Author Topic: 3,4,5-TMBA -> 3,4,5-TMNS  (Read 3196 times)

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KidCurry

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3,4,5-TMBA -> 3,4,5-TMNS
« on: May 06, 2004, 08:42:00 AM »
More stupid questions coming this way. :D
Just a quick one.
Shulgin does the Henry-reaction with nitromethane and cyclohexylamine as a catalyst in GAA. Is it possible to replace the GAA with methanol? Or is it specifically needed for 3,4,5-TMBA (the same condensation with 2,5-DMBA seems to work fine with alcohol). If not, is it possible to use nitromethane in excess as solvent as with the case when using ammonium acetate? Tried to use the search engine, but could not find any answer. Sorry if this has been covered before. I just want to be sure. ;)

EDIT: Also, is methanol a good choice to recrystallise mescaline freebase in, or is it so solvable?

imp

  • Guest
The MeOH/NaOH rxn works quite well with ...
« Reply #1 on: May 06, 2004, 11:43:00 AM »
The MeOH/NaOH rxn works quite well with 3,4,5-TMB. The yields are reported as 78% in literature, but SWIM usually gets 65% - maybe due to impure aldehyde. It is a very facile route. Make sure to use heavy stirring when dehydrating the nitroalcohol in HCl - it becomes an incredibly thick yellow sludge. You must recrystallize from MeOH or EtOH. Two recrystallizations are ideal.

Mescaline freebase cannot be recrystallized, it is an oil. For the hydrochloride salt, IPA/acetone works wonderfully as a recrystallization solvent. Apparently the sulphate recrystallizes nicely from water.

KidCurry

  • Guest
But for the condensation with cyclohexylamine...
« Reply #2 on: May 06, 2004, 11:50:00 AM »
But for the condensation with cyclohexylamine and not sodium hydrocxide as base/catalyst? I can't see why methanol would not work instead of GAA, but it's better to be safe than sorry.

Theoretically you would do this:
1. Solve 3,4,5-TMBA, nitromethane and cyclohexylamine in methanol.
2. Reflux on waterbath for 1h
3. Let stand overnight with stirring.
4. Pour into icecold water, and filter of 3,4,5-TMNS crystals.
5. Recrystallise

Does it seem ok?

Did not know that, many thanks for the help!
Just dissolve in methanol and make a salt out of it then. :)

hest

  • Guest
Mescaline
« Reply #3 on: May 06, 2004, 12:12:00 PM »
Mescaline is a special, quite problematic, compound to make. Serach my post's for mescaline (and thje synt at rhodium.ws.
For some reason, everyething is harder with TMBA than anye othe aldehyd.
Use one of Shulgins synths (he also write abouth some trouble he have making the styrene)
but It's wort the trouble, greath comp.
have fun

KidCurry

  • Guest
Yes, so I've heard. I can see 2 problems,...
« Reply #4 on: May 06, 2004, 01:09:00 PM »
Yes, so I've heard.
I can see 2 problems, where some people live you need a license to aquire GAA. (Forget that, just remembered that water is a big nono :D) The other problem is low yields/lots of biproducts with the ammonium acetate-condensation. That's why I asked if it was possible to replace the GAA with methanol (of course purelly theoretical). Nobody who could comment this? I'll guess SWIM just has to try it out and see what happens.

imp

  • Guest
Just do it this way!!
« Reply #5 on: May 06, 2004, 03:03:00 PM »
From J Prakt Chem, 1933, pp339.

A solution of 40 cc of nitromethane and 100 g. of trimethoxybenzaldehyde in 200 cc alcohol is cooled to 0 deg C and while it is stirred mechanically there is introduced a solution of 45 g. pure potassium hydroxide in 45 cc water and 90 cc methanol at the rate of about one drop per second, care being taken that the temperature does not rise. Fifteen minutes after the addition is completed the solution is poured into 500 cc concentrated hydrochloric acid mixed with sufficient fee to assure its presence throughout the slow addition and to maintain the temperature of -10 deg C. The precipitated nitrostyrene is separated by filtration and washing and may be purified by recrystallizing from 700 cc alcohol. The pale yellow plates which melt at 120-121 deg C are obtained in a yield of approximately 78% of theory.


Doesn't use cyclohexylamine, ammonium acetate, or GAA. Just keep the basic addition at -5C. At first, much of the aldehyde may precipitate from the alcohol, but as soon as you add about a mL of your base, everything will go back into solution. After the addition of the NaOH solution, you may notice the nitroalcohol solidify creating a slushy mixture - that's okay.
Also, to help make it easier in the dehydration step, dilute the HCl so that you can make stirring easier.

If you're determined to try it your way, go ahead and report back. If you want something that is easy and guarenteed to work, do it as above.

hest - mescaline isn't too bad. Some of those substituted-alkylthio-aldehydes can be a pain though! But in general SWIM doesn't believe in a "universal nitrostyrene catalyst". Every aldehyde has it's own unique character.

KidCurry

  • Guest
Many thanks! That sounds like a feasible and...
« Reply #6 on: May 06, 2004, 03:08:00 PM »
Many very grateful thanks to you!
That sounds like a feasible,very easy and good route, but a little bad yields (guess you can't have everything :)). I've heard that cyclohexylamine gives around 90%, but if GAA cannot be found at the moment I'll guess SWIM thinks low yields are better than none.

Just two questions, I thought water pushed the reaction to the aldehyde in the henry-condensation therefore lowering yields?

And what the heck do they mean with "concentrated hydrochloric acid mixed with sufficient fee to assure its presence"? :D (English is not my native language).

imp

  • Guest
Are you sure??
« Reply #7 on: May 06, 2004, 03:18:00 PM »
Where did you hear 90% yield from!!! SWIM doesn't believe it unless you show a ref!!
Shulgin himself doesn't even get 78% yield with cyclohexylamine (he gets about ~75%). That's why the MeOH/NaOH method is so good for this particular aldehyde.

Mix with sufficient fee - That means you should have strong stirring when you drip the rxn mixture in the HCl. That way the HCl will dehydrate the nitroalcohol immediately. - don't worry, learning english took SWIM a looooooong time!

KidCurry

  • Guest
Really sorry, I'm not sure.
« Reply #8 on: May 06, 2004, 03:23:00 PM »
Really sorry, I'm not sure. :D
All figures in my head from The Hive.
I'm probably just mixing up numbers.

KidCurry

  • Guest
Gassing M with HCl
« Reply #9 on: May 10, 2004, 08:33:00 AM »
One more question.
If doing a Zn/HCl reduction of 3,4,5-TMNS and the amine freebase is extracted with toluene in the final step (after cleanup). Is it possible to gas the toluene (dried with MgSO4 first) with HCl (HCl+CaCl2) in order to obtain crystals (if my calculations are correct about 5g of M would be in 200ml Toluene)? Or is the solubility of Mescaline-HCl too high in toluene so I need to remove it by destillation/under reduced pressure and then solve it in IPA/etc and gas?

Also, will it cause a problem to dry the toluene when the freebase is already in it? Because if someone dries it first, then extracts the amine it gets wet, right? And the whole point was to be able to skip the removal of toluene. :)

hest

  • Guest
M
« Reply #10 on: May 10, 2004, 02:07:00 PM »
Gassing in toluene is ok, but why not make the sulfate salt form wather ? you will get dammm nice xtals.
Remember taht you will eat 4-600mg of the salt, so make it clean (rextalise from ethanol (the hydrochloride) or wather (the sulphate)).

KidCurry

  • Guest
Because where SWIM lives it is nearly ...
« Reply #11 on: May 10, 2004, 02:26:00 PM »
Because where SWIM lives it is nearly impossible to aquire sulphuric acid (both concentrated and diluted (ie battery acid) nowadays require a license to sell/handle(!) and all car batteries are sold filled up). Recrystallisation would be done with IPA instead of ethanol (only denatured ethanol is avaible (MEK, methanol and colouring agent)).

Again, many thanks! I think everything is pretty clear now. :D

GC_MS

  • Guest
M(urder)
« Reply #12 on: May 10, 2004, 05:20:00 PM »
Remember taht you will eat 4-600mg of the salt, so make it clean (rextalise from ethanol (the hydrochloride) or wather (the sulphate)).

OK, before some kiddies are finished chopping down those giant San Pedro cacti and extracted all the mescaline, it should be said that 400-600 mg mescaline sulfate is quite a high amount for a novice. The very first time I consumed a psychedelic substance, I took 400 mg of M (sulfate salt, in one portion). I learned to treat some substances with more respect... I would advise 200 mg, to begin with. You can go to 400 mg and more once you know the dril. The substance is well fit for personal journeys, and taking additional amounts of it has been described not only here at the Hive.


amine

  • Guest
good luck with the Zn/HCl reaction.
« Reply #13 on: May 10, 2004, 07:59:00 PM »
Swim has had minimal experience when it comes down to reduction via Zn/Hcl. the entire proceedure is extremely tedious and painful. Have you looked into nitrostyrene reduction via Al/Hg (posted on rhodiums website). It uses GAA but that could be replaced with 60% acetic acid. (photochem companies sell this I believe).

Anyone know if this proceedure can be scaled up w/o much hassle?

hest

  • Guest
M
« Reply #14 on: May 10, 2004, 11:50:00 PM »
1: read GCMS's post he is ruiight. Start with 200mg (sometimes we 'old peaple' forget how the first ruch was)

2: It's my oppinion that the Al/Hg reduction is the most safe one. There are some stories abouth wolkanoes wit the zn/acetic.
Read all the poitives post from bandil and barium.

KidCurry

  • Guest
Crappy yield
« Reply #15 on: June 30, 2004, 07:22:00 AM »
Someone I don't even know apparently tried the above route (nitromethane, aldehyde + koh then acid).
Unfortunately he was not very concentrated, and had problems keeping temperatures down. You could say he was a bit sloppy.

Yield was only about 20-21g from 50g benzaldehyde after recrystallisation from methanol. But atleast it looks pretty nice. :)

Filtrate was put back in freezer to see if more crystals came out of solution. What do you think? Before the recrystallisation it apparently was a pretty huge mass of nitrostyrene all wet, like a paste which was dried overnight. Almost 400ml of boiling methanol had to be used to dissolve the mass.

Maybe boiling down the methanol would be an idea, but what to do with the fumes? Going blind sucks.




Rhodium

  • Guest
Nifty Lab Technique
« Reply #16 on: June 30, 2004, 07:33:00 AM »
Maybe boiling down the methanol would be an idea, but what to do with the fumes? Going blind sucks.

The last time I checked, distillation setups worked wonders to condense solvent fumes evaporating from a boiling solution.