07-10-02 06:51
No 330835
Swim has a question about methyl mans writeup over the solvent used. The writeup uses methanol, SWIM was wandering if ethanol would work as a substitute?
Clouds come and go and never stay still........
(Synaptic Self-Mutilator)
07-10-02 07:26
No 330842
UTFSE next time. Methanol, 95% ethanol and 91% & 99% isopropanol all work.
The answer to this question should be in the write up...
PS. This answer applies to the Al/Hg. SWIC has no experience with the MM Pd wacker.
(Stranger)
07-10-02 07:30
No 330843
I searched the search engine...I guess i wasnt typing in the correct keywords..and on methyl mans writeup i read the whole article and couldnt find anything...Thanx for the help!!!
Clouds come and go and never stay still........
(One Man Show)
07-10-02 09:44
No 330879
Chromic: that title is hilarious!
As for MeOH, if you can not find that easily within a 10 mile radius of you, then your endeavors will be greatly hampered.
"Have we descended to the level of dumb beasts?" Fear & Loathing
Be loved and blessed hp and cg!!
(Chief Bee)
07-10-02 09:53
No 330884
Are you talking about the Methyl Man Wacker or the Methyl Man Al/Hg?
(Stranger)
07-11-02 00:02
No 331192
Methyl Mans Al/Hg using Nitromethane
Clouds come and go and never stay still........
(Stranger)
07-11-02 00:04
No 331193
Methyl Mans Al/Hg using Nitromethane oh yeah and BTW i can find MeOH easily but not OTC. ethanol or IPA is OTC for me. Methanol is cheaper but i have to go to the chemical supply store which is known to be a "drug" trap....
Clouds come and go and never stay still........
(Stranger)
07-11-02 00:45
No 331204
Right now im not living in the US but i plan to soon :)...Never heard of Wallys though. I plan on using Denatured Alcohol for Methyl Mans Al/HG because it is 95% ethanol and 5% methanol...Thanks for your help
Clouds come and go and never stay still........
(Synaptic Self-Mutilator)
07-11-02 01:53
No 331221
This is how I'd rewrite the section in the MM Al/Hg:
It's been emphatically stated several times that some water is needed in this reaction to breakdown the aluminum foil and produce the hydrogen that drives the reduction of the imine to the amine etc. That may be true, but I know for a fact that it doesn't need to be added. That is to say, maybe there is some trace water in the MeOH Mr. A uses (Heet) that is fulfilling this function, and maybe it's even in all MeOH except expensive absolute anhydrous stuff. Perhaps enough is made as a byproduct of the reduction of nitromethane to methylamine or the formation of the imine from the ketone and methylamine. I don't know. But he doesn't add it anymore and it definitely doesn't hurt anything. I also know that someone who isn't Chromic has run an Al/Hg with up to 30% water in MeOH and has gotten excellent yields (beyond 1g of mdma.hcl for every 1g of mdp2p). The amount of water added, does not really seem to affect the yield! I'm sure 70% IPA would be fine as well. The only difference with IPA is that when it's basified, all the IPA will go to the top layer. IMHO, this makes it easier to extract all of the MDMA, but make sure that the washes are 5% NaOH (or brine) to make sure all of the ketone is pushed to the organic layer. Also, it has been SWIC's experience that 95% EtOH also works well, and has noticed that ethanol forms a separate layer after basification as well.
Before, Mr. A was adding about 25mL, but he likes how it's going now. It has been shown that a small amount of water has no effect on the yields with this technique one way or the other, and a larger amount of water (ie 30% water) will only cause the foil to break down even faster creating an uncontrollable reaction.
HoH, I really doubt water makes a difference one way or the other. If anything, I have noticed that yields go up with more water. I'm not sure if this is generally true with Al/Hg's or specific to the MeAm Al/Hg... or just because as I've used more water my technique has become better. In any case, I haven't done the experimentation to say for sure... but my intuition tells me that the amount of water in the rxn makes no real difference.
Perhaps other bees would contest this account?
(Hive Bee)
07-11-02 03:38
No 331243
Chromic, I mostly agree!!!!
In SWIA's experience water has never effected yields except in its absence when using LR grade methanol from a chemical supply house.
SWIA notices a little water really seems to help the al/hg nitro reaction when using methanol sourced as a car fuel.
Specifically, SWIA finds that yields for SWIA increased when first the nitro is added and refluxed for the appropriate amount of time, then water is added, then ketone is dripped in while still refluxing.
SWIA has also carried out successful al/hg animations using methylamine with 75% methanol/25% water as the solvent and got great yields.
However, I must point out that the aluminium is not the famed reynolds foil and is a much thicker sheet so maybe this is the reason for any differences that SWIA observed.
It does seem to me that the real key is getting the best conditions for the type/brand of aluminium that you are using.
Either way, forget the ethanol and IPA, methanol as the solvent is the easiest to extract from IMHO
Abacus
(Stranger)
07-11-02 04:22
No 331245
Chromic... If i can use 70% IPA im going to save a lot of money because I can get that for $2/gallon...sounds good Chromic
abacus..if i could find methanol OTC then i would but i cant so IPA 70% is what im going to use. How is methanol easier to extract over IPA?
Clouds come and go and never stay still........
(Hive Addict)
07-11-02 13:22
No 331377
It's also really easy to dry iso to about 98%.
dwarfer
(Synaptic Self-Mutilator)
07-11-02 13:35
No 331382
>However, I must point out that the aluminium is not the famed reynolds foil
I have also gotten great yields with regular aluminum foil -- not the heavy duty stuff. I don't think it makes a substancial difference one way or the other. I do notice that the reaction goes faster with thinner foil and with more water... if your condenser can handle it, then there's no troubles either way.
I honestly think that the Al/Hg is the hardest reaction to screw up. The only critical things I've noticed are:
1) let the foil amalgamate until it starts to vigorously bubble
2) constantly stir
4) make sure all the the foil has been digested before adding the NaOH
3) use the recommended amount of toluene for extracting
MaDMaX, I do think you're a psycho.
I've used ACS grade MeOH with no troubles. I never used a drying agent before hand though to prove your theory one way or the other... (and who in their right mind would?)
(Title on BackOrder)
07-11-02 16:07
No 331431
This reaction needs water to run, but only a small amount. I believe the methanol can pull all the water it needs out of the air in humid climates. When I first started running reactions last summer, I was adding no water and it ran fine. When winter came along and the air dried out, my yeilds dropped off. Adding a small amount of water made it run fine again. The reduction requires water in order to happen, yet some water is produced by the imine formation. You need a few milliliters of water to turn the nitromethane into methylamine.
Thin aluminum foil runs hot as shit! Accidentally add too much nitromethane at once and see if you'll ever use thin foil again, especially if there's enough water in the reaction to feed the reduction! I did that once and the flask started hopping off the magnetic stirrer. I had to take the whole flask and dunk it in the cooler being used for the condensor water to calm it back down.
All paths are the same: they lead nowhere
(Title on BackOrder)
07-11-02 16:09
No 331436
methanol stays with the water during basification, while IPA will separate out. When you extract will toluene, you will have 3 layers to deal with.
All paths are the same: they lead nowhere
(Synaptic Self-Mutilator)
07-11-02 21:22
No 331569
The reduction of nitromethane to methylamine produces water.
>methanol stays with the water during basification, while IPA will separate
>out. When you extract will toluene, you will have 3 layers to deal with.
Not true. When you basify the mix, the IPA will form a layer on top. When you add toluene, it will mix with the IPA. Then you extract that top layer, when you go to wash with 5% NaOH (what I recommend) you'll noticed the volume of the extract will instantly shrink. If you used 100ml toluene, and the net volume was 200ml (because it had also picked up some IPA) on the first 5% NaOH wash, the volume of the organic layer will drop back down to like 100ml.
(Hive Addict)
07-11-02 21:29
No 331574
Hehe, well only if there was no MDMA freebase in the toluene/IPA mix. It will add to the volume as well.
there's a big difference between criticizing your government and criticizing your country
(Title on BackOrder)
07-11-02 23:38
No 331607
Where does the hydrogen come from?
(2)Al +(3)H2O + MeNO2 ----> MeNH2 + (2)H2O + Al2O3
this is what I understood the reaction to be, requiring an extra mole of water to occur.
All paths are the same: they lead nowhere
(Hive Bee)
07-12-02 01:30
No 331628
I don't think it will go all the way to oxide. It will stay as the hydroxide. In this case the reaction takes a fair amount of water.
2Al + 4H2O + MeNO2 ----> MeNH2 + 2Al(OH)3
Possibly if there is less water some might go to the oxide.
2Al + H2O + MeNO2 ----> MeNH2 + Al2O3
which would mean
6Al + 2Al(OH)3 + 3MeNO2 ----> 3MeNH2 + 4Al2O3
I don't think that will occur but the favorable kinetics might push it that way.
(Synaptic Self-Mutilator)
07-13-02 03:42
No 332030
>(2)Al +(3)H2O + MeNO2 ----> MeNH2 + (2)H2O + Al2O3
Water is just an initiator for the Al/Hg. I'm pretty sure an alcohol will work as well. At the very most, perhaps one molecule of H2O is required to start the reduction. Again, no worries... no reason to add water. (unless you want to)
Again, I encourage everyone to save their waste acetone and when the container gets full, add an equal volume of water. put on the column, and redistill it for reuse! At my school we just dump it down the drain and say our hail-mary's... it's pretty sad that it's not reused and just dumped straight into the lake...
(Hive Bee)
07-13-02 06:58
No 332061
Can't really top the previous advice but I did notice:
Wonder if theres a way to speed up the amalgamation time?
Little newbee tip here, not sure how widely accepted it is, is to kickstart the reaction with a small amount of (aq)NaOH. Can't say I know why but this speeds up the amalgamation substantially, although I believe that it burns out much quicker, and may effect yeilds (can someone confirm?) But anyway thats an option.
Also, excess mercury salts are simply reduced to the element. You might try more foil, or better, thinner aliminum cut in smaller peices, to increase surface area which would speed up the reaction quite a bit as well.
Just make sure you got icewater recirculating through a condenser of adequate length and this reaction is very forgiving of these minor details.
Of course the big super secret clandestine trick is having good ketone in there in the first place. Someone who is really not myself and someone who is also not myself learned this the hard way awhile back.
Flip
(Title on BackOrder)
07-13-02 08:34
No 332072
water is consumed throughout the entire reaction. The only step that produces any water is the imine formation, which produces one mole of water for every mole of imine formed. The other two reactions require water to run.
All paths are the same: they lead nowhere
(Hive Bee)
07-13-02 08:56
No 332080
Osmium
(Stoni's sexual toy)
02-13-02 05:49
Post 269032 (Osmium: "Re: Hg Amalgamation rates", Chemistry Discourse)
An amalgam is an alloy containing Hg having the interesting property of overvoltage. This means the Al wants to react and dissolve badly with alcohols and water producing H2 in the process, but this reaction is greatly hindered (NOT completely stopped, just slowed down a lot!) since H2 doesn't like to be produced on Hg surfaces.
When there is anything reducable around, like a nitro compound or an imine the Al can dissolve without having to produce H2 gas, and it readily will do so.
This reaction involves electron transfers between the reaction partners, which is just another way of saying the Al is dissolving and gives up its electrons to the Hg which in turn transfers them to the organic reactand to be reduced. It's not the Hg salt that breaks up the Al. If there is nothing around to be reduced then the Al can't get rid of those electrons, and it will not dissolve. Al/Hg in an inert solvent like hexane or toluene should be quite stable for a while. Al/hg will react with oxygen because Al is a very reactive metal which is only protected by its oxide coating (passivation), once that coating is removed it will oxidise in air, but that is usually not an option when covered by a solvent since O2 solubility is very low.
The solvolysis reaction with an alcohol will be very slow with thick Al because it has a much higher Hg loading on its surface and a much lower exposed surface area than foil.
Al/Hg in a pure alcohol: only very slow dissolving via solvolysis. Greatly enhanced by water presence (since Al2O3 formation is very exothermic and the driving force) and change to basic pH
Al/Hg in water: exothermic, will heat up considerably and might eventually react violently
Al/hg with nitro in alcohol: very exothermic reaction due to water formation, and since nitro is hot stuff
Al/Hg with nitro in alcohol containing considerable amounts of water and a base: let's not go there, runaway reaction with foil, very exothermic with sheet
Al/Hg with an imine in alcohol with a littlewater: rather slow and gentle reaction
Foil reacts much faster than sheet!
Don't try to tweak the reaction too much and reinvent the wheel! Al/hg works, in up to 90% according to the literature and some bees experience. And when done without haste and with thick Al it can even be very volume efficient.
This is perhaps the best explanation I have found of the properties of the reaction. It seems to suggest, and please correct me if I am wrong, that the Al/Hg does not by itself break up into slush because H2, the product of the reaction, does not like to be produced on Hg surfaces, and that simply the prescence of the reducable compound and the presence of oxygen(proton source) allow the reaction to take place, ultimately with water as a byproduct of imine formation. Osmium does however state that water is a initiator as well. I think the main function of water is to make absolutley sure you have availiable oxygen to start the reaction, but if for some reason it was present anyway in the solvent I believe that would substantiate Chromic's statement about water's neccessity. I think this would be correct anyway, but i've been up 38 hours.
Or perhaps the solvent alone, rate depending on how strong of a proton donor the alcohol is?
No, Seriously, Chromic, Man, would this interpretation be correct?
Or do I need to read up on redox?
BTW For those of you who didn't know Osmium is obviously a genius.
My hat is off to you. Keep the wisdom coming.Flip
(Synaptic Self-Mutilator)
07-13-02 14:00
No 332159
Ugh, I take back that initiator comment.
(Synaptic Self-Mutilator)
07-14-02 21:12
No 332650
Agreed, Osmium did explain the best. That post is awesome and concurs with all the experimental observations I've made.
(Hive Bee)
01-09-03 23:21
No 396889
"Re: 1) let the foil amalgamate until it starts to vigorously bubble"
"Why does it always take 30-45 minutes for this to happen!? Yields are usually 10% less when rushed and started prematureley."
You have to reduce the amount of solvent covering your al. You will notice a big reduction in amalgamating time if the bare minimum is used to cover the foil. Mine jumped from taking 40 to 55 minutes to about 15. Initiating temp makes a big differnce in time too.