Beginners Long Wet Reflux

Twacked Out · Tue Feb 15, 2005 2:39 pm

For those who are new to the exciting field of organic chemistry, swim would like to introduce to you his favorite method of producing the best dl-"N,alpha-dimethylbenzeneethanamine hydrochloride" money can buy. Now swims sure youve probably heard of the lwr before, and he's sure you've probably heard of 500 or so ways to perform it. Swim is gonna tell you how to do it the best way he knows, its gonna require patience though so if you don't have any just ignore this post.

First your gonna need a few basic yet all important pieces of lab equipment, a heat resistant boiling flask of appropriate size and a water cooled condenser to fit it, a ring stand w/clamps and a fry daddy with thermostat. you can get the fry daddy @ wally world for around $30, the rest you can find online, flask, condenser, and stand for well under $100. This setup is the holy grail of this method and to perform it correctly you need all the above pieces, no exceptions. Second you will need precursers, Ephedrine, Red Phosphorus, and Iodine, you can find in other posts how to get them, they must be of top quality and you will need an equal weight of each one.

Now for an explanation of the reaction you are about to perform. Its called the reduction of ephedrine with Hydriotic acid or HI. Now the precursers you have are ephedrine-HCl, red phosphorus, and iodine crystals, so wheres the HI? your gonna make it. the red phosphorus, iodine, and water react to form it, so the amount of iodine you add to the rxn will govern how much HI can form. RP also plays a role as a facilitator, not a catalyst, in this reaction heat is the catalyst. now once the HI is formed and in solution it can reduce the E to dl-"N,alpha-dimethylbenzeneethanamine hydrochloride" via a 2 stage reaction. the first stage invoves replacing the OH group on the E molecule with an I, now you have iodoephedrine. thats called halogenation, the second reaction is called hydrogenation and involves replacing the I with an H, now you have dl-"N,alpha-dimethylbenzeneethanamine hydrochloride", sounds easy? well it is, a monkey can reflux, so can you!

so lets get started shall we, in your boiling flask your gonna first add your iodine, then water, then RP. lets say youve got 10 grams of E, so your gonna make that 10g of iodine, 10ml distilled water, and 10g RP. now put your condenser on and put the setup with the flask into the fry daddy, which is about 2/3 full of cooking oil or antifreeze, turn up the fryer to its lowest setting, during this time you should have water pumping through the condenser. as the mixture heats the iodine will seem to disolve, when all the crystals have disolved (20 min) you can either add your E through the condenser, or let the rxn cool and take off the stopper and add the E. now put it back on the fryer and turn up the heat to 150C or about 300F, now for the next 2-3 days all you have to do is check on the icewater in the bucket for the condenser pump, check every couple of hours, dont ever leave the rxn going and leave the place or go to sleep, you can split the time up if you like, if you must leave or sleep, turn off the heat first, then when you return just turn it back on. the rxn needs to go for between 48-72 hours, the longer the more E gets reduced to dl-"N,alpha-dimethylbenzeneethanamine hydrochloride"

so now after the time is up turn off the heat and let the reaction cool enough to be able to comfortably hold the flask, remove condenser and unstopper, now however much stuff you have you wanna add an equal amount of water, now heat it to a boil and remove from heat. using a funnel with 4 coffee filters already wetted with water, pour the reaction fluid into the funnel and into a beaker, now pour a little more water in the now empty flask and swirl it around, then pour that into the filter also.run the fluid through the same filter at least 4 times or until its a pale yellow pee pee lookin color, no red. then pour some more water into the filter to rinse the rest of the amine off the RP and into the beaker.

you'll notice all the left over RP left in the filter, thats because swim used an excess of RP. why? well using just enough RP to finish the reaction wont work, youll get low yields because the RP is there to keep the HI concentration up and since its insoluble in pretty much everything, including your reaction fluid, you need as much surface area on the RP as possible so it can find the iodine to react with to form HI.

that being said your gonna now pour the honey into a sep funnel, a sep funnel is a tear drop looking flask with a stopper on the top and a tube with a valve on the bottom. you can get one online for under $20, after you pour the fluid in the sep funnel add 1/2 the volume of the fluid toluene or xylene, swish it around a while then let it sit on the ringstand, you'll notice it separates into 2 layers, the top is the tolly and the bottom is your goodies, drain the goodies into a beaker and discard the tolly, do this again until the top layer is clear. now its time to basify, take 200g of Lye (NaOH) and dissolve it into 1 liter dH20 slowly, this will be your lye solution. now put the goodies and an equal amouont of tolly in the sep funnel, add lye solution until you reach a ph of 13, youll know this from litmus paper, or just add a little at a time until it stops clearing up. let sit for 15-30 min and drain the bottom layer, then put the top layer into another beaker. now put the bottom layer back in and add more tolly, then add a little lye and see if it clears up or not, if it doesnt swirl it around a bit and let sit again. then discard the bottom layer and add the tolly to the other portion of tolly you just removed. now all you gotta do is either titrate or gas, which you can learn in other posts in general chemistry section. make sure you clean all glassware and discard all solvents safely and have a good day, or should swim say week Wink

below are what the three main pieces of glassware should look like

THE MOON RULES --1 · voted for the moon

i've never made methylamphetamine HCI or seen anyone before but I was just wondering because I didn't understand one part, "you can either add your E through the condenser, or let the rxn cool and take off the stopper and add the E"
So when you do that reaction you stopper the top of the condenser? Its a sealed rxn?

methyl_ethyl · Riedel De Haen

Don't stopper the top of the condenser, unless it is a special stopper like device that evacuates to a gas trap or some other modification. This is not a "sealed" reaction.

Perhaps the poster was using a multi necked flask, in which one of the necks was stoppered and the other neck was fitted with the reflux condenser.

Also the pictures provided are not the best representations of what you should be looking for. A Graham condenser is probably not your best option for a reflux, and obviously the flask depicted does not have ground glass joints, which means fitting it with a reflux condenser would be at best impossible.

I can't comment too much more about anything else as I have 0 experience with this type of reaction. Hopefully the poster, some other members, or moderators can better help you understand this, and provide guidance as to what equipment would be optimal for this reaction.

just_my_thoughts

m_e

Twacked Out · Mon Feb 28, 2005 11:41 am

ok sorry about the misunderstanding, swim doesn't use ground glass because he likes a condenser with a tube so it can be ran through a rubber stopper, his reasoning on this is simply being able to use the condenser on a number of different size flasks, so maybe that better answeres your question

canibal · Mon Feb 28, 2005 12:10 pm

if not a graham condenser what kind should swim use? flask must have ground glass joints to accept condenser? by what means does swim get water from iced bucket to condenser? Question

can flask vent through condenser??? swim has never dreamed of a condenser...

IndoleAmine · Dreamreader Deluxe

The type with a water containing cooling coil inside, called "reflux condenser". If you plan to do only small rxns, a "liebig" condenser will be sufficient.

Ground glass joints are necessary to ensure a proper fit. Rubber stoppers fit very well too - but you have only a small hole for the vapors to escape the flask and enter the condenser, and a pressure can build up inside the flask, causing the condenser and stopper to pop off (and maybe fall on the ground and break).
So it is better to use ground glass joints, and you can't insert them incorrectly; they always fit ferfect (which is not the case with ruber stoppers!).

To get ice water from a bucket into your condenser, you could use a water pump Wink

, like the ones used in small room fountains for example... (be creative here, maybe check the aquarium equipment suppliers, hydroponics suppliers and similar)...

but for most rxns, cold tap water is cold enough...

The flask can vent through the condenser, provided that it isn't stoppered. You will want to attach a hose on top of the condenser and direct that out through an open window - the lwr produces toxic fumes IIRC... Wink

i_a

loki · guinea pig

i just wanted to say that a successful synthesis occurred in a simple oil-heated test tube with a fan blowing past the top of it recently to someone... two hours at about 95-105`C (it kinda got hotter about half way thru) yes, boring old 'dry' style synthesis...

but here was the key thing that occurred that this someone thinks was key - they made up a solution of sodium ethoxide with denatured ethanol and sodium hydroxide, and added it to the cooled reaction fluid after adding a quantity of naptha to cover it, and let the thing boil gently for about 20 minutes.

I don't know why anyone else hasn't grasped this yet, but the 'Ker Plunk' method is an inchoate version of an established form of de-halogenation used in environmental chemistry (for deactivating nasty halo-hydrocarbons such as 2,4 D and DDT) called 'Catalytic Transfer Hydrogenation'. The essence of this method is to put one's potentially halo-hydrocarbons into a mix with a strong base and with aliphatic hydrocarbons sitting on top, which are the source of the hydrogen (apparently). Using sodium ethoxide, this someone successfully demonstrated that this not only works but produces a high purity product, indeed 'purer and more potent' as the kerplunk method was suggested would be.

just to go a step further, limited experimentation into combining the CTH with a benzylic alcohol halogenation reaction resulted in a distinctly positive reaction, enough to suggest to someone that perhaps a more careful method would indeed yield the appropriate de-hydroxylated product as desired.

someone's theory is that the problem with the e/rp/i reaction system is that the whole thing depends on the formation of hypophosphorous acid from the phosphorus in the reaction, which happens only slowly, because, (look it up) hypohphosphorous acid is a well known de-halogenating agent...

need i say more? why cook it all night when it can be done in 3 hours flat??? same result.

IndoleAmine · Dreamreader Deluxe

You say:

Bluechip · Fri Mar 18, 2005 6:13 pm

Have you actually run this rxn with the ratio you propose?
@ 16:1 h2o:I2 That is one fucking wet dream I tell you.
I can see why it would take you 3 days to convert anything.

I thought you asked about this at wetdreams?

loki · guinea pig

damn... where the hell did i get the idea... i could have sworn i read somewhere about potassium hydroxide and a mineral oil which boils about 300 degrees which absorbed it... maybe I am completely mistaken...

well, despite this, I can say with certainty that when the intermediate compound iodoephedrine/iodomethamphetamine comes into contact with water, it does indeed undergo a re-hydroxylation. Obviously, because we are talking about an unstable compound, a benzylic iodide, if it only takes water to return it to the hydroxyl, the site which one finds the iodine is unstable, and does not take much to be pursuaded to react with something.

Is it possible that perhaps, in relatively dry conditions, as the iodoephedrine percolates into the aliphatic hydrocarbon, that at the interface, the conditions favour the base reacting with the iodine to form an oxyiodide (especially with a sodium alkoxide) because the iodide is unstable, whereas the oxyiodide is not so unstable... well, I conclude that I don't know.

But I do know one thing, and that is that the product that results after 20 minutes heating with naptha on top and sodium ethoxide basifying the reaction mixture is high-octane, as the terminology goes. If there were nothing else going on than 'purifying' then how exactly is anything going to be purified, surely basifying the reaction mixture will drive the freebase alkaloids into the solvent? How could this possibly be purifying anything, thats just the same as what happens in an acid/base extraction, and it is not specific for any alkaloid, just every alkaloid.

Is there any further musings on the ker plunk and what exactly it does that I can find in the archives? Has anyone ever suggested doing it without any significant water present before?

Taz · Fri Apr 01, 2005 5:20 am

Wouldn't tapeing a ballon on top of the condenser help keep the smell down espically on long cook?

Sektor · Sun May 22, 2005 8:30 am

like taz said, except for one thing, why does one taper a balloon to the top of the condenser? is it just the the smell factor? or the fact that as the balloon is inflated it is filled with hi gas(or whatever gas it is, i would like to know this) then deflated to 'push' the gas back inside the reaction flask to react.. obviously im a newbee.. anyway, help! swim is gonna try this shit soon, swims done a bit of research on this, but fuck, so many different ways! thank you all for your patience

walter · Tue Jul 05, 2005 3:33 am

i have a question
what if there was too much water added and it was like soup?
will it destroy the reaction?
can anything be done to reduce the water to a better size?
or should it be coked for much longer?
or is all lost?
thansk for any replies

Elementary · Fri Jul 15, 2005 5:43 pm

Firstly, why is this here "misc Stimulants" ? surely this needs to be moved.

This method seems to be based on Wizard X's procedure (procedure 2+note6) with a few tweaks

https://www.synthetikal.com/Rhodiums_pdfs/chemistry/----.hi-p.html

If you use less than 8 grams of E then you are gonna need to increase the RP used, but increasing the reflux time from 2.5 hours to 48-72 hours seems a bit of an over kill, did you make analytical samples of the cook over the time period to come to that figure ?

Using a fryer as a ghetto oil bath is inventive, although a saucepan with cooking oil in it and a thermometer can be just as effective.

The flask you use should be a round based type as this allows good circulation of the reagents under reflux, the size size of the flask should be twice the volume of the reagents (water+E+I+RP).
I would not recommend using anything but glass jointed glassware with a joint size of at least 24/29 if you are using a 500ml flask. The top of the condenser should not be pluged if you are going to be just refluxing 57% (approx) hydriodic acid, if you are going to be using less water then you will need a push-pull set-up to contain the HI gas etc.

The push-pull method is usually preferred to the 57% hydriodic acid reflux because less RP and I are needed although the reflux method is safer to perform with the correct equipment.

geezmeister · Busy Bee

The self-contained, cool-to-the-touch, adjustable heat deep fat fryers work very well for this purpose, in fact. Some come with thermal overlimit fusing, a very utile safety feature. For the clandestine chemist, the self-contained unit hides well among kitchen appliances. Sand baths in these units work very well, as do oil/sand baths, and oil baths. They are useful for maintaining a consistent temperature. The units are a safety factor for a reaction that must be left unattended for any period of time.

Most ---- cooks make their HI in situ and gas containment is necessary during the evolution of the HI gas. After the initial production of HI gas the top of the condenser can be capped with a loose cotton plug and this seems to contain odors well enough. A heavy balloon used during the evolution of the HI will contain the gas until it is, for the most part, absorbed by the water in the reaction. Allowing the balloon to remain on the condenser for the duration of the reaction is not necessary, but it does not have an adverse impact on the reaction. It additionally prevents the escape of odors. Such a reaction can be done in one room without persons in the next being aware of its presence, even with an open doorway between rooms.

Significant hands-on experience with this particular reaction and its variations suggest that the reflux method needs only the molar amounts of red phosphorous and iodine to be successful. The push pull methodology steals HI from the reaction and leaves it in the water in the tanks; success and good reduction in that approach require more of the precursors than the reflux method. The reflux additionally will produce higher yields and purer product than a push pull method, even if the latter is done with care and skill.

The 49-72 hours is overkill, as wet refluxes with up to 0.8 ml dH2O per gm of feedstock complete in 24-36 hours at a temperature no higher than 120C in the flask; with more than a 1:1 ratio of water to E, one may find refluxing for 48 hours necessary to get the last four or five percent of the yield. Longer cooking times will compensate for a dilute solution only to a point; at a 1:1.5 E:dH2O the reaction tends to stall. A too-dilute reaction cannot be cured by evaporating off the excess moisture as the HI will be evaporated off as well. The solution is to add additional I2 and red Phosphorous sufficient to correct their ratios with respect to the water already present. Lab Grade red phosphorous with clean pseudoephedrine HCl and good quality iodine have been reacted at a P:I:E ratio of 0.33:1:1 with complete reduction and only the smallest trace of red phosphorous in the filter after the reaction. Those ratios are not to be used if one has the slightest doubt of the purity of the red Phosphorous, however, and my standard recommendation is that red phosphorous be used at a 0.5:1 ratio; higher ratios are used for red phosphorous from matchbook strikers or previously used red phosphorous. The ratio of water to E in these reactions was 0.8 ml per gram of pseudo HCl. The reactions were done consistently for 36 hours at a temperature of 100C for the first 24 hours, raised to 120C for the last eight.

Ground glass joints are preferable to stoppers, but the tendency to pop stoppered condensers out of flasks is characteristic of drier cooks, and not a real problem with long wet refluxes. The HI is evolved more slowly in the wetter environment and more of it is absorbed by the water available than in the drier approach. Many LWR's have been done without so much as a clamp or tape on the stoppered joint. The balloon used for gas containment (a 9'' balloon when inflated) rarely swells beyond grapefuit size, and will stay that size for the duration of the reflux. The pressure in the balloon is very small and insufficient to affect the progress of the reaction. The "give" of the balloon provides sufficient pressure relief for the gas formation stage. A stoppered condenser will blow the stopper during that phase of the reaction.

(Elementary-- this writeup differs from WizardX's writeups, which begin with prepared HI, and are calculated to use twice the molar amounts of HI to insure complete reduction. )