Author Topic: future of safrole  (Read 11379 times)

0 Members and 1 Guest are viewing this topic.

homeslice

  • Guest
future of safrole
« on: April 12, 2004, 05:30:00 AM »
With sassafras oil and other safrole-rich oils being impossible to obtain in the U.S., least to the best of my abilities, what is the future of small scale mdma production? I know the simple answer is to look to the north, but lets say this isnt viable, for arguments sake. Also lets assume that one cant source sassy rich oils in the US from anywhere. So when safrole cant be sourced from oils anymore, whats next?

My questions would be what are bees doing now about the current situation or planning to do when they run out of and cant source safrole anymore? I'm sure it wont be too much longer before the north is the same as here.

Also how are bees in EU producing mdp2p on the majority?

How feasible is the demethylation of eugenol to safrole with the standard clandestine equipment used in mdma manufacture?

Post 485827

(eXcidium: "Eugenol ---> Safrole Revisited", Methods Discourse)
Not really revisited at all. At least not in that thread.

Overall, summarizing the above, how are bees acquiring safrole?

I really just want to see what other bees are doing, or planning to do? Like whats after sassafras oil is gone?


ApprenticeCook

  • Guest
dont say it dont say it ...
« Reply #1 on: April 12, 2004, 06:58:00 AM »
dont say it dont say it nnnnnnnnooooooooo.........
Happy thoughts, Happy thoughts, Happy thoughts....

Haha, no well your right sassy is getting impossible, swim is using reserves and only dreaming for personal use, screw the rest....

Rhodium has documents on the conversion to safrole on the site, have not used them but they are dictated out easy enough so they can be done... just need the materials.

Swim is in favour of growing your own sassy tree but its not viable for any amount of production, its been highly talked about around here and agreed its not really worth the trouble for the amount of e/o extracted.

GC_MS

  • Guest
You serious you don't understand the Game?
« Reply #2 on: April 12, 2004, 10:31:00 AM »
I really just want to see what other bees are doing, or planning to do? Like whats after sassafras oil is gone?

This is a simple question with a very simple answer. If the amount of sassafras oil available to individuals decreases, the number of clandestine MDMA cooks may shrink. Hence, you might think this may lead to less MDMA hitting the streets, which after all is what the Government wants (it says...). However, that is not what will happen, or at least will not happen as long as MDMA remains a Schedule I substance. Because the amount of sassafras oil available to legitimate commercial enterprises totals many tons, organized crime will use its long greedy tentacles and engage in the semi-industrial production of MDMA (which it actually is doing already). The markets will be flooded and prices will be "reasonable". This is the scenario the Government doesn't like (it says), but is very likely to happen. So there won't be an MDMA shortage even with less cooks.


Smilaxium

  • Guest
Large scale = large stock
« Reply #3 on: April 12, 2004, 11:08:00 AM »
There will be less cooks as GC/MS already mentioned. And even with only a limited number of cooks I guess still there will be plenty of MDMA hitting the streets. I bet those semi-industrial operations have a stock that is large enough to feed the world for another year of two  :o

Another point of concern is the emerging of all kind of fake MDMA pills, although that is most likely only to occur there were there is no stock or where it is difficult to smuggle MDMA in large quantities into the country ....


ApprenticeCook

  • Guest
Less lower scale cooks replaced by a handfull...
« Reply #4 on: April 12, 2004, 11:45:00 AM »
Less lower scale cooks replaced by a handfull of larger scale ones... gc is right, thats the direction of the times. Thats what govt hates, diversion is the key, everyone has a price.

weedar

  • Guest
come on
« Reply #5 on: April 12, 2004, 03:16:00 PM »
You all missed this thread's main question and you know
it.. What are the most viable alternatives to sassy?

Beeing a euro-bee I haven't heard of any other oils beeing
banned due to safrole-content, there are lots of options,
even if they won't bee as good as sassy.

Eugenol is available, so is catechol..But, the procedure
to get to safrole from those sources isn't nearly as OTC
as the rest of the safrole->MDMA procedure. I'd love to
see someone report on using PTC from comforter in the
reaction, the ones mentioned in

Post 427515

(moo: "OTC fabric softener phase transfer catalysts", Novel Discourse)



homeslice

  • Guest
I was talking about small scale production.
« Reply #6 on: April 12, 2004, 07:21:00 PM »
Im not talking about what is going to happen to the future of mdma im talking about what is the future of safrole? I dont care if big cooks replace small cooks or fake pills gets smuggled in or the black market takes care of the times. I wish i could have started the thread off with all these parameters but i thought i did i guess.

I was talking about small scale production. I also made sure to say that the oils were not available. Lets assume, again, there is no black market, and there is no sassy oil. It doesnt exist.

What then?

What about this? 

Post 451672

(Rhodium: "Novel Oxidative Demethylation of Eugenol", Novel Discourse)

Have any bees fucked around with this? Vitus hails this find as an end to sassafras oil but noone ever followed up on the post. Is this feasible?


_mu_

  • Guest
Lets assume, again, there is no black market,...
« Reply #7 on: April 12, 2004, 07:35:00 PM »

Lets assume, again, there is no black market, and there is no sassy oil.


Your assumptions clearly show your background. There *is* a black market, and there always *will be* a black market. It may not be accessible to everybody, but it is there. Guesstimates for the size of the total black market say that it is about 10-15% of the GDP. You think you can take that away with some paper regulations?

And trying to synthesize safrole from eugenol is something which has been discussed to death at this board. UTFSE.

Smilaxium

  • Guest
MDMA replaced ?
« Reply #8 on: April 12, 2004, 07:42:00 PM »
Well, if it would become very hard to obtain/manufacture safrol at a reasonabl cost(and thus MDMA), I guess there will be other types of drugs synthesized/consumed. In the end, MDMA isn´t that spectecular and there are enough alternatives...


homeslice

  • Guest
Ok mu. next time read my post
« Reply #9 on: April 12, 2004, 08:04:00 PM »
Ok mu. Apparently you cant see why i said that. Let me spell it out so you can understand.
I dont care about the black market. I dont care about large scale MDMA production, pill smuggling, or fake pills. I specifically asked about small scale mdma production. I really dont fucking care that it is 10-15% of whatever. Maybe i should have said this

Lets assume, again, FOR THE SAKE OF ARGUMENT, there is no black market, and there is no sassy oil. It doesnt exist.



You insult me "about my background". What the fuck does that mean?  Maybe you cant read english because your post answered this


I dont care if big cooks replace small cooks or fake pills gets smuggled in or the black market takes care of the times.



Maybe you missed the part about I DONT CARE. You should just delete your post, its completely irrelevant.
And i also know about the demethylation of eugenol to safrole. Im simply asking if people have attempted it. Hence the "Is it feasible?" You talk about the synth of safrole from eugenol being discussed to death yet i still see no bee talking about success with the proceedure. I found plenty of threads with no successful end to them. And if im wrong, point it out to me b/c id love to read a writeup about it. Really. Im UTFSE for the last 3 hours looking for a success story to the eugenol demethylation. Ya know id even argue that it hasnt been talked about enough.

Ok now, twice ive set parameters that have been overlooked. I kinda figured this was going to happen when i started the thread.

Ok lets get back on topic, once again. What is the future of safrole? Please read the post. **NOT** the black market, cooks, or mdma. And i really dont care about your theories.




_mu_

  • Guest
If you ask a question, and you don't get the...
« Reply #10 on: April 12, 2004, 10:45:00 PM »
If you ask a question, and you don't get the answer you expect, twice, what does that learn you about the way you're asking questions?

homeslice

  • Guest
No, the first time i wasn't as clear as i...
« Reply #11 on: April 12, 2004, 11:17:00 PM »
No, the first time i wasn't as clear as i should have been. The second post pretty much clarified where i was going with the post.

That second post, is the one that you didnt read. Ya know, the one that said not to talk about everything you did talk about.
[edit] is there a way to delete a whole thread and start it over?  :)


Vitus_Verdegast

  • Guest
I'm sorry but..
« Reply #12 on: April 13, 2004, 01:08:00 AM »
Vitus hails this find as an end to sassafras oil but noone ever followed up on the post. Is this feasible?

Why shouldn't it be feasible? Give me 1 good reason.
You have in front of you a paper written by researchers who investigated this method and reported their results in well-known reputable chemistry journal. This is not Uncle Fester's book, you know. What more can you ask?

Now get your lazy ass off that computer, into the lab, investigate the method and report your results!  ;)


homeslice

  • Guest
im gonna try it just gonna take a while
« Reply #13 on: April 13, 2004, 02:21:00 AM »
Im tryin to figure out what it means before gettin into the lab heh. Since i have absolutely no chemistry education whatsoever, it takes me a long time to look up and figure out what something like this means 4-Propenyl-benzene-1,2-diol [4-allylcatechol, 3,4-dihydroxyallylbenzene] It just takes a while :(

Im confused however by how it yields  "furnish 34 as a viscous orange solid" I understand that that big name up there is 34, but what exactly does this procedure yield? It says it is an Oxidative Demethylation of Phenol's. Ok lemme break that down.
With oxygen it strips off the methyl part of eugenol yielding safrole. Maybe? I dunno. That cant make sense then because why does it yields a "vicsouse orange solid"? That aint safrole... :(  
I can do it if it was in english but i just cant understand all those chemical names they confuse the fuck outta me. And when i think i figure out what Eugenol is in a chemical formula, some patent refers to it as something else lol.

Edit: After more hours of reading ive read that the demethylation of Eugenol yields catechol which then needs to be methylated into benzodioxole.


_mu_

  • Guest
This is not Uncle Fester's book, you know.
« Reply #14 on: April 13, 2004, 08:41:00 AM »

This is not Uncle Fester's book, you know. What more can you ask?


If it wasn't posted on this forum, it can't be true.

homeslice:Not to disencourage you, but if you have 'no chemistry background', you have a very low chance to succeed. Making mdma from scratch is way harder than making mdma from safrole. There's a reason that you won't find any posts of people saying that they succeeded in demethylating eugenol: it's damn difficult, and people who are able to do it are usually also able to get safrole legally. On universities, safrole (and 2,5-DMB, and 3,4,5-TMB) are just building blocks for other interesting things besides 5ht2a-agonists :-)


...and if this isn't what you wanted to hear, why did you ask your question anyway?

moo

  • Guest
Since i have absolutely no chemistry education
« Reply #15 on: April 13, 2004, 09:50:00 AM »
Since i have absolutely no chemistry education whatsoever, it takes me a long time to look up and figure out what something like this means 4-Propenyl-benzene-1,2-diol [4-allylcatechol, 3,4-dihydroxyallylbenzene] It just takes a while :(

In that case you might want to educate yourself. Don't make the basics harder than they really are, learn them.


homeslice

  • Guest
Well mu, not moo, right now im leaning toward...
« Reply #16 on: April 13, 2004, 08:58:00 PM »
Well mu, not moo, right now im leaning toward taking a stab at demethylation of eugenol to catechol then remethylating to safrole. In your post you say how hard it is. Have you ever tried it? Can you please show me some testimony from some bees who have tried it? I tried to look it up and came up with nothing. Just ppl with hopes of trying it then changing their minds. How do i know they changed their minds? I PM'd them and asked them how it went.
Well i thought tackling honey was going to be impossible, especially with everyone saying it was impossible w/ no chem background, and then i did it. And now that i did that im going to try something else. Its not really about making the money from the honey or enjoying the honey, its more or less just the conquering of a project that i put my mind to. I think it gives me alotta self confidence.  :)


There's a reason that you won't find any posts of people saying that they succeeded in demethylating eugenol: it's damn difficult, and people who are able to do it are usually also able to get safrole legally.



Your saying ppl dont do it because its too hard. But then you say ppl dont do it bc they can source it. Its a contradiction that i been looking into. It seems more and more that the latter is the truth. People arent really attempting it b/c they can source it. And they can. I mean i probably can. But back to the point, if it is damn difficult and if i fuck up and fail, i can say that it is truly hard and settle the contradiction.
I dont know anything about universities or building blocks?

This is exactly what i wanted to hear. Now theres a little contraversy and some discussion.
What are your thoughts on the demethylation and why its "damn difficult"? Im just lookin over the synths right now, but if you can or some bee can point out a real reason why its so difficult, id love it bc then i can save my money that would have been spent on wasted chems  :)




_mu_

  • Guest
Well then, that's settled.
« Reply #17 on: April 13, 2004, 10:27:00 PM »
Well then, that's settled. You try it, write a nice report on it and say how difficult it really is (or not), and as an added bonus you'll get some nice mdma x-tals.

homeslice

  • Guest
Sounds good Sometime in may ill write up what...
« Reply #18 on: April 13, 2004, 11:33:00 PM »
Sounds good
Sometime in may ill write up what i found  :)


eXcidium

  • Guest
sorry??
« Reply #19 on: April 15, 2004, 10:46:00 AM »
Sorry ppl?

What is hard about demethylating eugenol?
It's much simpler than MDP-2-P to MDMA
(except for the steam distillation, I wish I could "skip" over that one)

I 'm already on my way doing it and in some days I'll have some notes to tell ya all

It's not very OTC, but it's a solid procedure


weedar

  • Guest
great
« Reply #20 on: April 15, 2004, 12:04:00 PM »
I'm looking forward to reading it. :)


homeslice

  • Guest
Theres 3 bees besides me that ive been talkin...
« Reply #21 on: April 15, 2004, 03:44:00 PM »
Theres 3 bees besides me that ive been talkin to through PMs that are going to fuck around with eugenol in the next 3 weeks.

Shouldn't bee a problem, especially with the 4 of us  :)


ApprenticeCook

  • Guest
Re: It's not very OTC, but it's a solid ...
« Reply #22 on: April 15, 2004, 03:48:00 PM »

It's not very OTC, but it's a solid procedure


Well if its not OTC its going to be harder for some without access but oh well as long as the proceedure and yields are strong thats what matters.


eXcidium

  • Guest
Steam Distillation
« Reply #23 on: April 15, 2004, 06:30:00 PM »

Barium

  • Guest
Huh?
« Reply #24 on: April 16, 2004, 02:01:00 AM »
Is it that difficult to boil water? If it is, I strongly suggest you find another hobby.

eXcidium

  • Guest
wromg, mate
« Reply #25 on: April 16, 2004, 07:09:00 AM »
Is it that difficult to boil water? If it is, I strongly suggest you find another hobby.

It was not the boiling water part that was hard.. it was the overall technique, after using TFSE, I found an obscure port wich some nice pictures, but still not very usefull on "techniques" so i had to browse a few dusty tomes to find a nice answer, but thanks anyway  ;)


ApprenticeCook

  • Guest
Whats so hard? using a inlet tube imersed in...
« Reply #26 on: April 16, 2004, 09:00:00 AM »
Whats so hard? using a inlet tube imersed in flask contents pump steam through it.....  ::)

Cant imagine a book having any kind of an obscure part regarding this technique.... whatever.

Barium

  • Guest
Huh again...
« Reply #27 on: April 16, 2004, 11:32:00 AM »
It was not the boiling water part that was hard.. it was the overall technique

A regular distillation setup. Dump whatever goo you want to steam distill in the boiling flask together with water. Boil the water. I can see what you mean though. The overall technique in this case can be tremendously difficult to get the hang on.

Fastandbulbous

  • Guest
A "how to" of steam distillation
« Reply #28 on: April 16, 2004, 07:48:00 PM »
If you check any practical organic chemistry book, it generally will give details of steam distillation of aniline. After that, it's not too difficult to modify it to whatever you want to steam distill. Some books on perfumery also give details of steam extraction (read: distillation) of essential oils from plant material


eXcidium

  • Guest
great!
« Reply #29 on: April 18, 2004, 10:40:00 AM »
Thanks guys :)

That will do

My Vacuum pump arrived today so now i have to give it a go :)


starlight

  • Guest
no vacuum
« Reply #30 on: April 18, 2004, 10:59:00 AM »
You're not thinking of using a vacuum pump in a steam distillation are you?

Barium

  • Guest
Well you can steam distill under reduced ...
« Reply #31 on: April 18, 2004, 05:08:00 PM »
Well you can steam distill under reduced pressure too of course. I don't know what costs more, the energy for the vaccum to lower the bp of water to let's say 50 deg C, or boil water at STP?

starlight

  • Guest
do people actually do that though?
« Reply #32 on: April 18, 2004, 06:20:00 PM »
Do people steam distill under vacuum in often?

Wouldn't the lower temperature result in the vapour pressure of the higher boiling (desired) compound being lowered by a greater factor than the degree to which the vapour pressure of water is reduced? If so, it would mean that you got less product per amount of water distilled.

_mu_

  • Guest
Is't a steam distillation not a destilation...
« Reply #33 on: April 18, 2004, 09:19:00 PM »
Is't a steam distillation not a destilation and extraction in one apparatus? In that case, the liquid fase (water) helps you to extract the goodies from the stuff you're steam distilling. In that case, you would want to be the temperature to be as warm as possible (as this increases solubility of the good stuff in water).

Unless you've got one of these weirdass compounds that dissolve better in cold water than in warm water. But in that case you're better not steam distilling anyway.

eXcidium

  • Guest
nope
« Reply #34 on: April 18, 2004, 09:23:00 PM »

You're not thinking of using a vacuum pump in a steam distillation are you?




No, but thanks for the warning, hehe

I might have tried that someday, but each thing in it's own place

I'm just waiting for a cash-refill to go and buy the N2, and start playing around with eugenol, AFAIK, that is still legal, as long as i don't use the safrole for other purposes... (I didn't said I wouldn't)  ;D  ;)

Now i'm going to gather some info on the vacuum pumb, since the manual was badly translated from the chinese language (lots 'o mistakes, and regarding operations it doesn't say much).
I'll probabbly post something on the equipament forum

Get tuned next week for my results on the eugenol experiments




moo

  • Guest
The vacuum should increase vapour pressure of...
« Reply #35 on: April 19, 2004, 08:02:00 AM »
The vacuum should increase vapour pressure of the substance to distill in proportion to the vapour pressure of water though.


starlight

  • Guest
The vacuum should increase vapour pressure of...
« Reply #36 on: April 19, 2004, 12:25:00 PM »
The vacuum should increase vapour pressure of the substance to distill in proportion to the vapour pressure of water though.

That doesn't make sense. The vacuum will make water boil at a lower vapor pressure - therefore a lower temperature. The vapor pressure of the product will also be lower because the temperature is lower. Looking at a nomograph, it seems like a lowering of temperature from 100C to 50C will have more proportional effect on the vapor pressure of a compound that normally boils at 200C than a compound that normally boils at 100C (water). Maybe I am missing something obvious?

moo

  • Guest
It might be the language barrier.
« Reply #37 on: April 21, 2004, 03:41:00 AM »
It might be the language barrier. I meant that when you use vacuum the proportion of vapour pressure of the substance to the vapour pressure of water is higher compared to atmospheric pressure, not that the proportion stays the same.


CharlieBigpotato

  • Guest
yikes!
« Reply #38 on: April 21, 2004, 04:58:00 AM »
did sassafras trees die while i was napping?

no.

they did not.

(yet very many deciduous trees are in trouble...not sassafras)


psychokitty

  • Guest
Chin up . . .
« Reply #39 on: April 21, 2004, 08:58:00 AM »
In a world devoid of a sassafras oil source, eugenol is the answer my fellow bees.  No, I have never attempted a demethylation of it, but I believe that it is possible.  There are many potential ether-cleavage reactions out there.  But, I have to admit that so far, the SIBX oxidative demethylation is probably the best one so far developed.  Why?  Because it is simple, the reaction scheme is straight-forward, and most importantly, it seems that allylpyrocatechol is the only product that you get out of the reaction.  No byproducts, in other words.  Also, THF can't be the only solvent that can be used.  If one were to read the relevant articles on IBX chemistry, as I have, one would discover that virtually all solvents are suitable for these reactions.  That leaves acetone, MEK, toluene, xylene, 1,1,1,-trichloroethylene, and numerous others, available for potential application in the demethylation process.

Another important point is that SIBX is the stabilized form of IBX.  IBX was unstable in a few reported instances, and this made it unsuitable for expanded commercial use.  However, since the recent stabilization of IBX, and since, as an oxidant, SIBX is very specific to particular functional groups, SIBX is likely to soon to find wide use everywhere, just as trichloroisocyanuric acid and oxone have. That, or SIBX will at least find use  by virtually all researchers and industrialists who are looking for a specific and gentle oxidant to replace the current oxidants used in their industrial processes.

Another thing about SIBX is that it should be easy to get ahold of.  It's simply too new.  It's also not illegal and has so many potential uses as a general oxidant that it should present few obstacles for those who might be asked to present an intended use.  "I'm going to see if it will work in place of the potassium dichromate oxidant that I regularly use in a patent pending photographic process that I've been developing, sir"  or "None of your fucking business.  I'm not inclined to share my multi-million dollar secrets with a sales clerk".  A variation of either one should do.  But if it's of any help, only once have I ever been asked for a notice of intended use.  Stating a simple and generic reaction scheme was good enough in that instance.

As for using the SIBX reaction scheme to demethylate eugenol, I think it's most important for someone to actually be exposed to allylpyrocatechol to log its properties.  Does it really smell like smoke?  Is it stable under standard atmospheric conditions?  I suspect that it is much more stable that some have led us to believe.  For one, there is no need for a nitrogen atmosphere to distill it.  And contrary to popular belief, I do not believe that it will freeze in the condensor under vacuum distillation.  Why?  Simply because it's freezing point is somewhere around 48 degrees C at atmospheric pressure.  Notice how oils distill at a reduced temperature while under vacuum pressure?  Well solids melt at lower temperatures while under vacuum pressure too.  What will likely happen is what I have witnessed many times before when conducting similar distillations of oils that are solids at room temperature.  They will distill under vacuum as oils, drip over as oils, and then, when the vacuum is released, after about thirty minutes, they will freeze.  Then, to determine if one has the correct substance, apart from smell and/or taste, one could insert a thermometer into the crystal matrix, heat the fucker a bit, and when the mass of solids melts, record the temperature.  This has worked every time for me for the identification of like substances.

As for the methylenation, go with the DMSO/DCM/NaOH reaction.  The reason I say this is because it is so damned easy.  It's, in my opinion, idiotproof.  Granted, you need a decent magnetic stirrer to stir that fucker and you need a pretty good condenser to keep all of the vapor inside the reaction flask, but aside from the smell, which is just merely unpleasant (as opposed to horrid), it really is a fast, efficient, and facile process; furthermore, it's really not all that vigorous as stated in the write-up. Isolation of your product is also easy as the steam distillation is pretty straight-forward.  You just add water to the mixture, simple distill as per usual, and the desired product -- and only the desired product (along with just a bit of DMSO, but this is no problem as it mixes cleanly with the water) -- comes over forming an oil that lingers below the surface of the water layer.  The one time I tried this was when I synthesized benzodioxole.  Thinking that it was maybe still impure, I distilled it afterwards, but the only fraction that came over was the benzodioxole, which indicates that the end product is very VERY pure.  The process is detailed in TS II.  The only difference that I could point out was that I noticed a slightly different color scheme than that reported in the holy book.  But no big deal.  Also, I felt I had to use more water for the steam distillation than was suggested in the write-up.  While the application of this reaction to other methylenations MAY end in lower yields, it WOULD at least prove that the end product of the SIBX reaction is indeed the desired allylpyrocatechol.

For those that have so far been discouraged, don't give up hope.  The eugenol demethylation IS the HOLY GRAIL of, well, you know what. (Heh, heh) Look what Methyl Man did with Ritter's variation of nitromethane/Al-Hg reductive amination (not to mention his use of methanol as the solvent in the benzo-wacker).  And what about Chromic?  I may have first reported the potential use of oxone in the epoxidation reaction of propenyl benzenes, but he worked out the experimental details.  So too did he develop the homemade peracetic acid/glycolization reaction.  These are just two examples of hard-core newbees that made major contributions here.  Of course, there are many MANY other great members -- shit, too MANY to name here -- that have made great strides and gone against conventional thinking and wisdom to develop novel approaches to chemistry.  And so too can you, newbees . . .

Any questions?

PK

starlight

  • Guest
solvent volumes
« Reply #40 on: April 21, 2004, 11:54:00 AM »
The original procedure using SIBX (

Post 451672

(Rhodium: "Novel Oxidative Demethylation of Eugenol", Novel Discourse)
) uses a high solvent volume for a small amount of eugenol. Scaling this up proportionally would require 20 litres of solvent per mole of eugenol. Hopefully this could be avoided.

psychokitty

  • Guest
But not for identification purposes
« Reply #41 on: April 22, 2004, 07:40:00 AM »
The SIBX reaction is valuable particularly because it can yield allylpyrocatechol without complication.  Like I posted before, for identification purposes.

As for the solvent issue, so what?  I'm sure the experimental reaction scheme has not been optimized.  And besides, who knows what a little experimentation can accomplish?  Just look at how the other popular syntheses that were once thought to be immutable have now changed.  The Al-Hg reaction has been altered in regards to its ratios of solvent to reagents to substrate.  One now knows that the use of methanol is paramount to success whereas the use of other solvents is now discouraged.  Where once dimethylformamide was the only solvent thought to be applicable to the wacker, now virtually any educated bee knows that methanol will suffice.  But as for the demethylation of eugenol, there has to be a beginning somewhere . . .

PK

psychokitty

  • Guest
What about this method?
« Reply #42 on: April 22, 2004, 08:10:00 AM »
Maybe this reaction scheme is more desirable.  It uses less solvent, is relatively non-toxic, facile, quick, high-yielding, forms no dangerous byproducts and tolerates many functional groups, including double bonds.  Also, the reagents required are just as commonly available as those used in the SIBX reaction.

Tetrahedron Letters Volume 38, Issue 50, 15 December 1997, Pages 8749-8752
 
Chemoselective Aryl Alkyl Ether Cleavage by Thiophenolate Anion Through its In Situ Generation in Catalytic Amount

Abstract:  Catalytically  generated alkali metal thiophenoxide in NMP (1-methyl-2-pyrrolidinone) chemoselectively cleaves aryl alkyl ethers in high yields.

Rhodium

  • Guest
Aryl Alkyl Ether Cleavage by Thiophenolate
« Reply #43 on: April 22, 2004, 06:23:00 PM »
As mentioned in

Post 502219

(psychokitty: "What about this method?", Methods Discourse)


Chemoselective Aryl Alkyl Ether Cleavage by Thiophenolate Anion Through its In Situ Generation in Catalytic Amount
Mrinal K. Nayak and Asit K. Chakraborti

Tetrahedron Letters 38(50), 8749-8752 (1997)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/ether.cleavage.cat-phsh.pdf)
DOI:

10.1016/S0040-4039(97)10342-2



Abstract
Catalytically in situ generated alkali metal thiophenoxide in NMP (1-methyl-2-pyrrolidinone) chemoselectively cleaves aryl alkyl ethers in high yields.


starlight

  • Guest
sounds stinky!
« Reply #44 on: April 22, 2004, 11:56:00 PM »
Thiophenol smells pretty bad and its odor threshold is 0.6 ppb so maybe this isn't one to try in your kitchen.

psychokitty

  • Guest
Whoa! Whoa! WHOA!!!
« Reply #45 on: April 23, 2004, 08:39:00 AM »
I may have jumped the gun.

I looked up the citation to the LiCl demethylation of eugenol listed on Rhodium's page and it really looks like a winner.  Dimethylformamide and LiCl are about as easy to get as anything is.  Not exactly OTC, but who cares.  Certainly, the reaction is just as operationally simple as the SIBX reaction; however, it's a bit better when it comes the the volume of solvent required (but it's still pretty way up there; not as good as the Thiophenol method, but at least it's been proven to work in the literature).

Buuuut, there are a few typos that deserve mention. 

For one, eugenol has a molecular weight of 164.20.  So, as the patent describes, 354 ml could NOT possibly be 2.30 mmol!  It more likely has to be 2.30 mol, as this would equal 377.66 g, which, in turn, would likely equal 354 ml due to the density of eugenol.  Besides, 2.30 mmol of eugenol would be .377 g or .354 mL.  I zoomed in on the relevant text in the patent and there are no decimal points whatsoever to be seen.  So, basically, the patent should read 354 ml (2.30 mol) and NOT 354 ml (2.30 mmol).

Also, the time increments in regards to the additions of 292 g of LiCl should read 4, 22, and 29 hours, NOT 4, 18, and 7 hours.

What gives?

Cadenza

  • Guest
Demethylating Eugenol: Some Experiences
« Reply #46 on: April 24, 2004, 01:29:00 AM »
Hello all,

First of all, I would like to take a moment to say that Rhodium's chemistry page is one of the most comprehensive archives that I have ever seen on any subject.  I have always been staunchly anti-drug, but I admit that I have begun rethinking my stance after carefully reviewing current medical literature pertaining to entactogens, hallucinogens, etc.

I have attempted the demethylation of eugenol many times, although not for the purpose of MDP2P synthesis.  (My purpose is to obtain the anti-oxidant 4-allylcatechol, but one of the ways of proving it is to methylate the product to safrole).  This is not a straight-forward task; as Startinout/wacko-reaco stated earlier, the synthesis of 4-allylcatechol has not been well-studied in open literature.

I have a few comments regarding the properties of 4-allylcatechol and various methods that have been attempted:

1.  4-allylcatechol properties:

In response to Pyschokitty, 4-allylcatechol is indeed unstable under RT/exposure to light and air.  I have a dish of 4-allylcatechol sitting in the lab that has turned from a light clear-yellow color to a dark red over the course of three days.

However, it must be noted that 4-allylcatechol does not decompose very quickly, provided that Lewis acids are not used in the demethylation process.  Moreover, the "smokey" demethylated smell is due, in some part, to the interaction of AlCl3 with eugenol rather than some intrisinic property of 4-allylcatechol itself.  I believe this to be the case because the demethylated product from pyridine hydrochloride does not particularly smell like smoke.

2.  Pyridine hydrochloride

This method does work (I have never had problems obtaining 4-allylcatechol from pyridine hydrochloride) but the construction of a microwave reflux apparatus is probably necessary.  I believe that this method is the best way of obtaining a sample of 4-allylcatechol for analysis, since the catechol spontaneously recrystallizes in high purity in situ  following hydrolysis in an ice-bath.

3.  Triethylamine hydrochloride

Triethylamine hydrochloride, by itself, does not work as a demethylating agent under microwave radiation.  I suspect that the main reason is the high melting temperature (~260 C), but in the many trials that I have performed, the amine salt actually decomposes, leaving a polymerized tar substance.

4.  Triethylamine hydrochloride and aluminum chloride under microwave irradiation:

I actually succeeded in a one-pot synthesis of safrole from this combination, although the yield was so low that I didn't bother isolating the product (most likely < 5% yield of a clear oil with a candy-shop odour).

5.  Aluminum Chloride

Literature states that o-methoxy groups may be demethylated by the cleavage agent NaI/AlCl3, but I highly doubt that this will work, given the sensitivity of the double-bond to iodination.  Nevertheless I have not tried this, and experimentation is king.

I have attempted cleaving the ether using AlCl3 independently in both solvent and solvent-free conditions.  However, this does not seem to work, since product was not obtained after hydrolysis of the oxonium complex.

Thoughts:

Given that I have not tried SIBX, LiCl, AlI3, or other classical reagents such as BBr3, I cannot really say that (reasonable) demethylation of eugenol is impossible.  It is possible, but to obtain it in large quantities will require a lot more research.

If anyone has any suggestions (Psychokitty and wacko_reaco, you guys/gals seem to know quite a bit about o-ether cleavage, do you have any ideas?)


psychokitty

  • Guest
Perhaps an in situ demethylation/methyleneation?
« Reply #47 on: April 27, 2004, 08:09:00 AM »
If one demethylated using the LiCl method in refluxing DMF, one could then add the toluene as instructed to precipitate -- what? -- the suspected LiCl (complex?), filter, distill the toluene, which will take with it any water that may be found in the spent reaction matrix.  Then, assuming that tar is not the other 50% by-product of the demethylation reaction, DCM and NaI could be added, reacted to form DIM (diiodomethane) which would form NaCl as a by-product (no big deal).  Then, NaOH could be added all at once or incrementally so that a methyleneation reaction could take place.  Then, water could be added and -- viola! -- steam distillation should yield the desired alkene.  Hence, a straight-through reaction can take place without the need for isolation of the intermediate catechol nor purification of the final alkene through vac distillation. 

Again, assuming that the intermediate catechol is pure enough from the demethylation reaction, the above reaction scheme should work.

As far as other demethylation reactions, I have quite a few experimental ones listed in my arsenal.  Here are two really good ones:

SYNTHETIC COMMUNICATIONS,34(4), 641-649 (2002)
"IMPROVED METHOD FOR DEMETHYLATION OF NITRO-CATECHOL METHYL ETHERS"

Several nitro-catechol compounds,useful as inhibitors of COMT were obtained in excellent yield and purity via an improved proceedure for demethylation of the corresponding methyl ethers using aluminum chloride and pyridine in ethyl acetate.

AND

SYNTHETIC COMMUNICATIONS, 31(6), 869-875 (2001)
"NICKEL/ZINC-MEDIATED ALKYL CARBON-OXYGEN BOND CLEAVAGE OF ALKYL ARYL ETHERS"

Alkyl carbon oxygen bonds of alkyl aryl ethers bearing suitable coordination sites were efficiently cleaved by treatment with nickel(II)chloride and zince in p-xylene under neutral conditions.

Cadenza

  • Guest
in situ is ideal, but...
« Reply #48 on: April 27, 2004, 06:32:00 PM »
The difficulty lies not in the demethylation per se but rather the separation of the catechol and unreacted eugenol.  Solvent extraction does not work because eugenol and 4-allylcatechol are pretty similar in polarity.

I do not know the mechanism behind the LiCl demethylation-- the procedure looks simple, but it requires quite a large amount of solvent and a LOT of lithium salt.  Another potential problem with this scheme is the formation of polymerized catechol w/the addition of NaOH.

Now as to the first reference ("IMPROVED METHOD FOR DEMETHYLATION OF NITRO-CATECHOL METHYL ETHERS"), this works on vanillin, with a few caveats.  Both "startinout" and "bones" managed to get this working-- Startinout directly used Lange's method w/DCM as solvent, and bones used the optimized ethyl acetate.  I have performed this procedure and it is indeed very easy with vanillin (although correct pH and very vigorous stirring are required).

Incidentally, the procedure w/ethyl acetate does not work with triethylamine (Lange claims a 61.5% yield from triethylamine w/DCM as a solvent).

Startinout also performed this procedure with eugenol, with what he called "abject failures."  Having worked with eugenol and Lewis acids, I am inclined to agree- eugenol really should be kept away from AlCl3 and/or other Lewis acids if possible, to avoid vinyl polymerization and Friedel-Crafts interactions.

Another thing to keep in mind is that in these demethylation reactions involving eugenol, the side products will also end up as aromatic oils that steam-distill.  (For example, when I attempted a demethylation with conc. sulfuric acid w/subsequent PTC methylation, a clear oil smelling of fuel came over during steam distillation).

I really believe that the best way to demethylate eugenol is to use an amine-based hydrochloric salt (pyridine, etc).  In Lange's reference, a very interesting table was included:

(Robert Lange, 1962)
DEMETHYLATION OF VANILLIN WITH ANHYDROUS ALUMINUM CHLORIDE AND VARIOUS TERTIARY AMINES

Tertiary Amine         %Yield Protocatechualdehyde

2-methylpyridine              41.3
2-methyl-5-ethylpyridine   36.7
4-methylpyridine              72.7
Quinoline                         22.6
Dimethylaniline                33.1
Triethylamine                   61.5

The key factor in whether a given hydrochloride salt will produce yields under microwave demethylation is whether

a) it is sterically hindered
b) it has a appropriate melting point (~150 Celcius)
c) it will reflux to absorb excess heat

Based on these factors, I believe that 4-picoline hydrochloride (4-methylpyridine hydrochloride) and imidazole hydrochloride are worthy of investigation.


psychokitty

  • Guest
Some suggestions
« Reply #49 on: April 29, 2004, 04:34:00 AM »
Allylpyrocatechol can be separated from eugenol by several different ways:

1.) Steam distillation (eugenol should steam distill; allylpyrocatechol should not)
2.) Vac distillation
3.) Crystallization of allylpyrocatechol in either pentane or hexane.  Allylpyrocatechol is, at most, only sparingly soluble in these solvents; eugenol, I believe, is completely soluble in both.

To avoid polymerization of the allylpyrocatechol upon addition of sodium hydroxide, instead use either potassium carbonate, potassium flouride, or cesium carbonate for the methyleneation reaction.

Even if other aromatic oils are formed during the methyleneation reaction, separation of them from the desired alkene after steam distillation should be no problem as the bp of each is likely to be considerable.

Cadenza

  • Guest
allylcatechol purification / strong acid cleavage
« Reply #50 on: April 29, 2004, 07:00:00 AM »
Thank you for the advice, psychokitty.  Being a somewhat impatient person, I did not think about distillation as a means to separate eugenol/4-allylcatechol, but it sounds like a reasonable method to me.  The heat from a vac-distill should not affect the catechol in any significant way, as the demethylation takes place at 150 ¡ãC+.

Now I have an interesting demethylation question concerning acids.  In the past, HBr has been used to cleave ethers (notably vanillin w/poor yields).  I always assumed that HBr would add across the double-bond, so I did not think about pursuing this method.  In addition, I did not particularly wish to work with HBr.

However, the use of halo-acids is still appealing, since they are greener than most amine-bases (I am not fond of working with pyridine and triethylamine).  Also pyridine hydrochloride is ridiculously deliquesent-- generally a pain to use under atmospheric conditions.

Now, HCl is not generally an effective ether-cleaving agent, but I thought it might be interesting to conduct some microwave experiments with it.

Experimental:

10 mL of eugenol was placed in a 1000 mL roundbottom flask, and 20 mL of concentrated HCl was added slowly, causing the formation and subsequent separation of a green layer.  10 mL of water was added, and the flask was placed in a microwave reactor for 90 minutes under low-power.

Upon cooling and extraction with diethyl ether, a silver-green crystalline substance was obtained (2.5 grams).

I have not conducted any analysis on the product other than a very crude MP test (MP appears to be significantly higher than that of 4-allylcatechol), and I am curious if any properties of chloroeugenol are known (I assume that HCl will add across the double bond w/Markinokov addition)-- whether it cleaves the ether is very much in doubt.

Anyway, I will conduct a more precise MP test, etc. and get back to you on it.


psychokitty

  • Guest
You've probably got a sample of the eugenol dimer
« Reply #51 on: April 29, 2004, 10:58:00 AM »
I think I read somewhere sometime that both hydrochloric acid and/or hydrobromic acid cause both eugenol and isoeugenol to polymerize.

Here is an interesting reference to a patent I found online:

http://v3.espacenet.com/textdoc?DB=EPODOC&IDX=WO0106995&QPN=WO0106995



Unfortunately, the text is in German, so some German-fluent Hive bee will have to translate the relevant parts; namely, those areas which may (hopefully) describe the synthesis of hydroxychavicol (allylpyrocatechol), or, at the very least, list a few commercial sources and/or suppliers of it.

Organikum

  • Guest
The patent is based on the use of ...
« Reply #52 on: April 30, 2004, 12:00:00 PM »
The patent is based on the use of hydroxychavicol in plant extracts from piper betel - usual pepper leaf extraction with alcohol and ethylacetate is described (soxhlett). No synthesis. No suppliers.


CharlieBigpotato

  • Guest
a word on sassafras roots:
« Reply #53 on: April 30, 2004, 02:58:00 PM »
zib finds much irony in this post, as he lives in the southern appalachian mts. of the u.s.

these mountains are presently beeing raped and pillaged on a grand, heart-breaking scale.
in my zone (cumberland plateau) the hardwood forests are now beeing 'logged' for an ever smaller marketable commodity.
long gone are the big oaks and veneer quality black walnuts...now, its mostly down to trees large enough for pallet wood...or smaller...chips.

the massive chip mills on the tennesse river and navigable tributaries are buying trees that aren't big enough to make a 2x4  and shredding them up to make chip board and osb plywood, etc.

what am i getting at here?

that anyone willing to investigate this pillaging and 'follow' the bulldozers thru the once gorgeous hills will litterally trip over endless sassafrass roots that have been torn from the ground.

the smell alone will allow you to find them.
sassafrass is very common; very much not in demand; pretty much a weed tree.

a person could fill a pickup truck with root bark in a few hours without seeing another human beeing.

get it while it lasts?

(oddly enough, the adventure will also put you in touch with several of the substitute plants!)


hypo

  • Guest
great for you!
« Reply #54 on: April 30, 2004, 03:28:00 PM »
but it doesn't really help us people who don't live in the appalachians
or don't own pickpup trucks.

sad thing about your woods though. you should chase away the wood-killers  :P


Sredni_Vashtar

  • Guest
UK
« Reply #55 on: May 01, 2004, 01:43:00 AM »
There are a few sassafras trees growing in Hyde Park if you are interested.

...and there are quite a few juniper trees left, though they are in decline: no more gin - which is a good thing (Real Ale is much better for you.)

It would be great to have a natural UK source of safrole.

CharlieBigpotato

  • Guest
good for more than me, hypo
« Reply #56 on: May 01, 2004, 02:00:00 PM »
i wasn't trying to brag about my sassafras-rich enviorns, hypo...

just trying to pass on a tip to others who may bee able to locate such public logging operations and even rent or borrow a truck.

trying to actually dig up the roots would bee a tremendous chore, but the logging road construction efforts, which gwb has made easy, has also made collecting the root bark pretty damn easy.

might bee worth the trip for those who grok what is suggested.

ApprenticeCook

  • Guest
CharlieBigpotato, i have heaps of sassafras...
« Reply #57 on: May 01, 2004, 05:54:00 PM »
CharlieBigpotato, i have heaps of sassafras around here, but im talking oz... they are still Sassafras albidum but... heres the problem...

https://www.thevespiary.org/rhodium/Rhodium/chemistry/safrolefaq.html%5Bquote%5DJust

thought you might like to add some info onto your safrole FAQ sheet on your site. The Australian botanicals, southern sassafras and ziera smiithi have no safrole in their roots, bark, trunks or foliage. Southern sass has nothing worth mentioning whilst smiithi contains lots of methyl eugenol, which is where the confusion started I believe, the text 'poisionous plants of Australia' is fraught with errors and as much of the info in the current Safrole FAQ is lifted directly from this hence the errors. This will save readers much time I believe as I have wasted heaps of time collecting , seperating and steam distilling all the bits. The methyl eugenol's existence was confirmed through FTIR and NMR library matches so there is no doubt to the accuracy of this info. The only assumption I am making is that maybe safrole only seasonally appears in these species, as my samples were all collected in winter/spring.[/quote]"Southern sassafras"?? are they talking about Sassafras albidum in this description? or another type... same family lacking what we want...

-AC

demorol

  • Guest
Dealkylation with Niobium(V) Chloride
« Reply #58 on: July 10, 2004, 10:14:00 PM »
A Simple and Regioselective Carbon-Oxygen Bond Cleavage Using Niobium(V)
Shigeru Arai, Yukinori Sudo, Atsushi Nishida
Synlett 2004

DOI:

10.1055/s-2004-817766



Abstract
A simple and convenient method for the differentiation of alkoxy groups on aromatic rings is described. Niobium(V) is found to possess a strong Lewis acid property to transform alkyl arylethers smoothly to the corresponding phenols in high yields. The excellent regioselectivity was also observed in dialkoxy benzene derivatives under mild conditions.

Full text:


methymouse

  • Guest
Never going away
« Reply #59 on: July 12, 2004, 09:56:00 AM »
I'm with others on the forum that MDMA will never go away;  I suspect that four things will happen:
(1) Much more "fake" MDMA tablets will begin to appear on the streets, a perverse consequence of the government's policy.  MDMA is much safer than PMA, PMMA and the various cocktails consisting of mixtures cocaine, meth, ketamine, etc.
(2) More MDMA will be imported from the third world and former communist areas.  This will allow law enforcement to increase their budgets and power by earmarking money for MDMA border control operations.  The DEA seems to believe (erroneously) that they can much better control drugs being brought into the country than ones produced domestically, but the black markets on marijuana, cocaine and opium say otherwise.  Since MDMA sells at a higher per-gram cost than cocaine, the incentive to import it will be (and indeed is) very high.
(3)  Domestic MDMA manufacture will become a very specialized creed akin to LSD production involving either highly skilled chemists or chemists with the ability to obtain safrole or the like. 
(4) Clandestine chemists (or perhaps quasi-legitimate "legal drugs" chemical companies) will produce some of Nichols' MDMA analogues, which will then be marketed as MDMA.  Of course most of these are harder to make than MDMA, but if the various members of the hive put their minds together, some reasonable OTC syntheses would be produced.

Given enough time, skill and chemicals, one could make it from catechol, which can be made from aspirin (though at the moment there is not a substantial law-enforcement effort to control photochemicals).  Like the original poster, I haven't seen any reports of success with demethylating eugenol or vanillin in a clandestine setting, though clearly it can be done as there are numerous papers on this kind of ether cleavage.  The problems with this (and other direct syntheses) are the relatively low quality and variety of reagents available to the clandestine chemist, and the relatively low skill of most clandestine chemists (myself included).

Another possibility is the extraction of relevant chemicals from black pepper.  My roommate tried to do this, and ended up with a mess of gunk which refused to crystalize, but it's possible that a different extraction procedure could be found.  Pepper is, unfortunately, a much more complex mixture of chemicals than is sassafras oil, and the precursors are much larger molecules which makes them both more difficult to extract, and more fragile.

Based on what I've read and tried, small scale production is likely to be limited to people clever enough to get safrole, and people skilled enough to make MDMA directly.


homeslice

  • Guest
Ive said it above, i think more than once,...
« Reply #60 on: July 12, 2004, 08:20:00 PM »
Ive said it above, i think more than once, that i dont think the eugenol demethylation/remethylation procedure is as hard as ppl say it is. Its just another example of the information being there and everyone theorizing about it, but noone testing it out. Any of the "small scale" cooks out there that have been around for a couple of years probably have drums of sassy in the shed in their back yards, so they could care less about eugenol. I think one bee out there is going to break it all open, possibly writing a newbee-friendly pictorial writeup similar to the wackers and aminations on how to demethy/remethylate. Its probably going to be a newbee as the older bees are the ones with the drums in their toolshed.  :)


armageddon

  • Guest
too difficult
« Reply #61 on: July 13, 2004, 12:52:00 AM »
Hi! I don't think the eugenol demethylation/methylenation is as easy and suited for "backyard chemistry" as you think: especially the demethylation reactions require pyridine, nitrobenzene, lithium diphenylphosphinate or similar (not very OTC) chemicals, and the only "simple" methylenation reactions are those using a PTC (DMSO isn't exactly one of the compounds every newbee has access to  :) ) - and these difficulties in obtaining the needed chems, in connection with the multiple bad-yielding steps (at least with the routes that use more common chemicals, i.e. using DCM instead of DBM), are the reasons why unexperienced newbees might not be able to arrive at satisfactory results with this route...

(and I think the more xperienced bees would rather use said reagents in the synthesis of some 3,4,5-trimethoxybenzaldehyde rather than making piperonal..  ;) )

..But maybe the LiCl2/DMF eugenol demethylation, together with a KF catalyzed methylenation, would be the way to go for making "homemade" safrole? The reagents seem to be a *lot* more OTC than DMSO/DBM/pyridine and so on...

Greetz A


ApprenticeCook

  • Guest
Re: especially the demethylation reactions...
« Reply #62 on: July 13, 2004, 07:42:00 AM »

especially the demethylation reactions require pyridine, nitrobenzene, lithium diphenylphosphinate or similar (not very OTC) chemicals


What about the AlI3 method from rhods site, easy enough and OTC.


methylenation reactions are those using a PTC (DMSO isn't exactly one of the compounds every newbee has access to )


DMSO is not as hard sourced as it is made out to be. Would DMSO work as the PTC for such reaction?

DIM and DBM can be made from DCM via NaI/NaBr in warm acetone, making a better yielding methylation rxn than by using DCM. (that right?? DCM + 2NaI -->warm acetone--> DIM + 2NaCl sorry cant remeber where i read that)

Personally have not tried it yet but sassy supplies are running a bit low so ill get around to putting my money where my mouth is some time soon. And safe suppliers are running thin...

All up Al foil and I2 are easy enough and DCM, NaI, acetone are easy enough, only problem is PTC, someone come up with something on the PTC req and we will be set...

-AC




methymouse

  • Guest
fabric softener
« Reply #63 on: July 13, 2004, 08:02:00 AM »
Most fabric softeners are supposed to work as PTC's.  Just look for one with a "cationic sufactant" and little else in it.  UTFSE for "fabric softener".


ApprenticeCook

  • Guest
methylmouse, seen that many times from ...
« Reply #64 on: July 13, 2004, 08:54:00 AM »
methylmouse, seen that many times from utfse'ing for otc ptc's but i was looking for another way...

how would one go about synth of tetrabutylammonium iodide?
NH4I + 4BuOH -->H+??-->NBu4I + 4H2O ??
doubt it... but would be nice. i tried google for it but came up with no info on synth only use. UTFSE here came up wth nothing direct on synth.

Otherwise it looks like my safrole will come out all silky and smooth, and what a smell...... safrole + fabric softner....

-AC


Rhodium

  • Guest

Nicodem

  • Guest
didecildimethylammonium chloride?
« Reply #66 on: July 13, 2004, 09:12:00 AM »
Fabric softeners sucks as PTC, because they are very long chain quarternary amines. This makes them much more soluble in the organic phase than water slowing the transition beetwen the two. Not to mention the enourmous molecular mass making a 5 mol% weight more than the  reactant.

What about didecildimethylammonium chloride?
It's OTC and available all over the world as a disinfectant. It has a similar molecular mass like TBAB. Does anybee have any experience with it?


armageddon

  • Guest
misunderstood?
« Reply #67 on: July 13, 2004, 09:53:00 PM »
Hi! In my above post I wrote:

"the only "simple" methylenation reactions are those using a PTC (DMSO isn't exactly one of the compounds every newbee has access to)"

On this a bit of clarification  :) : I referred to DMSO being used as a solvent in connection with DCM/KOH (500ml for 110g catechol are used) - the PTC reaction doesn't need DMSO, nor did I mean using DMSO as kind of PTC (sorry for expressing myself rather unclear, App.Cook..)

But what about using potassium fluoride catalyst with DCM in DMF solvent? Looks pretty OTC to me, too - at least more newbee-friendly than DMSO. And yields are around 90% of theory (calculated from catechol). No PTC needed, and the demethylation can also bee done w/o PTC in case one has already some DMF at hand - lithium chloride is not that hard to get at all. (but then again, yields are only 50% with LiCl2) - seen from this point of view, the only difficulty would be aquiring some DMF..

Greetz A


ApprenticeCook

  • Guest
Rhodium......... isnt there an easier ...
« Reply #68 on: July 14, 2004, 07:51:00 AM »
Rhodium......... isnt there an easier way................
the 3 chems req for those methods are not the easiest to source....

armageddon, ahhh no i see.... sorry bout that, didnt read it carefull enough...

DMF solvent? Looks pretty OTC to me


Nope, DMF is not an easy thing to get in oz, cat 2 on our restricted chems list. DMSO is not on any of our restricted chems list in oz so its easy enough to get, just got to look hard enough in the right places.
So no PTC req? whats your reference for this? Sounds interesting if one can get the DMF and KF.

Nicoderm, im looking at the PTC your talking about... does anyone know anything about this?

-AC




armageddon

  • Guest
good ole Rhodium's
« Reply #69 on: July 15, 2004, 02:40:00 AM »
Hi!

My reference for the DMF/KF methylenation is

https://www.thevespiary.org/rhodium/Rhodium/chemistry/methylenation-kf-ch2x2.html

....  ;)

"To date, the ionizing base for catechols has always been an alkoxide, alkali hydroxide or carbonate. Our method offers an alternative route to methylenation involving the use of an alkali metal fluoride and DMF via an H-bonding mechanism. The method is fast, efficient, provides high recoverable yields and avoids strongly basic conditions. Furthermore, it would seem that by using caesium fluoride and dichloromethane, intermolecular condensations may be kept to a minimum. These results offer further striking evidence for the potential general significance of the method of H-bond assisted reactions to synthetic chemistry."
(Yield for 3,4-dihydroxy-BA->piperonal is 90%, for catechol->benzo-1,3-dioxole 80%)

 (every time again surprising what gems Rhods site contains)

And DMF can be made by heating dimethylammonium formate - which in turn can be made via a tweaked methylamine procedure (usually these methods use certain tricks to suppress dimethylamine formation and favor the formation of MeAmine - for example using excess ammonium chloride, keep temp. below certain level. I would guess that a lot of dimethylamine would be made if these conditions were "reverted", i.e. heating to over 190°C or using excess formaldehyde/hexamine/whatever..). The so obtained diMeAm*HCl is easily converted to the formate salt by dripping a amine*HCl solution onto solid NaOH and directing the gaseous diMeAm (stinks heavily, like dog urine!!) into dil. formic acid, then concentrating the formate salt solution under vacuum to get crystalline diMeAm-formate..

But this would mean having to perform three time-consuming (and maybe not-so-high yielding) steps only to get the solvent. Much work.

So maybe the PTC route is the better choice - if one can get hold of a good PTC...

(BTW I think KF is quite easy to obtain in large quantities, at least it is not watched - or is it? And if lithium chloride is obtainable, too - make LOADS of DMF, demethylate eugenol with DMF/LiCl2 and methylenate with KF/DMF, and ready is the OTC route, unluckily involving several days of DMF production  ::)  - but Eugenol, DCM, hexamine, HCl, alcohol, NH4Cl, LiCl2, KF and some formic acid is a manageable "to-buy-list", even if OTCness is desired - right?)

Greetz A


Rhodium

  • Guest
Methylenations
« Reply #70 on: July 15, 2004, 06:30:00 AM »
But this would mean having to perform three time-consuming (and maybe not-so-high yielding) steps only to get the solvent. Much work.

The authors also informs us that "a number of workers have reported the high-yield methylenation of several substituted catechols using dimethylsulphoxide on N,N-dimethylformamide as solvent", so I believe that you can use any dipolar aprotic solvent here, not only DMF. Try acetonitrile or DMSO if you have easier access to them than DMF.

So maybe the PTC route is the better choice - if one can get hold of a good PTC...

Polyethyleneglycols such as PEG-200 and PEG-400 are good PTC's if you cannot get any quaternary amine PTC's - but you should really have no problem with that -

UTFSE for "OTC PTC"



I think KF is quite easy to obtain in large quantities, at least it is not watched - or is it?

You might need to sign an "End user declaration" as it can be used in the prep of certain nerve agents:

Post 519153 (missing)

(Vitus_Verdegast: "Monitored for reagents used in chem weapons", Law and Order)


And if lithium chloride is obtainable, too - make LOADS of DMF, demethylate eugenol with DMF/LiCl2

Please note that lithium chloride has the formula LiCl and not LiCl2 as you have written in a few of your latest posts.


ApprenticeCook

  • Guest
every time again surprising what gems Rhods...
« Reply #71 on: July 15, 2004, 07:21:00 AM »
every time again surprising what gems Rhods site contains
Tis isnt it.... never even know some of these things are there coz i just read straight over it.... tisk tisk tisk.

And DMF can be made by heating dimethylammonium formate
Sounds good...
made via a tweaked methylamine procedure
Sounds nice... how would you seperate diMeAm and the now impurity MeAm???
Or would you bother? if you could turn the tables of yields far enough you would get a end product of methylformamide and DMF which could be seperated by disto??? hmmmm.....
theres this recently from a newbee, watch for answers...

Post 519452

(r2e3: "extracting dimethylamine hydrochoride", Newbee Forum)

This is the answer (i think!)-->

If formaldehyde is present in excess, at least some of the methylamine is converted to dimethylamine. If too little formaldehyde is present, the methyleneimine polymerizes to its trimer, (CH2=NH)3. Trimethylamine is never formed, as long as the temperature of the solution never exceeds 110°C. With an excess (4 moles) of formaldehyde, enough water and a reflux temperature of 115°C, dimethylamine is the main product, as the temperature rises, more dimethylamine is formed. Dry heating of paraformaldehyde and ammonium chloride produces trimethylamine through reaction of dimethylamine with formaldehyde, giving rise to tetramethylmethylenediamine and formic acid, and the base further reacts with HCl, giving trimethylamine hydrochloride and methyleneimine hydrochloride. A mixture of HMTA and HCl boils between 105 and 110°C, while NH4Cl/CH2O boils at 115°C. No temperature control is really necessary in the former case, as long as your heating plate isn't too hot. If the reaction is carried out at a lower temperature, less dimethylamine is formed, and the yield is higher. Vacuum reflux and distillation can yield at least 95% yield, in contrast to the 45% gotten at 104°C.


What is thought??? so keeping it a wet reflux of 4 moles of formaldehyde to ammonium chloride will produce a nice yield of dimethylamine for use as described.... and running the freebase through formic acid (dilute?? i would say rather conc instead....) to produce formate salt then heating to dehydrate to the formamide(s).

As for KF i dont think it is... not on any of my lists....
As for liCl only LAH and Li metal is on the list for Oz...
The process to make DMF shouldnt be too difficult and yields would be reasonable enough to sustain production, the purchase of DMF in oz is a no go... so this sounds good to me...

-AC




armageddon

  • Guest
yep that's what I was thinking
« Reply #72 on: July 15, 2004, 09:16:00 AM »
Hi!

Nice - you found a post describing more exactly what I was thinking - cool to read that my above rambling wasn't that wrong (where did you copy this text passage from? I hope the source is reliable?)...  ;D

for separation of mono- and dimethylamine just extract the solid amine*HCl mixture several times by boiling with chloroform (maybe DCM works too, dunno), the combined CHCl3 extracts contain the dimethylamine, leftover is pure methylamine..




Rhodium: this would mean DMF isn't a must? But what's the rationale behind using it? Is plain formamide aprotic/dipolar btw?

(D'oh! Li(1)Cl of course!  :-[ )

And about PEGs as PTCs: What about this one - a *really* OTC approach?


Methylene chloride is, of course, the halide of choice for large-scale preparation, and Laskina12 worked out a procedure for methylenating catechol with this halide at atmospheric pressure. With ethylene glycol as solvent, sodium carbonate as base, and with a temperature of 122-124°C, the yield was 38-43% after 8-12 hr. To maintain the high temperature, methylene chloride was introduced gradually.(...)
References
(...)
12)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/methylenation.laskina-2.html

"



(taken from

https://www.thevespiary.org/rhodium/Rhodium/chemistry/methylenation.bonthrone-cornforth.html

- BTW READ THIS ONE, App.Cook!)

I like these russian methods using automatic separators/traps and other fancy glassware, together with rather easily obtained chemicals - elegance and simplicity, together with additional economical benefits and a lot of fancy lab-tech to play with/lots of possibilities for tweaking the rxn/lots of fun for the little child inside me.. :)

Greetz A


ApprenticeCook

  • Guest
Good source
« Reply #73 on: July 15, 2004, 10:10:00 AM »
Its on the notes of the methylamine FAQ from rhodiums site...

https://www.thevespiary.org/rhodium/Rhodium/chemistry/methylamine.html



Well the DMF synth sounds easy enough, apart from making HUGE volumes of it, ie several litres, would be a pain...

What about the demthylation... could there be another way to do this apart from LiCl and AlI3 (req ptc)?
LiCl method shows a pain with the volumes and amounts of addition req.... time is rather lengthy and yields are somewhat eh....

A solution of 354 ml (2.30 mmol) of eugenol and 292 g (6.89 mol) of lithium chloride in 3.7 L of N,N-dimethylformamide was refluxed for a total of 44 hours (h), and after 4 h, 18 h and then 7 h, a further 292 g (6.89 mol) of lithium chloride were added each time. (!!!!) After cooling, 2 L of toluene were added and the resultant precipitate was filtered off with suction and extracted with toluene. The organic extracts were combined and concentrated on a rotary evaporator. After flash chromatography (ether/pentane, 1:1, Rf = 0.37) on silica gel, 173 g (50%) of 4-allylcatechol were obtained


For 354mL eugenol you need to add 3.7L DMF and 1168g LiCl is req?!?!? or am i reading this wrong......

As for PTC for AlI3 method, polyethylene glycol???
Could the PEG in auto coolant be used? (dont know type of PEG sorry)
EDIT: UTF google and answered my question... PEG-200 = polyethylene dimethyl ether correct?
so polyethylene glycol could be made to PEG-DME by methanol and a few drops of conc sulphuric acid catalyst? i dont know im just spurting shit coz im so tired... ill look at this more after i get some sleep. Night all.

Armageddon, the methylenation reaction is well covered and shouldnt be a problem, but the demethylation.... well...
As i said above, hope im reading it wrong because using ~1.1Kg's LiCl per ~350mL of eugenol in 3.7L of DMF is not great... and a 50% yield for this? nah....

-AC

EDIT: Couldnt help myself....
TBAB - as you said rhodium... TBAB by tributylamine + butylbromide = TBAB...... hmmmm we only need a tiny bit so.....
NH4Br + Butanal --> Butanimene
Butanimene + 2Butanal --> Tributylamine bromide
Would this work the same as -
"Dry heating of paraformaldehyde and ammonium chloride produces trimethylamine"
As per the methylamine synth??

Butylbromide would just simply have to be bought or made from n-butanol? as would the butanal from the previous step or oxidised from n-butanol.

So buy n-butanol, oxidise some to butanal and covert some to butylbromide and should be right to go?

-AC (seriously, going to bed now...)




armageddon

  • Guest
typo/correction
« Reply #74 on: July 15, 2004, 11:12:00 AM »
I once read somewhere (maybe it was even in this thread) that the mentioned writeup has several typos - 4h, 18h and then 7h isn't exactly what I call linear timetable!

The right text should read:


Demethylation of Eugenol to 4-allylpyrocatechol with LiCl/DMF

LiCl (292 g, 6.89 mol) was added to a solution of eugenol (354 mL, 2.30 mmol) in DMF (3.7 L), and the mixture was refluxed for 44 h, with additional portions of LiCl (292 g, 6.89 mol) being added after 4 h, 22 h and 29 h. The reaction mixture was allowed to cool down to room temp., and diluted with toluene (2 L). The formed precipitate was filtered off and washed with toluene, the washings were combined with the organic solution and concentrated in a rotary evaporator. Silica-gel FC (Et2O/pentane, 1:1, Rf = 0.37) provided 4-allylpyrocatechol (173 g, 50%).



Hmm, 354ml eugenol being 2.3mmol?? Must again be some typo..
And I agree in that the amounts of reagents are more suited for preparing analytical samples!  :(


But luckily, I have this demethylation procedure on my HD  :)  (but it's of course available at Rhod's too):


2,3-dimethoxybenzaldehyde (1.0g; 6.0mmol) and LiCl (0.76g; 18mmol) are heated in boiling DMF (10ml), the reaction being monitored by GLC (2m SE30 packed column). When the starting material has disappeared (22h), 10% aequous NaOH solution (30ml) is added, the solution is washed with Et2O (2x25ml), then acidified with 10% aequous HCl (50ml) and extacted with Et2O (2x25ml). The organic phase is washed with brine (30ml) dried (Na2SO4) and concentrated in a rotavapor; yield {of 2-hydroxy-3-methoxy-benzaldehyde} 0.88g (98%); mp 42°C, mixture MP with a commercial sample (Aldrich): 42°C."


full text:

https://www.thevespiary.org/rhodium/Rhodium/pdf/ether.cleavage.licl-dmf.pdf



Still much (~3.8L) DMF is used, but at least not >27 moles LiCl any more - only ~290g necessary for 2.3 moles of eugenol..

I wonder if the above demethylation won't do anything to eugenol - or if it will work just fine (with 2,3-diMeO stuff, the meta-located MeO is cleaved, but with m-MeO-p-OH compounds, it could be different..)

(does anybody know?)

Greetz A


armageddon

  • Guest
other demethylation procedures
« Reply #75 on: July 15, 2004, 12:53:00 PM »
Hi!

Just searched a few minutes - there are many other demethylations:

a) SIBX-mediated oxidation (SIBX is a mixture of 22 parts benzoic acid, 29 parts isopthalic acid and 49 parts o-iodoxybenzoic acid)

https://www.thevespiary.org/rhodium/Rhodium/pdf/eugenol.demethylation.sibx.pdf

, especially entry 4a in table 5 (page 3), eugenol demethylation with 77% yield...

b) Ni/Zn-mediated dealkylation

https://www.thevespiary.org/rhodium/Rhodium/pdf/ether.cleavage.zn-nicl2.pdf


(It seems that a nitrogen atom has to be present in the molecule to be dealkylated; maybe usable when first 3-hydroxy-4-methoxy-phenyl-2-nitropropene would be made through Knoevenagel/EtNO2, followed by borohydride reduction to the nitropropane, and then by cleavage of the 4-MeO and methylenation to arrive at 3,4-methylenedioxyphenyl-2-nitropropane? Sounds nice - but will it work? Or what about making 3-OH-4-MeO-P2P oxime, then demethylation/methylenation?)

c) selective mono- or di-demethylation using methanesulfonic acid (CH3SO3H) and microwaves

https://www.thevespiary.org/rhodium/Rhodium/pdf/ether.cleavage.msoh.mw.pdf



d) demethylation with TMS/I (trimethylsilane/iodine; -> in situ formation of trimethylsilyl iodide)

https://www.thevespiary.org/rhodium/Rhodium/pdf/ether.cleavage.tms-i.pdf




(...)




Armageddon, the methylenation reaction is well covered and shouldnt be a problem, but the demethylation.... well...

Huh?  ;)  Simply everything about this topic is covered in

https://www.thevespiary.org/rhodium/Rhodium/pdf/ether.dealkylation.review.pdf

...

(nothing more to add)


greetz A


amalgum

  • Guest
Look people, methyleneation isn't the problem.
« Reply #76 on: July 16, 2004, 11:58:00 AM »
Look people, methyleneation isn't the problem.  It's easy and OTC, and according to several patents SWIM has looked at you don't even need DMSO or DMF.  Methyleneation can be done with alkali metal hydroxides in plain ol' H2O.  Beleive it or not.  Couple that with an already made amine thats protected and a salt and theres no need for a PTC. That amine being 3,4-HO-methylamph for those in the know about my endeavours in that area (and boy it's looking like SWIM is going to have some juicy long-awaited details very soon, bwahahahaha).
Really the problem is, is there is no problem.  It's just time we stop griping about a safrole problem and do what we do best, that is work around it.  The hardest part is just actually doing it.
Right now eugenol to me is looking to be a very viable 3,4-methoxylated amphetamine precursor, as well as viable starting point for both TMA's, and mescaline.  Screw safrole, we don't need it.


armageddon

  • Guest
not the only one
« Reply #77 on: July 16, 2004, 01:14:00 PM »
Right now eugenol to me is looking to be a very viable 3,4-methoxylated amphetamine precursor, as well as viable starting point for both TMA's, and mescaline.  Screw safrole, we don't need it.

What about vanillin?

Greetz A


amalgum

  • Guest
What about it? Yes it's a viable precursor as...
« Reply #78 on: July 17, 2004, 12:56:00 PM »
What about it? Yes it's a viable precursor as well, but above I meant isoeugenol oxidation by chromic acid or something similar, which gives vanillin.
But vanillin in SWIMS opinion would be more viable to get to mescaline than any amphetamine.  Mainly just because it is an aldehyde, and to SWIM it is less attractive to have to synthesize nitroethane to proceed from the aldehyde to nitropropene and so on.  Any other route would just add more steps than it'll be worth IMHO.  So as far as the amphetamines go like MDMA, it's probably within your best interest to start from an allyl- or propenylbenzene (aka eugenol/isoeugenol).

armageddon

  • Guest
probably right - but how 'bout sharing knowledge??
« Reply #79 on: July 17, 2004, 04:11:00 PM »
Yup, when the nitroethane has to be synthed by yourself, it may be advisable to avoid going via nitropropene->ketone->amine and probably easier to start with propenylbenzenes instead - but I would at any time prefer mescaline over MDMA  ;) ..

And vanillin hasn't only drawbacks (besides of requiring NE to arrive at amphetamines) - it usually is sold in "very pure" grade AT LEAST, whereas eugenol has to be distilled (several times maybe) to get a pure starting compound...

But your idea of first making the dihydroxy secondary amine and THEN methylenating it is pretty cool, dare I say - I would guess that my proposed "x-nitropropene -> x-nitropropane -> methylenation of x-nitropropane / reductive amination" will work too? Or is the nitro group more easily attacked (espcially with Zn/Ni), compared to the secondary amine protection you suggest?

Look people, methyleneation isn't the problem.  It's easy and OTC, and according to several patents SWIM has looked at you don't even need DMSO or DMF.  Methyleneation can be done with alkali metal hydroxides in plain ol' H2O.  Beleive it or not.

Actually it is hard to believe, because you didn't back up your statement with any facts or details..

(heaven can be coloured red by throwing open cans of red paint into the air - believe it or not!  ;D )

And yes, now it has been posted several times that the methylenation is well covered and no problem (why did some bee ask about it then?) - amalgum: how about sharing some of your knowledge by giving the patent numbers instead of just talking about having read'em!? Just writing down vague details isn't exactly what helps - and referencing to patent numbers is the simplest of all things!! Espacenet!

I mean: you know about a patent dealing with exactly the problem several bees seem to have (OTC and easy methylenation) - and don't share this knowledge??

...égoiste...

:)  A


psychokitty

  • Guest
Clove Oil is good enough
« Reply #80 on: July 18, 2004, 06:02:00 AM »
". . . whereas eugenol has to be distilled (several times maybe) to get a pure starting compound..."

The above statement is total bullshit.  Clove oil is nearly virtually 100% eugenol and is readily available OTC just about everywhere. 

Use as is directly in any reaction you feel necessary.

ApprenticeCook

  • Guest
Hey all, Psycokitty, i have seen clove LEAF...
« Reply #81 on: July 18, 2004, 11:34:00 AM »
Hey all,

Psycokitty, i have seen clove LEAF and clove BUD oil, which one is more eugenol or is it the same?

And as for methylation, the link above from armageddon for the Kf/DMF/DBM provides high yields with as stated no (or very little) by products or polys... where as the DCM/NaOH method has far lower yields with the problem of poly's of the catchetols.
Im still yet to be convinced about a reliable and good yielding OTC (or close to otc) method for demthylation, the closest iv seen is the AlI3/PTC method as seen on rhodiums site, still yet to find a easily obtainable PTC.
TBAB could be made with only 4 non OTC purchases, n-butanol, potassium dichromatem, acetonitrile and NaBr. (NaBr OTC??), as for acetonitrille, could be made from chloromethane and sodium cyanide? any other way which could be made otc'ish....?
Butanol -->oxid--> butanal
NH4Cl (from many sources) -->NaOH--> NH4OH
6Butanal + NH4OH --> tributylamine + 3butyric acid (right?)
2NaBr + H2SO4 --> 2HBr + Na2SO4
HBr + Butanol --> H2O + butylbromide
butylbromide + tributylamine -->acetonitrille-->TBAB
Right?

Well thats some food for thought...
PTC ideas anyone? (rhodium put forward PEG-400, but where to buy?)

-AC


armageddon

  • Guest
no bullshit
« Reply #82 on: July 18, 2004, 02:01:00 PM »
". . . whereas eugenol has to be distilled (several times maybe) to get a pure starting compound..."

The above statement is total bullshit.  Clove oil is nearly virtually 100% eugenol and is readily available OTC just about everywhere.


Stop! I didn't say distilling eugenol is necessary - only that vanillin has without doubt a higher grade of purity (FOOD GRADE) WITHOUT having to purify, whereas eugenol from essential oils is a natural product - and you have to distill to get a similar purity..

This is absolutely NO bullshit, and BTW not every bee uses essential oils containing 100% eugenol (as you might know! AppCook for example might use clove bud or leaf oil - both contain eugenol, but they surely aren't BOTH 100% pure!!)...

Maybe you can well use clove oil without purifying it - but when you analyze clove oil GC/MS, you'll NEVER get ONE peak - probably more with food grade vanillin..

And if you like using the purest chemicals possible, distillation of eugenol is necessary. quot.

A


ApprenticeCook

  • Guest
Acetonitrile.... another way....
« Reply #83 on: July 19, 2004, 02:26:00 PM »
Acetonitrile.... another way.... maybe a little more OTC??

NH4Cl -->NaOH+heat--> H2O + NH3(gas) + NaCl
NH3 + GAA --> Acetamide + H2O
Acetamide -->P2O5--> Acetonitrile + H2O
?
Access to P2O5 is not so bad... once again not OTC but it would be explainable... glass manufacture i think?

And permangentate could be used to create butanal instead of dichromate, constant distillation of the more volitile butanal could save an ok yield???

Also..... butane gas refils.... could these be used as a source? they are butane, couldnt these be sprayed over a heated copper plate to be oxid to butanol's?? then seperated by disto of the different isomers?

Thoughts on this and my above mention of TBAB?

-AC


lutesium

  • Guest
Aldehydes can be reduced to alcohols and ...
« Reply #84 on: July 21, 2004, 06:15:00 PM »

armageddon

  • Guest
right thought - but..
« Reply #85 on: July 22, 2004, 03:44:00 AM »
Although this is only true with BENZaldehydes (acetaldehyde will never result in benzyl chloride  ;) ) - everything else is correct so far.

But unfortunately this thread is not about how to get active compounds from (benz)aldehydes; but rather about how to make 3,4-methylenedioxy stuff from either 3,4-dihydroxy or 3-Meo-4-OH substituted aldehydes (or from similar compounds).

Your suggested reactions assume that one has piperonal - this thread is about how to make it...

Greetz A