02-22-02 00:53
No 271643
I have become rather interested in finding out about synthing DMT recently, and after diving in to KrZ's synth and trying to understand the whole thing, as well as working out what the TiHKAL synth (from tryptamine) was all about, I have come up with an idea. This is a bit of a 'novel' synth idea, but really I am just trying to work out an alternative to LAH and less importantly, ethyl formate.
Okay, so you know what I am referring to, the TiHKAL synth involves refluxing ethyl formate with tryptamine, resulting in a formamide (I can't imagine what a proper name would be), and then reducing the =O's on the formamide resulting in methylamide of dmt.
Anyway, I understand ethyl formate is hard to get, and LAH is watched, so I have two propositions as to how to get around these problems.
First the formate: If one made formic acid by oxidising methanol (my idea is to reflux and bubble air through it with a ceramic fishtank bubbler, but perhaps there is a better way. I also thought of using a ozonator to introduce reactive oxygen), then put formic acid with methanol, and some HCl or H2SO4 and refluxed for an hour or so, you would have methyl formate (after you separated the acid and water out of the mix). Since the reaction results in the formate substituting for the hydrogen on the amine tail, surely it doesn't matter which alcohol you use. Methyl formate would inherently lower the reflux temperature, which might slow it down. Perhaps use IPA-formate instead of Me-formate? This reaction takes 15 hours in the book. Perhaps using isopropyl formate would reduce the rxn time by allowing a higher reflux temperature?
Second, the LAH: I thought - well, if the primary purpose of the LAH is to donate hydrogens to the formamide, which would transform the formamide into methylamide (and presumably a molecule of water too), then perhaps any suitable method of donating hydrogens would work. All the hydrides, borohydride, cyanoborohydride, they are expensive and require special conditions to work. I looked at all the catalytic methods, and tossed aside all electrolytics for the requirement of the cell separator and palladium/platinum on carbon, which leaves hydrogenation catalysis. I have heard that raney nickel is very reactive and even dangerous, and on rhodium I found urushibara nickel, which is very safe and easy to make.
I am asking a question of any catalytic hydrogenation veterans, would there be any problem with using urushibara nickel - would the reaction mix need a carboxylic acid to prevent quaternisation or deamination?
Also I had the thought of doing the reaction in the gaseous phase, which would save a lot of reagents, by using the AA variant of the catalyst and boiling the formamide by placing the rxn chamber in a boiling water bath. This would of course require quite a strong reaction chamber, which could handle up to 90°C. - and at the end you'd have DMT condensing as crystals too, making collecting them very simple. It's just an idle idea though. I figure it would accelerate the reaction quite a bit if it could be done, especially if one flooded the chamber with hydrogen so that nothing other than hydrogenation could happen - and the temp would make it super fast. Though it might be dangerous. Anyway, again just an idle idea. Any advice wise bees?
***
An extra note: I was looking at the idea of using methyl formate as a decarboxylation catalyst for tryptophan, I drew up the molecules with ISIS and as I was looking at the decarboxylation next to the formamidisation, I thought: 'That could be all done in one pot'. And as I was thinking I also thought - you could do it just in a closed container, and when you find that it doesn't significantly gas upon opening (after a previous occasion of minimal gassing), that would probably mean the decarboxylation was over. And if one used roughly the correct moles of methyl formate (2x the number of moles of tryptophan: about 204:60 tryptophan to methyl formate by weight) you would know the formamide was formed by the lack of the smell of the methyl formate, which smells sweet, and it would smell of methanol only. Violent agitation and room temperature should do it, though it might take a few days. Of course one would need excess methyl formate to ensure total reaction occurs. Also it would be a suspension, not a solution. Perhaps merely stirring it with a stirring thing (magnetic would be okay) would do the trick. Some sort of chemical indicator of carbon dioxide, or an electronic carbon dioxide meter would be useful to monitor the decarboxylation - or even just a manometer.
I know this is all hellishly speculative. But if I am right, holy shit! DMT from tryptophan in two easy steps. Almost kitchen chemistry that is. Theoretically all of the reactions could be done without chem glassware. It might take longer, but the money saved on glassware would make it worthwhile.
(Hive Addict)
02-22-02 05:12
No 271772
You've touch on a bunch of issues some that leave me thinking "do you have a clue what you're talking about?", some that are worth discussing...
One interesting idea that you've brought up, is applying Urushibara reduction catalysis to making DMT. KrZ has, of course, posted this:
Tryptamine hydrochloride (10 g, 62.4 mmol) and sodium cyanoborohydride (6.28 g, 100 mmol) in a mixture of methanol (400 mL) and glacial acetic acid (11.76 g, 196 mmol) were cooled to 0C in an ice bath over a steady stream of nitrogen. A solution of 4.20 g formaldehyde (140 mmol, 11.05 mL of 38% Aq. CH2O) in 125 mL of Methanol was added dropwise to the solution over a period of one hour with mild stirring. See rest of msg in Post 264588 (Rhodium: "Re: DMT syntheses", Tryptamine Chemistry)
And a most interesting idea would be to apply Urushibara nickel, tryptamine hydrochloride and formaldehyde. That would be awesome if you got it to work. (opinions anyone?)
(Stranger)
02-22-02 05:56
No 271786
Actually you might be right about using U on KrZ's synth.
Just incidentally did you know that the stochiometry is all screwy in KrZ's stuff? The first is almost completely screwed, the second one hasn't got enough GAA and he read the mol weight of freebase tryptamine rather than HCl.
I don't understand - which bits are 'I don't know what I am talking about'? Formic acid? methyl formate? hydrogen? I have never witnessed a catalytic hydrogenation I admit it.
I know that the ketone group ( =O ) will go to a hydroxyl with catalytic hydrogenation, resulting in a CH2OH rather than CHO. I'm not sure about the further reaction - the CH2OH going to CH3, though if those folks over at the meth boards aren't lying that they got eph reducing to meth, then it should work all the way.
Why is everyone so in love with KrZ's synthesis? I wouldn't even consider doing a reaction that resulted in less than 90% yield.
Also, do you think it would be crazy to do the reduction in the gas phase? If you make U nickel catalyst such that it stays stuck to the Al beads it can be used for gas phase hydrogenation. Tryptamine freebase boils at 137°C, but even at 100°C its liquid and would react a lot with the hydrogen/nickel. Perhaps it would be better to use an oil bath for the gas phase reaction, so you could bring it to boiling.
I'm looking for more info on formic acid btw.
C12H16N2
(Hive Addict)
02-22-02 06:52
No 271820
Upon closer examination, KrZ's post makes SEVERAL errors:
1) 62.4mmol of tryptamine hydrochloride is 12.26g of tryptamine hydrochloride
2) 140mmol of HCHO is 4.20g of HCHO is 11.05g of HCHO is 10.23mL of formaline. PLUS, if he actually conducted this synthesis he would not report the values of volumes to two decimal places, that's ridiculous!
3) The melting point of N,N-DMT is 44.6-46.8C
Has anyone ever verified this synthesis? Was KrZ just making this stuff up?
Btw, I believe the point of HOAc is not for changing tryptamine hydrochloride in any way shape or form, but to increase the rate at which NaCNBH3 breaks down.
Does anyone have the original J Med Chem 44(23), 3881 (2001) handy?
(Stranger)
02-22-02 07:08
No 271832
Chromic, do you mean acetic acid when you say HOAc? My understanding is that the acetic acid prevents deamination - or perhaps it might be quaternisation. methinks deamination cos where else would ethanoic acid h-bond, and thus reduce the chance of H substitution?
The value for the weight of the formaldehyde is correct (assuming one has a -40°C chamber with cold-accurate scales to weigh pure formaldehyde with) and as a solution with formaldehyde it would be (oh shit I worked it out the other day how much our water/formaldehyde would weigh)... But I couldn't tell you how much ml that is.
I'm still looking for a workup for formic acid...
I've seen one so far which uses chromic acid.Yes, I don't think that KrZ actually did either synth myself. Maybe the first one, but what a bad result!
C12H16N2
(Stranger)
02-22-02 07:14
No 271835
This is just to report a hypothetical synthesis of formic acid that I have found about the place which uses CO2 and H2 and some sort of catalyst.
Of course that's gonna take a goodly strong pressure chamber to make any decent amount but there you go. With all that pressure, the catalysis will result in a rapid fall in the pressure inside.
Hmmm... Keep looking huh?
C12H16N2
(Stranger)
02-22-02 07:31
No 271845
Well, here's another possible idea for formic acid:
hydrochloric, sulphuric, nitric etc, strong acids are strong oxidising agents. Ever tried storing metal next to a bottle of HCl? My mother did, with a soldering iron, and now it's got all these pretty brown crystals, and blue-green on the working surface.
So, then if one added a significant amount of HCl to methanol, and cooked it up a bit, with a little agitation or aeration, it would burn into formic acid.
The only thing that concerns me is that strong oxidation in the presence of alcohols and carboxylic acids is that they then turn into esters
. This synthesis I propose requires the formate only as an ester anyway, so cook away I reckon. I don't think that you can oxidise any further than esters.That's a relief.
That's pretty darn simple to prove too, all I need is some methylated spirits and HCl (just gotta get some metho...) and contrive a reaction chamber for it. It'll make mostly ethyl acetate, but hey, if it smells pretty that proves the idea doesn't it? I might do it slow-like in a jar and just shake it and vent (or would that be fill with air) every now and then.
C12H16N2
(Hive Addict)
02-22-02 08:03
No 271870
I don't think formic acid is a stumbling block for most bees. I know realize that I'm mistaken about the role of acetic acid, your answer is closer to the truth.
Btw, sorry about the above confusion on point 2, that should read:
"2) 140mmol of HCHO is 4.20g of HCHO gas is 11.05g of HCHO 38% HCHO in water is 10.23mL of formaline." In either case, he messed up writing it down.
I'd love to hear some writeups and possible modifications to this method. I'd also like for someone to tell me why a exact ratio of 2:1 isn't used for formaldehyde to tryptamine.
(Hive Bee)
02-22-02 08:52
No 271889
KrZ is a very smart guy, and I have alot of respect for him, but he does make stuff up, usually to stir the pot a little I think.
(Stranger)
02-22-02 08:55
No 271891
Dammit! why does everyone want to talk about KrZ's synth so much. Chromic, a 1:2 ratio of formaldehyde to tryptamine WOULD be needed, otherwise you'd get a lot of NMT and unreacted tryptamine in the final product. It wouldn't hurt to overdo the formaldehyde a little, because it will just degrade into methanol in the presence of the reducer. Less than neccessary will not methylate completely.
Again I think that KrZ's synthesis is speculation dressed up as a writeup. Maybe not the first one, but the second one, to make him not seem so stupid bothering with a 30 something % yield reaction. It would be good for everyone if KrZ would tell us his source for that second one.
If formic acid is no stumbling block, then the only difficulty with the TiHKAL synth is the LAH, and you could just as easily substitute that for NaCNBH3/GAA or a hundred other reducing mechanisms.
Urushibara Nickel is the safest, easiest and cheapest hydrogenation catalyst, so why not?
Experiments in ester manufacturing shall be done soon to test the idea of making esters in one pot with an acid catalyst.
We already know that U nickel is excellent at turning ketones and aldehydes into alcohols and alkanes, and Mister Urushibara did it with steroids (estradiol). There's a post on Rhodium describing the use of Urushibara Nickel to synth amphetamine (it is REALLY simple and safe). In that one they use aluminium and HCl to introduce H2 into the mix.
I don't see why it wouldn't work on (would someone give me the proper iupac way to name it) the formamide formed by refluxing a ethyl formate or (in my idea) methyl formate with tryptamine. All it needs is something to strip off the oxygen (probably into water) and replace it with two hydrogens.
I would like to know if anyone can think of any undesirable reaction that would take place between tryptophan and methyl formate, because if not, my idea of one-pot from tryptophan to (dammit) formamide would work.
C12H16N2
(Stranger)
02-22-02 23:49
No 272207
hai,Urushibara i would like to reply to your DMT sythesis questions: if you are looking for an easy accesseble route for making DMT and the yield is not your first consurn than you could the following route ((and YES i tright it out my self so i know it works!!)
)All the chemicals you need are so far i know not watched,at least not in my country,
Start with dissolving 10 grams of tryptamine in 100 ml of isopropylalcohol and wen it all is dissolved(somtimes i warm it under the warmwatertap this helps to dissolve the tryptamine) i put 30 grams of methyliodide (iodomethane) to it,you can use a erlenmeyerflask or a roundbotomflask of 250/500 ml and a stirringbar to stir and stir this sollution for the next 12 hours at roomtemperature,filter the formed N,N,N-Trimethyltryptamoniumiodide (or DMT-iodomethylate) and wash it 2 times with a little bit of isopropanol,press it dry between filterpapers and let it futher dry untill completely dry.
then you take 10 grams of this tan-colored powder and mix this with 40 grams of ethanolamine cheap and very easy to get and reflux this in a roundbotomflesk with refluxcondenser for 15/20 minutes,give it a good boil.
after you have let it cooled down you mix it with 100 ml demi water and extract this 3 times with 50 ml ethylacetate.
sepperate wash the ethylacetate one time with NaCl or CaCl sollution and 2 times with demi water,dry with MgSO 4
destill of as much as possible under waterjetpumpvacuum the ethylacetate and put the residu in a small beakerglas and let evaporate,with heating,i use the heater in my room,of all the rest of the ethylacetate with ventilation of cors.
after that you with have a nice deep orange-golden oil,wich you crystallize by putting it in the freezer for the night an the next day you will have nice DMT crystals
(Stranger)
02-23-02 01:25
No 272276
How does ethanolamine make the N,N,N-trimethyltryptammonium iodide into DMT? that sounds like pure bs to me. Where's the reducing agent? In TiHKAL a similar process is used in the first reaction described (making the methiodide thing), but to turn the N,N,N stuff into DMT you have to use lithium triethyl borohydride. There's a process which changes it from a methiodide into a chloride salt, but it requires silver chloride and picric acid (kaboom anyone?).
You sure you're not making it up? If not, please explain the reaction mechanism, because I just can't picture it. It sounds dead simple, but if what you are talking about is merely a way to purify the miniscule DMT out of the largely N,N,N-triethyltryptammonium iodide, then seriously, what is the point? Who's going to throw all that expensive tryptamine down the plughole for a piniscule amount of DMT? Even decarboxyating tryptophan to tryptamine to use in this reaction, it would still be totally uneconomic. I'd rather try and extract DMT from 20kg of phalaris arundinacea.
I'm not looking for the simplest way neccessarily, rather the most accessible and uncontrollable way (ie with nothing that could ever be watched). My aim is a process that requires a minimum of equipment and chemicals.
C12H16N2
(Chief Bee)
02-23-02 02:02
No 272300
How does ethanolamine make the N,N,N-trimethyltryptammonium iodide into DMT? that sounds like pure bs to me.
Don't say something is bs until you have researched the subject. Refluxing a quaternary amine salt in ethanolamine transfers one of the methyl groups from the quat to the ethanolamine.
N,N,N-trimethyltryptammonium iodide + ethanolamine (large excess) => DMT + N-methyl ethanolammonium iodide
See Post 223131 (PoohBear4Ever: "Re: You can't dimethylate tryptamines with MeI or", Tryptamine Chemistry) for an example of this reaction.
(Stranger)
02-23-02 02:04
No 272301
Oh by the way, I've come up with a name for the product of refluxing (m)ethyl formate with tryptamine: N,N-dimethal tryptamine. The 'al' because it's basically a ketone once it binds to the amine, leaving behind the (m)ethanol.
Oh, and I've been doing some gas calculations, and can anyone tell me the max pressure that a champagne bottle can take? I have figured a rough value of about 300kpa evolving from 10g of tryptophan in decarboxylation in a 700ml gas space in an enclosed vessel that was closed initially at -18°C. That could use acetone, but I think if one wants the formamide anyway, methyl formate could catalyse decarboxylation while it methalates (spelling intentional) (you could say formalates, but that's not proper iupac). (also proper iupac would call formaldehyde methaldehyde and formic acid methanoic acid).
I think nobody actually knows what would happen inside an enclosed chamber, because all the professional chemists prefer to use their reflux to pressure-safe chambers if possible, and high bp solvents if high temp is needed. It does obfuscate the process of separating our decarboxylated product using a high bp solvent, since it will evaporate before the solvent when it gets down to the last bits where the product saturates the solvent. Since it's best to use freebase, this means high bp solvents require an acid/base extraction to bring our tryptamine back to freebase out of the heavy solvent.ramble ramble
C12H16N2
(Stranger)
02-23-02 02:20
No 272306
So how good does such a reaction yield? I see the sense in the mechanism now. Can someone give a hint at yield: ie moles of tryptamine to moles of DMT (even just a rough weight ratio would be helpful to give a rough idea)?
Sorry, I said it sounds like pure bs because I didn't know (d'oh). Think twice about calling bs huh? Just say 'refs please' instead? I know finding refs is a hassle, but we're all here to learn and teach aren't we (and occasionally throw some HCl into the NaOH
)C12H16N2
(Chief Bee)
02-23-02 02:32
No 272308
Read up on your organic chemistry again. A carbonyl bonded to a nitrogen is called an amide, in this case it is N-formyl-tryptamine. You cannot attach two formyl groups at the same time to the same amine, so first N-formyl-tryptamine is formed, then reduced, then N-methyl-N-formyl-tryptamine can form, which finally can be reduced to DMT.
(Stranger)
02-23-02 02:44
No 272311
Rhodium you kick ass!
So that's why in the TiHKAL synth ethyl formate is added again in the middle of the reduction. Interesting the second reaction only needs 2h refluxing. So in my hypothetical scheme, gas phase or no, more methyl formate would be needed during the nickel-catalysed reduction.
Food for lots more thought. Thanks heaps dude.
So is it IUPAC to call it N-formyl tryptamine? I think it would be proper to say N-methal tryptamine. the 'form' prefix is commonly understood to mean formaldehyde, but methal more clearly says 1 carbon, 1 ketone group and excess hydrogen to fill carbon's bond sites.
Anyone know what the pressure capacity of a champagne bottle is? Rhodium?
anyone?C12H16N2
(Newbee)
02-23-02 15:36
No 272508
Okay peoples, thanks for everyone's help, I've put together a draft pre-experimentally proven synthesis for DMT which uses methyl formate, urushibara nickel/hydrogen and cheap reaction vessels.
it's posted on the web at: http://elfspice.tripod.com/dmtsynthesis.
I've done a lot of fiddly gas/pressure calculations in it, which might be a little fucked in places (Though I kinda doubt it), they should help people work out whether it could work (and I still don't know what the gas pressure of champagne is, or what the strength of champagne bottles is)...
Here's a question: assuming sufficient heat (kinetic energy) and that the reaction vessel can contain the pressure of gasses evolved from the reaction, can't decarboxylation still occur? Since pressure affects only the gas phase (liquids are by definition incompressible), and restrains evaporation from the liquid phase, if there's enough motion induced by the temperature in the solution, though the gas phase will be more active (ie pressure) the liquid will still be at the same temperature, just unable to escape liquid phase - surely that will cause the reaction to occur. I understand that pressurised gases tend to force their way into liquids (like CO2 in soft drinks) this would not interfere with the reaction significantly, and in fact the double bonded oxygens on either end of the carbon dioxide might participate as catalysts too? Anyone have a definitive answer? Anyway, the idea is used in the proposed reaction.
One plus about the synthesis I have conceived is that it won't be very much expense to test it out.
It is all theoretical, so if anyone has some empirical evidence to contradict the hypothesis, I would love to hear it, before I TP (telepathic communication) with my friends from a parallel earth where at the very least DMT isn't subject to governmental suppression, and suggest they try the synthesis
C12H16N2
(Stranger)
02-23-02 19:05
No 272545
Urushibara,as you see my synthesis is not bs,the yield is not high,82 grams of tryptamine makes 23.1 grams of DMT,but you can reprocess the tryptamine,and you don`t need watched chemicals like formicacid,methylformate or ethylformate and use difficult stuff like LAH wich is difficult to work with.
and it is a easy straidforword proces wich can hardly been fuckt`up so who needs pressure equipment and routes wich are not treight befor,if you can process the not used tryptamine than i think this is a good alternative
by the way i tright the ethylformate?LAH synth. its a pain in the ase,if you do kitchenchemistry and don`t have a high-tech lab.
so i stick to this route and i will try the route as in
journal of medicinal chemistry vol.44/n023 page 3892 2001
i will let you know how it went,rhodium,is there a differance in using thyptamine or thryptamine HcL in this synthesis.
(Newbee)
02-23-02 23:45
No 272649
If you actually spent the time reading the document on the link I gave you would find that it's not very much pressure that I am talking about (3-4atm). And I haven't done the precursor experiments yet, but in my experimental process the methyl formate is manufactured from methanol. Nickel Chloride is easy to get in 'electro-less' nickel plating kits, more than enough to make heaps of very reusable nickel catalyst. And if the process works you barely even have to raise an eyebrow at the chem supply, all you need is methanol, which plenty of people use to make essential oils and plant extracts. The rest is just pool acid, glacial acetic acid can be used to make the U-Ni-AA catalyst, but it isn't neccessary to use it, though it makes catalyst recovery a bit simpler, and can be bought from a photographic supplies shop.
Esters are very easy to make, you almost don't even have to heat them (I remember it was just mix acid and alcohol, add HCl, cook for 5-10 minutes and voila, stinky ester). Ethyl acetate, for everyone out there, should be easy to make from ethanol and glacial acetic acid cooked with a HCl catalyst.
I figure if a strong acid can oxidise methanol into formic acid (dichromic acid is what they usually mention in chemistry books, but HCl is a stronger oxidising agent so should work faster). Formaldehyde is not easy to make in even lab conditions, but we see vinegar spoiling wine all the time, which is made via enzyme catalysis.
Anyway, if methanol can be turned into formic acid (a strong oxidiser is needed, formaldehyde can be made via a weaker oxidiser), and the very same catalyst makes acids and alcohols form esters, then doesn't it figure that while part of the mix goes to formic acid, the methanol will be joined to it by the same oxidiser?
I am not sure about the handling conditions or how to get the HCl out of the ester (since methyl formate is fairly soluble in water - possibly it could be separated using salty water to decrease its relative solubility).
I could follow the process you use, but if you'll follow my logic, it was a new idea not all that long ago, at least when used on DMT anyway. Stick to it if you're happy with it, but I want to try something new.
And from what I have worked out so far, the final product is in freebase form and only contaminated by methanol with a small amount of methyl formate, both of which will disappear into the atmosphere in very short order, or better still in the freezer after salting with anhydrous salts to remove the water, to leave behind nice big fat rocks of waxy pure DMT, no muss no fuss. Nothing that could ever be controlled (except for the tryptophan, but that is more likely to become uncontrolled when enough people realise that one of the most essential aminos is illegal to sell for human use). I might be a new bee, but I did high-school chemistry, and I've absorbed a lot of organic chemistry in the last month or so. I always try to be a person to do something a bit different from others, I like to be on the cutting edge. But that's an ego trip, and hell my idea might be completely screwy. But I'm going to keep looking for a new way to do the chemistry. This idea has been gestating for a few weeks now, and has changed several times to account for better information (ta rhodium).
I will shortly be testing the ester manufacturing idea on ethanol with hydrochloric acid, using an oil bath for heat and a sealed reaction vessel (champagne bottle). As for the rest of the process, that's illegal isn't it?
I'll TP my parallel self and his friends and they'll do it in their DMT friendly parallel world, so we can find out and tell y'all whether it works (and that parallel world has all the same rules of physics and chemistry my parallel self tells me, so it won't be bs if he says it works)C12H16N2
(Newbee)
02-24-02 02:51
No 272718
I've just been reading a comprehensive materials spec on methyl formate and there's a few caveats with using it: It decomposes in water in 8h, and in 24h in acetone. It is moderately toxic: 1.622g /kg ld50, 10000ppm of the vapour.
So, it should definitely be prepared immediately before use, and dry as possible.
It produces 1 atmosphere of gas pressure at 32°C (which figures, seeing as that's its bp). It's quite flammable, and similar to petroleum ether, it is heavier than air. (I toasted myself due to the heavier than air factor with petroleum ether a month ago -scary), so be careful with venting it hot around a source of ignition. Autoignition point is 456°C.
Thus it might be a good idea to freeze the reaction vessel to -18°C in the freezer before putting the methyl formate in it, and don't open the reaction vessel until it's fully back to room temperature.
Also it is incompatible with acids, specifically mentioning oxidising agents. HCl is not a super strong oxidiser like perchoric or nitric acid, but it does oxidise. Anyway, making the ester is very likely a fairly short process, less than an hour. It would need to be salted thoroughly with dehydrated salts to remove all the water from the HCl solution immediately it was ready to reduce the amount of reaction that took place. Might be problematic... Experiments will point the way.
Just looking around a little further, it seems that ethyl formate is a common fragrance chemical, and definitely not watched, and can be substituted for methyl formate. The only thing that puzzles me is that the mp of ethyl formate is lower than methyl formate. this may or may not have implications for the process.
Ethyl formate is about $40US for 500ml, which enough for 7 reactions as I have described in my theoretical synthesis. Which at a hopeful 90% yield is results in about 62g elfspice.
If methyl formate can be made via the method I have described, though it must be done immediately before use, it would prove a lot cheaper than that.
Revisions will be made on the synthesis to add a method of producing catalyst, as well as making methyl formate shortly.
Perhaps an ester makes a poor decarboxylation catalyst. No matter, acetone is freely available. Is there any reason to suspect that the ketone group will mess up any other part of the tryptophan other than the carboxylic acid? If there isn't, then why not just use the ketone alone? Also, somebody answer the question: does decarboxylation require a normal atmospheric pressure in the gas phase or can it get as high as (say) 4atm without significantly interfering with the decarboxylation? Does anyone know? Preliminary experiments with glutamic acid could help (just an amino that I have handy) Tyrosine would be better, would make 4-hydroxy-phenethylamine as a product. Not useful probably, but would confirm the decarboxylation worked if it came out as a freebase waxy thing that boiled somewhere between 60 and 140°. If I use this, I could do a parallel experiment using ethyl acetate made from ethanol and acetic acid with HCl catalyst. And see what happens! The N-Formyl 4-hydroxy phenethylamine would be a bit different, but I would assume it would have some characteristic which would make it identifiable.
Watch this space for experimental writeups of precursor processes.
Here's a quote from a site describing a process of removing water from slurry (peat, etc) to make it into a useful fuel:
http://www.eerc.und.nodak.edu/facilities
When heated under pressure to temperature, carboxylic groups attached to the coal structure decompose to form carbon dioxide, which forces liquid water out of the pores and into the carrier medium
Which suggests that decarboxylation can occur under pressure. ?
I'm having trouble finding proof either way at this point.
C12H16N2
(Moderator)
02-24-02 05:09
No 272765
Post 272576 (Lilienthal: "Welcome at the Tryptamine Forum...", Tryptamine Chemistry)