urushibara (Stranger)
02-21-02 16:33
No 271669
      Decarboxylating Tryptophan  Bookmark   

Some more questions and ideas from a new bee:

It seems to me that the simplest routes to synthetic DMT start with tryptamine, and tryptamine can be easily made by carboxylating tryptophan, so I am looking for ways to make decarboxylation easier.

Firstly I will explain decarboxylation as I understand it (from my searches on the web). Decarboxylation is the release of CO2 from a carboxylic acid. According to most accounts I have read, this is a simple reaction with dicarboxylic acids, which is due to the close proximity of a double-bonded oxygen to the carboxylic acid group. Okay, so that's why all the methods thus far posted involve a ketone, as the ketone catalyses the oxidation. (just a question: does the ketone degrade or is it left untouched, just behaving like a good catalyst should).

So, having thought quite a bit about it first I want to find out whether just using a ketone as the solvent to catalyse the reaction, as opposed to dissolving the ketone in a heavy non-polar solvent (hexanol, tetralin) would work. That is to say, dissolve tryptophan in acetone and reflux. If =O is crucial to the reaction, then surely lots of it will make it go faster?

My second idea is a different one. What about using esters to dissolve the tryptophan. Esters have =O's on them, some more than others - for example, diethyl fumarate would have two on it. Esters are very easy to make, one just needs to mix an alcohol and a carboxylic acid in the presence of a strong acid (HCl, H2SO4) and voila. If we want a big molecule that won't boil until at least 150 C, one could use ascorbic acid and cyclohexanol (cyclohexyl ascorbate ester). It would have the prerequisite =O group on it and a nice high bp.

I would think that it would be better to use a lower bp solvent though, since ultimately at the end the best product for the next reactions is freebase (since it is hydrophobic and anhydrousness is important to most reactions involving alkylation) and a nice volatile solvent will separate from our higher mp freebase more easily, methyl formate would evap very quickly (bp: 32 C). Perhaps isopropyl citrate or tartarate? A low mp ester such as methyl formate would be useful in that the whole reaction would be self-agitated by the convection in such a light liquid. Also it would be very easy to do the workup for it (methanol oxidises--> formic acid; mix formic acid w/methanol + HCl heat--> methyl formate). Perhaps it would take a lot longer...

Still, what is the hive's advice on using esters in decarboxylation?

C12H16N2
 
 
 
 
    hypo
(Hive Bee)
02-22-02 00:21
No 271904
      Re: Decarboxylating Tryptophan  Bookmark   


Okay, so that's why all the methods thus far posted involve a ketone,



wrong. see decarboxylation via the copper chelate of tryptophan.


I would think that it would be better to use a lower bp solvent



i do not understand. the point of using heavy solvents is that the reaction needs lots of heat. the only way to achieve that in a low boiling solvent is pressure => push the CO2 right back in...tongue

 
 
 
 
    urushibara
(Stranger)
02-22-02 01:11
No 271923
      Re: Decarboxylating Tryptophan  Bookmark   

I saw that copper chelation method, and it seemed rather convoluted and messy when all that is needed is some way to stimulate the CO2 to release from the amino acid.

As to the bp thing, exactly how does pressure make the CO2 go back in? Back in where? CO2 is pretty stable, it might make carbonate if there was water around otherwise it would just dissolve in the methanol/ester solution. Making carboxylic acids is a little more complicated than that, in fact you have to oxidise alcohols, and our hypothetical high-pressure carbon dioxide environment wouldn't allow much oxidation to go on. Also, CO2 release from carboxylic acids is a one-way reaction. That's why it doesn't take much energy to do it.

And the temperature thing is just a time factor. Using methyl formate, as I have suggested, may take 24 hours, maybe 48. In case you didn't notice, we are not in an absolute zero environment, and room temp would prompt quite a bit of decarboxylation with the presence of the ketone group catalysis (which an ester would provide).

If a suitable reaction vessel were used, something which could handle the pressure of our solvents at about 80-90C, (I was thinking that a champagne bottle, but maybe soda glass wouldn't like being that hot and pressurised - and if it was used a few times could be a bit liable to crack open), it could be cooked at pressure, though it would probably need to be cooled (slowly slowly unless you got borosilicate) and vented a few times to get the CO2 outta there.

Anyway, the point is that using methyl formate would decarboxylate (via the =O group on it), and then with more time would make the formamide (it might be the opposite order - there's something to discuss). Reflux might be better, but the pressure you spoke of would keep the solvents in liquid phase, which is equivalent to higher bp solvent at reflux. There would still be a lot of kinetic energy in there making both decarboxylation and formamidisation happen at a reasonably decent rate.

You wouldn't want to do it with an ester unless you wanted the acid end of the ester on the amine tail of the tryptamine anyway. I have just such a synthesis in mind in another thread. I was just casting about to see if anyone could find any major objections to having an ester provide the =O catalyst for decarboxylation. (other than the byproduct I have already mentioned).

C12H16N2
 
 
 
 
    urushibara
(Stranger)
02-22-02 01:20
No 271927
      Re: Decarboxylating Tryptophan  Bookmark   

Pardon me, esters wouldn't be all that good, but the question is, could you go from amino acid to formamide via a something-formate? A big acid, like ascorbic (in the aforementioned hex-something ascorbate) might be okay because there's no way that ascorbate ions could stick on the end of the tryptamine - or is there? Hmmm...

Perhaps hexanol/formic acid ester would be good for its higher bp, if one desired the formamide at the end.

I thought of a way to name the formamide at last: N,N dimethal tryptamine. al for the aldehyde thing (really it's not just formic acid groups on the N, it's aldehydes, H-CO=O). Or N,N dicarboxyl tryptamine? I'm leaning towards the methal personally, since there isn't an OH on it.

C12H16N2
 
 
 
 
    hypo
(Hive Bee)
02-22-02 01:36
No 271935
      Re: Decarboxylating Tryptophan  Bookmark   


I saw that copper chelation method, and it seemed rather convoluted and messy



not so! the first step is a wonderful reaction with consistent yields. the second step is done in 10 minutes. the only problem we have to solve is the workup.


As to the bp thing, exactly how does pressure make the CO2 go back in?



now come on... don't take everything so literally. high pressure will not favor CO2 release...


And the temperature thing is just a time factor.



an exponential factor...

all in all - i don't know... tetraline is one of the cheaper solvents and you need a vacuum pump anyway.

 
 
 
 
    hest
(Hive Bee)
02-22-02 11:28
No 272114
      Re: Decarboxylating Tryptophan  Bookmark   

----------------------
And the temperature thing is just a time factor.
----------------------
No, you need a sertain amounth off energee before the reaction start to run (just as gasoline don't burn in the tank)
And why work with the decarboxylation of trypthophan, in cuclohexanol and with a ketone with a high boilingpoint the yeald is in the 90'

 
 
 
 
 
 
    terbium
(Old P2P Cook)
02-22-02 11:54
No 272132
      Re: Decarboxylating Tryptophan  Bookmark   

Personally, I am getting tried of urushibara's ramblings. He does not do a very good fman impersonation. Until he can improve his fman act he should move this stuff over to the Couch.
 
 
 
 
    urushibara
(Stranger)
02-22-02 15:47
No 272253
      Re: Decarboxylating Tryptophan  Bookmark   

I agree that reflux is better than a pressurised rxn vessel in some ways. Mainly when we try to decarboxylate our carboxylic acid in a quantity that would evolve more gas than the strength of our vessel can withstand.

22.4L of CO2 (at 0C and 101.3kpa) must evolve from every mole of tryptophan (204.2g). I don't see how gas pressure, which does not affect our liquid phase reaction except by limiting evaporation when the gas is saturated, and furthermore, so long as there's enough heat making things all jumpy, enough so the carboxylic acid deforms and breaks off with the help of our ketone group (in whatever form we introduce it). A reasonable amount of the CO2 will stay dissolved in the solvent, not much, but a little, and more with greater pressure, and the gas phase will just get denser and denser (higher and higher pressure).

I did some gas pressure calculations with regard to a hypothetical .048 mol of tryptophan (10g) in a 700ml (space for gas) reaction vessel, and the gas pressure of 700ml of that much CO2 is 238kpa, or 2.3atm at 137C, which is not all that much - you could probably generate that much pressure in that space with your breath. If you cooled the reaction mix to -18 in a freezer with the lid open, close it once it's temp is as low as the rest of the freezer, ( I imagine a champagne bottle with the pressure holding cage on the 'cork'), then put your reaction vessel into an oil bath at a steady 140C, I think that the total gas pressure would scarcely exceed 300kpa (or about 3atm) which should be perfectly safe in my imagined vessel) Could anyone tell me what the maximum pressure that champagne bottles must withstand? I imagine it's something around 6-7 atmospheres. A buchner flask or thickwall flask should be able to handle it too. If you put the vessel in the freezer first (-18C), the air in the bottle is at sub atmosphere pressures (like about 1/4 - I could calculate it but I'm being lazy). when that amount of gas is heated to 150 it would barely reach atmospheric, which the CO2 will happily dissolve into the gas phase at least up to two atmospheres, but I reckon it could do it up to three. And by then we've decarbed 10g of tryptophan. If one wished to decarb more, I imagine one could cool the vessel down to below the bp of our solvent, open it and vent the CO2, cool it right down in the freezer again, close up and do it again. Gas pressure will not stop the decaboxylation, gas pressure will just increase with the rate of the decarb. Kinetic energy powers the reaction, which relies on a ketone bumping hard into the O-H and the H on the tryptophan chain next to the carboxylic acid group, enough so the bonds can exchange, the O from the O-H double bonds with the carbon and the H bonds with the carbon on the now tryptamine (well, after it happens). Gas pressure only affects evaporation of the solvent, it does nothing to stop explosive quantities of gas evolving from the liquid through other mechanisms which involve reactions or what have you. It does affect the reaction when the gas pressure gets so high the liquid phase becomes saturated with the pressurised gas though, but again, not all that much, and with CO2 it might actually help the reaction by providing more possibilities of an =O crashing into the carboxylic acid and releasing yet another carbon dioxide.

Yes I am rambling now. Somebody around here says that I ramble. Well, I say that I'm just verbose. Nobody suffers when verbosity enters a scientific discussion. More detail is always helpful.

C12H16N2
 
 
 
 
    slappy
(Hive Bee)
02-23-02 21:46
No 272789
      Re: Decarboxylating Tryptophan  Bookmark   


Yes I am rambling now. Somebody around here says that I ramble. Well, I say that I'm just verbose. Nobody suffers when verbosity enters a scientific discussion. More detail is always helpful.




The disscussion suffers when that verbose person is talking out of thier ass. You don't understand what you are talking about well enough to be so verbose about it. You need a good dose of humility.

And I would recommend that you read up on thermodynamics and organic reaction mechanisms.

 
 
 
 
    dely72
(Newbee)
02-25-02 01:03
No 273269
      Re: Decarboxylating Tryptophan  Bookmark   

Wise man once say:  "Those who know the most say the least, and those who know the least say the most."

Very wise man indeed in my opinion.

Some care more about impressing others with their supposed knowledge than making the finished product. Why waste time trying to develope novel synths that are in no way easier than known ones when there are perfectly fine synths requiring perfectly easy to obtain precursers?
 
 
 
 
    urushibara
(Newbee)
02-25-02 16:25
No 273483
      Re: Decarboxylating Tryptophan  Bookmark   

(chastened)

Can anyone give a definite answer on the effect of pressure on decarboxylation?

I saw a thing on creating coal-like fuels from peat and other organic carbon-rich things, and the first step was cooking the stuff up at high pressure, like a pressure cooker, and one of the things that was said to happen in this high pressure environment was decarboxylation. Since aminos will not spontaneously decarboxylate, they  need a catalyst, one suitable catalyst is acetone. I feel that a test of decarboxylation at pressure needs to be performed.

Thus an experiment will be undertaken: create a pressure-chamber with galvanised steel pipe and end caps that can be removed to add and remove contents. Tyrosine extracted from tablets (using relative insolubility of tyrosine to isolate lactose binder from amino acid) added to chamber with a quantity of acetone. Chamber is placed in an oven preheated to 200C, baked for 10-15 minutes. Allow to cool, empty contents. If successful the product will boil at a much lower temperature than the amino acid.


C12H16N2
 
 
 
 
    Lilienthal
(Moderator)
02-25-02 19:21
No 273563
      Re: Decarboxylating Tryptophan  Bookmark   

Don't kill yourself!!! If you have no training in (high-pressure) chemistry don't do it!

Why not using published procedures with higher boiling solvents (or OTC variations)? Use the search engine for turpentine thinner (tetraline and decaline) and see Post 175553 (element109: "Tryptophan to tryptamine: practical xperiences", Tryptamine Chemistry) for use of thujone as the ketone catalyst. Checking that out would be of great significance compared to the kamikaze-type high pressure reactions you are planning wink.
 
 
 
 
    urushibara
(Newbee)
02-25-02 22:52
No 273648
      Re: Decarboxylating Tryptophan  Bookmark   

I don't know Lil, I think that assuming I seal the pipe with ptfe tape and really REALLY tighten it, 200C should be okay. If it starts leaking I will find out in the water/test phase. And as you would know, water at 200C is higher pressure than acetone at the same temp, so a water test will be conclusive. And also to add to that there is the idea of filling the pipe up so the gas space is only like 50-100ml, which will account for liquid expansion and give less gas space to build up enough pressure to make it pop. If it doesn't pop with water, it definitely won't with acetone. Oh bottom end sealed with locktite, or something similar.

C12H16N2
 
 
 
 
    Lilienthal
(Moderator)
02-26-02 06:38
No 273780
      Re: Decarboxylating Tryptophan  Bookmark   

Add shielding, stay away, NEVER fill more than 1/3 so you have at least 2/3 gas space!!! Better don't do it!
 
 
 
 
    urushibara
(Newbee)
02-28-02 02:33
No 274687
      Re: Decarboxylating Tryptophan  Bookmark   

Lilienthal, I just thought you might wanna know that I dreamed I made a pipe-bomb reactor out of galvanised water piping (a 3 inch double-nipple piece with two round end-caps), sealed with teflon tape (I even did one side dodgy with the tape going anti-clockwise).

In my dream I used vice-grips and a multigrips to tighten it up, tight as hell I made it. The pipe contained about 30ml of acetone and (well, I don't know really how much) of tyrosine. Anyhow, in the dream the pipe didn't leak in boiling water at 101 (I live next to the sea, I'm guessing that my thermo is a little inaccurate), so I put it into the oven at 200C, turned off the oven while it sat in that temp for five minutes. Opened it up and no tell-tale smell of 'tone, so I amped it up to 250, left it on for ten minutes. Still no boom. No dream about getting 3-OH phenethylamine out of it yet... soon, soon.

Disclaimer: everything I said I pulled outta my arse laugh
 
 
 
 
    urushibara
(Newbee)
02-28-02 02:57
No 274695
      Re: Decarboxylating Tryptophan  Bookmark   

In a subsequent dream I opened up the pipe, it was at room temp now, so if nothing happened there shouldn't have been gassing, but there was gassing, just a little pffft. And the most joyous thing of all was that the previously white powder that I thought was probably tyrosine, there's still a little white, probably chalk that got through the filter paper; but the solution is orange, and so is the bulk of the solids in there. It kinda looks fluorescent, but there was no handy UV light in my dream so I couldn't test that one.

Dwarfer's bin playing around with pressure pipes for ages, I wonder why no-one else dared to. No boom boom risk so long as you really REALLY tighten the hell outta the pipe. And with decarbing, as we all know you don't need much acetone mixed with the tetralin, 30ml would probably easily decarb 5g of stuff. Well, another thing I can report from the dream is that the liquid was still acetone, it doesn't change, it only encourages the carboxylic acid to go poof. Thus my dream pipe-reactor, with a total volume capacity of about 55ml, is plenty for up to about 10-15g of aminos.

I wanna get me some tryptophan goddammit. Wish I wasn't so fuckin broke. Wish I wasn't in a country with such a piss-poor exchange rate with US $. Fuck. Well, there'll be more dreams coming, involving getting this orange stuff and heating it with flames from underneath on a spoon to see if it boils easy. Don't have a thermo to do that proper either... Won't be entirely conclusive dreams, but color-change is a big deal, nonetheless.

Disclaimer: everything I said I pulled outta my arse laugh
 
 
 
 
    urushibara
(Hive Bee)
02-28-02 06:55
No 274747
      Re: Decarboxylating Tryptophan  Bookmark   

And I fell asleep again and had another dream. In the dream the orange stuff was dried out and scraped up. The smell is vaguely reminiscent of solder flux, but somehow different. There was also a trace of a menthol type smell, possibly residue in the acetone or from in the pressure pipe (it had some kind of grease in it, which I hadn't cleaned up properly. When placed on foil and heat from a lighter applied, it boiled violently, releasing smoke, very much reminiscent of some bad DMT extract I once smoked a few times, bubbling and letting a white looking smoke that stank the place up quite a bit.

Unfortunately in the dream I had no device to measure the bp of the stuff, but from memory lighter flames are somewhere about 300C, so though there might have been some remaining amino acids in it, it had obviously been changed as it boiled almost immediately, and the smell had distinctly changed from the original material, though some of that element may have been contaminants in the acetone and in the pipe. Oh the other thing which suggests it to be an amine: it was bitter.

I put some of it on a piece of plastic, and magickally it appeared as a jpeg on my computer's hard disk in the real world, I discovered upon waking. I have posted a scan of it at 1200dpi, which you can find at http://www.angelfire.com/darkside/urushibara/index.htm

This stuff smelled contaminated with the solvent, but there was no trace of the original amino acid smell either. I've never seen meth freebase, only DMT freebase, but it sure seemed a lot like freebase. And it boiled like freebase. Though there might have been traces of everything else from the tabs.

Anyway, swim's gonna be getting some pure aminos for the next experiment, cos something definitely happened.

What yas think about the picture?

Oh, sorry, that white stuff is the original stuff that underwent the change to the brownish orange (presumably tyrosine). In my dream there was no methanol for me to use, so nothing's crystalline. Next time recrystallisation will be dreamt.


Disclaimer: everything I said I pulled outta my arse laugh
 
 
 
 
    urushibara
(Hive Bee)
03-01-02 15:11
No 275484
      Re: Decarboxylating Tryptophan  Bookmark   

Swim did a second experiment. About 3g of lysine this time, in the same apparatus, tightened fully. Placed in boiling water, no signs of gas leaking. Placed in oven set at 250C, oven left on until thermostat turned off the heat, then switched off oven and left overnight to cool (did not open until morning).
   Again no signs of stress, nothing to suggest the pipe was holding more pressure than it could handle.
   Inside the pipe the acetone had turned yellow. Swim'll be posting his pictures soon, the starting material, Lysine behaves very peculiarly when it's crystallising, when the water is saturated, it forms a skin around the water. It had to be baked at 200 to get it to dry properly. Weighed on a dye scale it weighed in at 24g, which was the expected quantity, it just looked a lot more bulky than the weight suggested (lysine makes very fluffy crystals obviously). Anyway the stuff put in wasn't fully crushed so lots of it didn't react. Pictures will be at the same url as the last post shortly.
    Lysine decarboxylate freebase is very different, not very soluble in acetone or water. I think part of the colour changes has been cooking the additive in the acetone, which turns it yellow and makes it smell like menthol. I was wondering if it was adulterated. Evidently the acetone cooks the additive into something else too.
   The address again: http://www.angelfire.com/darkside/urushibara/index.htm
   Second experiment proves that the pressure pipe can withstand 250C.
   Swim's not planning on doing another experiment until he gets some tryptophan. Possibly also he might get a bigger pipe.

An addendum: The substance which swim thought was a byproduct of contamination dried out, the menthol evaporated, and a free-base looking gum was left behind. It was still slightly contaminated with the menthol smelling stuff, as evidenced by the smell of it when boiled on foil with a lighter, but a distinct freebase type smell was also produced. Furthermore, the material had a strong bitter taste.

Swim's not entirely sure what the insoluble product was. Possibly high-pressure acetone does more than just decarboxylate. The other possiblility is that it was the remains of the tyrosine from the first experiment that had been previously baked in with the container open, and perhaps this brown stuff was the binder used to make the insoluble tyrosine stick to the chalk. Or possibly swimm did the extract wrong, and there was very little chalk and he threw away the chalky stuff, which might have been the very insoluble tyrosine.

Anyway, the decarboxylated lysine stuff, the gummy freebase looking stuff - swim's redissolved in acetone and with luck it will recrystallise, so pretty pictures can be taken... stay tuned.

Sigh. Swim had better hurry up and get tryptophan powder...


I know naaaathing.
 
 
 
 
    Student
(Stranger)
03-04-02 06:50
No 276680
      Re: Decarboxylating Tryptophan  Bookmark   

An Exspearmint with Tryptophan


Add 500 mg of tryptophan and 15 mg (1 drop) of spearmint oil to a 10 by 150 mm test tube and wash down the sides with 5 mL of xylene or turpentine. Add boiling stones or a stir bar and cork the tube gently. Boil the mixture at a rate sufficient to heat the tube an inch or two above the liquid until all the suspended solid has dissolved. Turn off any stirring and let the tube of clear yellow liquid cool undisturbed. The next day pour off the colorless liquid into a dish and place the hose from an aquarium air pump into the tube and let the solvent evaporate. The yield (using xylene as solvent) of yellow crystals of tryptamine in the tube is 61-87%, melting at 104-105C (Merck 118C). There is a small additional crop of crystals from the evaporated mother liquor.

Notes:

1. The tube is corked to prevent the solvent from evaporating. The system is not intended to be sealed.

2. If xylene is used as the solvent the reaction will require about a week to complete but all the product tends to separate as crystals. If turpentine is used the reaction takes several hours, but part of the product comes out as an oil.

3. The rate of boiling needs to be sufficient to prevent the reaction mixture from being exposed to air. Air exposure causes a dark deposit to form on the test tube walls and no product can be isolated even by acid extraction.

4. Other oils which will probably work are caraway, dill or pennyroyal oil.

Suggestions for future refinement:

1. Try using butanone instead of spearmint oil with turpentine as the solvent, giving the reaction a week to complete.

2. After a reaction using turpentine, place the test tube in boiling water to cool. After a few minutes add a seed crystal and let the water cool slowly with the tube in it. This may allow complete crystallization of the product.

3. Increasing the amount of tryptophan, or adding more tryptophan at the end of the reaction and waiting for it to react, may increase the yield or reduce the required proportion of solvent and catalyst.

4. Determine the optimum concentration of catalyst.

Bonus question:

Why does spearmint oil catalyze the reaction better than butanone?
 
 
 
 
    foxy2
(Distinctive Doe)
03-04-02 07:02
No 276684
      Re: Decarboxylating Tryptophan  Bookmark   

Student
Did you do this??
If so how did you boil xylene for a week in a test tube with only a cork to prevent it from evaporateing?

Something tells me that this won't work
please elaborate
Foxy

Make a Difference Donate Now!! (http://www.lp.org/drugwar/)
 
 
 
 
    Student
(Stranger)
03-04-02 07:26
No 276698
      Re: Decarboxylating Tryptophan  Bookmark   

Yes, those yields are legitimate, but rather than a cork, a test tube with a screw cap was used and the cap was left slightly loose. I suggested the cork because that will work with common test tubes. Occasionally the heat needed to be lowered during the reaction to reduce solvent loss, but usually not.
 
 
 
 
    urushibara
(Hive Bee)
03-04-02 15:06
No 276886
      Re: Decarboxylating Tryptophan  Bookmark   

Foxy, you didn't read right, that's terpentine (or tetralin or something similar) with butanone, not xylene.

I know naaaathing.
 
 
 
 
    Student
(Stranger)
03-04-02 18:42
No 276977
      Re: Decarboxylating Tryptophan  Bookmark   

No, Foxy read correctly. Decarboxylation occurs in either xylene or turpentine under the conditions specified. The confusion may be about how to reflux the reaction mixture without a condenser. In this case, the wall of the test tube above the liquid surface serves as an air condenser. Air condensers are very effective with high boiling liquids, and even xylene boils high enough in this case to be made to work. The important thing is to keep the vapor part way up the tube, so that air doesn't reach the liquid nor does vapor climb to the mouth of the tube (heating the entire tube to xylene's bp) and escape. Of course there is nothing wrong with using a reflux condenser if you have one.
 
 
 
 
    foxy2
(Distinctive Doe)
03-04-02 18:56
No 276987
      Re: Decarboxylating Tryptophan  Bookmark   

"The important thing is to keep the vapor part way up the tube, so that air doesn't reach the liquid"

I HIGHLY doubt that effectively keeps air out,
Why not just purge with inert gas and tape a ballon to the top?  Or maybee you would need to use a nitrile glove so it has some xylene resistance.

Make a Difference Donate Now!! (http://www.lp.org/drugwar/)
 
 
 
 
    Lilienthal
(Moderator)
03-04-02 21:43
No 277055
      Re: Decarboxylating Tryptophan  Bookmark   

Did you use real turpentine oil or decaline / tetraline (thinner)? Did you use other methods to be sure it's tryptamine?
 
 
 
 
    Student
(Stranger)
03-05-02 06:45
No 277185
      Re: Decarboxylating Tryptophan  Bookmark   

The reason I think that the solvent vapor is excluding air is that when the reaction is simmered it turns dark and deposits solid and no product can be isolated. When the reaction is boiled more rapidly, the solution only becomes yellow and there is no solid whatsoever deposited below the surface of the liquid, and crystals of product form upon cooling. I haven't used an inert atmosphere because it doesn't seem to be necessary, and I wanted to keep the procedure as simple as possible.

The turpentine was from a can from the hardware store labeled "Turpentine", though I haven't analyzed or purified it or measured the temperature of reflux. The xylene was distilled once. The product melted a bit low, but it was crude product after all, and it smelled the way a tryptamine ought and was one spot on TLC. It also dissolved well in hot solvents, unlike the side product I got when the reaction was exposed to air.

You may be surprised that the reaction works even in xylene, which boils lower than any successful reaction solvent reported so far. If a regular ketone like butanone were used, the reaction would fail, as expected, since the temperature is 60 degrees below tetralin's bp, and even in tetralin the reaction takes hours. A week of reflux with butanone in xylene lead to no apparent decarboxylation. frown
 
 
 
 
    Lilienthal
(Moderator)
03-05-02 07:22
No 277197
      Re: Decarboxylating Tryptophan  Bookmark   

Sounds great! Which type of mint oil did you use? Spearmint contains 50% or so of carvone (unsaturated ketone) while peppermint is mostly menthol (?) (useless).
 
 
 
 
    Student
(Stranger)
03-05-02 09:19
No 277244
      Re: Decarboxylating Tryptophan  Bookmark   

Why, yes, carvone is an unsaturated ketone (an enone)! smile I forget the brand of spearmint oil, but it is the pure, essential oil used in aromatherapy. My first success was by extracting crushed caraway seeds with xylene and using the xylene for the reaction, but the product wasn't as pure.
 
 
 
 
    foxy2
(Distinctive Doe)
03-05-02 10:22
No 277275
      Re: Decarboxylating Tryptophan  Bookmark   

Yes you found the right OTC ketone!
It definately appears that enone's allow the decarboxylation to happen at lower temps.  The references without them appear to bee more along the lines of brute force(high temp) decarboxylations.
smile

Here is a thought
I'll bet that useing menthol(5-methyl-2-(1-methylethyl)-Cyclohexanol) as the solvent would dramatically speed things up.  Its close to cyclohexanol in structure and boils at 212C, while turpentine boils at about 155C.  Or limonene, BP=176C and you can get pure otc.


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    Student
(Stranger)
03-05-02 12:00
No 277303
      Re: Decarboxylating Tryptophan  Bookmark   

The Merck has 154-170 for turpentine, and if it were distilled you could take your pick within that range. The reaction with turpentine was done after 10 hours, but it may have been done well before then. I just didn't get around to checking it. I don't think menthol would be worth the expense and difficulty of evaporating from the crystals, but at least it would smell nicer.wink One improvement I though of was using a dienone. Maybe the trend would continue, and decarboxylation would be fast in toluene? I couldn't find any OTC dienones. Beta-ionone, used in perfumery, is the closest. However, Rhodium just suggested benzalacetone as a catalyst Post 277174 (Rhodium: "Re: New Tryptophan Decarboxylation Reference", Tryptamine Chemistry), and although it isn't as convenient as carvone, dibenzalacetone is made by the same method, and that is a dienone.
 
 
 
 
    foxy2
(Distinctive Doe)
03-05-02 12:41
No 277321
      Re: Decarboxylating Tryptophan  Bookmark   

"The Merck has 154-170 for turpentine, and if it were distilled you could take your pick within that range."

Not Really
Trust me, this would bee WAY WAY WAY more work than just buying a higher boiling solvent.  You cannot easily separate compounds with such a narrow boiling range.  Limonene is citrus solvent, you can find it sold 100% and that smells 1000 times better than turpentine, Oranges.

"I don't think menthol would be worth the expense and difficulty of evaporating from the crystals, but at least it would smell nicer"

The reason to use it is to do things faster, and smell helps.  No need to evap the menthol, just add say 1X toluene when the reaction is done.  Then you will have liquid menthol/toluene which you can extract the Tryptamine from with acidic water. (As shown below.)
Then you can evaporate off the toluene and recover your menthol.
toluene BP=111C
menthol BP=212C
And the Toluene azeotrope will dry the menthol, bonus.


../rhodium/chemistry /tryptophan.html
Purification of Tryptamine

A good way to purify tryptamine without having to resort to distillation under strong vacuum is to dissolve the crude tryptamine hydrochloride in water, adjust the pH to between 7.6 and 8.2 and extract the solution with chloroform. The pH is then adjusted to 14 with NaOH and the pure tryptamine is filtered off with suction and air dried.

Also
Menthol can bee had easily for less than $30/kilo. 
That should last you a while.

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    urushibara
(Hive Bee)
03-05-02 15:12
No 277386
      Re: Decarboxylating Tryptophan  Bookmark   

Student was saying that excluding air from the reaction seems to assist it. I wonder if starting with hot acetone or giving it a good fuckin shake before fully sealing it up would be helpful in the same way for the pressure pipe. In one of the experiments swim did there was a dark brown insoluble mass formed. Though swim isn't sure that the dark brown stuff wasn't a byproduct of not cleaning the pipe from the first one.

Anyway, thankyou to the interested mathematician on the crystal board (lythande) the working burst pressure of swim's pipe was 1600psi, or 108 atm. It generated about 6.6atm at 250C, according to my calculations, though it could be + or - 20%. Still well under half the burst pressure, and well under half the acetone decomposition temperature/pressure. Under by a factor of 6. I think that it could be called safe.

Swim's got some nice pure aminos planned for the near future, and some good scales to give a quantitative result. Tryptophan this time he says. Should provide a more conclusive experiment.

I know naaaathing.
 
 
 
 
    Student
(Stranger)
03-06-02 06:45
No 277831
      Re: Decarboxylating Tryptophan  Bookmark   

Your idea of using acetone under pressure is very inventive, and I wouldn't be surprised if it works. Pure acetophenone works, according to an abstract I saw once. Although shaking with the acetone will displace some of the air with acetone vapor, you could replace all the air by blowing propane, butane or carbon dioxide into the pipe before sealing it. Butane may be the most convenient. The only problem I see with your method for the hobbyist is that not everyone is as safety conscious as you are.

When I researched a better way to make tryptamine my goals were to use cheap OTC materials and to make the procedure as simple as possible, not for my own sake but for the benefit of the people who use this forum. I started with Drone's procedure using xylene and butanone, which are highly available, but it didn't work. I didn't know that menthol or limonene were commonly available, so I tried other solvents, and finally found success with xylene and turpentine when using an enone catalyst. The smell of these solvents, or the time needed for the reaction, were not major concerns. All the solvent except what evaporates from the crystals can probably be used directly for the next batch. There was no smell during the reaction. Tryptamine may not crystallize from menthol, in which case extraction would be mandatory rather than optional. If I use an Erlenmeyer flask for the reaction, all I have to do for work-up is pour out the solvent and leave the flask on its side for a few days until the cake of crystals on the bottom is dry. As long as this reaction requires heat, I don't see how the procedure could be further simplified.
  I just checked out the product from using turpentine. Even though it had several days to dry in a stream of air, it still smells or turpentine and is a bit gummy. The yield is above 90%, but it remains to be seem whether further drying will reduce this. I suspect that this turpentine may have a non-volatile residue and will require distillation before use. Limonene might be a nice alternative.
 
 
 
 
    urushibara
(Hive Bee)
03-09-02 00:04
No 279340
      Re: Decarboxylating Tryptophan  Bookmark   

Dwarfer seems to be convinced that 250C in acetone is dangerous. I keep on seeing the figure 235C and the word critical in msds' does this mean the acetone goes supercritical, or thermal? I thought acetone needed to be at 523C to go thermal (chemical breakdown/oxidation boom).

Dwarfer also said that at 250 the pipe was at 1000psi. He didn't tell me what numbers he calculated from, or what formula. My calculations came out twice as 100psi, or 6.6atm. fuckin bastards with all these 500000 million bloody pressure units.

Oh it definitely works - and it seems also that the material doesn't have to fully dissolve, so long as it is pure aminos the acetone works on it anyway. From pulling the device out of the oven at 200, when it is gently jiggled it doesn't sound like there's anything in the pipe.

My experiments with amino acids have been somewhat messed up by the need to extract from tablets - at this point I am not sure about insoluble bits from the reaction, whether they are contaminants or what. Tyrosine produced something dark orange which didn't want to dissolve in acetone, separate from the freebase oil. The lysine too, had a solid un-changed element in the product. Again, I can't rule out that it was in fact CaCl or whatever, or lactose or whatever. The tabs don't specify 'no lactose'.

Can anyone tell me - is acetone supercritical at 250C, or unstable and liable to cause a big boom? I have already established it can't flash on the basis of oxygen in the air that the acetone is dissolved in, it snuffs itself out.

I know naaaathing.
 
 
 
 
    Student
(Stranger)
03-11-02 07:25
No 280659
      Re: Decarboxylating Tryptophan  Bookmark   

Don't let the term "critical" scare you. It has a different meaning in this context than it does in nuclear physics! smile In this case it means that the phase boundary between the liquid and gas phases disappears.

Even though you may not see your ingredient dissolve at room temperature, it is very likely dissolved at 250C.