A Complete MDMA Synthesis for the First Time Chemist Introduction Thanks to Strike, Rhodium, Ritter, Osmium, r2d3, Semtex Enigma, Spiceboy, ChemHack, Labrat, Eleusis, Ketone/LabGrrrl, and a personal hero, Dr. Shulgin. And to the object that made this possible - the Internet. Disclaimer: This is for theoretical argument only. IF someone chooses to follow this synthesis, note that the product has been 'Scheduled 1' by the United States Government, and offenders can be prosecuted. In no way do I condone this activity. This is a hypothetical synthesis for: 3,4-methylenedioxy-N-methylamphetamine. Or MDMA.HCl. Or Ecstacy. The synthesis as described 1. does not put off nasty fumes, 2. requires suspicious chemicals, and therefore is 3. perfect for the clandestine chemist. The synthesis itself can be performed in a series of weekends or in a straight shot. If one were to follow this exactly - with no shortcuts - buying everything they're told - doing exactly what is written - they and they're friends will have a lovely spring. For those who think they are better than the instructions as written - be prepared to screw it up at least 4 times before success (or you finally figure out I'm right). Be prepared to invest ~$800. Be prepared to read and learn. It's also a good idea when investing in chemicals to buy 5x what is needed for a synthesis - this way you can repeat it without buying it again. Read the whole thing before you start. There is some prep-work that can be done ahead of time, or while you're distilling. Good luck. Overview: 1. Distillation: of Natural Oil to obtain pure Safrole 2. Rxn: Formaldehyde + Ammonium Chloride -> MethylAmine.HCl (MeAm.HCl) 3. Rxn: Safrole -(Wacker Oxidation(PdCl2+Benzoquinone))-> MDP2P 4. Distillation: of Reaction contents to yield pure MDP2P 5. Rxn: MDP2P -(Al/Hg Amalgam (MeAm.HCl) -> MDMA oil 6. Crystallization: (MDMA oil + HCl in IPA/Xylene) (anhydrous conditions) What you need: This list is the basics. Do not even start this without ALL the Chemicals and Apparatus. Apparatus and Glass: · http://www.amazon.com/exec/obidos/ASIN/0471387320/qid=996507700/sr=2-1/ref=aps_sr_b_1_1/104-5586371-4861548"]'The Organic Chemistry Lab Survival Manual' by James W. Zubrick. (A must, throughout this text, pages from this book will be mentioned. ~32$) (and very handy pictures of glass set-ups) · Distillation Apparatus(1x500mL and 1x1000mL Round Bottom Flask, 1x250mL Round Bottom Flask, condenser, distillation adapter, vacuum adapter, thermometer adapter) (Get Ground Glass Joints. These are the best. 19/22 or 24/40 - my first set was 19/22 - and is still used to this day.) · Thermometer (0°C to ~300°C) · Stand (Home Depot - (2x10in., flange, 2 ft. of ½in pipe)) · Clamp (Buy it. Trust me its worth it) (for holding the glassware to the stand - these support several hundred dollars in glass - buy a nice one!) · Hotplate/Stirrer combo (got to have it, its worth it) (www.labx.com - spend $200) · Magnetic stir bar (look on the Web) (teflon coated) · Water Aspirator (or a good vacuum source. But aspirators are cheap <$20) · Boiling Stones (for distillations. Small shards from a broken coffee mug) · Tubing (about 10ft. total (3 meters) - hardware store - vacuum tubing is better than dialysis tubing - but both will work) · Vaseline (not much - for coating of the ground glass joints) · Measuring Cups (Prefably pyrex, and in milliliters (mL)) · 10 various sized glass containers/bottles (250mL, 500mL, 1L, 2L etc) · Scale (a three beam analytical balance are great - and can be found for less than $100 - www.balances.com - they can weigh as much as a kilo and as little as 0.1g - perfect!) · pH paper (chemical supply) (just one roll will do - ~10$) (nothing specific, just need to tell the difference between an acid and a basic solution) Chemicals: · Safrole (160g)(sassafras oil, yellow camphor oil) (Natural/Essential Oil distributor) · Dimethylformamide (DMF) (350mL) (Diethylformamide or Formamide will work) · p-Benzoquinone (Quinone, Benzoquinone) (120g) (Photo Shop, or Chem supply) · Palladium Chloride (PdCl2) (2g) (Photo Shop, or chem supply) · Methylene Chloride (DiChloroMethane, DCM) (this can be distilled from automotive solvents (just go into Nationwise, PepBoys, Sears, AutoZone And read the labels) Or a Liter can be bought from a Chem supplier.)(Zip-Strip furniture polish remover) · Hg-salt (1 gram of: HgCl2, Hg(NO3)2, Hg(acetate)2, HgCl, It can be anything, and 1g should last you a long time.) · Isopropyl Alcohol (IPA, Pharmacies 91% Isopropyl Alcohol will be available)(get +3L)(don't get the 70% stuff) (or you can get pure stuff from a chem supplier) · Epsom Salts (Magnesium Sulphate) (MgSO4) (grocery store/pharmacy) (Spread out on a cookie sheet, and bake in the oven at 200°C for 3hr to dry them - pretty useless if you don't dry it) · Thick Al foil (heavy duty, or pie pans from the Grocery store) · Muriatic Acid (31.45% HCl)(Pool pH down, Driveway cleaner, ~3$/gallon) · Sodium Hydroxide (NaOH) (Drain Cleaner Crystals) (Read these labels, Get the stuff that is JUST NaOH.) (Red Devil Lye, Lye - Hardware Store) · Ammonium Chloride (NH4Cl) (Photo Store or Chem Supplier) · Paraformaldehyde (Hardware store) (called Mildewcyde or DiGas - made by the same people who brought you Damp-Rid - hint-hint) · Peanut oil (this is a high boiling oil that we will use as an oil bath on the hotplate/stirring plate combo) · Acetone (for cleaning your glass and crystal work-up) (Paint Section of Hardware Stores) · Xylene (for crystallization) (paint section - thinner - get it specifically) 1. Distillation: of Natural Oil to obtain pure Safrole. A Comprehensive Description of this Step by Chromic Set up for a vacuum distillation like on page 53 of Zubrick. Always put a little Vaseline on the ground glass joints - this way they won't stick when you try to take them apart. Put as much Natural oil (Sassy, Camphor, ect) as you have, but not more than 300mL, into the 500mL Round Bottom Flask (RBF) with several Boiling Stones. Put one of your 250mL RB flasks as the receiving flask. Set up your Water Aspirator Vacuum, in the sink (this may require setting this up a day before - parts, trips to the plumbing store, etc.) and attach the vacuum hose to the aspirator and then to the vacuum adapter on the distillation set up. Start turning up the heat slowly! SLOWLY! The slower you do it, the better/purer your safrole will be. At normal pressure safrole boils at 232°C - but under your vacuum, it may boil at anywhere from 110-160°C. Whatever temp it starts to come over at - make a note of it. And if the temp is higher than 160°C - check your seals on the tubing and glassware - More than likely there is a little leak. Remember that Vaseline! At the end of the distillation, you should have a water white oil that really refracts light - And has a lovely smell - a little like potpourri. Distillation set-up: Set up the distillation set-up on your bed, before you try to put it together on the stand. You will get a good idea about how the pieces go together, and become familiar with the fragility of the whole thing. Read Zubrick for advise about where to place the clamp. The Peanut Oil: A bowl with a flat bottom rests on the Hotplate. It is filled with Peanut Oil. The distillation flask sits in the bowl but not touching the bottom, so that the Hotplate heats the bowl, the bowl heats the Peanut Oil, the Peanut Oil heats the distillation flask. This is VERY effective. And will be perfect for all your distillation needs - especially if you do it under vacuum. Step 2. (2 hour work + 4 hours wait + 4 hours work) 2. Rxn: Formaldehyde + Ammonium Chloride -> MethylAmine.HCl In your 500mL RBFlask: (Thanks ChemHack/Labrat!) Set up for distillation (not vacuum). In the distillation flask (your 500mL RBFlask) put: 108g of NH4Cl, 120g Paraformaldehyde (molecular ratio 1:2, remember this when scaling up!) and 320ml of water and several boiling stones. Start heating very SLOWLY. Remember to turn on the water in the condenser! At 80°C a clear solution was obtained. Heating continued - The temperature was maintained for four hours at 104°C (this temp is VERY important - if you over shoot it - don't worry - bring it back down and try to stabilize it at 104°C) Once you've got it at 104°C start the stop watch and do it for 4 hours. At 104°C, a small amount of distillate will come over - very slowly - this is good. We are removing methylal, and methylformate from the reaction contents and therefore driving the reaction to the right - or getting more of what we want. After four hours and while the solution is still hot, set up to vacuum distill (IE its already set-up - now just add the vacuum hose!) - but don't turn on the vacuum yet. Turn up the heat. Within 30 minutes or so - liquid should start coming over - the internal temp of the mixture should not go over 200°C - Keep distilling off the liquid until 1/2 of the solution remains - (IE distill off half of the solution.) Then, take your flask off the Hotplate and let it sit in an ice/water bath. Crystals should start to form in several minutes. Filter off these Ammonium Chloride Crystals. Now set up for distillation of the remaining liquid again - Add a couple more boiling stones. Distill off half of the remaining liquid. When half remains (or a 1/4 of the original solution), turn the vacuum on SLOWLY! VERY SLOWLY! - you don't want the whole mess of liquid jumping out at you. At some point the whole mass will crystallize into a yellow-white solid. This is ~95% MethylAmine.HCl, ~2% Ammonium Chloride, and 3% DiMethylAmine.HCl. This is fine for the next step. It may be a little wet, but if you let it crystallize hot (spontaneously in the flask with heat) it should be fairly dry. Seal it in a wide mouth jar until needed. As a way to check your product - if you live in a relatively humid area, you can put a crystal of your product on the table - walk away - and when you come back a small puddle of water will be on the table where your product was. MethylAmine.HCl is said to be HYGROSCOPIC. Another way is to put 20mL of water in a cup then add 5g of the NaOH to it. Stir to dissolve. Now, drop several crystals of your product into it - it should smell like rotting fish + ammonia. If you do the same with Ammonium Chloride, it will just smell like ammonia. You'll recover about 1/3 of the ammonium chloride for recycling and after a lot of evaporating. You'll get ~80g of pure (95%) MethylAmine.HCl, which corresponds to ~80% yield. Congrats. This can be stored at room temperature, forever. I've heard of people using 40+ year old MethylAmine.HCl with excellent results. Paraformaldehyde is the polymerized form of formaldehyde - but unlike most polymerization processes - this one is reversible - so Paraformaldehyde and formaldehyde can be interchanged at will. If all you can get is formaldehyde solution - remember that if its 37% formaldehyde then 100g of the solution contains 37g of formaldehyde - or just go ahead and change your amounts in the flask to - 324g of 37% Formaldehyde Solution, 108g NH4Cl, 205mL water. Step 3. (2 hours work + 7 hours of wait (sleep?) + 1 hour work) 3. Rxn: Safrole -(Wacker Oxidation (PdCl2+Benzoquinone))-> MDP2P This step has been called the Wacker Oxidation. It uses PdCl2 as a catalyst to put and oxygen across a double bond. This step has been worked over many times so do not change the amounts for the fabled 'scale-up'. If you do this correctly, you will have more MDMA.HCl than you know what to do with. (Thanks Strike!) Procedure: Put the following into your CLEAN 1000mL RBFlask: 300mL of dimethylformamide (DMF), 50mL of tap water, 120g of p-Benzoquinone 2g of Palladium Chloride (PdCl2), Magnetic Stirbar. (PS - Don't skimp on the catalyst!) Start the stir bar on 'slow stir'. Mix 160g of Safrole and 50mL DMF in a cup/jar. Drip the Safrole/DMF Mix into the solution at room temp (30C) over 30min time. After the addition, the solution was dark reddish orange. Almost black. Make sure the stir bar is spinning - Now - Walk away. Go to bed. Go somewhere else. Set your watch alarm to wake/remind you 7 hours later. NOTE: This reaction requires NO additional heating! Just stir! Strikes comment: "After 4.5 h the solution will progress on its own to +45°C. Obvious exothermic reaction. After 7 h solution will be back to ~30°C." The reaction mix was flooded with slightly acidic water (~50mL of Muratic Acid (HCl) in 1.5L of water). The oil fell out of solution to the bottom. It was black/blood red in color. This is when its nice to have a Big Sep Funnel. Now we need to define several things. The upper layer (in this case!) Is the aqueous layer - IE it's the layer that contains the WATER - the bottom layer is the organic layer (in this case!). IE it contains oil and other ORGANIC type molecules (IE the stuff you want!). After you flood the reaction contents shake the container to mix the solution, give it about 10 minutes to settle - two layers will form. The upper aqueous layer was a lighter blood red/pink. The upper aqueous layer was decanted from the oil (IE it was poured off). The aqueous Layer washed with 2x100mL DCM (Methylene Chloride / DiChloroMethane). If you can't see the layers, hold the container up to the light, so that the light shines through the container. Keep the DCM washes - They contain the goods. You now should have about 200mL total of DCM washes. You should also have about ~100mL of the 'Organic Layer' that you separated from the reaction contents. Pour the DCM washes and the Organic layer together. Now wash the DCM/Organic layer with 2x150mL 10% NaOH (30g NaOH in 270mL water). This will remove the other reaction by-product - hydroquinone. If you don't do this step the hydroquinone will clog your condenser when you try to distill. Keep the DCM/Organic layer. The NaOH layer (Aqueous: is still on top) can be tossed. (Thanks Osmium!) You can stop here and wait for another day - put the DCM/Organic Layer into the freezer. Define Washes - 100mL of DCM was poured into the aqueous layer and then the aqueous layer+DCM was shaken so the two would mix - then it was put down to let it settle out again. When it was settled (notice that the layer now is a different color) the aqueous layer was poured off again into another jar where it was washed again with another 100mL portion of fresh DCM = 2x100mL washes. Step 4. (4 hours work) 4. Distillation: of Reaction contents to yield pure MDP2P Pour the DCM/Organic layer into your CLEAN 500mL RBFlask. Put several boiling stones in too. Set up for vacuum distillation. This time we are going to collect a particular fraction in the flask - there is DCM (BP 40°C), water (BP 100°C), DMF (153°C), safrole (232°C), ketone (BP est. ~290°C), and polymerized crap (BP ~300°C+) Now remember when we distilled the safrole? What temp did it come over for you? Well - that temp plus approximately 25°C is the temp that the ketone will come over under vacuum. For example, if your safrole comes over at 150°C, then the ketone will come over at 175°C. If your safrole comes over at 130°C then your ketone will come over at 155°C. Get it? WEIGH the receiving flask! Write the weight on a piece of tape and tape it to the flask! Start your vacuum distillation by first turning on your vacuum - if you remembered your boiling stones, then it will begin to boil immediately. This is the DCM coming off first. The boiling may be very vigorous, So watch it, and be prepared to vary the pressure so it won't fly into your receiving flask. Turn on the heat (Hotplate) SLOWLY! and let the temp climb to just over the temp at which safrole came over (SLOWLY: it should take at least 2 hours to reach that temperature - if you do it in under 2 hours you are going WAY to fast). You are going to have to change the flask, when the temp gets to above the safrole temp. This is a bit tricky, because you are going to have to release the vacuum. Release the vacuum at the pump/aspirator and change the flask quickly - you may just dump it out, rinse it once with acetone, or IPA (IsoPropylAlcohol) - and put it back. Start the vacuum immediately, but be careful here, because the Organic layer that you are distilling might jump out of the flask and into the receiving flask - so if you can - vary the vacuum so that the vacuum comes on GRADUALLY! (IE with an aspirator, turn on the water slowly.) The ketone oil is a clear white/yellow hint of green oil. Re-weigh the flask for your yield calculation - you should have over 100g of ketone. With an aspirator you can vary the vacuum when you are turning it on. You simply turn on the water slowly. IE Increase water pressure slowly. By turning it off, you can make water jump into the receiving flask because there is a 'vacuum' in the distillation apparatus and it will suck water out of the aspirator - SO - when you turn off the vacuum, do so by removing the hose from the aspirator - while the aspirator is going. You can also vary the vacuum by removing the hose PARTIALLY - This will take some practice so play and have fun. Strike's excellent post read: "With high vacuum at 100-140°C ~18g safrole came over. At 166°C came over ~125g ketone." When she did this method... Keep the ketone. Smell it. Look at it. Look at how it refracts light. For the brave: taste it. Note all of these 'properties' and remember - After you have judged its properties, put it in the freezer. Note: it won't freeze. It will become a very viscous liquid. If you try to distill the ketone at atmospheric pressure (no vacuum), you will get to about 220°C and then the whole flask will polymerize. Total waste of effort, time, and precursors. So don't mess around and get a vacuum source. The ketone is unstable. It won't explode or anything, but if left to its own devises, it will rearrange. And then it will be useless. At room temp, it will rearrange in about a week - depending on where you live - if you keep it in the freezer - it can last months - FREEZER! After its in the freezer you can stop for today. Step 5. 5. Rxn: MDP2P -(Al/Hg Amalgam (MeAm.HCl) -> MDMA oil (Thanks Ritter, Osmium, Shulgin!) This is called the Al/Hg Amalgam. This process utilizes the electronegative properties of the Aluminum. Now, something that most people don't realize, is that all aluminum is actually coated with Al2O3. This is the oxidized form of Aluminum. We will remove this part of the foil so that the aluminum can reduce the imine with elemental Al. This reaction actually has two parts. First, there is the ketone -> imine condensation. This reaction reacts the ketone with methyl-amine to form an imine - water is produced as a product. Second, the imine is reduced (Hydrogen is added across the double bond) to the amine. The condensation really needs anhydrous (no water) conditions, and the reduction actually needs water - so there is a fine balance here - IE don't mess with the procedure. What you need to have prepared ahead of time: · CLEAN 500mL RBFlask. · 20g of thick aluminum foil cut into ~1cm squares. · 0.1g of Hg(salt) (any mercury salt will do, not Hg Metal) (Note: Hg=Mercury) · Disposal Jug (milk jug) · 1L of Clean water · 25mL of 25% NaOH solution (dissolve 25g NaOH in 75g of water, then 25mL of it) · 50g of MethylAmine.HCl dissolved in 300mL of 91% Isopropyl Alcohol · 40g of 'ketone' dissolved in 50mL of 91% Isopropyl Alcohol · Cool water bath. (A milk jug with the top cut off) · Ice (don't screw around, buy a bag) (or have at least several kilo's handy) Set up your stand and clamp so that, when the flask is clamped to the stand the bottom of the flask is about 4 inches (10cm) from the table top. This is so that you can put the heating plate and stirbar combo under it. Have your thermometer already in its thermometer adapter so you can throw it in the flask at any second. Prepare the following, put them in a jar and have them ready at a moments notice: · 50g MethylAmine.HCl dissolved in 300mL 91% Isopropyl Alcohol · 40g 'ketone' in 50mL of 91% Isopropyl Alcohol It is very important that these are ready before you start! BEFORE YOU START! 20g of Al squares are put into the 500mL RBFlask. They are covered with ~350mL of H2O (water). 0.1g of Hg(salt) (or just a very small spatula) is placed in with the Al squares, and given a good stir. Amalgamation was allowed to proceed until there was the evolution of fine bubbles the formation of a light grey precipitate, and the appearance of occasional silvery spots on the surface of the aluminum. (Thanks Dr. Shulgin!) Basically here the Al2O3 is being destroyed, the water is reacting with the Al2O3 to form Al(OH)3 and H2. This should take between 15 and 30 minutes. Just be patient. When amalgamation is complete, pour out the water into the milk jug. Pour in another ~350mL of water and carefully shake the flask to stir up the contents. Pour it out into the jug. Do it again with another ~350mL of water. So basically, you wash the Al pieces with 2x350mL of water. Dump out as much of the water as you can in 10 seconds or so - then immediately go to the next step - leave the Al foil in. This will remove most of the Hg from the solution. Don't worry, the Hg will be completely removed in the successive washes during the work up. If you let the Al squares sit in between washes, they will heat up and re-form the Al2O3 in a matter of seconds. So be quick and have the ingredients ready for the procedure. Now, immediately, add in THIS order: · 50g MethylAmine.HCl dissolved in 300mL 91% Isopropyl Alcohol · 40g 'ketone' in 50mL of 91% Isopropyl Alcohol, then drop in a Magnetic Stirbar. Try to get the stirbar going - it might take several minutes. Now drip this in 25mL of 25% NaOH solution over several minutes. Put the thermometer in the solution. Start being very paranoid about the temperature. The temperature of the reaction flask must not climb above 60°C. Its best if the temp is kept around 50°C. Stirring is necessary so, with the heat off, stirbar on, flask sitting in the cool water bath. When the temp gets to about 50°C, put several chunks of ice in the bath. If the temp falls below 40°C, take some of the ice out. But whatever you do, make sure the temp remains below 60°C. The whole time you are doing this the contents are a grey sludge. Remember to keep the stirbar going! If the stirbar is difficult to start going. Don't worry, trying to get it started seems to work just enough. At some point you'll notice that the temperature is not rising like it had been (in about 4 hours or so). You have reached the end of the ketone -> imine condensation - Look inside the reaction flask and see if you still see any pieces of Al foil - if you do - continue stirring until the Al foil has been depleted. This reaction should go no less than 6 hours. Now, after you are convinced that the reaction has stopped (6 hours later) - IE the temp of the solution is room temperature, and there is no more foil chips in the mix. Pour in 25mL of the 25% NaOH solution. Stir the contents some more, and then let the stirbar stop and then let the solution rest for at least 30 minutes. The NaOH solution will make that grey sludge into a filterable consistency. If you can't tell there has been a change in the consistency - put in another 25mL of 25% NaOH solution. The grey sludge should abruptly change from a uniform grey to a chunky white/grey blob. Then in a matter of minutes the whole thing will be resting on the bottom of your flask. The reaction contents will settle out. The grey sludge will settle to the bottom, and a clear yellow liquid will rise to the top. Pour off the clear yellow liquid. Save it. Put 200mL of 91% Isopropyl Alcohol into the reaction contents, stir the solution, so that the whole thing is disturbed and swirling in the flask and again wait. Pour off the 2nd clear yellow liquid once it settles. Add the 2nd clear yellow liquid to the first. Do this several times, or until the clear liquid is no longer yellow. This is an extraction out of the reaction contents. The more you do this process, the higher your yield. So don't do it once and get excited and try to complete it with just the first extraction because you will just waste half of your product. You've gone this far - don't fuck it up now. After you have gotten as much of the yellow liquid out as you could. Put the grey sludge in the same milk jug waste container. Dispose of it properly - the milk jug contains elemental Hg - Not a lot - less than 0.1g. But you should dispose of it properly. Not down the sink. Take it to a High School or A University, To the Chemistry department - tell them you broke a thermometer, and then couldn't figure out what to clean it up with. Set up for vacuum distillation (Boiling Stones!) but we're not going to distill. We are going to evaporate the Isopropyl Alcohol (IPA) from the reaction contents. Under an aspirator vacuum, the IPA should come over around 35°C. Make sure you get the alcohol out. When the alcohol is close to being gone - the solution might spontaneously separate in your distillation flask. Not to worry - the top layer is probably your product, and the bottom is water. Don't try to separate it, just dump the whole thing into the next procedure. The next two paragraphs out line a procedure known as an Acid/Base extraction. This works very well for our target molecule, and any molecule that contains an amino group. If the next two paragraphs are not done, then plan on not having any crystals when you're done. After the alcohol has all gone, Take the brown oil that is left and put it into 500mL of ~0.5M HCl solution (470mL water + 30mL of Muriatic Acid). Stir or shake it up. A lot of the brown oil should go into the acid solution. Now pour into this solution 30mL of DCM. Shake again and let it settle. You will notice two layers formed - The top layer is the Aqueous layer - which CONTAINS your product, and the bottom layer contains the DCM, polymerized crap, and non Nitrogen containing molecules. Pour off the top layer (That CONTAINS your product) and discard the DCM layer. Wash the Aqueous layer again with 30mL of DCM, and repeat the process. NOTE that the AQUEOUS LAYER CONTAINS THE PRODUCT - DO NOT DISCARD THE AQUEOUS LAYER! You can discard the DCM washes, because they contain nothing useful what-so-ever. Discard! Now, slowly add 50mL of 25% NaOH solution to the aqueous layer. When you do this the Aqueous layer will turn a milky white and may heat up just a little bit. Not to worry. A light brown oil will fall out of the solution. This is your product (in the freebase form). Before collecting it, wash the 'now basic' Aqueous layer with ~50mL of DCM. Shake and let it settle out. Pour off the top Aqueous layer, and KEEP THE DCM THIS TIME! The DCM washes CONTAIN THE GOODS! Wash the aqueous layer twice more with 50mL of DCM. Combine those DCM washes that contain your product, and continue. Set up for vacuum distillation, and once again, just boil off the DCM (Boiling Stones!). There might be a little water in it, so this time when you are boiling off the DCM, let the temp of the distillation flask reach ~50°C for several minutes. That should be good enough. You should have a light brown oil in the flask - it kind of looks like thick Newcastle Beer. Step 6 (2 hours work) 6. Crystallization (MDMA oil + HCl in IPA/Xylene) This must be done in anhydrous conditions. If its not, then you will not get crystals. Anhydrous means 'no-water'. If water is present, then you can expect to get crapola. Procedure: This first step can be done ahead of time. Like, during a distillation or reaction: Get a fresh bottle of 91% Isopropyl Alcohol, and pour out approximately 100mL. Now get some of your DRY Magnesium Sulphate (Epsom Salts) (about 100mL worth) and dump it into the 91% IPA. There might be a little heat evolution, but not to worry .... Shake it up and then let it sit till the MgSO4 settles out. Pour off the IPA, and then put more fresh MgSO4 into it (about 100mL worth). Now shake the bottle and let it sit for 15 minutes. You must do this at least three times - It really is much better to do it four times - Why fuck it up now right? After three times you will have 'Dry' IPA. You can actually do this while you are distilling or waiting for a reaction to proceed. Make a mixture of 100mL 'Dry' IPA and 150mL Xylene. Pour it into the flask that contains the MDMA oil, and drop the stirbar in too. Stir so that the whole thing is mixed up real well - Now drip in Muriatic Acid slowly. Test with pH paper every 5 drops or so - keep adding the Muriatic Acid until the pH of the solution is 5-6 - or just barely acidic. Set up for vacuum distillation, and distill the solution, distill this with the stirbar in instead of the boiling stones - IE When the solution has reached a pH of 5-6 - Start distilling. Be careful not to let the solution get above 120°C - When a lot of the solution has boiled away, crystals will spring to life in the flask. Under vacuum, the solution should never get above 70°C. Filter these with a coffee filter, suspended over a jar - This gets the excess IPA/Xylene out. Scrape the crystals on to a plate and let the crystals dry, by letting the IPA/Xylene (mostly Xylene at this point) evaporate - this might take several hours - a 60 Watt lamp 6 inches (20cm) away from the crystals shining brightly helps. Stir the crystals to promote even heating. The crystals will be a brown-yellow color. Now scrape the crystals into a jar, and pour ~20mL of acetone onto them. Swirl the mixture. The crystals won't dissolve - but a lot of the brown will. The brown-acetone is poured off, and the acetone wash is repeated. After the acetone wash, dry the crystals. You should have around 15g of dry crystals. That's 150 hits. The now 'almost white' crystals have melting point values over the range from 145-153 ° C, depending on how much water was in there during crystallization. And these crystals are ready for consumption. 60mg is not enough. 80mg is great for my wife. 100mg is a great dose. 125mg is balls-to-the-wall. 150mg is too much. For me at least. Fun for me is actually 80mg MDMA+70mg MDA in one pill. WHOH. But I guess you'll have to do another synth - right? If you have completed this, congrats. Fucking Fantastic. Now Teach Someone Else! If you do - we WIN! Dig it?
Manufacture of "Ecstacy" from Chemical Abstracts 52, 11965 (1958) For Informational Purposes Only. The authors & distributors do not advocate the use of illegal drugs and assume no liability for the use or misuse of this information . The procedures described are dangerous and should not be attempted by persons inexperienced in Organic Laboratory techniques. This formula is exemplified for MDA (3,4-Methylenedioxy- phenylisopropylamine); substituting N-methyl formamide results in MDMA or N-methyl MDA (Ecstacy). To a cooled mixture of 34 g 30% H2O2 and 150 g formic acid, add dropwise a solution of 32.4 g (0.2M) isosafrole in 120 ml acetone, (keep temperature below 30 degrees) Let stand twelve hours and evacuate in vacuum. Add 60 ml methanol and 369 g 15% sulfuric acid to the residue and heat on a water bath three hours. Cool, extract with ether or benzene and evaporate in vacuum the extract to give 20 g 3,4,-methylenedioxybenzylmethyl ketone. Add 23 g of above ketone to 65 g formamide and heat at 190 degrees for five hours. Cool, add 100 ml H2o2, extract with benzene and evaporate in vacuum the extract. Add 8 ml methanol and 57 ml 15% HCL to residue, heat on water bath two hours and evaporate in vacuum (or basify with KOH and extract the oil with benzene and dry, evaporate in vacuum) to get 11.7 g MDA. The above occurs as a yellowish brown oil; this is active orally, but somewhat inconvenient; to convert to powder (salt) form, reflux in Hydrochloric acid and evaporate. Safrole, an allyl benzene, occurs naturally in oil of sassafras, about 70%. Can be extracted with simple distillation. It is con- verted to isosafrole (a propenyl benzene) by adding equal weight of KOH flakes and absolute ethanol and heating on steam bath or refluxing for 24 hours; dried and evaporated in vacuum or added with two time its volume in water and extracted with ether or methylene chloride and dried, evaporated in vacuum. Hexane is used for recrystalization. Formamide and N-methyl formamide are closely watched by the DEA. Many people have been busted by small suppliers where it was easy to get; those are "sting" operations that tail the buyer home.
Sassafras oil is an orange-colored liquid with a smell just like licorice. It is a complex mixture of substances which is easily purified by distilling. To obtain pure safrole from sassafras oil, the glassware is set up as shown in Figure 13 in Chapter Three. The distilling flask is filled about 2/3 full of sassafras oil, along with a few boiling chips, and then vacuum is applied to the system. A little bit of boiling results due to water in the oil, but heat from the buffet range is required to get things moving. Water along with eugenol and related substances distill at the lower temperatures. Then comes the safrole fraction. The safrole fraction is easily spotted because the "oil mixed with water" appearance of the watery forerun is replaced with a clear, homogenous run of safrole. When the safrole begins distilling, the collecting flask is replaced with a clean new one to receive it. The chemist is mindful that the safrole product is 80-90% of the total volume of the sassafras oil. Under a vacuum, it boils at temperatures similar to phenylacetone and methamphetamine. When all the safrole has distilled, a small residue of dark orange-colored liquid remains in the distilling flask. The distilled safrole is watery in appearance, and smells like licorice. With a liberal supply of safrole obtained by distilling sassafras oil, work can then commence on converting it into 3,4 methylenedioxyphenylacetone.
Methylamine Methylamine is very high on the do-not-everpurchase-through-regular-commercial-channels list. As such, any meth production scheme that uses the phenylacetone route will also have to produce its own methylamine. This is no great challenge, hi the days before methylamine became commercially available, researchers and practical cookers in industry always had to make their own. To our benefit, they left good directions for us to follow. See Organic Syntheses, Collective Volume 1, pages 347-9. The reaction to produce methylamine is cheap, but requires a lot of labor. Two molecules of formaldehyde react with ammonium chloride to produce a molecule of methylamine hydrochloride and formic acid. Both starting materials are easily obtained in 5-gallon-pail or 50#-bag sizes from commercial chemical outlets serving industry. The glassware is set up as shown in Figure 11 in Chapter Three. The chemist places 1000 grams of ammonium chloride and 2000 ml of 35-40% formaldehyde in the 5000 ml flask sitting in the pan of oil. (These chemicals need not be a very high grade; technical grade is good enough.) He puts a thermometer in the oil next to the flask and heats the oil to 105° C or so, with the aim of heating the contents of the flask to about 100° C or so. A thermometer inserted into the flask is used to monitor its temperature. A bubbling reaction kicks in, and a condensate made up of formic acid and methyl collects in the receiving flask. When this distillation slows in a couple of hours, raise the temperature inside the flask to 104° C, but no higher. Continue heating at this temp until no more distillate comes over (4 to 6 hours). Periodic applications of aspirator vacuum to the batch will increase yield of methylamine because it pulls the CO2 out of the reaction mixture. Then he turns off the heat and removes the flask from the pan of oil. Some liquid will have collected in the 2000 ml flask; he throws it out and rinses the flask with water. The 5000 ml flask is set in a pan of room temperature water to cool it off. A good amount of ammonium chloride crystals precipitate from the solution. He does not want these chemicals, so he filters them out. He returns the filtered reaction mixture to the 5000 ml flask and again sets up the glassware as shown in Figure 11. A 250 ml flask is used as the collecting flask. The reaction mixture should be clear to pale yellow. He turns on the vacuum source and attaches it to the vacuum nipple of the vacuum adapter. He boils off the water and formic acid in the reaction mixture under a vacuum. Heating the flask in the oil pan speeds up the process, but the oil is not heated above 100° C. When the volume of the contents of the flask is reduced to about 1200-1300 ml, he turns off the vacuum and removes the flask from the oil pan. The flask is put in a pan of room temperature water to cool it off. Some more crystals of ammonium chloride come out of solution. He filters out these crystals and pours the filtered reaction mixture into a 2000 ml flask. He sets up the glassware as before, and again boils off the water and formic acid under a vacuum. He does not heat the oil above 100° C. When the volume of the reaction mixture has been reduced to about 700 ml, crystals of methylamine hydrochloride begin to form on the surface of the liquid. It looks a lot like a scummy film. When this happens, the vacuum is disconnected and the flask is removed from the oil bath. The flask is placed in a pan of room temperature water to cool it off. As the flask cools down, a lot of methylamine hydrochloride crystals come out of the solution. When the flask nears room temperature, it is cooled off some more with some cold water. This will cause even more methylamine hydrochloride to come out of the solution. The chemist filters out the crystals and puts them in a Mason jar. The crystals look different from the crystals of ammonium chloride, so he should have no trouble telling the two apart. These crystals soak up water from the air and melt, so he does not waste time getting them in the Mason jar after they are filtered. He pours the filtered reaction mixture into a 1000 ml round bottom flask and again sets up the glassware as shown in Figure 11. He reattaches the vacuum and continues boiling off the water and formic acid under a vacuum. When the volume of the mixture reaches 500 ml, he removes the flask from the hot oil and places it in cool water. As it cools off, more crystals of methylamine hydrochloride appear. He filters the cold reaction mixture to obtain these crystals. He transfers them to a beaker and adds 200 ml of cold chloroform to the beaker. He stirs the crystals around in the chloroform for a few minutes, breaking up any chunks. This dissolves any dimethylamine hydrochloride in the product. He filters the crystals in the beaker, then puts them in the Mason jar along with his first crop of methylamine hydrochloride crystals. He throws away the chloroform and returns the reaction mixture to the 1000 ml flask. He boils the reaction mixture under a vacuum again. When its volume reaches about 150-170ml, he turns off the vacuum and removes the flask from the hot oil. He pours the reaction into a beaker and stirs it as it cools down, to prevent it from turning into a solid block. Once it has cooled down, he adds 200 ml of cold chloroform to the slush. He stirs it around with a glass rod for a couple of minutes, being sure to break up any chunks. The mixture is then filtered. The crystals of crude methylamine hydrochloride are kind of gooey, so it may not be possible to filter out all the chloroform. This batch of crystals is added to the Mason jar along with the rest of the crude product. The yield of crude product is around 425 grams. It absorbs water easily from the air, and melts. Its smell has been described as "like old woman's pussy." The main contaminant of the crude product is ammonium chloride, along with some dimethylamine hydrochloride, and some of the reaction mixture. The 425 gram yield of crude product is therefore deceivingly high. Purification would best start with drying under a vacuum. This could be conveniently done by placing the crude crystals into a large vacuum flask, stoppering the top of the flask, and applying aspirator vacuum for about half an hour. Gentle heating of the flask with warm water during the vacuum drying helps speed along the process, as does some shaking around of the contents of the vacuum flask. If one has an aspirator that likes to spit water back into flasks under vacuum, then one should use a vacuum pump. Now to get nice and pure crystals of methylamine hydrochloride, we leave those crude crystals in the filtering flask, and add around 3/4 of a quart of 190-proof vodka to the crystals. One hundred- ninety-proof vodka won't dissolve ammonium chloride, but it will dissolve methylamine hydrochloride when it is hot. Leave the top of the filtering flask stoppered to prevent steam from getting into the flask, then warm up the flask using hot water. Water fresh off the stove, almost boiling hot, would be best. Swirl around the flask as it warms to get the methylamine hydrochloride dissolved. Once the alcohol solution gets hot, stop swirling to let suspended crystals settle out. Then decant off the alcohol solution, taking care to keep the crystals inside the flask. Filtering is necessary. Then put the alcohol which has been decanted from the flask in the freezer. As it gets cold, methylamine hydrochloride crystals will come out of solution. When the alcohol is good and cold, filter to collect these pure crystals of methylamine hydrochloride. Store them in a Mason jar with a lid. Return the filtered cold alcohol to the filtering flask containing the crude product. Once again heat the alcohol with swirling to dissolve some more methylamine hydrochloride. Then let the suspended crystals settle once again, and decant the alcohol as before, and cool that down in the freezer to get another crop of pure methylamine hydrochloride. A few cycles through this process will get all the methylamine hydrochloride soaked out of the crude product and recovered as pure recrystallized methylamine hydrochloride. The yield of pure methylamine hydrochloride will be around 350 grams or so. Sometimes, the methylamine hydrochloride is used directly as such in the reaction, such as, for example, in reductive alkylation using aluminum foil as the reducer. More generally, the free base is used. To obtain a strong solution of methylamine in water, 100 grams of methylamine hydrochloride is placed in a flask with 50 ml water. This is chilled in an ice-salt bath to a temperature nearing 0° F. Then a cold solution of 60 grams of NaOH in 100 ml water is slowly added with stirring. The addition must be slow enough, and the cooling strong enough, to avoid losing the free base as a gas. Methylamine solution produced in this way is roughly comparable to the commercial 40% methylamine, except that it also contains salt, and maybe a little NaOH if too much was added. This solution should either be used immediately, or stored in a tightly stoppered bottle. Refrigeration of the solution is optional, but desirable. The reader should be aware that chloroform is a poison for Raney nickel catalyst, so if that particular method is going to be used in meth production, the crystals must be vacuum-dried. Also, it is possible that the excess NaOH may interfere with methods using catalytic hydrogenation. I can't say. If it does, an apparatus like that in Figure 18 can be used to boil out the methylamine free base into a stirred, chilled solution of alcohol. Other methods of making methylamine exist, but they are not well-liked by the pioneers mentioned at the beginning of the chapter. Presented here is their preferred method. For example, it can be made in 71% yield by reacting methyl iodide with hexamine, also known as hexamethylene tetramine. Good directions for making this substance from ammonia and formaldehyde can be found in Home Workshop Explosives by yours truly. The production details for methylamine are found in the Journal of the American Chemical Society, Volume 61, page 3585 (1939). The authors are Galat and Elion. It can also be made by degrading acetamide with Clorox. See Journal of the American Chemical Society, Volume 63, page 1118 (1939). The authors are Whitmore and Thorpe, and the yield is 78%. It can also be made via the Curtius reaction in a yield of 60%. See Helvetica Chimica Acta, Volume 12, page 227 (1929). The authors are Naegeli, Gruntuch and Lendorff. References Journal of the American Chemical Society, Volume 40, page 1411 (1918).
Methylamine Synthesis by ChemHack ----------------------------------------------------------------------- The way I figure it, Hexamine is a lot less nasty (fume-wise) to make then Ammonium Chloride and just as easy. The Hexamine and the Ammonium Chloride procedures are essentially the SAME. Adding HCl to Hexamine causes it to degrade into Ammonium Chloride and Formaldehyde and is not a nasty reaction AT ALL, just raises the temp a little bit. If you want methylamine.hcl the easy way then follow my advice. Make your hexamine the way that you have been. Boil away all the water in a stovetop safe glass frying pan. (a Teflon pan coated regular pan will also work) This produces a buttload of nasty fumes but in my opinion the smell of ammonium is not as bad as having HCl gas in the air as you would if you just made ammonium chloride directly. You want to do it in a separate room with a window if you don't have a fume hood. The fumes of formaldehyde are worse than HCl so make sure that the solution you are boiling away has excess ammonium instead of excess formaldehyde. Once you boil all the liquid away you will be left with white hexamine powder. Add the HCl and stir it around real good. Some heat will be evolved. Let it sit overnight and in the morning there will be a buttload of Ammonium Chloride crystals sitting in the bottom of your flask. Rig up a large reflux device by attaching a long hose to the top of a large glass bottle. Now put the bottle in a pot and add cooking oil. If you put to much oil in then the thing will float so be careful. Now just heat the oil up until the thing starts bubbling. Turn off the heat and swirl it around. Notice how it continues bubbling even after it is no longer boiling? Tiny bubbles? That is CO2 being released. Now heat it again and this time let it keep bubbling. Swirl it around a lot to make sure the evolved gas can get out. I like to use a big-ass hose as the "reflux" area and then stick a smaller hose through it down into the solution. Attach the smaller hose to a fish tank bubbler and let the bubbler do the stirring for you. This will also help blow the evolved CO2 out of there. To make sure your little bubbler hose wont melt or distort because of the heat, test it in boiling water first. After a couple of hours the thing will no longer bubble when it is not boiling. The boiling point will go up from 100 to about 108. This is a good sign that the reaction is done. For 340g of hexamine I let it go 5 or 6 hours total but some of that time was just heating it up. Oh yeah, heat and cool slowly when using a regular bottle because the glass can't take quick temperature swings when it is that hot. The last thing that you want is a bunch of nasty formaldehyde/methyamine/ammonium water boiling below a layer of hot oil! When your heating is done allow it to slowly drop to room temperature on its own. Maybe best to just leave it overnight again. A bunch of ammonium chloride will fall out of solution again. Filter this off and set it aside for later. Using the same frying pan, evaporate the liquid solution. Again, there will be nasty fumes. If you have boiling flasks and an aspirator you may choose to use that instead because you suck those fumes right down the drain. Personally, I don't have any 2 liter boiling flasks and I don't wanna wait to do successive smaller amounts. I just boil them away in the spare bedroom with the windows open. Go back and check often because you don't wanna boil all the water away and scorch your goodies. At some point during the evaporation, more ammonium chloride will start to come out. Remove it from the heat and cool quickly. Then filter out the crystals and set them aside with the others. Put it back on the heat and let it go all the way until it is mushy. It won't get completely dry but don't worry about it. Take it off the heat and it will get nice and solid. Scrape this stuff up and combine it with the other crystals. You now have a much of methylamine and ammonium chloride. Get two large flasks with pouring spouts. Pyrex measuring cups work great. Put the crystals in the larger one. Pour a couple hundred mls of hardware store denatured alcohol in the other one and heat it to boiling in the microwave. Add the boiling alcohol to the crystals and stir like mad for a few seconds. The alcohol will probably take on a yellowish tint. The less yellow the better because that means you have fewer by-products but don't worry if it is bright yellow. You can worry if it is orange. Pour the hot alcohol off into a separate container. Put this container in the freezer and go smoke a cigarette. When you come back to the freezer you will see magic crystals! Keep repeating the procedure with fresh alcohol until you don't get any more crystals. Then do it one more time for good measure. The bright white crystals left in the measuring cup are ammonium chloride. Load them up in funnel with a coffee filter and pour one last bit of hot alcohol over them. Add the alcohol to the other and spread the ammonium chloride out on a plate to dry. Now put all of the alcohol extracts (even the ones that solidified) back into your frying pan and evaporate. Be extra careful to notice when no more alcohol is coming over because it might still be slushy even though all the alcohol is gone. These are the liquidy impurities. Once all the alcohol is gone the temperature in the frying pan will go way up so pay attention! Purification: Once the alcohol is all gone remove it from the heat and allow it to cool down and get nice and solid again. If you have any chloroform then now is a good time to use it. It dissolves the di-methylamnine impurities but leaves the good stuff behind. If you don't have any chloroform then pour out about 100mls of alcohol and put it in the freezer until it is very cold. Add the cold alcohol to your methylamine and impurities and stir it around real good. Not very much of the solid will dissolve but the alcohol will take up a bunch of the yellow crap leaving the crystals much lighter. Decant off the cold yellow alcohol and repeat with fresh cold alcohol until you reach the point of diminishing returns. This is the somewhat subjective point where you are starting to get more of your good stuff than yellow stuff. With this first round you can probably go until the cold alcohol coming off the crystals is completely clear. Put these crystals in an airtight container. They are the purest ones but you can still get lots more. Now evaporate the yellow alcohol as before. You will get a somewhat more mushy yellow product than before. Repeat the purification with fresh cold alcohol as before but this time adjust the amount of alcohol down because you have fewer crystals to purify. If you are really careful then this second batch of crystals, although much smaller, will be almost as pure as the first batch. If so then put them with the first batch. Otherwise put them in a sealed "Not-So-Pure" contianer. You can continue the process over and over again until you are left with an orange sludge that pretty much dissolves completely in the amount of alcohol needed to get the orange liquid away from the paltry amount of powder. It is probably a waste of time to take it this far because you've already got a load of perfecty good, relatively pure methylamine.hcl. Next time you want to make more you'e already got a bunch of ammonium chloride to start with so you can skip the hexamine step and instead add the ammonium chloride to the formaldehyde and boil from there without any HCl. -------------------------------------------------------------------------------- force: "I did not dry it thoroughly- it seemed to be more like paste than powder, so i mixed this with HCL..." Well this is the reason that you never got hexamine powder. If you would have been more patient you could have dried the hexamine out into a fluffy white powder. Adding HCl to hexamine causes it to break down into formaldehyde and ammonium chloride! When you tried to "evaporate" this mixture...well everyone knows that when you heat formaldehyde and ammonium chloride together they react leaving methylamine hydrochloride, formic acid, carbon dioxide, and garbage. If the temp goes above say 110C you will also get some di-methylamine. It is the methylamine, not the hexamine, that is soaking up water from the air and melting. If you are intent on ruining your hexamine this way (haha) then the best thing to do is heat the hexamine/HCl mixture under reflux for a few hours until the temp reaches 110C. If you just evaporate it straight away most of the formaldehyde will escape as gas before it can react to form methylamine. Be careful with the reflux because a lot of CO2 gas will be released causing the boiling flask to bubble over. If you don't see any bubbles by the time it reaches 102C then take off the reflux apparatus and stir it briefly with a glass rod (you could use a chopstick instead.) This should get you on the way with thousands of tiny gas bubbles. The gas bubbles generally look smaller and more numerous than bubbles from simple boiling. You WANT these bubbles to come out of solution so that the CO2 doesn't stay in solution. If you don’t already have a stirring solution then one nifty way to stir it while it is refluxing is to find some small hi-temp plastic hosing that you can run down through the condenser to the bottom of the boiling flask. Connect the hose to a fish tank bubbler to force bubbles into the solution to agitate it. Anyway, depending on the size of your batch you should expect to heat it for several hours. Stop the heating when the temp goes above 110C. If its been over 100C for 4 to 5 hours but the temp is still sitting at 108 you can stop adding heat but continue to stir. If the tiny gas bubbles are no longer coming off even when stirred by hand then it is safe to assume that you are done. One interesting thing to note is that even though the gas bubbles probably won't start to come off until you reach about 100C, once they do start you can remove the heat and they will continue to come out until the temp drops into the 80s. When you are done heating allow the mixture to slowly come to room temperature. Lots of little white crystals will fall out of solution. They are ammonium chloride and you should filter them off and put them in a big ass jar. Then evaporate the remaining liquid on a steam bath. You really don't want to just put it in a frying pan and heat on the stove because the temp will go to high. Also, if you have an aspirator I STRONGLY recommend that you use it because there are some seriously nasty fumes that come off and it is best if they are sucked down the drain. If you do it in open air then, in my opinion, the only acceptable way to do it is in a separate room of your house with the window open and a fan blowing. The fumes will burn your eyes and lungs and I'm not kidding one bit! Don't cheat on the drying like you did with the hexamine and it will be much easier to purify your product. As you dry it out it will reach the point where it is a little mushy at 100C but quickly hardens as it cools. Now you have a bunch of white to beige-ish yellow chunks of methylamine and ammonium chloride. Scrape this stuff up and put it in the big jar. Go to the hardware store and buy a gallon of denatured alcohol for ~$10. Estimate the amount of alcohol that would be required to cover the crystals with about an inch of alcohol. Put this amount of alcohol in a microwave safe (pyrex) measuring cup and heat it to boiling in the microwave. Pour the boiling alcohol into the jar of crystals, replace the lid, and shake the hell out of it for a minute or two. Bright white crystals of ammonium chloride will quickly settle to the bottom. Carefully decant off the alcohol (which should still be fairly hot) into another container. The alcohol will have probably have taken on a yellowish color but it is actually good if it hasn't. Repeat the process with more boiling alcohol and add this alcohol to the first. For good measure do it one last time with about half as much alcohol. This time instead of merely decanting the alcohol, hot filter it. Sparkly crystals of ammonium chloride should be left behind in the filter cake. Evaporate the combined alcohol extracts to leave methylamine.hcl. Make sure it is good and dry and then wash with chloroform to get rid of any di-methylamine that might be hanging around. If there was any water in your product before you did the initial alcohol extraction then there is probably still a bit of ammonium chloride in your product. Add boiling alcohol with stirring and see if all dissolves. If it doesn’t then this is the ammonium chloride that escaped with the water the first time... filter it out. Once you get rid of all that ammonium chloride you can do a cool trick with your mehtylamine.hcl. Add just enough boiling alcohol to dissolve all of your product and then let it cool down slowly without stirring. It will crystallize into a huge chunk of fairly pure methylamine. Now put it in the freezer to reduce the solubility even more. When it is good and cold you can take it out and pour the small amount of methylamine laden alcohol into an evaporating dish. If you skipped the chloroform wash then this alcohol will contain mostly yellowish di-methylamine garbage and the solid chunk of crystals will be your clean stuff. Points to remember: Ammonium Chloride is not soluble in alcohol. Methylamine.hcl is much more soluble in hot alcohol than cold. Both are soluble in water. Minimizing water aids separation. Methylamine.hcl is not soluble in chloroform. The dimethylamine(?) impurities are more soluble in alcohol than methylamine. If you read what people have written about the separation most will tell you that methylamine.hcl and ammonium chloride look different. This is really only true AFTER you separate them. In a homogenous mixture it is much more difficult to point to any particular grain and identify. With a mixture of methylamine.hcl and ammonium chloride, leaving it exposed to the air results in a mushy mess. -------------------------------------------------------------------------------- Now for some clarifications on my previous post: There is no reason that you need to totally dry your hexamine at the beginning except to know what your TRUE YIELD of hexamine really is. You want to know how much you actually have so that you don't add too much HCl. Any extra HCl you add will come back to haunt you if you plan on evaporating the stuff in the open air. It is easy to add too much based on the weight of the hexamine because it is capable of holding a HUGE amount of water. I evaporating to dryness the first time you make hexamine and keeping careful notes of how much formaldehyde and ammonium hydroxide was used. On subsequent runs you can use this information to more accurately estimate the amount of hexamine likely to have been produced and avoid the long wait for dryness. "If its been over 100C for 4 to 5 hours but the temp is still sitting at 108 you can stop adding heat but continue to stir. If the tiny gas bubbles are no longer coming off even when stirred by hand then it is safe to assume that you are done." To clarify, if you remove the heat but continue stirring and gas bubbles DO continue to come off then you are NOT yet done. Continue heating. You should be able to tell the difference between the tiny gas bubbles and the larger "boiling bubbles" without removing the heat but since the gas bubbles will continue to come off below the boiling point this is a good way to be certain. I don't if there is an upper limit to the size of this reaction. The largest glass container for sale at my local supermarket is a 1.5 liter apple cider jar. The OceanSpray bastards have replaced all of their glass bottles with plastic ones so this cider bottle is all that is easily available to me. The cider jar easily withstands the heat if you do it slowly. Plunging a jar full of room temperature liquid into a pot of hot oil results in a cracked bottle and a nasty oil/water mess! The key is to start with everything at room temp and raise the temp slowly. Even starting at room temp, immediately cranking the power up to max results in a cracked bottle. Three feet of 1/2" inner diameter hose from the hardware store cemented into place through the lid of the bottle makes for a perfectly effective air-cooled condenser. This method makes it easy to remove the condenser for a quick manual stir to get the gas bubbles going and the tube is wide enough to run the small fish-tank bubbler hose down through the middle of it and into the liquid to provide bubble-agitation. This setup is good for processing the hexamine from 4 packets of mildewcide with a yield of ~190g of very pure methylamine.hcl and quite a bit of unpure material that seemed like to much of a pain in the ass to recover. Cost of materials: 4 packets of mildewcide --> ~$6 (~$1.50 each) Muriatic Acid --> ~$2/gallon (there will be lots left over) Ammonium Hydroxide --> ~$10/gallon (lots left over) --------------------------------------------------------------------------------
the op'ers post is so out of date, strike all ready served his whole sentence and is out of prison now, and that tek is like 10 years old..most of it has been fucked with to the point where you need a new route for most precursors..make it if you can though, i won't bitch
(from 3,4-methylenedioxyphenylacetone) This key intermediate to all of the MD-series can be made from either isosafrole, or from piperonal via 1-(3,4-methylenedioxyphenyl)-2-nitropropene. To a well stirred solution of 34 g of 30% hydrogen peroxide in 150 g 80% formic acid there was added, dropwise, a solution of 32.4 g isosafrole in 120 mL acetone at a rate that kept the reaction mixture from exceeding 40 ° C. This required a bit over 1 h, and external cooling was used as necessary. Stirring was continued for 16 h, and care was taken that the slow exothermic reaction did not cause excess heating. An external bath with running water worked well. During this time the solution progressed from an orange color to a deep red. All volatile components were removed under vacuum which yielded some 60 g of a very deep red residue. This was dissolved in 60 mL of MeOH, treated with 360 mL of 15% H2SO4, and heated for 3 h on the steam bath. After cooling, the reaction mixture was extracted with 3x75 mL Et2O, the pooled extracts washed first with H2O and then with dilute NaOH, and the solvent removed under vacuum The residue was distilled (at 2.0 mm/108-112 ° C, or at about 160 ° C at the water pump) to provide 20.6 g of 3,4-methylenedioxyphenylacetone as a pale yellow oil. The oxime (from hydroxylamine) had a mp of 85-88 ° C. The semicarbazone had a mp of 162-163 ° C.
Do you really think it's a good idea to post synthesis teks on a wide open forum where the majority of people have no real chemistry knowledge and aren't going to bother reading any recommended safety manuals? i post extraction teks but never synthesis. Even this makes me nervous. Just being a Devil's Advocate i guess. Peace & Love, Spicey Cat Hissss!
so learning distillation of sassafras root bark and pipe hisderpernum will essential oils in which we redistill to distill pure safrole which makes the synthesis possible. I know there are other methods but going over the internet research posts. Shuligen pretty much explains it right. I missed it. He originally starts it from mda in his first synth. he gives 3 in his exp. http://www.erowid.org/library/books_online/pihkal/pihkal109.shtml
