posts on the al/hg bond. He tries adding the nitro early and shows no increase in yields.

Post 206591

(Archaeoptrix: "Re: Project Blackbook", Methods Discourse)

When swim was preparing to try this 2 days ago, he just searched for what baal had to say, he knows his shit when it comes to the al/hg.

Swims looking to attempt this again in the next  2 days. Hes thinking about maybe using less HgI2 tincture fluid. Maybe half? 7.5ml?
Can someone comment on this? Did swim use too much hg? Swims hgi2 is the only variable that swim can pin point. Like the nitro weighed exactly so it was good. The mdp2p was good. Everything was good cept no hgcl2, just hgi2 from tincture, which works, but maybe 900mg was too much. Baal says he uses like 130mg hgcl2 in his alhg and he yields like 27g salt from 25g ketone. Any ideas on swims tincture? What should swim use?

A key point is that swims al/hg, after the addition had finished, never got thick at all. It was the same consistensy the entire time. Why? What would have caused this?

DeeM: swim waited for bubbles and it was extremely exothermic. The meoh was definately cloudly, almost to the point that he could not see the Al. Next time swim will stir for 5 minutes continuously. Let it sit a minute. Then begin the addition regardless of bubbles or not but will look for dull greyness of the Al.
Bond: Swim did add a lil extra dh2o, about 2-4 ml's. Definately nothing like 100ml's. Swim thinks this is a little overkill maybe?


Bond_DoubleBond

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swim's not talking about preloading the ...
« Reply #6 on: January 06, 2004, 11:12:00 AM »
swim's not talking about preloading the reaction mixture with meno2, he's talking about letting meno2 reduce to methylamine before any ketone is introduced.  if you start adding ketone at the same time as you start adding nitromethane, some of the initial ketone WILL reduce to an alcohol since it hasn't been aminated yet.  and since all literature says that an excess concentration of meam is necessary, swim believes that a lot of you are wasting a good many of those first drops of ketone that you add.

swim is still gonna try his altered mm al/hg.

homeslice

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Sorry then bond
« Reply #7 on: January 07, 2004, 03:28:00 AM »
My bad bond, i misunderstood. Yeah swims definately interested in your version and would like to see the results. Is your ketone prepared and all? How long are you estimating til your al/hg?


superman

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Bond_DoubleBond: i'd be interested to know if...
« Reply #8 on: January 18, 2004, 01:48:00 AM »
Bond_DoubleBond:  i'd be interested to know if you have any results to report, please keep us posted

Mercury

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You started the addition way too early
« Reply #9 on: January 18, 2004, 02:34:00 AM »
If you read the posts on using HgI2 in MM Al/Hg Reduction, you would have realized that HgI2 is not as soluble as HgCl2, and HgI2 requires more time to amalgamate the aluminum. From what I have read, HgI2 will require at least 30 minutes to turn the foil into a dull and less shiny form of its original self, and this is the magic moment that MM speaks of.

If I were you, I would not use HgI2 from a tincture bottle simply because you don't know exactly how much Iodine is in the tincture. If you have some Iodine laying around, then make the HgI2 yourself; it's very easy. Just mix elemental Mercury with Iodine, and presto, you get a very fine dark red crystal; it looks beautiful.

So, how much HgI2 do you need for a typical 25g ketone MM Al/Hg reduction? Simple, just do the math....

Hg 200.59
Cl 35.453
I 126.9045

This is for Al/Hg using HgCl2...
2(35.45)CL + (200.59)Hg = 400mg

M = .001473350768 (the number of moles you need)

Don't forget that for each Mercury you have 2 Iodines, so you need 2 moles of Iodine for every 1 mole of Mercury.

[373mg (I) + 295mg (Hg)]

So, you need exactly 669mg of HgI2 for a 25g ketone MM Al/Hg


SWIM ran a test amalgamation by scaling the reaction down to 1/4. No ketone was used. This was conducted for observing the behavior and time required for the amalgamation using HgI2, instead of HgCl2.

6.9g Al
187ml Methanol
167mg HgI2

The HgI2 was first dissolved in the methanol, then the solution was added to the flask containing the foil boils previously grinded in the coffee grinder. The flask was stirred every 5 minutes.

After 15 minutes, small bubbles are observed rising from the bottom of the solution. The aluminum is still shiny.

After 30 minutes, the bubbles have increased slightly, and the aluminum is beginning to lose it shiny appearance. The solution is grey.

After 45 minutes, all the aluminum has lost its shiny appearance and the solution is beginning to thicken, but only slightly. The flask is getting very warm. It is at this point that the addition should be started. It's the magic moment.

So I think it is safe to conclude that you started you addition too early. On your next run, simply wait a bit longer and see how your yield is affected. If your yields go up, then you'll know for sure.

terbium

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Mercuric iodide from iodine tincture.
« Reply #10 on: January 18, 2004, 04:55:00 AM »
If you read the posts on using HgI2 in MM Al/Hg Reduction, you would have realized that HgI2 is not as soluble as HgCl2, ...
Yes, but when mercuric iodide is made using tincture of iodine the potassium iodide that is used in the tincture to make the iodine soluble in water has the same effect on the mercuric iodide - increasing its solubility.

If I were you, I would not use HgI2 from a tincture bottle simply because you don't know exactly how much Iodine is in the tincture.
You don't know how much iodine is in the tincture?? Umm, doesn't it say so on the label on the bottle? It does where I live. This is not quantitative analysis, you don't need to know the amount of iodine to 4 significant figures. A small excess of mercury is fine because the presence of the KI that is in the tincture stabilizes the mercuric iodide relative to mercurous iodide.

If you have some Iodine laying around, then make the HgI2 yourself; it's very easy. Just mix elemental Mercury with Iodine, and presto, you get a very fine dark red crystal; it looks beautiful.
The tincture method is easy too and this gives you the added benefit of the KI to solubilize the mercuric iodide.


Mercury

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Why on earth would you want to introduce extra
« Reply #11 on: January 18, 2004, 09:50:00 AM »
Why on earth would you want to introduce extra iodine and pottasium iodide from the tincture into the reaction is something I don't understand. Hell, you might even introduce unreacted mercury.

Making HgI2 from tincture might be easy, but do you really want to wait around 1 week for all the mercury to dissolve? If accessible, just use the pure reagent. That's what this place has taught me.

terbium

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Mercury amalgam reagents.
« Reply #12 on: January 18, 2004, 06:47:00 PM »
Why on earth would you want to introduce extra iodine and pottasium iodide from the tincture into the reaction is something I don't understand.
Yes, your degree of understanding is very obvious. The reason for the potassium iodide was already explained to you. Try to pay attention. A trace of iodine is not going to hurt.

Hell, you might even introduce unreacted mercury.
Introducing metallic mercury, ehh? And what do you think happens to the mercuric salt when it amalgamtes with the aluminum - it is converted into metallic mercury. You had best have a purification procedure that will remove metallic mercury.

Making HgI2 from tincture might be easy, but do you really want to wait around 1 week for all the mercury to dissolve? If accessible, just use the pure reagent. That's what this place has taught me.
It is nice that you consider yourself an expert on this subject. At least that makes one person.


Mercury

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You're right, I wasn't paying attention.
« Reply #13 on: January 18, 2004, 07:23:00 PM »
You're right, I wasn't paying attention. I missed that in your post. I wasn't aware of the beneficial effect of potassium iodide in the reaction.

But I never said I was an expert!  :-[  But someone else reading this would probably think you're the expert! HAHA

homeslice

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Used HgI2
« Reply #14 on: January 18, 2004, 10:21:00 PM »
Swim didnt want to wait a week for the mercury to sit in the tincture so swim used HgI2. Swim used 650 mg of HgI2 and let it stir in the meoh for about 30 minutes before introducing the aluminum. Before adding the Aluminum, the water was a slightly yellowish pinkish color. Hard to describe, next amalgum swim will take a picture since he just got a nice camera  :)
After adding the Al and with some intermittent spins after about 7 minutes there were tiny bubbles followed by larger ones at around 10 minutes and this was when began his addition, swim added a little too fast and some meoh poured out his 400mm allihn, but thats a dfferent topic. End of the story is that swim got about 18 g's after the whole thing and was his best dream so far, prolly woulda been better if he watched his condenser better but now he knows what to look for.

From what swim reads from other bees, especially baal, its extremely important to add the tone in under 20 minutes like 3 drops a second and get the flask so hot that its very hot to the touch. Also swim layered his addition funnel nitro, meoh, then ketone. If they are added slowly on a slant they seperate fairly easily in the funnel. This was correct right? Like how fast swim added and the layering?
1 last question about gassing. Swim gassed and filtered a couple times and on his last gas the solution turned colors indicating no more honey and over acidification, i think. Now... there was a tiny bit of honey left in the beaker so swim decided to filter that solution by pouring it over the honey already in the buchner and filtered it through like he had been doing. He does this and most of his honey turned tan  :o
It didnt affect the rolls and after choppin it up its barely noticeable. Swim just was wondering, chemically why?
Of course next time swim will empty his buchner after ever filtration, he was just lazy last time heh.


baalchemist

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Baals' theory is that the fast refluxing MeOH...
« Reply #15 on: February 13, 2004, 03:20:00 PM »
Baals' theory is that the fast refluxing MeOH 'holds & re-introduces' the methylamine down in the reaction more effectively thus allowing it to readily react as its being produced, otherwise alot of MeAm gas is just pushed out the condenser top on a less vigorous run. Baal also dampens a piece of paper towel and 'lightly' plugs the condenser top to help hold back stray gasses. Another interesting tidbit Baal has noticed is that doing the addition thru the top of the condenser as opposed to a flask neck, gives a higher yield. That may be because the condenser is full of MeOH & MeAm and it all gets well mixed prior to hitting the Al/Hg. 100g's ++ of product from 100g's of ketone consistently in under 4 hours...........


Osmium

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> Baals' theory is that the fast refluxing...
« Reply #16 on: February 14, 2004, 12:01:00 AM »
> Baals' theory is that the fast refluxing MeOH 'holds & re-introduces' the
> methylamine down in the reaction more effectively thus allowing it to readily
> react as its being produced, otherwise alot of MeAm gas is just pushed out the
> condenser top on a less vigorous run.

Nice theory, but it's the other way round. The opposite is true.


hellman

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ahh,
« Reply #17 on: February 14, 2004, 01:30:00 AM »

baalchemist

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Osmium-clarify what you mean exactly by the...
« Reply #18 on: February 15, 2004, 09:10:00 AM »
Osmium-clarify what you mean exactly by the opposite is true. I may have not worded my point exactly true to what I meant(as I am no schooled chemist), but I know that I am correct in my initial statement as to what is happening inside my reaction setup. MeAm gas IS NOT escaping Baals setup, it is being flooded/saturated continuously with MeOH and falling back into the reaction. It is not traveling out of the condenser top because it is plugged. Or could it be the ever elusive Houdini MeAm that all the anal retentive schooled chemists speak of?


Rhodium

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Dangerous practice
« Reply #19 on: February 15, 2004, 06:49:00 PM »
What he is saying is that the harder the boil, the more MeNH2 will escape through the top of the condenser. Performing the reaction in a closed system by plugging the top of the condenser is dangerous, and may lead to explosions.