(Hive Bee)
11-23-02 07:09
No 382493
(Rated as: excellent)
Here’s my virtually foolproof method to process hundreds of grams of ketone via al/hg using nitromethane in 1 day, and more importantly never fails.
The procedure is to reduce the nitromethane to methylamine in a methanol solution, recover the methylamine/methanol from the sludge, and use the recovered methylamine laden methanol to process a large amount of ketone with a small amount of aluminium.
The beauty of this method is that nitromethane can be used to make heaps of methylamine in a lot less time than making it from hexamine or formaldehyde, with a lot less hassle IMHO.
Reaction
There are two reaction equations that explain the al/hg using nitromethane as follows:
Hydroxide Mechanism
2 Al + 6 H2O > 2 Al(OH)3 + 6 H
6 H + CH3NO2 > CH3NH2 + 2 H2O
2 Al + 4 H2O + CH3NO2 > CH3NH2 + 2 Al(OH)3
Which means 4 moles of water and 2 moles aluminium are needed with every mole nitromethane for that to be converted to methylamine. This reaction occurs when sufficient water is present and is very exothermic.
Oxide Mechanism
2 Al + 3 H2O > Al2O3 + 6 H
6 H + CH3NO2 > CH3NH2 + 2 H2O
2 Al + H2O + CH3N02 > CH3NH2 + Al2O3
Which means only 1 mole of water is required for every mole nitromethane to produce the methylamine.
My experimental observations seem to confirm both equations seem to work depending on how much water is in the reaction.
However I believe that the reduction of the ketone via imine to the amine is via the hydroxide mechanism as follows:
Methylamine Mechanism
Reaction Between Ketone And Methylamine
3 Ketone + 3 Methylamine > 3 Imine + 3 Water
Now the imine is reduced to the amine only by the hydroxide mechanisms as follows;
Hydroxide Mechanism
6 H2O + 2 Al > 6 H + 2 Al(OH)3
6 H + 3 Imine > 3 MDMA
3 R2CO + 3 CH3NH2 + 2 Al + 3 H2O > 3 R 2CHNHCH3 + 2 Al(OH)3
Which requires 1 mole water per mole ketone.
This is consistent with the typical MM type reaction because the “heet” that he used had enough water in it for the oxide and hydroxide mechanism reductions of the nitromethane as well as the methylamine.
Scaling up the MM type reaction is very unpractical and prone to failures in my experience.
The best way for a larger scale al/hg using nitromethane as the methylamine source is to make the methylamine separately and then carry out the al/hg with ketone as follows:
Stage 1: Making Methylamine In Methanol Using Nitromethane And Al/Hg
Processing 1 mole of ketone will require 2.5-3 moles methylamine dissolved in methanol as follows:
Procedure
Cut 162g aluminium flashing into small squares and place in a 2 neck 2L, or ideally 3L flask with 1500mls methanol and add 0.5g HgCl to amalgamate. Let amalgamate for 5 –10 minutes.
Mix 54mls water with 183g (162mls) nitromethane in addition funnel and add 100mls methanol to form a solution.
Then pour in about 30mls of this nitromethane mixture into the reaction flask and let it heat up until refluxing.
This will cause a vigorous reflux, then slowly drip the remaining nitromethane mixture in until it is all gone, this will take about 30 minutes or more.
Ideally place a hose from the reflux condenser to a 10-30% HCL bubbler solution to stop escaping methylamine gas from stinking the lab out.
Stirring isn’t really needed, just occasionally swirl the flask by hand to help break up the aluminium sludge.
Let reflux for about an hour until the reaction cools and reflux stops. Then add 200ml cooled 50% NaOH solution. This will start another vigorous reflux for an hour or so.
NB: The NaOH helps finish the reaction, breaks up the aluminium sludge and then forces the methylamine gas out on heating.
When reflux stops, change the glassware setup for distillation. Place hose from vacuum outlet on the bent receiver to HCL bubbler to again stop lost methylamine gas from stinking your lab out. Care should be taken to stop any suck backs.
Turn on the hotplate and distil the methanol with methylamine from the reaction flask until the stillhead thermometer reads around 80-90DegC. This ensures all of the methylamine and methanol has been recovered and there should be around 1400ml in the receiving flask with a small amount of elemental mercury at the bottom.
Don’t heat until completely dry as the sludge will heat up and smoke.
Wash the hardened sludge residue from the distillation flask with warm water.
The distilled methanol should now contain enough methylamine to animate well over 1 mole Ketone.
Ideally titrate a small sample of methanol/methylamine solution to neutral with 10% HCL to work out exactly how much methylamine is recovered.
I normally find I get a 6% methylamine solution. This means I have almost 3 moles methylamine recovered in the methanol, which is perfect for the next step.
Time to this stage is around 5 hours.
Stage 2: Animating 1 Mole Ketone
Use your favorite aluminium foil or flashing. Foil will react faster and probably won’t need external heat to kick-start the reaction.
Cut 30-40g aluminium into small squares (for 0.3mm thick flashing) and place in a 2L flask.
Mix 0.1-0.2g HgCl with 100 mls clean methanol and then add this to the flask containing the aluminium to amalgamate.
Then pour in the recovered 1400mls 6% methylamine methanol solution from the previous step, add 178g ketone, and 30mls water and stir.
If using thicker aluminium use external heat to bring to reaction to reflux.
Magnetic stir bar stirring works very well as there is a very low amount of aluminium and sludge to deal with and quite a bit of solvent.
Let reflux for 3 hours (using sheet aluminium) with gentle external heat when needed and magnetic stir bar stirring.
NB: If using thin foil, the reaction should proceed much faster.
Extraction And Acid Base Wash
Remove the leftover aluminium by pouring the methanol/sludge through a sieve.
Then filter the methanol/sludge/product solution through a Buchner funnel.
Scrape out the filter cake into a container, basify with 1L 30% NaOH and add 1L Xylene or Toluene, add to separating funnel and extract the left over product into the non polar layer then remove the bottom aqueous layer when the layers separate. Set this first non-polar extraction aside.
Distill most of the filtered methanol solution away until 2 layers form then add 200mls 10% NaOH, then add the first non-polar extraction (xylene or toluene) extraction into the flask to dissolve the rest of the MDMA and pour back into the separating funnel.
Separate the NaOH layer from the xylene or toluene in the separating funnel.
Wash this toluene or xylene with 100mls 10% NaOH once or twice and remove bottom wash layers.
Add 1L 5-10% HCL to the separating funnel and shake. This extracts the MDMA into the HCL solution. Separate and extract non polar once more with 100mls water.
Combine HCL extractions back into the cleaned separating funnel and slowly basify with 10% NaOH solution until MDMA falls to the bottom of the separating funnel and pH >11
Yield of raw MDMA base usually around 160g.
Extract MDMA with 200ml DCM washes and combine.
Time to this stage is around 10-12 hours.
Then, strip of DCM, water, and vacuum distill the freebase to be left with very pure MDMA base.
Yield of distilled freebase is around 135g, which is molar yield of 70%.
Crystallize using your method of choice.
I prefer to dissolve the distilled MDMA freebase in 4 times the volume of acetone and gas without any need for drying with magnesium sulphate. Then the gassed and filtered MDMA.HCL is re-crystallized from an equal weight of boiling ethanol.
Abacus
(Chief Bee)
11-23-02 07:19
No 382496
Don't take this as critizism, but have you investigated where the other 30% of your ketone went?
It seems very strange to me that you have 160g of raw freebase (amine, as it went through an acid-base extraction), but only isolate 135g pure MDMA. Is there 25g of polymerized goo left in your distillation flask? How strong is your vacuum?
(Hive Bee)
11-23-02 07:31
No 382500
Only get about 80-85% yeild MDMA from ketone and who knows where rest of ketone goes.
Then when distilling freebase get around 83% of starting raw MDMA. I recently found I was letting my oil bath temperature getting too high with a crap vacuum source seemingly "burning" the base when distilling and I hope to improve distilling yield in the future.
I admit I need a better vacuum source as I use a water aspirator @ 20mmHG which is marginal for freebase distillation, comes over at 165DegC.
BTW over all yield from 1 kilo sassafrass is 475g MDMA.HCL after crap vacuum distillation AND recrystallising so I don't complain really.
EDit: But I think the "kilos" i purchase may be a bit big coz I end up with 1050mls Isosafrole from them and after checking notes I got 550g MDMA.HCL from the last one after vacuum distillation of freebase, gassing in acetone AND recrystalling (twice) in ethanol.
Abacus
(Hive Bee)
11-23-02 07:42
No 382505
Very descriptive, thank you.
>>Scrape out the filter cake into a container, basify with 1L 30% NaOH and add 1L Xylene
>>or Toluene, add to separating funnel and extract the left over product into the non polar
>>layer then remove the bottom aqueous layer when the layers separate. Set this first
>>non-polar extraction aside.
I may be reading this wrong, but are you saying to basify the filter cake?? I may be reading this wrong..
(Chief Bee)
11-23-02 07:47
No 382507
Of course not, you're doing a great job! But I just become so curious when reading detailed writeups like this, I always feel a drive to optimize every reaction I come across, even if it takes me half a day to optimize something from 85 to 95% and the savings just amounts to 5-10 bucks, I still do it.
(Hive Bee)
11-23-02 07:58
No 382511
Bling
Do what you read. There is quite a bit of product trapped in the filter cake. I found its up to 20-30g.
You can either boil the sludge up with more methanol to extract it OR do as I do which is basify the sludge and extract that 20-30g into non polar as I said.
Abacus
(Hive Bee)
11-23-02 08:07
No 382516
This is different, and sounds like fun. Do you actually witness the mdma freebase oil drop out of the aq. layer in the step below?!
>>Combine HCL extractions back into the cleaned separating funnel and slowly basify with
>>10% NaOH solution until MDMA falls to the bottom of the separating funnel and pH >11
If it wasn't saturday night, I'd be half way to the bat cave right now. :p
This method of isolating the freebase oil is very interesting and sounds like a big time saver!
(Hive Bee)
11-23-02 09:13
No 382530
I don't mean to "knit pick" but the reaction mechanism looks a little different, I believe.
The production of aluminum hydroxide (a biproduct):
Hg++
4Al + 12H2O -----> 4Al(OH)3 + 2H2 + 8H+ + 8e-*
*The reality is that a great deal of that "H+" will become H2(g). I placed some of that in there. It's just a guess. I'm leaving out the production of H2(g) in future equations and won't try to account for electrons. I don't know the status of the electronegativity in the reaction environment or how much H+ ion (simply free electrons and protons) is actually available. I don't know. I probably wouldn't understand ther math if there was some so I'm not going to mention it.
It is in this environment that reductions occur. In organic chemistry a reduction is the addition of hydrogen or the removal of oxygen. That doesn't really apply above but I want to focus on the reduction of three (3) reactants (all organic). The ketone (3,4-Methylenedioxyphenyl-2-prpanone), nitromethane and the intermediary imine.
The reduction of the nitromethane and ketone occurs in the reaction environment created by the oxidation shown above, so we pick up there:
4Al(OH)3 + 6H+ + CH3NO2 -----> CH3NH 2 + 2H2O*
*I'm cutting out several imtermediary steps. I was also not real careful to balence anything. Sorry
!In much the same way:
2Al(OH)3 + 6H+ + CH2O2C6H5CH2COCH3 -----> CH2O2C6H5CH2CH(NCH3)CH3+ + H2O
Reduction of imine to amine:
2Al(OH)3 + CH2O2C6H5CH2CH(NCH3)CH3+ +3H+ -----> MDMA
Correct me if I'm wrong but the reaction mechanism, though ol' Moriarty took the shortcuts, looks more like that than it did in the first post. I am only posting so that we may all better understand the process. I probably made errors and hope some smarter bee will correct me but a deaper understanding is what I desire and I believe we all need. So, was that shortcut description accurate? Let a bee know if you are in the know and have the time. Thanks
!By the way, I don't believe Al2O3 is ever created in the amalgamation. That offends my understanding of the reaction.
Who wants to play cops and dope fiends?
(Hive Bee)
11-23-02 10:09
No 382541
You should really go back and balance those equations Moriarty. I share your opinion that the Al2O3 is not formed, but I also see no evidence of the hydroxide sludge playing any significant role in the reaction, as you said, it is a byproduct. The way your equations are laid out are rather confusing on this point. Even if the co-efficients of the equations are not balanced out, you should at least reflect the same molecules on both sides of the equation, or it won't be too good for illustrating the reaction.
I believe we all had a rather tiresome debate on this issue a couple of weeks back, I won't bother to link the thread but you can pull it up.
Pr(+)tium
(Hive Bee)
11-23-02 10:36
No 382544
I studied that debate and many others. I have spent almost 2 kilos ketone, and 3 months of experiments, and many hours trying to work out the water, oxide, hydroxide etc issues to finally end up with this procedure that works for me every single time.
Maybe the oxide isn't formed and all the water does is help the aluminium break down.
I know for a fact that when no water is present the aluminium swells up to fill the flask and when the right molar amount is present for the hydroxide pathway, the hydroxide sludge fills the solvent stopping the reaction half way anyway giving crap yields of methylamine.
I believe the nitro "burns" the alumninium giving the oxide as the by product, then if heaps water is present this converts to the hydroxide (as some oxides do in the presence of water)
In any case, I don't care about the process and feel free to correct my chemistry, but I point out that this works for me every single time.
All I care about is the end result and this works for me.
Abacus
(Hive Bee)
11-23-02 10:43
No 382546
Tonight, it's late brother. Moriarty's tired. You very well might see me do just that (balence those equations) tomorrow in this post. I know I laid it out in a fairly confused manner. I kept picking up each reduction at Al(OH)3 becuase I wanted to write between the margins, so to speak. What I was trying to accomplish was to bring the reader back to the original inorganic oxidation that makes the reductions occur (there are more than one). This is redox. An oxidation occurs and that creates a reduction. So, if I had done a better job, I'd of included every reactant in the reaction and simply showed the progression, line-by-line. This I did not do for two (2) reasons. One, my chem is rusty and I didn't want to risk making embarrassing mistakes. Two, that would have taken several lines. If I showed everything that happens, I would have lost the ability to clearly show (detracted from the reactions I wanted to talk about) the reductions of each reactant as they occur because they might have been lost in the "mess" somewhere. In truth, I was just lazy but legitimately didn't want to focus on anything but the reductions and their cause. I know I confused it but just go back to the right side of the reaction between Al and H2O and that's where I was hoping you'd pick up. In reality, most use methanol and that's a whole different deal. Sorry if that was confusing. Pick it up at the right of the amalgamation and that will better illustrate my ill-conceived point. I'll fix it tomorrow.
By the way, I'm glad people (referring to the chemist who started this thread) help to refine the process. Not a great deal of refined chemical equations are necessary to really explain that and I respect that for what it is. You get results, and help others to get results by sharing your experiences, and that's cool. I just want us to all understand it better. I include myself in that, of course, as my post was more of a question than an answer. Thanks for the reaction details. Let's break this reaction down with methanol tomorrow. Cool?
Oh, yeah, as for Al2O3 being created, absolutely not! Maybe very small amounts but I think not! Not that the old Brightstar write up is gospel but the chemistry behind it is solid and he notes that the Al2O3 that coats the Al foil is destroyed in the amalgamation and it is inferred that it must occur first for the mercuric chloride to coat the foil and foster proper amalgamation rates. I don't want to get into that old thread discussion but there are a series of reasons why aluminum oxide is not created. It's not. Period.
P.S. Mods: Sorry if I lead this thread off point but I believe my post has intrinsic value. I hope you agree.
Who wants to play cops and dope fiends?
(Old P2P Cook)
11-24-02 19:25
No 382854
Correct me if I'm wrong but the reaction mechanism, though ol' Moriarty took the shortcuts, looks more like that than it did in the first post.
Yes, your description is confused to say the least.
I am only posting so that we may all better understand the process.
You certainly didn't achieve this.
I probably made errors and hope some smarter bee will correct me but a deaper understanding is what I desire and I believe we all need.
Then read Abacus' description in the first post in this thread or:
Post 348175 (terbium: "Aluminum reductant stoichiometry.", Chemistry Discourse)
Post 348185 (terbium: "Imine/Aluminum reduction stoichiometry.", Chemistry Discourse)
Baseline Does Not Exist.
(Old P2P Cook)
11-24-02 19:39
No 382859
Tonight, it's late brother. Moriarty's tired.
OK.
You very well might see me do just that (balence those equations) tomorrow in this post.
It has already been done, by Abacus in the first post in this thread and by me in an earlier thread.
I know I laid it out in a fairly confused manner. I kept picking up each reduction at Al(OH)3 becuase I wanted to write between the margins, so to speak. What I was trying to accomplish was to bring the reader back to the original inorganic oxidation that makes the reductions occur (there are more than one). This is redox. An oxidation occurs and that creates a reduction.
Yes, we know what "redox" means. Still, all you seem to be doing is confusing things with lots of words.
So, if I had done a better job, I'd of included every reactant in the reaction and simply showed the progression, line-by-line.
Abacus and I have already done this.
This I did not do for two (2) reasons. One, my chem is rusty and I didn't want to risk making embarrassing mistakes. Two, that would have taken several lines. If I showed everything that happens, I would have lost the ability to clearly show (detracted from the reactions I wanted to talk about) the reductions of each reactant as they occur because they might have been lost in the "mess" somewhere.
Both Abacus and I have clearly shown all the details without any loss of clarity.
In truth, I was just lazy but legitimately didn't want to focus on anything but the reductions and their cause. I know I confused it but just go back to the right side of the reaction between Al and H2O and that's where I was hoping you'd pick up.
Yes.
In reality, most use methanol and that's a whole different deal. Sorry if that was confusing. Pick it up at the right of the amalgamation and that will better illustrate my ill-conceived point.
Yes, you are confused again.
Let's break this reaction down with methanol tomorrow. Cool?
Abacus and I have already done that.
Oh, yeah, as for Al2O3 being created, absolutely not! Maybe very small amounts but I think not! Not that the old Brightstar write up is gospel but the chemistry behind it is solid and he notes that the Al2O3 that coats the Al foil is destroyed in the amalgamation and it is inferred that it must occur first for the mercuric chloride to coat the foil and foster proper amalgamation rates. I don't want to get into that old thread discussion but there are a series of reasons why aluminum oxide is not created. It's not. Period.
Yes, you shouldn't get into this discussion because you are confused again.
Baseline Does Not Exist.
(Stoni's sexual toy)
11-25-02 11:42
No 383107
Finally someone is doing this MeNO2 prereduction.
You can reuse the post-reduction solvent too, after distillation. I always kept and reused the rotovapped EtOH solvent which I used, it contained a lot of MenH2 according to its smell, even though it was distilled under vacuum.
Thank for the writeup abacus. I'm glad people are finally realising how well this reaction works. Since the MeOH/MeNH2 mixture is distilled you can use RC fuel bought OTC without cleaning it up! A great simplification for many of the bees!
Only thing I don't quite like yet is the relatively small amount of water you add to the amination reaction, and the relatively big solvent volume of ~1400ml for 1 mole of ketone. 30-40g Al is roughly 1-1.5 moles, so you should have 3 times (1-1.5) moles of water present. I used 94% azeotropical EtOH as the solvent, and added the MeNH2 as a 40% solution in water, so there was quite a bit more water present in my case and the results were still excellent yield-wise.
Also, losses of freebase from distillation of an A/B cleaned raw product will usually be in the lower percentage range, 3% or so being typical when you use proper vacuum and glassware.
I can also recommend the following crystallization procedure: dissolve freebase in IPA, gas with HCl, and then crash out the product with excess acetone. Store at -20°C for some time and filter. Save those mother liquors, still some goodies in them!
This does not mean I think your writeup sucks! Not at all! I like it alot!
I'm not fat just horizontally disproportionate.
(Stoni's sexual toy)
11-25-02 11:48
No 383108
Almost forgot, try this:
Add the ketone dropwise over several hours to the Al/Hg/MeNH2 amination. This way every ketone molecule will have a huge excess of MeNH2 available to react with, my results using this 'starved feed' ketone addition method were pretty good.
I'm not fat just horizontally disproportionate.
(Hive Bee)
11-25-02 19:59
No 383229
LOOK into getting NaBH4 instead of HG/Al + methylamine.
Swims smurf friend got excellent yields with distilled ketone...
100g of ketone == over 99g of mdma.hcl..
I love the smell of Ketone in the morning.
(Synaptic Self-Mutilator)
11-25-02 20:45
No 383236
An optimized Al/Hg will give the same yields. I've gotten back 1g mdma.hcl for each g of ketone. Although I agree, if you can get NaBH4 easily... go for it. It's much less messy.
(Old P2P Cook)
11-25-02 22:40
No 383273
Although I agree, if you can get NaBH4 easily... go for it. It's much less messy.
Could borohydride also be used to reduce nitromethane to methylamine? If not then the Al/Hg reduction still would be a good way to obtain the methanolic methylamine.
Baseline Does Not Exist.
(Hive Bee)
11-25-02 23:34
No 383293
So say you make methylamine via al/hg and end up with 1000ml's of a 6% MeAm/meoh solution. You would just use that basic methylamine laden methanol in the NaBH4 reduction??
How much ketone and boro would be needed to make use of the 1000ml's of MeAm solvent?
(Stoni's sexual toy)
11-26-02 00:09
No 383301
> Could borohydride also be used to reduce nitromethane to
> methylamine?
No. For that reaction to take place you need different reducing agents, like BH3 under anhydrous conditions, presence of hydrogenation catalysts etc. And even if it worked, it wouldn't be economical to reduce nitromethane with NaBH4, since such a big excess of methylamine is required in that reaction.
I'm not fat just horizontally disproportionate.
(Master Searcher)
11-26-02 00:43
No 383311
How about hydrogenation of nitromethane using a nickel catalyst? Post 53425 (KrZ: "Raney Nickel Nitromethane Reduction", Chemistry Discourse)
http://www.geocities.com/dritte123/PSPF.
The hardest thing to explain is the obvious
(Hive Bee)
11-26-02 02:48
No 383342
Osmium
I found I needed that amount of solvent in the nitro reduction. The sludge produced is a lot and I needed that much solvent and it is a lot for 1 mole ketone but I could'nt find a way around it.
Also, some water is distilled over with the methanol/methylamine solution but point taken, more water may be good.
Finally, I too have had very good results by dripping in ketone over a few hours while refluxing, and then adding even more but I didn't want to confuse anybody.
Recycling the methanol/methylamine solution is always carried out and reused in the next reaction.
Abacus
(Stoni's sexual toy)
11-26-02 09:56
No 383432
> I found I needed that amount of solvent in the nitro
> reduction. The sludge produced is a lot and I needed
> that much solvent and it is a lot for 1 mole ketone but I
> could'nt find a way around it.
I see. Yes, I guess you're right. It's been a long time since I did a nitro Al/Hg.
Ever tried to neutralise the distilled MeOH/MeNH2 with HCl and removing the MeOH by distillation?
I'm not fat just horizontally disproportionate.
(Hive Bee)
11-26-02 10:11
No 383435
Osmium, you are right if the goal is to reduce the solvent volume, but I never bothered and use the 6% solution as it is.
The rationale was trying to process up to 200g ketone in 1 day using nitromethane in medium size glassware, which was due to serious time constraints, and eliminating the need to mess around forming the hydrochloride only to basify it once again.
The large solvent volume was the price to pay.
Abacus
(Hive Bee)
11-26-02 10:15
No 383437
>>Ever tried to neutralise the distilled MeOH/MeNH2 with HCl and removing the MeOH by distillation?
Yes and all I ended up with was a yellowish oil, about 5ml's that refused to evaporate. Was expecting only a few grams of MeAm.hcl. Let the oil sit out for a few days and when I returned, it was still an oil.
(Stoni's sexual toy)
11-26-02 10:22
No 383439
Dry it in a desiccator. Or play around with different solvents (IPA should work) until it suddenly crystallizes.
I'm not fat just horizontally disproportionate.
(Hive Addict)
12-01-02 00:42
No 385030
Swim just went ahead and tried this at 56% scale (in order to aminate 100G ketone)in a 3L 2n flask with foil. Not reccomended! He dripped in 17mls of nitro/water/meoh solution, and then started a slow drip (1/2 seconds). Within 5 minutes, he had a runaway rxn (this is with 2 leibig condensors 200+400mm stacked on eachother, plus a vigreux with a fan on it) and a full bag of ice in the cooler- he managed to get it calmed down after stopping addition, but after resuming, he lost control again (at a slightly slower drip rate) and ended up watching the flask dry out as his MeOH solution basically hovered within the vigreux and condensors, all the while escaping through the hose he had attached on top of the vigreux. At least no valuable precursors where lost, and the fumes where safely pointed out the window.
Off to the store for some flashing...
Im not the bearded man upstairs, Im a bald guy with a healthy penis. So open yer pie-hole!
(Hive Bee)
12-01-02 02:48
No 385066
Wowa! SWIM has NEVER had a run so exothermic! How many mL of solvent were used? Swim used an 8% azeotropic mixture of nitromethane/methanol and never had a problem with runaway rxn. and he only used a 200mm Leibig condensor. He also used Reynolds Heavy Duty aluminium foil (ground up with coffee grinder).
Sink or SWIM
(Hive Bee)
12-01-02 03:54
No 385076
Your using foil, thats why!
Ronald Mcdonald figures a rxn using more than 50g of foil should be done with a larger mouth'd vesel and condensor.
Invest in a 45/50 5L and a 45/50 reflux condensor if you want to use large amounts of foil
(Hive Addict)
12-01-02 04:45
No 385083
yessa, (snip, snip)
I's went to tha 'yella' place (snip...)
got me 5X7 100 pack (snip...)
aint gonna mess with dat foil no moe
Im not the bearded man upstairs, Im a bald guy with a healthy penis. So open yer pie-hole!
12-01-02 04:56
(Rated as: insignificant)
(Hive Bee)
12-01-02 19:27
No 385193
[r]Since the MeOH/MeNH2 mixture is distilled you can use RC fuel bought OTC without cleaning it up! A great simplification for many of the bees![/r]
Osmium, Does this mean that swim can use the RC fuel with all the oils in it and it should still work? Does the oil react in the al/hg at all? swim just wants to recover the 6% methylamine methanolic solution.
If he can use RC fuels with oils in it then it just saved him a day of distilling fuel!
WOW, thanks abacus! You saved me alot of time trying to make methylamine.hcl from paraformaldehyde/ammonium chloride because it took me a full day just to get a mere 40g
AWESOME I LOVE IT!!!
Sink or SWIM
(Hive Bee)
12-01-02 22:36
No 385237
>>Does this mean that swim can use the RC fuel with all the
>>oils in it and it should still work?
I doubt it will interfere with anything, for the oil is just castor, but why not turn the lightbulb on and go buy a gallon of pure nitro for a whopping 20 bucks! It's not watched AT ALL! THERE IS NO EXCUSE!
Your wasting more money on RC fuel!
(Hive Bee)
12-02-02 02:48
No 385284
What temperature was your Methanol when you started drip?
Also, how much Hg Chloride did you use?
(Hive Addict)
12-02-02 09:53
No 385429
Sorry, didnt take any temps- everything was started at room temp, and a little under 300mgs of HgCl2 were used. (remember, everything was at 56%)
Im not the bearded man upstairs, Im a bald guy with a healthy penis. So open yer pie-hole!
(Stoni's sexual toy)
12-02-02 12:05
No 385460
> why not turn the lightbulb on and go buy a gallon of pure
> nitro for a whopping 20 bucks! It's not watched AT ALL!
> THERE IS NO EXCUSE! Your wasting more money on RC fuel!
Not everyone is able to get pure NM.
I'm not fat just horizontally disproportionate.
(Hive Bee)
12-02-02 19:56
No 385565
>>Not everyone is able to get pure NM.
It's not available in every country? I just assumed it would be being that most countrys enjoy race cars and experiment with rocket scientry. Although, I can see how 3rd world countries wouldn't have any available.
(Chief Bee)
12-02-02 20:14
No 385574
Not having access to *pure* nitromethane does not equal a complete lack of RC hobbyists. Why do you americans always go from one extreme to another? There is always a middle road, even if that is not as fantastic as either or.
I have a neighboring country where 99% NM is nowhere at all to be found, as it is not legal to sell anything containing over 50% nitro OTC. Hence they only have brands containing a lot of methanol, some nitromethane and a dab of oils.
(Stoni's sexual toy)
12-02-02 20:33
No 385582
> It's not available in every country?
Obviously not. Since there are an estimated 200 nations on this planet you can bet your right thumb that some will have outlawed NM for obvious reasons.
> I just assumed it would be being that most countrys enjoy
> race cars and experiment with rocket scientry.
Nitro cars aren't that common outside the US. And even if they were, not everyone is willing to acquire a race license to be able to buy it. Or not everyone is willing to go through all the hassle of obtaining pure NM when the widely available RC fuel will do just fine.
Which hobby rockets use nitromethane? I am not aware of any.
Besides, rocketry is illegal in many countries too, and would be a pretty stupid excuse to acquire NM because it simply raises too much questions and eyebrows.
> Although, I can see how 3rd world countries wouldn't have
> any available.
Not too long ago all the NM dealers in the not quite third world country of the US were questioned by gov officials about their customers, because someone had blown up a federal building somewhere in Oklahoma. Remember?
Different countries, different laws. You can get a lot of interesting shit in thirld world countries that we all are uncontrollably drooling for. Money can buy you everything you want in thirld world countries. It's the first world countries where stuff is unavailable.
I'm not fat just horizontally disproportionate.
(not quite as irritable lately)
12-03-02 00:00
No 385636
WOW, thanks abacus! You saved me alot of time trying to make methylamine.hcl from paraformaldehyde/ammonium chloride because it took me a full day just to get a mere 40g
Any moron who can follow simple directions should be able to make methylamine from paraformaldehyde & ammonium chloride by the kilo in half a day.
Intelligence is not the recall of knowledge, but the ability to use it. (Rainman was a retard)
(Hive Bee)
12-03-02 01:13
No 385660
Any moron who can follow simple directions should be able to make methylamine from paraformaldehyde & ammonium chloride by the kilo in half a day.
I dont own large glassware so I have no reason to make that much!
Besides, abacus method of making methylamine in methanol is great.Have a GOOD day!!
Sink or SWIM
(Hive Bee)
12-03-02 13:34
No 385792
It took me 5 days just to make 1/2 kilo methylamine.hcl using hexamine/HCl and formaldehyde/am.cl.
Using the same size glassware I can be finished processing 900g ketone in 5 days with nitro as I outlined.
DON'T use foil for the nitro reduction, you must use thick aluminium as GOD found out. Also a bit more 50% NaOH may help.
Finally, keeping the oil bath temperature below 210DegC when distilling the freebase eliminates the problem of charing the freebase and has increased yields with only about 5% being lost when distilling as Osmium suggested.
Thanks to all
Abacus
(Hive Addict)
12-03-02 16:14
No 385818
200 grams of methylamine in 2 liter flask in one day is piece of cake.I also have 10 liter flasks,so 1 kg/day is more than i could use next day.
For those about to synth,we salute you
(Hive Bee)
12-03-02 22:41
No 385889
Lucky you,
I own 19/22 glass joint sizes with my largest flask of 500mL. The 19/22 joint sizes works well for distilling ketone without loss of much product.
Also abacus,
Why would one want to add NaOH to post nitromethane reduction? Wouldnt this release the methylamine gas and cause it to come out of the methanol? I would want as much methylamine gas when distilling over in my methanol as possible. I understand the point of basifying when reducing ketone but why post-nitro reduction?
Sink or SWIM
(Hive Addict)
12-03-02 22:49
No 385892
ok- swim switched to Al flashing thats about half as thick as Abacus' reccomendation. MUCH gentler rxn... 400mm condensor took care of things just fine, plus a vigreux with cold assed air beeing fanned from an open window.
Of course, now there is a new set of problems/questions
-first off, swim forgot to take into account that there would bee more surface area considering the fact that his Al is half as thick. He used the same ratio of HgCl2 as called for. He added Al, dumped in his Hg salt, then added the methanol. While that was sitting, he measured out his nitro/DH2O and also separated the initial part of that mix from the addition funnel. He took his time (10-15 minutes), looked down at the flask and saw that the Al had dulled, and there where little bubbles coming up. He figured all was well, so he started the rxn. He noticed that it appeared as if only one side of the Al amalgamated- when peices where floating around, one side would bee brown-near black, and the other side would bee shiney Al. This was pretty consistant with almost every peice that he saw (some had little blotches on the shiney side) -is this because swim shoulda waited a little longer to start his addition, or is it a sighn that his flashing may not bee the right stuff? (sorry, this is a newbee question, but I have one or two more related to this procedure)
-Swim noticed that unlike when he used foil in the past, everything seemed to settle on the bottom more (all the crap) whereas with the foil, he would often find that the crud seemed to float. He had left stirring on for the greater part of the rxn figuring he didnt want to hand swirl so much seeing as how he didnt know how vigarous of a rxn to expect. When he did swirl, he saw quite a bit of unreacted Al on the bottom (lots o shiney stuff even past an hour into the rxn, MUCH more unreacted stuff than what he was used to with foil). He also noticed that even as the floating peices that appeared to bee near used up moved around, they seemed to remain in tact, and it was as if the flashing had retained its shape, but grown in thickness from the dark side, and it looked like its shape was beeing held together by the shiney, unreacted side(s) of the square -once again, is this normal, or is it an indication that there might bee some kind of coating on the flashing?
-Last question, upon addition (swim did it slowly with his addition funnel) of NaOH solution, what kind of color changes (if any) are expected to occur? Swims solution turned a lighter shade of grey with light green-tan swirlies in it to a darker tan-green-grey to a dark, brownish color.
Im not the bearded man upstairs, Im a bald guy with a healthy penis. So open yer pie-hole!
(Hive Bee)
12-03-02 22:59
No 385895
When swim did an al/hg nitromethane reduction 572 years ago,with Hg2I2 (tincture of iodine). His aluminium did not change colors (he used thick aluminium pie pans). After addition of tincture 45minutes it started to bubble and a grey sludge formed on the bottom. The solution was cloudy and grey and that is when he slowly poured in nitromethane. After the reaction finished he added 600mL of 25% NaOH and a strong fish/ammonical smell was released and things started to get nasty. The solution started to boil and then it calmed down. The post-al/hg was a light brownish, he used RC fuel, and some dark sludge was on the bottom.
It seems to me, GOD, that it worked out for you! Using thicker aluminum is good! Aluminum foil is probably better for ketone reduction with methylamine as it isnt as exothermic.
Sink or SWIM
(Hive Bee)
12-03-02 23:34
No 385901
I had similar problems using pie tins once. Even after 50 minutes the metal was still shiny. I don't remember if it had dark spots on it but that does sound vaguely familiar. Im waiting to watch other have more success as I see many of us are switching to flashing/pie tins before I try my luck again with it. My post reaction mix after NaOH addition is either dark grey or after a 12+ hour reaction black.
(Stoni's sexual toy)
12-03-02 23:35
No 385903
> It seems to me, GOD, that it worked out for you! Using thicker aluminum is good!
Goddammit! Of course it is good!!!
Why do you think I'm fucking preaching to use thick Al for 5 fucking years?!? There's no need to reinvent the wheel!
And when did it become fashionable to skip using the search engine or reading Rhodium's site?
Fuck this, just go on everyone fucking up the signal/noise ratio a little more.
I'm not fat just horizontally disproportionate.
(Hive Bee)
12-03-02 23:59
No 385917
Why don't you go back and read what I wrote, then read osmium al/hg on Rhodiums site, UTSE to read what Osmium wrote about the al/hg. Its all there.
I repeat, alumimium sheet EQUAL or GREATER than 0.3mm thick. The sheet chem suppliers sell is 0.6mm thick so thick is good for very exothermic reactions such as with nitromethane.
Then use your favorite foil for the ketone if you like.
Some pie tins etc seem to be alloys which don't work that well. Try and get soft uncoated aluminium flashing, then test it with a little hgcl and nitro first.
ALso, there is some leftover aluminium after the reaction, so feel free to use less.
I used 50% NaOH for a reason, which was to help break up the sludge without adding too much water, to help finish (speed up) the reduction of any left over nitro, and to help drive out the methylamine gas when distilling. I said that at the beginning damn it! And yes, the sludge turns brown.
Feel free to try it without any NaOH, I just never got around to trying to distill out the methanol/methylamine without it.
Thats all I'm going to say, the improvements can be someone else's problem.
Abacus
(Hive Bee)
12-04-02 00:15
No 385925
Thanks!
Have a HAPPY day
Sink or SWIM
(Hive Bee)
12-04-02 15:22
No 386186
Sounds like it had some sort of coating on it, plastic or similar. Some flashing is treated that way so it doesn't weather so fast when exposed to the elements.
Take a piece of your Al, and scrub BOTH sides with steel wool then throw into some Hg solution and see what happens. That should confirm if the Al is coated.
(Hive Bee)
12-05-02 08:54
No 386453
Broadcasting to the DEA that you regularly produce kilos of MDMA is not a very safe practice. You should assume that the DEA has read this and knows your I.P. address. If this address happens to be linked to a connection under your name (in other words, you access the hive from your home computer) you can assume that they know who you are and where you live. It's amazes me, the stuff that some people say around here. If I were producing anywhere near that large of an amount, I wouldn't even log onto the hive unless it was from a remote location (i.e. - the library). I'm not trying to put you down or anything; just don't want anyone to become another victim of Uncle Sam.
(Hive Bee)
12-05-02 09:56
No 386462
I'm not producing anywhere near that amount.
Pr(+)tium
(Hive Bee)
12-05-02 10:50
No 386470
Im protected by the retired bee act of 2002.
(Hive Bee)
12-05-02 18:44
No 386535
Remember!
No one actually makes this "stuff" its all talk.
Sink or SWIM
(Hive Bee)
12-06-02 07:43
No 386736
EDit: But I think the "kilos" i purchase may be a bit big coz I end up with 1050mls Isosafrole from them and after checking notes I got 550g MDMA.HCL from the last one after vacuum distillation of freebase, gassing in acetone AND recrystalling (twice) in ethanol.
This is the specific example I was talking about. If I were a DEA agent, he would be under constant surveilance. Never underestimate an agency that recieves billions of dollars a year to do shit like this. Your best chance of not getting caught is to not let them know you exist and assume that every word you speak is being recorded at their headquarters. If they can intercept the communications of those terrosist bastards, they can intercept your's as well if they are looking for someone who does what you do.
Also, it doesn't matter what kind of code words or evasive phasing you use. When someone writes "SWIM just cooked up a successful batch of 1 kg of product" the DEA knows that 9 times out of 10, the word "SWIM" can be replaced by "I". If they even suspect that you are doing something like this, they will enter your name into their list of people to get fucked. Remember - they don't have to play by the rules if no body finds out. Although they can't use an illegal wiretap as evidence, they can still gather information from it. Eventually, they'll have enough information to intercept you while you are actually performing some illegal activity (i.e. - transporting) that would grant them a search warrant. It's all over from there.
(Hive Bee)
12-06-02 07:47
No 386738
Yeah but, doesn't the DEA need the help of the hives ISP which I understand it won't get.
Also, SWIM's access to and connection with the hypothetical lab has finished, so no problem.
Abacus
(Hive Bee)
12-06-02 14:12
No 386821
They might not be able to get the IP from this website, but if I understand correctly, they can trace it through your ISP router. Besides, how do you know that the Hive wasn't set up by the DEA and Rhodium is really Asa Hutchinson himself? I hope not, but the feds set up sting operations in a similar manner.
(Hive Bee)
12-06-02 15:55
No 386842
Lab bitch
I live in Asia, how the fuck is the DEA going to get my IP address without the help of the hives ISP and how the fuck are they going to find my ISP router. Do you think the US will invade Asia to find it?.
Stop shooting up that meth and get a fucking grip.
Abacus
(Hive Bee)
12-06-02 17:07
No 386864
As long as you follow your countrys laws the DEA cannot do jack shit. The US in general, and the DEA in particular, has a hard time realizing thir laws aren´t applicable worldwide yet. As long as you follow your laws, and your government isn´t too quick bending over to the DEA cocks, you should be alright.
Catalytic hydrogenation freak
(Newbee)
12-06-02 18:56
No 386904
They might not be able to get the IP from this website, but if I understand correctly, they can trace it through your ISP router.
Even if they know you are accessing the hive, they are unable to tell one username from another because of the ssl encryption. The only way they could determine what user you are from your ip would be by checking the time of post on the hive and comparing that to the time your ip sent information to the hive. To prevent this problem either all packets sending and receiving need to be same size (they may already be, I dont know, does anybody know for sure?) or all posts need to be queued until a certain number of posts, say 10 or 20 are made before the hive software updates the message board, each post having the same time. Even in the case of the latter it would still be possible to deduce which username you have (provided you make enough posts over a long enough period of time) by the process of elimination, so the former is definitely the best solution. Of course,what are the chances that your ISP (or your ISP's ISP, etc.) would deploy this method. If they know an incriminating post was made during the time you were accessing the hive there's a one in however many people were online at the hive at the time chance it was you (provided posting and reading packets don't differ). Actually I do wonder if "post" packets differ from just "read" packets or PM packets. If they did the ISP could easily tell the exact time each time you made a post, then look at the message board and find the username that made a post at each of those times. If nobody knows if they do differ or not swim will sniff the packets and find out. But I'll get back on topic: good work abacus
(Old P2P Cook)
12-07-02 02:26
No 387013
The last half dozen or more posts have been completely off topic. Start a new thread if you want to continue this off topic conversation.
Baseline Does Not Exist.
(Hive Bee)
12-07-02 02:34
No 387015
I'm mainly talking to people in the U.S. It's a simple precautionary step. You don't go around telling everyone in your town what you do, so why should you post this information on the net? The NUMBER ONE reason that people get busted for anything is that they didn't keep their mouths shut when they should have. Generally, if something doesn't need to be said, then don't say it. I just know too many people that have fucked up like this and are now serving 10 year sentences in state prisons. Whether or not posting that you make kilos of product is a real risk, why take it if it's completely unnecessary? Sorry if I'm being a little paranoid, but in the U.S. this shits no joke. If they want to fuck you, then they will. Even Osama and friends (FUCK THEM!!!) can't avoid our security. In fact, I wouldn't produce shit like that in the U.S. to begin with. Talk to someone who's spent the past ten years in prison and get their opinion. Performing research is one thing, but the second you start spitting out mad product, the question does not become whether you're going to get caught, but when. That game is no joke! Sorry if I'm making anyone trip out, but I may just be doing you a favor.
(Hive Bee)
12-11-02 10:03
No 388359
in a dream, the largest flask swim has is 500ml. so he used it to reduce 144g 15% MeNO2 using 20g extra heavy duty foil. (for a 21g ketone amination) it ran out of control, climbing up 2 200mm condensors, but swim chilled it out running cold water directly onto the flask as needed. lots of hydroxide sludge was produced.
dammit, he soaked the hotplate and now the heat won't switch on only stirring. grrr... it was his nicest piece of equipment and switching the fuses inside doesn't help... grrr...
so unless it magically revives after drying out overnight swim can't distil the MeNH2. he read the methylamine faq and brightstar's synth on Rhodium's, but can't decide-
1) should he titurate the ~150ml of MeOH + castor oil + 11.8g NaOH + 15ml h2o to find out the MeNH2 concentration and add it directly. he sees a problem putting NaOH into the reaction, he could neutralize it with HCl possibly.
2) should he just extract 3-4x 20ml dcm, add HCl until slightly acidic, and (this is a worst case scenario) boil off the dcm and trace h2o on the ol' stove. then weigh it and do like the Os man says
so, uhm, methylamine responds to standard a/b extraction like all the other amines, right?
please advise, otherwise swim can just run 5g MM type reactions with some previously distilled 8% MeNO2. but a smooth MeNH2/al/hg would bee so much nicer.
needless to say, this is only a temporary handicap...
(Hive Bee)
12-11-02 10:54
No 388365
>>needless to say, this is only a temporary handicap. but he's got to run an amination now with what he's got.
Well then you have your answer. This thread has nothing to do with your problem. You should of posted in the stupid mistakes thread instead. Pouring water over the flask with an electric hotplate below?!
Sober up when working. It could save your life, or someone elses.
(Hive Bee)
12-11-02 11:05
No 388366
after one basifies the post nitromethane reduction sludge, can one extract the MeNH2 with a nonpolar solvent instead of distilling it?
as for swim's idiocy, sure he put it on a cold water bath, then it started running away again anyway. whatchagonnado??? i suppose this is old news to bees used to running 25g MM aminations... in 2L flasks, heh.
(Hive Bee)
12-12-02 08:50
No 388697
For the last time, I said to use THICK aluminium greater to or equal to 0.3mm thick. Geez, its like playschool, you have to repeat everything about a million times.
Don't use heavy duty foil, its way too thin which will cause the effect you described unless you add it very SLOWLY.
The methylamine is highly soluble in aqueous solutions, even if you basify most of the methylamine will stay dissolved in the NaOH solution and wont go into DCM.
Your only way forward that I see is to distill out the methanol with some methylamine from the flask. That way you know you leave any unreacted nitromethane behind (too much unreacted nitro may stuff up any ketone animation attempt).
Abacus
(Hive Bee)
12-12-02 10:30
No 388716
swim thought it might work on 1/8th scale with extra heavy duty foil...
anyway, he realized MeNH2 is soluble 10:1 in water, so lacking a hotplate, he added some ceramic chips and distilled it on an oilbath on a gas stove. the MeOH came over starting at 70C (past the 65C where 8% MeNO2 comes over, whew) and climbed to 80C at which point the castor oil got too thick and heat was removed to stop the excessive bubbling. 30ml of water and oil in two layers remained.
uhm, i know this was slightly dangerous, can someone quantify how much?
abacus, how do you know for sure any nitro will be left behind by distillation?
just by observing that adding the MeNH2/MeOH to an amalgam is not exothermic?
tituration determined the concentration was 1.5%, about 1.5g total in 125ml MeOH. he suspected yeilds would suck as the voluminous purple sludge looked to be about 400cc. this was from a 21g MeNO2 reduction with 20g Al and about 300ml MeOH. the sludge held 200ml of MeOH even after filtering with aspirator vacuum.
ah, well. practice makes perfect. the MeOH was super-wet it turns out (crack in the nalgene bottle). so the 4ml of h2o added with the MeNO2 sure didn't help things out...
(Hive Bee)
12-12-02 21:48
No 388856
this must be the easiest synth ever posted, if you are haveing problems just run the MM nitro synth without the ketone then distil before basifying, voila 6% MeAm in MeOH.
I have now performed this method three times (with 50, 50 and 500mg (ha ha)) and it is killer, important though to stick to the instructions.
Congrats ab babe for the no brainer method.
I use foil in the ketone reduction step and a water bath set on 70C (reaction temp approx 60C, rxn time 8hrs)
wacka wacka wacka
(Hive Bee)
12-13-02 07:48
No 389030
Finally!!! Thanks wacko
Also, I forgot that nitromethane and methanol forms an azeotrope so distilling doesn't necesarily leave the nitro behind.
Madprosr, you have a long long ways to go, pm me if you want specific help
Abacus
(Hive Bee)
12-14-02 01:07
No 389244
I know it really doesnt matter with nitromethane being in the methanol but is there any test for unreacted nitromethane from post-distillation of contents? I have about 1L of some distilled suspected 6% methylamine/methanol which smells strongly of methylamine but I want to make sure there isnt any nitromethane because nitro makes an 8.3% azeotrope with methanol.
Sink or SWIM
(Hive Bee)
12-14-02 02:49
No 389278
Pour it into a flask with some amalgamated aluminium. If it heats up there must some nitro in there.
I never got any nitro distilling over when I did as it was always reduced to methylamine.
So amalgamate say 30g aluminium, pour in suspect methylamine solution and see if you get any temperature rise after a few minutes (you probably won't), if not, then pour in the ketone (around 120g) a little water and gently reflux and away you go.
Abacus
(Hive Bee)
12-15-02 05:44
No 389578
-thats the best confirmation in my book, if your are worried about lesser concentrations then use more of the MeAm/MeOH as excess of this reagant will in no ways hinder the rxn. Also in my previous post i said i used foil where in fact i meant flashing, 0.3mm, sliced into ~0.5-1mm strips using a gulotine (spelling), for cutting up decent amounts i suggest everyone buy one, you can thinly slice 1kg of aluminium sheet in about 15mins if you go hard or 30minutes if your a a slacker, much better than sissors.
The only drawback for some with this method will be the neccessity to redistil the freebase, but you all should do that anyway as the differnece is noticeable. And now that we don't have to bother distilling the sass or the iso you should definetley redistil the freebase.
wacka wacka wacka
(Chief Bee)
12-15-02 10:05
No 389603
What's this talk? Are you proposing to skip both the distillation of sassafras AND the post-isomerization mixture? To skip one of them is not good, but skipping both is completely fucked up!
If you haven't run into any problems doing that, then you must be extremely lucky with your source of sassafras oil, as most types contain 10-20% terpenes, and only 80-90% safrole. Those terpenes will easily be carried through the isomerization, and some of them will undergo peracid oxidation forming who-knows-what. These impurities simply MUST be removed by fractional distillation before doing the peracid oxidation, preferably by distilling the sassafras oil before isomerizing, but at least when distilling the isosafrole after the isomerization.
Doing anything else is irresponsible, if not downright stupid in some cases. Remember that you are making something that people are going to ingest!
(Hive Bee)
12-15-02 16:25
No 389669
YES,
You are totally correct. SWIM has tried a epoxidation with undistilled "suspected" isosafrole/safrole/NaOH Mix and it did NOT work at all (couldnt get any epoxide or glycol to form). (AS EXPECTED) But swim just had to try.
It is essential to purify EVERY step of the way to maximize yields and minimize impurities! SWIM had to find out the hard way
Sink or SWIM
(Hive Elder)
12-15-02 20:19
No 389708
That has to be one of the only times I've ever seen Rhodium get so pissed off as to swear!!! Don't piss off the Chief bee you BASTAGES!!!
Mean People Suck
(Chief Bee)
12-15-02 22:20
No 389738
Pardon my french, but just minutes earlier I had in Post 389594 (Rhodium: "Shortcuts can easily become detours", Methods Discourse) strongly argued against Ruth's proposal to skip distillation of isosafrole because he could not afford spending time on that, as he considered himself a "production chemist", and now this outrageous statement that one should take crude sassafras oil and subject it to isomerization directly followed by performic oxidation to MDP2P without any isolation or purification at all of the intermediates - and all this without any purity checks.
It is bad enough if Mr Ruth actually practices such sloppy lab technique in his garden shed, but coming here and suggest that other people should lower their standards to his level - then even I become somewhat agitated...
(Hive Bee)
12-15-02 22:26
No 389740
Karma patrol catches up with people like that. No worries.
(Hive Bee)
12-23-02 12:04
No 391961
but swim ran a 3g MeNH2/al/hg Osmium style yielding 2g of the hcl salt, 52%. not quite sure what's holding back the yields, maybe he balled the extra heavy duty foil too tight and dripped in all the ketone over 1h while not enough Al was exposed. it took all night for the foil to finish breaking down.
then swim ran a 4.1g MM reduction. timed it very nicely, 1h of ketone drip and 15 minutes later the Al was gone. basified with 43.3g NaOH in 50% aqueous solution. pH went up to 14 and sludge turned black (argh). 10% yield.
previous 1.6g MM reduction gave 41% yield, nothing special there.
so swim got some flashing, amalgamated 12.75g in 50ml MeOH, dripped in 96g of 15% nitro (14.4g MeNO2, about 77ml MeOH, some castor oil, no water added), let reflux 2h, added 15.7ml 50% NaOH, let reflux and stirred overnight. swim boiled it over trying to distil out of a flask 4/5 full (please, laugh...), switched to a bigger flask, and distilled 60ml of 4.6% MeNH2. sludge didn't swell up during gentle distillation.
so, abacus (love your synth, i really do) reduces 3mol of nitro and gets 1400ml of 6% MeNH2 ~= 2.2mol (disregarding the density of MeNH2 <shrug>), 73% yield. swim may have alot to learn, but at least he knows to add more MeNH2 than this to 178g of ketone... for 2.2mol MeNH2 use 130-156g ketone. pm me for details.
anyway, swim reduces .236mol nitro (undistilled 15%) and gets .0725mol, 31% yield.
so basically, swim recovered half the MeOH added origionally and got half the yield expected. any suggestions? add more MeOH to the sludge and distil again? use distilled 8% MeNO2 (doubling the solvent volume) next time? its probably the fukkin castor oil... bad shortcut.
anyway, closer to the origional topic, how do you gas 100+ grams of amine? it seems to me that dripping hydrochloric onto sulfuric, the sulfuric is going to get diluted and useless before enough gas is put out. so who prefers NaCl + sulfuric for gassing alot of product? or do you add pregassed IPA, then crash the salt with acetone (or ether)? last is probably the most idiot-proof large scale option if you weigh the IPA, determine HCl concentration, and add an exactly equimolar amount.
(Stoni's sexual toy)
12-23-02 13:24
No 391972
> so basically, swim recovered half the MeOH added origionally
> and got half the yield expected. any suggestions?
Do it at a bigger scale.
> anyway, closer to the origional topic, how do you gas 100+ grams
> of amine? it seems to me that dripping hydrochloric onto sulfuric,
> the sulfuric is going to get diluted and useless before enough gas
> is put out.
One solution to this problem is using more H2SO4. A gas generator suited to generate enough HCl gas for 10g freebase will most likely not cut it when you want to gas 300g with it.
Isn't that kinda obvious?
I'm not fat just horizontally disproportionate.
(Chef d'Equippe)
01-04-03 05:31
No 395270
Lab Bitch should just shut the fuck up. People dont give a fuck about your views on the DEA or anything else for that matter. Go hang out in a teen chatroom and preach, they still may be reachable. This is a chem board discussing production in case if your fuckin' blind or in this case, just plain stupid.
GODISNOWHERE
Shoot Narcs, Not Drugs
(Hive Bee)
01-05-03 10:29
No 395548
baal, you 'da man even if you freeze your safrole upside down! power to the people!
anyway, my apologies to abacus who's 6% solution i interpreted as grams MeNH2/grams MeOH. if abacus says he gets 3mol MeNH2 in 1400ml MeOH (ie 1400ml of 2.14M solution) then i believe him completely.
swim ran his synth at 1/10 scale using 120g of 15% nitro in a 500ml flask.
15.9g of pretty thick flashing were cut in thin short strips and curved slightly.
the nitro contained about 100ml MeOH already so the Al was amalgamated in just 50ml MeOH (undistilled, yellow-bottle) with sufficient HgI2 to cause immediate bubbling. as the nitro was dripped down the condensor over an hour a cold water bath was needed to permit continued dripping. the Al swelled up with sludge rising partially out of the MeOH and three times ~25ml MeOH was added and the flask shaken to redistribute the sludge.
after reflux stopped another ~15ml MeOH was added and the flask heated to slightly below reflux for 4h. it was left stirring overnight, but the top layer congealed at some point. in the morning heat then shaking were applied to get everything moving again. swim observed that the square corners of many pieces of Al were now rounded. the mix was heated to slightly below reflux again for 2h, until most of the Al was gone. swim got tired of waiting and added 19.6ml 50% NaOH which heated it up somewhat. he then carefully distilled 220ml MeOH from about 400ml sludge until the castor oil got thick and it bubbled up.
so it was a messy amalgam, but swim measured MeNH2 concentration at .00137mol/ml, ie .3014mol total. ie 220ml of 1.37M solution. this is starting from .2951mol MeNO2 if weight and concentration were exact. but swim knows he went a drop over as he titrated 1ml using 1.65ml of 2.7% HCl because the pH went from 8 to 2 with that drop.
and nothings exact, but swim got damn near quantitative yields at 1/10 scale with 15% nitro.
swim bets if you use 20-30% nitro and start with more MeOH it will run great.
however, swim tried using 8% nitro he distilled (21.6g nitro) in a 400ml reduction and got bad (28.6%) yields. it was stirred for 36h with occasional heating but the Al did not break down. it was strained out. this sucked...
swim thinks his last reduction of 96g of 15% nitro yielded only 31% because he added base only 1h after finishing the nitro drip. the reflux had stopped, but the reaction was nowhere near done, and heating it all night after that did not complete it, only drive off some MeNH2. don't basify too soon with thick Al and a small reaction.
anway, the .3mol MeNH2 works great:
swim used .1mol in a 5.4 gram ketone reduction ala Os and got 4.6g hcl salt.
used 2.55g Al and 75ml MeOH (undistilled, yellow-bottle). heated and ran overnight. only 10ml of 25% NaOH were used to reach pH 12, even though Os's amount is 200g NaOH/ 55g ketone. extracted 3x 40ml toluene but the MeOH mixed completely with it. used alot of brine, careful rocking, to separate the MeOH without emulsifying everything, then washed the toluene. back extracted the alcoholic mother liquor + first washes + all emulsions with 10x 20ml toluene, until it stopped pulling light yellow color. (yeah, swim knows its not supposed to be yellow, but he didn't separate the iso from ketone when using a new 250micron pump for the first time). anyway, he gassed and filtered 4x, overgassing the last time, turning that last crop of crystals pink, which was fixed by an acetone wash, yielding 4.6g before recrystallization.
so kind sirs, does swim really need to add 10-20g NaOH to a 5.5g MeNH2/al/hg, definetly giving pH 14, possibly turning the sludge black, in order to keep the MeOH from mixing completely with toluene?
swim figured his was a problem of density, MeOH being .81 and toluene .87, ya gotta add h2o until the MeOH/h2o is heavier. how is it you guys get toluene extraction to work so easily???
swim is almost ready to try xylene, or some friggin' dcm. he just prefers to pipette solvent off the top, rather than having to vacuum filter the sludge. he supposes with two filter-funnels (one evil, one not) this is no problem.
or is it the dang undistilled MeOH, and using it for the h2o source???
anyway, now that you have gotten this far, i have perhaps a very good idea...
1) distil safrole+iso after KOH isomerization as a mixture from 70-80C with your overpowered vacuum pump.
2) throw the mix on an equal volume of frozen safrole in the freezer for a day.
3) pour off pure iso with the safrole frozen out
some iso will stick in the container, no big deal...
so what do you guys think? swim's going to treat some mixed safrole/iso this way then do a bp test for purity shortly. anybee know for sure already if it works?
(Chief Bee)
01-05-03 14:32
No 395562
trans-Isosafrole melts at 6-8°C (see Post 385627 (Rhodium: "Isosafrole Physical data", Newbee Forum)) so you cannot separate safrole (mp 11°C) and isosafrole by freezing like that.
(Hive Bee)
01-05-03 23:39
No 395629
Rhodium, swir's seen trans-iso freeze from a mixure of both isomers? At what temperature?
last time around, swim isomerized 30g then added the pure iso vacuum distilled from 150-158C (sassy forerun was at 140-144C) to 15g safrole crystals in the freezer for a day. swim recovered 26g, so it doesn't seem that significant amounts of trans-iso froze out.
i guess swim is just looking for a way to use a lower distillation temperature, without adding a fractionating column.
what swim wonders is whether the sassy freezes out 100% or not???
(Hive Bee)
01-06-03 16:18
No 395808
if it don't hurt the reaction and you are good at purifying the product (distillation, re-crystallisatin, chromotography, whatever), then why bother, that's all, rhodium your boss, if you want me to shut-up about this then fine
lisa 'i did it my way' minnelli
wacka wacka wacka
(Hive Bee)
01-10-03 13:03
No 396921
Sure you need to add a bit of heat but its gentle and no boil over. You can add all the nitromethane at once. Longer run time but way easier to cut that into a few pieces than cut up flashing. Chop saw :) 4 pieces fit in the flask and hit the 162 grams.
Not a chemist I just follow directions on the box mix
(Hive Bee)
01-23-03 10:34
No 400744
Unless you have a disposable reaction chamber. Probably lost the flask.
Not a chemist I just follow directions on the box mix
(Hive Bee)
01-25-03 00:49
No 401223
There was some trouble making this procedure work, which I just figured out (I hope). Some Al flashing has a very thin coating of plastic on it, I presume to prevent corrosion against the elements. This coating, IME can affect the rate of the reaction, if it works at all, and generally screw things up. This was discovered on inspection of the amalgamated Al squares, which appeared to have been reacted on the corners only.
To deal with this problem, I am going to try a wire wheel on a drill before slicing the Al up.
you can tell if the Al is plastic coated by scraping it with a knife. If it is coated you will find a small residue coming off.
I hope this helps anyone having problems with this reaction.
Worker bees can leave
Even drones can fly away
The queen is their slave
(Hive Bee)
01-25-03 01:57
No 401237
Can someone try this with coke can's and report back? I never read one post where someone had success with soda can's, yet there has been alot of "use can's" talk in the past.
(Hive Addict)
04-14-03 16:15
No 426623
Cans are coated with paint outside and thin plastic coating inside.Raf has tried to to amalgamate one of those and it didn't work.
For those about to synth,we salute you
(Hive Bee)
07-02-03 02:45
No 443879
yep its fool proof im a fool and it worked perfectly :)
hehe and I used realy thin foil for the nitro and it worked
a dream :)
not a single problem just took my time adding the nitro
and ran my aspirator water pump through my condensor so a larger volume of water would go through my column.
admitadly the liquid was halfway up the condensor and
the reflux was one winding off the top but the condesor
is only a little 200 mm so all in all I am very pleased.
personaly I think (it is a though so please corect me if I
am wrong)
that so long as you control the reaction the harder you run
it the better.
next any one done an aminomerciation of safrole.
will this work out for asarone.
keep up the good work guys and girls thank abacus.
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