LaBTop (Stranger)
07-12-00 12:42
No 23325
      Detailed Methods for Non-chemists Edit: IT'sDONE!  Bookmark   

           DETAILED METHODS for NON-CHEMISTS
             ============================

LIST of SYNTHESIS (red list-text = method new/altered) :

I.------Sassafras rootbark -or- (chemical synthesis)--> SAFROLE.

II.-----SAFROLE--> IsoSAFROLE--> MDP2P ketone--> MDMA , MDA, MDEA.


III.----Lowpressure Catalitic Reduction--> P2P ketone--> METHAMPHETAMINE, (METH, ICE).

IVa.----2,5-Dimethoxybenzaldehyde + PTC (PhaseTransferCatalist)--> Nitrostyrene--> 2C-H (2,5-DMPEA , 2,5-dimethoxyphenethylamine)--> 2C-B and many more highly interesting unexplored 2C-(X) analogs,
-or-
IVb.----MESCALINE--> MESCALINE Nitrostyrene--> 2C-H--> 2C-B etc.

V.------2C-B a la Lycaeum.

VI.-----AMPHETAMINE PRECURSORS CLEANING/WORKUP.( The Cure)

VII.----EPHEDRINE to METHAMPHETAMINE + RP/I2.

VIII.---SIMPLE HCl GASSING/BUBBLING APPARATUS.

IX.-----NITROMETHANE --> MDMA.

X.------FORMALINE + NH4CL --> METHYLAMINE.HCL

XI.-----DMF O2 WACKER.

XII.----MDP2P + NMF --> MDA ( Leuckart big scale)

XIII.---Bright Star's MDMA synthese.

XIV.----Rhodium's SAFROLE to ISOSAFROLE routes.

XV.-----LaBTop's d- and l-isomerisation procedures


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METHODS :

I.------Basic-Extraction -or- Supercritical-Extraction--> Steam-Destillation.

II.-----Fractional destillation--> Aliquatt336+KOH (a la Osmium)--> Classic Performic (a la Ritter)--> Al/Hg (a la Osmium) -or- NaBH4 reductive amination (a la LaBTop) -or- lowpressure reduction (a la KrZ).

III.----Lowpressure hydrogenation (a la KrZ)--> Destillation--> Reductive Amination NaBH4 (a la LaBTop) -or- low pressure technique (a la KrZ).

IVa.----Addition + PhaseTransferCatalist (a la Rhodium and Beaker)--> Lowpressure Catalitic Nitrostyrene Reduction (a la KrZ) or Beaker's synthesis--> --> Addition (a la Shulgin). Or 2C-B synthese a la Lycaeum,
-or-
IVb.----Supercritical-extraction -or- (chemical synthesis)--> Nitrostyrene synthesis (a la Rhodium)--> Electrochemical Reduction (a la Uncle Fester)--> Addition (a la Shulgin).

V.------2C-B a la Lycaeum.(Andrew Edmond)

VI.-----AMPHETAMINE PRECURSORS CLEANING/WORKUP : The Cure (Placebo)

VII.----EPHEDRINE to METHAMPHETAMINE + RP/I2. (Placebo)

VIII.---SIMPLE HCl GASSING/BUBBLING APPARATUS. (Psychokitty)

IX.-----NITROMETHANE --> MDMA.(Methyl Man)

X.------FORMALINE + NH4CL --> METHYLAMINE.HCL. (Vogel)

XI.-----DMF O2 WACKER. (Strike, KrZ, Grouch)

XII.----MDP2P + NMF --> MDA. ( Leuckart small/big scale, LT/)

XIII.---Bright Star's MDMA synthese.

XIV.----Rhodium's SAFROLE to ISOSAFROLE routes.

XV.-----LaBTop's d- and l-isomerisation procedures



**And anything else found economical interesting for the creative home brewer**

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METHODS merits :

First of all :

Dr. Alexander Shulgin : No need for words, the greatest !
Paul Nels Rylander : for his extensive work on practical hydrogenation techniques. Hat off !
Strike : For creating this place, and giving a wealth of information in her books. A big hug ! (Still did not received your books, how come?).
Eleusis : For starting a really interesting discussion in the early days of this board, ultimately costing him his freedom.
The Lycaeum : For sheltering this place for so long allready, against mainstream US policy, and not interfering with our freedom of speach.
Rhodium, for collecting all that priceless information on his website, the best there is for the underground chemist or cook.

Secondly:

Overall methods :
Rhodium, Osmium, Rev drone, Labrat, Cesium, Spiceboy, Ritter, Beagle boy, KCN, Station, Sunlight, Sumerian, Gyrogearloose, iudexk, Ymir, Methyl Man, Psychokitty, Chem_Guy, Bankrobber(and some more, fill them in later).

Hydrogenation :
KrZ (mainly !), Rylander, pHas3d, Titanium, Equarius (and some more, I fill them in later).

Electrochemical Reduction :
Uncle Fester (mainly !), Dwarfer, Worlock, WizardX etc.

O2 Wackers :
KrZ, Strike, Bright Star, Grouch, and more will follow


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SAFROLE:

Materials :
Same as for IsoSafrole.

Chemicals:
16-18 L non purified safrole oil 70-90% pure.
20 L industrial Silicone oil or Peanut oil for oil-heatingbath.

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++

Method :
S1. - First you have to clean your safrole oil by fractional distillation.
S2. - This means that you separate different fractions of your impure reagens fluid (safrole here), those fractions will have different boiling points. That way you split the impurities from your desired oil.
S3. -You start heating up your impure Safrole and let it first come to a steady constant boil at the first temp where this will happen, under your vacuum, reached by your vacuum pump; keep the temp at that point until no more fluid comes over in the collecting flask, put that aside after releasing the vacuum, put the cleaned/dried collecting flask on again, and put vacuum on again, and then slowly incline the temp until boiling starts again, repeat as many times that you reach different boiling temps (at least 5 C apart from eachother).
S4. - You will at a certain temp (here ~ 130-145 C , depends on the strength of your vacuum), get the biggest fraction, which is safrole, and the other fractions will be only very small. These other fractions can be used ~ 5x again in next batches (see below at S8.).
S5. - If you use a 22 Liter 3-neck flask for it, and you don't have a big magnetic stirrer, you must use boiling chips in it, about 1 % oil-volume procent, so for a ~3/4 filling = ~16-18 liter filling (never use more then ~3/4, or fluid, not vapour, will boil into your condenser) you need 160-180 ml chips roughly (~).
S6. - Measure them in a measured beaker in ml volumes, don't worry about the loose spaces between them.
S7. - If you use a magnetic stirrer bar ( MUCH better!) and an aluminium pan as an oilbath, filled with peanut- or silicone oil, so you can use the stirrer, because the pan is from aluminium ( stirring strong and big enough), then there is no need for boiling chips, they would even damage the flask in one run. They would work as a grinding machine on the innerside of the glass flask, together with the big magnetic stirbar; or if you use a overhead stirrer, like a variable speed drill, or a non-sparking induction electro-motor; together with the stirrer propellor.
S8. - Any for-or after-run(s) at a temp more then 5 degrees C different from your main safrole body, you must throw back in the next 16-18 L safrole batch you start up after some day(s). After 5x doing this, you throw both away, it's more rubbish then safrole by then. You re-use these fractions 5x because they allways will still contain some pure safrole oil.
S9. - Pure safrole oil is light yellow and smells a bit sharper sweet then the ketone, MDP2P (MethyleneDioxyPhenyl-2-Propanone), which has a much softer sweeter smell and is a bit more yellow then the pure safrole; if you work perfect, the pure safrole and the pure ketone will have no color at all, and the ketone will be a bit more syruppy (thicker) then the safrole.
S10. - Safrole can be fractionally distilled at ~130-140 C temp using a new refridgerator pump(as your vac source, 1/8 horsepower, buy them from a fridge repair shop, $120) or a normal oil-filled vacuum-pump or much better: use allways a diafragm-vacuumpump, no oil which can and will be contaminated every time you use a oil filled pump, so it looses its vacuum-power; and standard glass distillation setup with a 40-60 cm icewater cooled fractionating/reflux-condenser and using a 22 L roundbottom flask hanging in an oilbath filled with peanut oil or better silicone oil as an egally heating source, and a big collecting flask.
S11. - Under the aluminium oilbath you would use a magnetic stirrer/heating plate with enough electrical power/watt's. Don't let the 22 L flask touch the bottom of the aluminium pan, keep it ~1 cm above the bottom, to prevent extreme hot-spots which could decompose your safrole or ketone.
S12. - Grounded standard glass-connections/fittings should allways be used on your distilling glassware.
S13. - Cold circulating water for the condenser comes via 2 tubes (one hanging loose at the water level in the icewater bucket) from an aquarium water-pump (expensive ones 70-80 dollars, cheap ones 10-20 dollars), submersed in a styrofoam isolated bucket or drum filled with ice cubes in water, which you re-new from time to time.
S14. - Distillation generally takes 4-5 hours depending on size, and heat applied. Always a good idea to insulate the fractionating column, and 22 L flask-neck with the condenser/refluxer on it; with heavy duty aluminum foil. Just wrap it around all the glass parts. Make ~1 cm2 holes, 5 cm apart from each other, in the aluminium wrapping then, to see what happens inside the glass parts.
S15. - The main safrole oil body (ca. 15.5-17.2 L), which boils (at~ ~130 C) and comes over at your vacuum ( should be 20 mbar or lower), you collect to proceed to make:

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ISOSAFROLE (Aliquatt336/KOH method) :

Materials :
1--Magnetic stirrer/heating combi plate + minimal 1 big magnetic eggshaped stirrerbar, to use in roundbottom flasks, and 1 straight one, for flatbottom flasks.
or:
1--Kg boiling chips. (Pumis-stones, crushed raw flowerpot pieces, crushed raw porcelaine, cat-litter).
and :
1--22 L round-bottom, 3-neck, glass vacuum-flask with 3 standard grounded neck- fittings.
1--portion High-vacuum silicone-grease (Merck f.e.), to thinly grease all grounded glass-fittings, allways both male and female grounds.
1--Still head, to connect one of the grounded necks of the 22 L flask to the grounded inlet of the condenser.
1--40 to 60 cm glass condenser, preferably the one you see with ~ 8-12 glassballs blown inside ( for use as reflux condenser).
1--big enough (min. 5-10 liter) collecting glass-flask with standard grounded fitting.
1--Vacuum glass-alonge with male and female standard grounded fittings and vacuum-tube fitting.
1--Vacuum tubing, 3 meter long, shorten it to the minimal length from alonge to pump, must fit tight on the alonge and the vacuum pump. The shorter, the better the vacuum. The remaining part you use for your aspirator vacuum, you will use it for volatile solvents removal/recovery.
1--Water driven PTF, Nylon or PVC vacuum aspirator, connected to a water tap with sufficient pressure and cold enough water, to use in case of electrical power failure and for evaporating low boiling vapours, f.e. methanol, acetone, dichloromethane etc. Never use an oil-filled vacuumpump to do that. A diafragmpump can do it, but why should you take the risk of damage to your expensive pump, when you can use a $40 aspirator for simple solvents evaporation ?
1--Big thinwalled flatbottomed aluminium pan, to fit the 22 L flask in. Buy it at a chinese restaurants supplier-shop.
2--Glass or digital thermometers, -30 to+300 C, one to use in oilbath or icebath and one in the flask-neck, long enough to reach the fluid inside. The best would be to have another one with small grounded glassfitting in a 2-neck Claisen type still-head setup between the 22 L flask and the condenser, to measure vapour temps.
This is not directly necessairy, but is handy to see if the vapour temp suddenly varies, that means you have to put vacuum off and collect that last fraction, because the next fraction is coming.
1--10 L jerrycan with peanut oil or better silicone oil (the big oil-company brands suppliers have it, such as Exxon, Shell, Mobil).
4--Big lab-stands with 8 lab-clamps to rig up your distillation setup.
1--Big bucket or drum, isolated with styrofoam or insulation blankets used in building industry, to use as ice-water circulating tank for the reflux/condenser.
1--Aquarium or fish-pond water-submersable circulation pump in that bucket or tank..
1--5 meter long water tubing, cut in half to fit the condenser and the watertap or circulating pump.
1--Multiple (6) electrical connections box with main ON/OFF switch. Panic : all electricity OFF.
1--Fire-extinguiser, for those unlucky moments. CO2 or special chemical-gas filled one. Better not a powder filled one, you will find out why, when you have to clean that stuff.
1--Drying oven, up to 350 C. old household-one sufficient enough, preferable electric. Gas burning type gives off water vapour and an open flame is not safe in a lab environment.
1--10 L filter flask, heavy walled, with vacuum side-adapter fitting. With some creativity you can use a big thickwalled glass Chianty wine bottle with a 2 hole stopper, one hole for the Buchnerfilter and one for the vacuum.
1--5 Liter (~) PTF or PP or PE or PVC or porcelaine or glass Buchnerfunnel.
1--Set of commercially sold rubber V-shaped rubbers in different sizes, for Buchner and to fit in mouth of filterflask.
1--Pack of round filterpapers, to fit nearly exact in the Buchner filter funnel. Attach the filterflask fitting to the tapwater-aspirator-vacuum pump for a safe vacuum.
1--~20 L clear plastic carboy used in drinking water utilities : ( to use as a self constructed separator-funnel : cut a 5 cm hole in the center of the bottom to use as filling opening, which you can close later with a 5 cm rubber stopper, so must be nice round, and push firmly a big rubber stopper with a center hole, in the excisting mouth at the top of the carboy. Fix the stopper with iron wire, so it can never plop out, or safer, use any clamp which fits the mouth of the carboy and covers the stopper ~half. Push a tight fitting glasspipe, with a glass-valve attached to it with a small piece of silicone-tubing which tubing you strap with those nylon straps used in car-repairshops, into the stopper, not extending above the other end of the stopper. Voila !)
4--25-30 Liter PTF or PPP or PE plastic jerrycans, cleaned and dried.
1--Box of heavy duty Reynolds wrapping aluminium .
1--Big steady lab table with a vinyl, or the like, coating.
2--Comfortable chairs, to sit in during those long waiting hours.
1--Small TV with antenna. Less entertainment-greedy persons can help themselfs with a ghettoblaster radio/tape-recorder/CD-player.
1--Pile of Playboy's, Hustler etc. or a big vibrator, also very handy to separate layers in your home-made separator funnel ! Just keep it tight against it. Must be ON then. It vibrates the oil out of the fluids !

Chemicals:
15.5-17.2 L purified safrole oil >98% pure.
5.611 kg KOH flakes (~98%, industrial grade).
1 kg Aliquatt336 (Methyl-tri-octyl-ammonium-chloride) ~>98% pure, from Merck or Fisher etc.
3 kg Florisil (=magnesium silicate=CAS 1343-88-0 )~>98% pure.
5 L DiChlorMethane ~>98% pure.
1 kg pack of silicagel beads 2-5 mm from Merck, Fisher etc.; or 1 kg MgSO4.7H2O industrial grade.
5 L Silicone oil from Shell, Exxon etc.
Tapwater (H2O) from your government, and lots of ice cubes or blocks .

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++

Method :
I1. - If you have any doubt that your now pure Safrole oil is not dry, so has some water in it, first dry it by shaking or mixing in your 22 L flask (or a suitable 20 L jerrycan) with a stopper in all necks at least 1 hour with 5% weight/weight silicagel beads or MgSO4.7H2O which are both first dried in an oven for 3 hours at 250 C. Then decant(in case of silicagel) or filter the MgSO4 off and proceed as soon as possible. Your oil MUST BE DRY !
I2. - If you must filter MgSO4 off, then use the big Buchner filter with a round filter paper in it, pre-wet the paper with some oil, push all airbubbles away formed under it, and carefully decant your oil/MgSO4 mix in the middle of your filterpaper, better use a big spoon laying in the middle of your paper to pour slowly in, so you don't disturb the fixation of the filterpaper, until at least a 2 cm layer is reached, now put your aspirator vacuum on, attached to the 10 L vacuumflask, take the spoon out, then you can proceed somewhat faster decanting while the vacuum sucks much faster then mother earth's G-force. The MgSO4 stays behind on the filterpaper. Don't leave any MgSO4 in the container, swirl from the beginning to have it good mixed with the fluid. Otherwise you have a truckload of MgSO4 left in the container, wetted with Safrole, and how do you get that out then ?
I3. - Pour 10 kgmoles safrole oil ( ~16.219 kg) in an open 22 L flask, only a thermometer immersed in the fluid, add carefully 12 kgmoles KOH flakes (~5.611 kg) via a widemouth plastic funnel (the solution will immediately turn black.brown): crush the KOH to not too small particles, ~1-2 cm, first, f.e. in a thickwalled plastic bag with a big hammer, ONLY if they are really big. Normally you don't need to do this! Don't get carried away by your enthousiasm and slam it, just push, be carefull, KOH in your eyes is not pleasant at all. Don't crush it too small, you must be able to decant or filter the oil later easily.
I4. - Stir for 10 minutes with the magnetic stirrbar or overhead stirrer , the solution will warm up allready caused by some exothermic effect, nearly no KOH will dissolve, which is no problem at all and is normal.
That's why there may be NO water in this stage of the reaction ! Or the KOH will dilute in the water and can not be filtered off later, and more washing steps are then needed.
I5. - Keep stirring and add 5 kgmol% pure PTC (PhaseTransferCatalyst)= here Aliquatt336 (~811 gram), and everything will 'seem' to slightly change color and take a slight shift in viscosity.
When adding aliquat, the aliquat will float on top until the temperature rises,then it mixes all up into one fase.
I6. - Now commence heating/stirring and read your thermometer in the fluid, after ~ one hour it will reach 80 C , keep the heat at 80 C for only 5 minutes, then the heat must be shut off totally, then allow the fluid to stir until roomtemperature is reached again. Don't forcefully cool with icewater or so. This will take ~2 hours.
I7. -After cooling to room temperature, the mixture is poured out of the flask into a 25-30 L jerrycan, trying to keep as much KOH flakes in the flask as you can without loosing too much oil, wash the flakes with 250 ml DCM and add that to the IsoSafrole allready poured out, and then you dilute the decanted IsoSafrole with 5 L DCM (DiChloroMethane), shake thoroughly, and pour out and filter that mixture over 1 Kg Florisil (=magnesium silicate=CAS 1343-88-0 ) in 3x equal portions, the second and third time renewing the Florisil again (1Kg) in your Buchnerfilter setup. Just scrape the old, used Florisil away with the big spoon, a littlebit left on the filterpaper will do no harm at all. Try to not move the filterpaper, and wet it a bit with a spoonfull new oilmix again, before you pour the next 1 Kg portion Florisil in the funnel. So remember : you need 3 Kg Florisil , filter in 3 portions of 1 Kg.
I8. -Wash then all Florisil, collected together, with 333 ml DCM 3x, so 1 Liter DCM totall, and add that DCM, after you let the Florisil precipitate, to the main IsoSafrol/DCM mix. If it is cloudy with some Florisil , use a new filterpaper in the Buchner funnel, and pour those 750 ml DCM with the washed out IsoSafrole in it through the filter into the main mixture.
I9. -You now have a mix of pure IsoSafrole and DCM in the vacuum flask, which you have to pour out 3x into a normal, for chemical storage used, 25 L plastic polyphenyl PTF or polyethylene PE jerrycan.
I10. -DCM is then removed at ~60 C oilbath-temp under reduced pressure from your water-aspirator in your 22L destillation setup.
I11. -You now have pure isomerised olefin, IsoSafrole, purity ~>96 %, left in your destillation flask and recovered also your again pure DCM from your collector flask (change the flask several times) to use again.
I12. -[THIS STEP IS ONLY NEEDED WHEN THE pH IS TOO HIGH -or- YOU THINK THERE IS STILL TOO MUCH WATER LEFT IN THE ISOSAFROLE].
Check the pH of the pure IsoSafrole with a pre-waterwetted pH paper, and if it is extensively higher then pH 11 , that means there is still too much KOH in the oil, which quickly will decompose the oil when you have to store it, so then you wash it 1x with 1 L water to get rid of any KOH, which will dissolve in the water part.
In a big 20 L carboy separator funnel, fill the IsoSafrole and the 1 Liter water, shake as hell, and separate the water on top of the oil then as carefully as you can, so no water will stay in the oil. Test then if the pH of the IsoSafrole is not too high, should not exceed 11.5 .
Now you add 5% in weight, dried silicagel to this still littlebitt water holding IsoSafrole oil, to remove all traces of water. Shake 10 minutes and then decant the oil or leave it in until you proceed with the next step and then decant in your clean 22 L destillation flask or whatever you use in that step first.
I13. -You proceed with this IsoSafrole to make :

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MDP2P : MethyleneDioxyPhenyl-2-Propanone (Classic Performic acid method) :

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

Isosafrole --> MDP2P via Modified Classic Performic Acid :

Materials :
Same as for ISOSAFROLE, plus :
1--minimum 500 liter stainless steel milk coolingtank, with a big-ass cooling coil in the double walls, preferable in the bottom also.
1--Mixer motor, 220 Volt, non-sparking, induction type, for :
1--Mixer propellor + axle (diam. 1.5 to 2 cm), stainless steel, diam. 40 to 60 cm.
1-- 100 liter plastic container to prepare the PerAcid mix.
and/or :
1--big-ass 80 liter dripping funnel, stainless steel, plastic or glass. Homemade is cheap.
1--1 meter cooled refluxing column, glass or stainless steel, to fix on the only opening of the milktank which is left open to the air.
5--meter heating cable, chemicals resistant, to use in milktank for the hydrolisis step with 15 % H2SO4.

Chemicals :
Reaction :
27 kg IsoSafrole, purity >/= 96 %.
99.7 kg DiChloroEthane, ClCH2CH2Cl, Industrial quality >/= 98 %.
or :
99.7 kg DiChloroMethane, CH2CL2, Industrial quality >/= 98 %.
8.3 kg SodiumBiCarbonate, NaHCO3, pure.
41.5 kg Formic Acid, HCOOH, 86 %.
25.1 kg HydrogenPeroxide, H2O2 30 %.
22.43 kg Sulfuric Acid, H2SO4 Industrial quality ~99 %.
127.07 kg water, H2O, pure.
42.4 kg Methanol, CH3OH, Industrial quality >/= 98 %.

Extraction :
To extract from 218,9 kg hydrolized Glycol/15%H2SO4/CH3OH mix :
60 liter DCM or DCE = 3 x 20 liter, Industrial quality >/= 98 %.

Method :
Here are the original figures from literature in grams, for a 27 KG batch of Iso-safrole to MDP2P :
---(all figures multiplied with: 27000 grams devided by 16.25 grams = multiply them with 1661.54 ) ---

M1. - Combine 16.25 grams [or 27 kg ] of Isosafrole with 50 ml=60 gram (1 liter DCE or DCM = 1,2 kg), [or 99.7 kg] DCE (DiChloroEthane) or DCM (Dichloromethane) plus 5 Grams [or 8.3 kg] Sodium bicarbonate (Sodium Hydrogen Carbonate : NaHCO3).
Can be made by bubbling CO2 gas in a strong soda solution (Na2CO3.10H2O ), the sparsely soluable NaHCO3 will precipitate.
M2. - Let it vigorously stirr for 2 or 3 hours, depending on the strength of your mixer [a total of 135 kg ].
This gives it time to form a pH-buffering complex which facilitates the next reaction enormously.
M3. - Seperately s.l.o.w.l.y combine (under external cooling) 25 gram [41.5 kg] 86% Formic acid and 15.1 grams [25.1 kg] 30% fresh Hydrogen Peroxide (to create Performic acid) and cool to 0 C.
Note : It is critical to cool when preparing this mixture or else it will, after sitting for 3 or 4 hrs without cooling, start boiling and nasty fumes will fill your lab and you will have to evacuate the place.
M4. - Then drip this cold Performic-acid [66.6 kg] VERY VERY slowly , into the 135 kg ISO-DCE-Sodiumbicarbonate mix, keeping temp under 40 C with external ice-bath or other means of cooling until all is in , CO2 bubbles out of the reaction mix while dripping in (and watch the temp for the following 1-2 hours, after completing dripping in, closely, so it still can not exceed 40 C).
M5. - Stir !VIGOROUSLY!, preferably with an overhead stirrer, for a total of 6(six) hours.
M6. - Stop stirring and move the whole batch in portions to a big seperatory funnel, and let it sit for one hour in there.
M7. - It will be orange-juice color DCE/pre-MDP2P(Glycol) mix at the bottom and clearish performic acid mix (H2O2/HCOOH) on top, the orange layer with the pre-MDP2P (Glycol) and DCE is heavy, so it goes fairly fast to the bottom of the funnel.
M8. - Important Note: --------------------------------------Many members have reported a switch of layers when they used DCM. Iso/DCM layer on top OR at bottom !
There is a perfectly logical explanation for this phenomenon : The one's who's cooling equipment functioned o.k. and thus kept the temperature between 36-40 Celsius will see the Glycol/DCM at the bottom after separation period, because they still have all their DCM left in the mix. The one's who were not so lucky and let the temperature get out of hand will see the orange layer at the top, due to an extensive loss of DCM which evaporated into thin air. The densities of the normal Glycol/DCM mix and the PerAcid mix lay close together, so if you evaporate too much DCM this balance is switched and suddenly the PerAcid mix is the heaviest layer, and falls to the bottom. You will notice then a light yellowish PerAcid mix at the bottom and a orange-juice coloured Glycol/DCM mix on top. This is no reason for real worry, unless you boiled most of the DCM away (not good for your health if you were in the same room (carcinogenic) AND not good for the reaction which did not have enough cooling capacity anymore in the last stage, depending on how high you overshoot the temp. Boiling temp of DCE = 83 C, DCM = 40 C , that's the reason WHY you must keep the temp under 40 C when you use DCM! And you must also do this when you use DCE !
Instructions are allways given with a reason, which is in literature expected to be common knowledge, but not here at a forum crowded with C(r)ooks (hehe) and a few real chemists.
Thought I owed the Cooks the explanation for this reason.
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M9. - Seperate into a new empty container and evaporate (low-vacuumdistillation, but KEEP the TEMP under 60 C!! so use more vacuum , so go lower then 700 mbar if the temp rises too high) the DCE off and stock that recovered DCE for future use.
M10. - You should add now 180 grams [but in reality, in contradiction to the official reference, only HALF the amount necessairy!, so 90 grams = 149,5 kg] of 15% Sulfuric acid (H2SO4) [so : add 22.43 kg 99% H2SO4 to 127.07 kg water], boil it until it starts refluxing back with slight addition of 60ml=51 gram Methanol [only HALF! needed, so 25.5 gram = 42.4 kg Methanol (1L methanol=0.85 kg)] through the cooling/reflux condenser added on the distillation kettle for 2 hrs. No longer then 2 hours !!! Or you will begin to loose product-yield. You now converted the Glycol to raw MDP2P, mixed with some pollutants.
M11. - Let it cool and extract 3 times with enough DCM (or DCE), (minimum 10 reactionvolume-percent per extraction).
M12. - Combine the DCM or DCE extractions and then boil the solvent (DCM or DCE) off (in fact no vacuum needed, but if you are in a hurry:)with one or more aspirators combined or diafragm vacuumpump to get brown oil that is peppery and cardamon smell.
M13. - You get around 16 grams [26.6 kg] -dirty- MDP2P.
M14. - To get the real clean MDP2P, you will have to vacuum-distillate this dirty MDP2P-base again to get a reasonable yield of about 73-75 % (grammole-percent)= 17.8 kg clean MDP2P which should be light yellow, or if you distill exact and have no leaks to let tiny amounts of air in, and you don't let the temp go over 170 C, at ~20 mbar vacuum, it would be clear with no color.

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
Note:
In weight/weight procents you get 16 / (16.25 / 100%) = 98.46 w/w % , but yield is scientifically allways given in Mole-percents, so:
(16 gram x 178.188=molecularweight MDP2P / (16.25 gram x 162.188=molweight Iso / 100%) = 2851.008 grammole / (2635.555 grammole / 100%) = 108.17 mole %.
But the effective mole % after distillation (=ultimate clean-up, no washings then necessary!) is 75%.
20 mbar x 0.01450138 = 0.29 psi, which is good enough for all distillations we work with !
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

Here are the four threads on the old board I found back again which are relevant for the classic performic:

1. Post 107771 (smokemouth: "LaBTOP/Gyro performic results - Sumerian", Methods Discourse) LaBTOP-Gyro performic results - Sumerian .
2. Post 107780 (smokemouth: "LaBTop/Gyro's Modified Performic Questions - Synthia", Methods Discourse) LaBTop-Gyro's Modified Performic Questions - Synthia.
3. Post 107770 (smokemouth: "New Performic Scale Up Question? - artech", Methods Discourse) New Performic Scale Up Question - artech.
4. Post 107739 (smokemouth: "The correct way to mdp2p via performic - gyrogearloose", Methods Discourse) The correct way to mdp2p via performic - gyrogearloose .

And this is the original Classic Performic post in the thread :
http://hive.lycaeum.org/ubb_board/Forum3/HTML/000613-3.htmlNaBH4 question : solution: One Pot ! :

Classical Per-acid oxidation of Isosafrole to get Piperonylacetone (MDP2P):

(Iso.) [R]-CH=CH-CH3 ----> [R]-CH2-C(=O)-CH3 (Pip.Ac.)
R=Methylenedioxyphenyl

The PerAcid solution is made from 25 g. HCOOH (formic acid)(86% ,starting from 99% HCOOH) and 15.1 g. 30% H2O2 (hydrogen peroxide).
This sol. is added to a mixed sol. of 16.25 g. Isosafrole(>/=90%) and 1,5 g. NaHCO3 (!!) in 50 ml CH2Cl-CH2Cl at 35-40 C.
The temp. is during 6 Hrs. mixing regularaly checked and kept within 35-40 C.
The solvent is evaporated (vacuum, keep TEMP! UNDER! 60 C.!).
Residue is boiled with 180 g. 15% H2SO4 for 2 Hrs.
Extraction with 3 x 100 ml.CHCl3, wash with water,dry over MgSO4 and evaporation of the solvent gives a brown oil (purity >/=90%).
Supplemental purifying by Kughelruhr destillation (~70 C, 0,2 Torr) gives 70-75% yield of MDP2P (>/= 95% pure!)

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

And this is the latest info from Ritter, who by the way posted this method first, then Beagle_boy , then me, then Gyrogearloose, so this method needed 3 times posting to get the attention needed, so lets call it from now on the Classic Performic, to avoid any misunderstandings:

Ritter
(Stranger)
06-20-00 14:26
Re: LabTop modified performic method?

The reaction runs best as described in my writeup! Adding carbonate to formic/peroxide first would surely lead to a nasty volcano and would not help any. Carbon Dioxide is emitted as performic is slowly added to alkene/carbonate solution. As far as advances are concerned a few things have been realized. Extremely vigourous stirring, such as that produced by a mechanical stirring rig, seems to increase yields. If a considerable amount of isoalkene is recovered during vacuum distillation an easy solution is to add more performic acid mix to rxn. This is usually an indicator that the peroxide used has degraded somewhat below 30%.
With this MDP2P you proceed to make :

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~



NaBH4 : REDUCTIVE AMINATION of MDP2P and P2P :
-------------------------------------------------------------------

REACTION MECHANISMS :

              H
              |    H   H   CH3
              C2    \ /   /
            //  \    C   N
   //    \  / \ / \
       O--C3      C1   C   H
   H2C/   |       ||   |\
      \   |       || H3C H
       O--C4      C6
           \\    / \
            \\  /   H
                      C5
      |
              H
.
.
.                     C11H15NO2
.
.     3,4-METHYLENEDIOXY-N-METHAMPHETAMINE
.
.                      EXTASY

.
.
.
      O
      v
    O    CH2CCH3
   / \ //\ /
H2C   |  ||      +  H2NCH3  -- Methanol ->
   \ / \\/
    O
.
.
MDP-2-P    + Methylamine gas in Methanol ->
.
.
.
.
      NCH3
      v
    O    CH2CCH3    __> Extract with Silicagel
   / \ //\ /   /
H2C   |  ||      + H2O --- NaBH4 --->
   \ / \\/
    O
.
.
IMINE + adsorped Water   --- add boro --->
.
.
.
.
      NHCH3
      |
    O    CH2CHCH3
   / \ //\ /
H2C   |  ||
   \ / \\/
    O
.
.
3,4-METHYLENEDIOXY-N-METHAMPHETAMINE

NOTE : We know now, july 2000 , that it's much better to follow the basic rules from the P2P to Methamphetamine synthesis also for the MDMA and MDA synthesis, in fact you MUST use silicagel (pre-dried at 300 C for 2 hrs) in all relevant steps, especially, when you make first the imine and later the amine conversion by adding NaBH4 to the Imine.
MDP2P/Methanol/Methylamine mixing converts already to the Imine plus water, so you add silicagel to obtain the perfect results, for both MDA and MDMA and also for Methamphetamine.
So keep this in mind when you read the following texts.

The imine is formed when you mix MDP2P with 10% w/w MeNH2 / MeOH,( so then allready you must have added the 20% w/w pre-dried silicagel beads, to directly take up the water formed by the imine reaction mechanism), not when you crystalize, mixing acetone, that you do with the pure distillated freebase. No imine left there. The imine is hydrolized with the flooding with 8x water (ev. mixed with 5% NaOH or KOH, as Sunlight happily found out for the MDA One Pot ammoniumacetate and NH3 gas route ).
You see a picture of the total mechanism into the MDA route, with molecular drawing of the imine, right above here, many seem not to know what the exact mechanism is, it will help you out.

If you make the acetone/HCl mix in advance for the crystalisation of your destillated clean amine-base, you must use it as soon as you can, or it will even become red, depending on how much HCl you bubble in.
And add the acetone/HCl mix then slowly to the MDA (or MDMA or MDEA or Meth)-freebase while medium stirring, not the other way round, that would lead to decomposition when you start adding a part of your base, due to too acidic conditions.
It has been seen that vigorous stirring results in very fine crystals ; medium and at the end slow stirring results in more voluminous crystals, which is a logical effect of giving the crystals time and a more undisturbed medium to grow together.
The best is to keep your percentage of HCl fairly low, to avoid early decomposition.

------------------------------------------------------------------

MDP2P--> MDA :

Materials : Still looking for the best yield possible, using basicly the description of the Methamphetamine ICE OnePot synthese (see below) and some minor or major changes, so you change only P2P to MDP2P and Methylamine to Ammoniumacetate or NH3 gas, see the ongoing discussions in the Methods forum for all possible improvements.
Changing the solvent, Methanol, to Glycol,  and Ammoniumacetate to Hydroxylamine f.e. could do the trick, research is going on.

Chemicals : The indicated route to MDA with Ammoniumacetate below will result in no more then between 30 and 60% yield for less experienced members, so for the time being you have to live with that, or improve yields by following the basic rules from the Methamphetamine One Pot.
Work with ANHYDROUS Ammoniumacetate, and dry all steps with Silicagel or MgSO4 or Na2SO4.
------------------------------------------------------------------

Method :

To simplify life for you all, here's the ULTIMATE FOOLPROOF EASIEST WAY to make:
MDMA, MDA, MDEA (use ethylamine instead of methylamine) if you have the chems available!
A practical way to make Honey (tinted bases) is as follows:

  Parts	|  M D A -base		||	Parts	|    M D M A -base


   0,5 |  MDP2P (oil) || 1,0 |    MDP2P
   3,0 |  MeOH (solvent) || 3,0 |    MeOH
   1,0 |  A.Acetate (salt) || 0,3 |    MeNH2(gas)
   0,1 |  NaBH4(reductor) || 0,1 |    NaBH4

These quantity-parts are in weight!
So: you can choose if you want to work in gram OR kg.

Following starting quantity is 25 kg MDP2P or ev. gram, but then you must divide all other quantities by 1000, so kg's and/or liters ):

Prepare 6x20 L yerrycans in wich you can fill each 12,5 L cooled, (-20 C) MeOH. In each yerrycan you dissolve 1,25 kg methylamine in the cooled MeOH (methanol).Let the MethylAmine dissolve in the -20 C cooled MeOH which you already put in the freezer one night before!
Use a upside down laying gastank with MA (30-45' angle)and fill with a thick synthetic black rubber hose the liquid-MA as deep as possible in the MeOH. SLOWLY! It takes ca. 10 min., per yerrycan.
The yerrycan stands on a digital balance, so you know the weight added.
Surround the hose with a wet towel at the filling opening of the yerrycan for the unhealthy smell.
When ready fill all the yerrycans with the MeOH/MeNH2 mix in the reactiontank. [Add in case of (MDA) now the AAcetate (in the pure methanol) instead of the MeNH2 gas !].
Cool now the reactiontank to +5 C and start the mixer anticlockwise, so the fluid circulates from bottom to top. This way no air is mixed in, so less oxidation. Add at +5 C the 25 L. MDP2P .(pre-cooled).
Start then directly (because a slow reaction starts already), every ca. 5 min, addition of the NaBH4, ca. 3 soupspoons per time. Use a funnel and wash every time with a little methanol. Keep all holes closed inbetween or it stinks! Because of the excessive cooling the temp. will not rise much, only to +15 C. Wait again till ca. +7 C to add again. Are you impatient and add to quick, then the mix will start heating, evenso boiling! This may never occur,then your product will be lost !
This process takes ca. 7 hours. Ending temp. will be ca. 25 C. Stop after 7 hrs. the cooling and let react with mixer on for 29 hours.
After this time, you prepare 200 L clean water, which you mix with 10 Kg NaOH or KOH, until all is dissolved.
This 5% water/NaOH-mix you add to the cooling tank (fast), then you measure the pH, should be between 11,5 and 12. (If you add coincidently acid instead of NaOH base, greenish fat form in and on the fluid). Stop after 10 min. the mixer and let the raw brown base precipitate 30 min to the bottom and tap off the base through the valve at the bottom. Stop tapping when you see lighter color (water) coming.
Add now 3 liter methylenechloride (dichloromethane=CH2Cl2) to the tank, mix 10 min., stop the mixer, wait again 30 min. and tap off the rest of the base, now diluted in the CH2Cl2.This gives totally ca. 43 L raw base.
Now we remove the CH2Cl2, Methanol and the water in a simple distillation setup, with low vacuum circa 500 mbar, with magnetic mixer/heater, mixerpin teflon, glassware with NS29 connections ( 20 L 2-neck flatbottom flask PYREX!, thermometer, cooler 60 cm, glas-alonge and 10 L collecting flat-bottom erlenmeyer flask).
Start at 35->55 C for CH2Cl2, then 55->85 C for methanol and 130 C for all the water. Re-use the CH2Cl2 and the methanol! Now you are left with ca 28 L half-clean MDA or MDMA amine-base (depending on the fact if you used Am.acetate or MeNH2 gas, colour is light brown).Now we will clean the raw base by 2 times recrystallisation with acetone 98%, (m)ethanol 98%, and after that washing min. 3 times with acetone 98%. Use 20 L P.P. plastic buckets to do this.
Mix 5 L base (cold) and 10 L icecold acetone. Leaf inductionmotor-mixer on. Bubble HCl-gas 99% through with 1 meter StainlessSteel pipe, (inner diameter min 5-8 mm) until white crystals form. Stop when pH= 7,0 and start with the next 5 L base. The first one will rise again to ca. pH=8,0.
Later you can bubble again a littlebit HCl-gas through until again pH=7.0 or even to pH 5.0 . Let the crystals precipitate and pour the upper acetone off.
Re-dissolve the wet crystals now in the minimum quantity of HOT(nearly boiling) methanol or ethanol in a metal bucket (because its hot !) until you see no more crystals, so you now have a saturated solution in (m)ethanol!
Pour 5 L of this solution back in the plastic bucket, and add 5 L Acetone, which is -15 C.
When cooling down, you will see crystals form again,in a dirty solution. Wait until no more crystals come, pour off again and dissolve again in hot (m)ethanol. Do this as many times until you have snowwhite crystals. Dry on glasplates on the floor with blower.
You now have H(M)ONEY in the Bank.

-------------------------------------------------------------------

MDP2P--> MDMA Another write-up.

Materials : idem

Chemicals : idem

-------------------------------------------------------------------

Method :

-------------------------------------------------------------------
Preparation of MDMA by reductive amination with sodium borohydride
by Labtop (written by Quicksilver, editted by LaBTop)
-------------------------------------------------------------------

- Introduction

Until recently reductive amination with NaBH4, for the production of MDMA, was assumed to be inferior to the well-known NaCNBH4 route (that has been popularized by Alexander Shulgin for the production of MDA) and other synthetic routes, like aluminum amalgam. The following method proves that the NaBH4 reduction actually is superior to all other common routes used in clandestine chemistry.
The method is relatively simple, it doesn't require complicated equipment. The work-up on the reaction mixture is simple and efficient. The method is very usefull for big scale production of MDMA and gives high yields (+90%!).
There is a relatively rapid formation of the imine and the imine is reduced relatively rapidly.
There's no reduction of the ketone to the secundary alcohol, as one might expect(2). In similar reactions, the water!! that is produced during the forming of the imine (Schiff Base) is removed from the reaction before the imine is reduced.
As we know now,much better with pre-dried (3 hrs in oven, 300 Celsius) Silicagel beads, 3-5 mm diameter, take a quantity of 20% weight compared to your MDP2P weight. Because of the stability of the imine, this is not necessary for the production of MDMA, but should in fact allways been done, to reach maximum yields !
This reaction is an improvement of a known synthesis (1), a similar reduction in an aqueous sollution of ethanol was performed, but the yields were only 31%.

- Synthesis :

MDP-2-P + methylamine-> intermediate imine +H2O-> MDMA freebase-> MDMA HCl salt.

- Ingredients
MDP-2-P 1000 g
Methanol 3000 g (>99%)
MeNH2 (gas) 300 g (99,9%)
(Be very carefull with MeNH2-gas: it is toxic and carcinogen, but when handled with care, no problems.
I advice to not use a gasmask, because when you smell it, you can avoid it, but with mask you are not warned and it can be uptaken through your skin! Use wet towels to avoid problems at ev. leaking points!).
NaBH4 100 g .
(NaBH4 is a common reducing agent. Do not spill NaBH4 on hands or face without noticing it(e.g. whiping sweat off your face), or you will be punished with red spots there which will never go away!
It takes minutes before you feel the pain, and then its too late.
So wash face and hands with water, frequently.).
filtered clean H2O.
33% HCl .
conc.NaOH solution .
DCM (DiChloroMethane).
Acetone >98%.

- Equipment :

*-- There are several options for the reaction vessel. One could think of a 500 to 1500 L stainless steel milk cooling tank, that is modified to ones needs. But a fermentation tank (plastic or stainlees steel, from 20 to 8000L), with small modifications will do just as fine. Or one could buy a 1m3 (=1000 L.) plastic tank everywhere at second hand tank and cans stores. Have a handy manhole to clean, are totally airtight and as a bonus, have a nice tap-valve at the bottom.They ship NaOH ,33% HCl etc. all over the world with them.
*-- A solid diaphragm vac.pump is recommended for the vac. distillation. For example a Vacuubrand Type MD 4C, 3.0 m3/h. It sucks from 1.7 to 11.2 m3/hour, ask for Chemistry Design(PTFE) series.
*-- MeNH2-gas is made by reacting MeNH2.HCl with conc.NaOH. (An other option is to react 40% MeNH2 with dry KOH.) (I will add a lot more on MeNH2 synthesis shortly.)

- Step by step :

1) Preparation :

Dissolve 300 gram, not ml ! methylaminegas in chilled 3000 gram methanol (-20 C). Cool in the mean time the reaction-mixture to +5 Celsius.
Start the mixer (anticlockwise so no air is mixed in) and add the 1000 gram MDP-2-P.
NOTES: Make 300 gram MeNH2-gas by reacting MeNH2.HCl with NaOH. Or dissolve the methylaminegas at hand from a gas cylinder in methanol, using an upside down laying (45 degree's) gascylinder with (fluid) methylaminegas in it, no pressure regulator on it. Attach a thick black synthetic rubber hose to the valve, open that valve slowly ,while the hose is down at the bottom of your first jerrycan with icecold Methanol, which stands on a big flat digital balance. Surround the hose with a wet towel. Add slowly 300 gram gas in the jerrycan. Be aware of a popping sound when the gas implodes when it enters the Methanol. Don't let suck back, close the valve everytime suddenly.

2) Reaction :

Start adding NaBH4, one teaspoon ca. every 5 minutes, H2-gas bubbling has to disappear before adding again, temp. should be between 8-18 deg C. (Wash down with methanol). Adding of the white NaBH4 powder will take 7 hours. With mixer on let it sit for 29 hours more.(4 hours will do for people that are in a hurry,loss 20-30% yield).
NOTES: When the reaction vessel is opened it should be covered by a wet towel, so the methylamine-gas can be absorped by the water. (1 L water absorps 1000 L NH3.) An airlock might be sufficient for that goal too.
Do not airtight the flask, let a thin tubing out the window,wrapped at the end with a WET towel!

3) Work-up I :

Leave the mixer on. Add 8 L clean H2O with 1%=80 mL 33% HCl. (The 80 mL HCL is redundant, don't add it at all!).
(When making MDA as your endproduct, you add 5 weight % NaOH or KOH to the water, to facilitate a good separation in the following separation procedure).
Liquid will be greenish brown, pH=10,5 (11,5 is better than 10). !!When green soap possibly starts to form: you made a mistake, you added far too much HCl ( To avoid any risk: do not add it at all. Redundant!!)...
Brown freebase will sink to the bottom of the vessel. Tap off, till a bit clear water is coming out of the valve. Close then the valve. Add 200 mL DCM to the reactionvessel and mix for 10 min. Stop the mixer and wait 30 minutes. The DCM with the rest of the freebase will sink to the bottom. Tap off. Combine the two. There will be app. 1750 mL of base fluid + DCM.

NOTES:

You can again basify the water with conc NaOH sol. to pH =13-14 and tap off the last oil.
The 8 mL 33% HCL (1%) is added to the water to make sure any unreacted NaBH4 is neutralised, but is not needed, in the following steps this is taken care of automatically.

4) Work-up II :

A vac.distillation setup is prepared. First the methanol, DCM, water and other lowboiling stuff are removed, then at 165 C the clean freebase comes over. Approx. 1.0 L. freebase.

NOTES:
Step 1. The water and other lowboiling stuff comes over at 130 C. Remove when nothing more comes!
Step 2. Set on 165 C. At first around 140-145 C you see the first little drops of clear oil condensate and at 160-165 C and 20-18 mbar it starts Running!
To distill of the water, methanol and other low boiling stuff from the reaction mixture, the use of an aspirator is sufficient! To get the freebase out, the use of a decent vacuum pump is recommended.

5) Crystallization :

Mix the base 1:4 with clean,cold(-10 to -20 C) acetone and bubble through with a Stainless steel pipe 8 mm x 1 meter with HCl-gas 99%. SLOWLY! After ca. 5 min a thick, white crystal mass will form. Check frequently with pH-meter ( aquarium shops sell good ones from Hanna Instruments for circa US$ 60.- ), or pH papers from Merck, until pH = 7 to 5 . If the mix get too hot, place back in big freezer to cool and proceed with next cold batch. Be very carefull not to go under pH=7 to 5, because then your powder will solute again and you must add base again until pH comes up again to 7. So keep always at least 20 mL freebase ready in case of mistakes ! Dry the acetone/powder mix in a Buechner-funnel with aspirator vacuum. Dry again on glassplates on the floor under airconditioner or slow blowing fan's in a dry room.

- Epilogue :

There are reasons to believe that the salt form of the amine can be used, ( I don't think it will be interesting, without high decrease of yields LT/ 10-07-2000) but the gas method is by far preferrible.
Ethylamine can be used to produce MDEA.
Ethylamine is a gas above 17 C, but a fluid under 17 Celsius, so very convenient when first placed in a freezer,  just pour it in the icecold methanol then.
Ammonium acetate or NH3 gas to produce MDA is another possibility, Sunlight and Cesium have researched the Ammonium Acetate process further and reached yields of ~ 50-65 %.
The same method was tried with P-2-P, first with unsatisfactory results when NO !! water was removed, because the imine that's formed here isn't as stable as the MDMA or MDA imine. When you remove the water while forming,with a drying agent, Silicagel, this also works (12-07-2000) perfectly, even better !!! Quantitatif yield near 100%.
 
- References

1. Noggle, F. T.. Jr., DeRuiter, J., and Long, M. J.. "Spectrophotometric and Liquid Chromatographic identification of 3,4-Methylenedioxyphenylisopropyl-amine and its N-Methyl and N-Ethyl Homologs." Journal of the Association of Official Analytical Chemists, Vol. 69. No. 4. 1986, pp. 681-686.
2. Shellenberg. K. A.. "The Synthesis of Secondary and Tertiary Amines by Borohydride Reduction." Journal of Organic Chemistry, Vol. 28, Nov. 1963 pp. 3259-3261.
3. J. Weichet, J. Hodorova and L. Blaha, "Reductive amination of phenylacetyl-carbinols by sodium borohydride." Coll. Czech. Chem. Commun. 26, 2040-2044 - CA 56, 5864c (1962)

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

MDP2P--> MDEA :

Materials : Same as for MDMA.

Chemicals : Same as for MDMA, except :

1.--- A equimolar amount of Kg Ethylamine, CH3CH2NH2, compared to the amount of Methylamine in above One Pot's. A gas at +17 C, a fluid gas under that temperature !

-------------------------------------------------------------------
Method : Same as for MDMA.
Only switch methylamine gas for ethylamine gas or fluid-gas.


~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

 
 
 
 
    LOONYTOON
(Newbee)
07-13-00 10:51
No 28253
      Re: Detailed Methods for Non-chemists .  Bookmark   

Thank You Thank You Thank You THANK YOU

This is exactely the kind of information i've been looking for. For some reason everyone assumes that just because you want to learn how to make drugs you either have to get a phd or you'll kill yourself. Everyone assumed i just wanted to be told how to it step by step, when all i really wanted to know is what i have to know and what i don't have to know, you know? I just didn't want to pour over tombs of knowledge that have nothing to do with what i want to learn, at least until i can find the time to do so. But i didn't want to go about it blind either. You gave me exactely the kind of shortcut i needed, which really isn't a shortcut at all, just cutting through all the bs.

Stupid people have it easy. (I made that up, aren't i clever? Don't answer that)
 
 
 
 
    sunlight
(Newbee)
07-13-00 14:40
No 28318
      Re: Detailed Methods for Non-chemists .  Bookmark   

LabTop, in the cryystalliztion mehod, you mix the amine with acetone, may be MDMA difficultly form the imine with acetone, but with MDA it seems easier, so we are afraid this crystallization method can yield imine. HCl instead of amine HCl, what's your opinion ? does it work sure ?
Recently we have tested bubbling HCL in acetone before, as you told time ago, using the acid acetone soon, it degrades quickly to a yellow/green solution froming some kind of chloro subproduct, and we found this very volatile (as we supposed) and very very toxic and nasty. We didn't like it, although it's a good option.

 
 
 
 
    Shambhala
(Stranger)
07-13-00 17:39
No 28357
      Re: Detailed Methods for Non-chemists .  Bookmark   


hank You Thank You Thank You THANK YOU

                    This is exactely the kind of information i've been looking for. For some reason everyone
                    assumes that just because you want to learn how to make drugs you either have to
                    get a phd or you'll kill yourself. Everyone assumed i just wanted to be told how to it
                    step by step, when all i really wanted to know is what i have to know and what i don't
                    have to know, you know? I just didn't want to pour over tombs of knowledge that
                    have nothing to do with what i want to learn, at least until i can find the time to do
                    so. But i didn't want to go about it blind either. You gave me exactely the kind of
                    shortcut i needed, which really isn't a shortcut at all, just cutting through all the bs.

                    Stupid people have it easy. (I made that up, aren't i clever? Don't answer that)


Who has that WTF happy face?  I don't think this thread should be filled with ________ posts (fill your descriptive word for the above post on the line). 

 
 
 
 
    LOONYTOON
(Newbee)
07-14-00 03:12
No 28521
      Re: Detailed Methods for Non-chemists .  Bookmark   

You know what? After reading your post a little more thouroughly, i think i overestimated this info at first glance. If this is supposed to be for non-chemists, then you must have something against them. Pretend for a second you have no knowledge of chemistry. Then read your post.


Stupid people have it easy. (I made that up, aren't i clever? Don't answer that)
 
 
 
 
    LaBTop
(Moderator)
07-14-00 21:00
No 28797
      Re: Detailed Methods for Non-chemists .  Bookmark   

Don't start ANY chemistry then, you will fail.
If you can't understand chewed out proposals like these, then you better start a career as a barber, having the advantage that you see a lot of people (a cook does/must not), and you can talk a lot, to amuse your customers. Think about it, it's a good, solid profession ( This all must be taken lightly, btw, did I tell you that I hate tags? ). LT/
PS: posts like the above even more hardened my desire to write-for-the-masses, what a relief, one less to worry about.
PS2: Au contraire, this post is exactly meant to post all replies in, the original locked sticky thread is at the Newbee forum at the top. It gets periodically updated and cleaned from all barbershop-talk.
PS3: Nevertheless, thanks for the first enthousiastic response, but it shows (in your own words later) that thoroughly reading is not a barbers strongest point.
Behold, no harm done, it's even an advantage for that trade.
Never saw a barbershop blow up, never read about it either, must be a safe haven from the malice of modern society.
hehehehe arrrr fuckin hilarious reaction arrrh...
PS4: By far not ready yet, next one is Methylman's synth, that should be an easy one for analfabetes.
PS5: If you feel in any way harassed by these words, save your breath, I probably saved your life and/or freedom, and gave you some solid free advice for a thrilling career, nearly forgot that.
(All advice given in a modestly hilarious mood btw.)

WISDOMwillWIN
 
 
 
 
    LaBTop
(Moderator)
07-14-00 23:29
No 28867
      Re: Detailed Methods for Non-chemists .  Bookmark   

The imine is formed when you mix MDP2P with 10% w/w MeNH2 / MeOH,Edit 15/07( so then allready you must have added the 20% w/w pre-dried silicagel beads, to directly take up the water formed by the imine reaction mechanism)End Edit not when you crystalize, mixing acetone, that you do with the pure distillated base. No imine left there. The imine is hydrolized with the flooding with water (ev. mixed with 5% NaOH or KOH, as you happily found out for the MDA One Pot route.
I will fill in a picture of the total mechanism soon into the MDA route, with molecular drawing of the imine, many seem not to know what the exact mechanism is, I'll help you out.
Yep, if you make the acetone/HCl mix in advance, you must use it as soon as you can, or it will even become red, depending on how much HCl you bubble in.
Edit 15/07 And add the acetone/HCl mix then slowly to the MDA (or MDMA or MDEA or Meth)-base while medium stirring, not the other way round, that would decompose at the start a part of your base, due to too acidic conditions.
It has been seen that vigorous stirring results in very fine crystals, medium and at the end slow stirring results in more voluminous crystals, which is a logical effect of giving the crystals time and a more undisturbed medium to grow together. End Edit

The best is to keep your percentage of HCl fairly low, to avoid early decomposition. LT/

WISDOMwillWIN
 
 
 
 
    zooligan
(Hive Bee)
07-24-00 19:19
No 32604
      Re: Detailed Methods for Non-chemists .  Bookmark   


Never saw a barbershop blow up, never read about it either, must be a safe haven from the malice of modern society.


From http://www.thesmokinggun.com/archive/albertan1.html

"Back in 1957, crime boss Albert Anastasia was gunned down as he got a shave in the barber shop of New York's Park Sheraton hotel. The murder of the bloodthirsty Anastasia, who was alternately known as the "Mad Hatter" and "Lord High Executioner" of Murder Incorporated, was never solved. Here's a selection of documents from the official investigative files on the Anastasia killing."

 
 
 
 
    LaBTop
(Moderator)
07-28-00 18:41
No 34234
      Re: Detailed Methods for Non-chemists .  Bookmark   

Repaired it myself, thanks. LT/

WISDOMwillWIN
 
 
 
 
    sunlight
(Hive Bee)
08-25-00 10:28
No 45035
      Re: Detailed Methods for Non-chemists .  Bookmark   

LabTop, our first test with am acetate and NaBH4 yielded 50 % +, but next tests have produced low yields, 25 - 30 %, and it is not a problem with the work-up as we thought the first time with low yields. Finally we realized that our first test was done with conservative proportions of am. acetate-ketone, using the amounts of TSII, and by the way, we don't remember the amount of NaBH4. It should be studied better, our experience is that using your proportions yields are around 30 %.
Even using your exact recipe for MDMA, usual yields are 78-80 %, and adding a 20 % more of NaBH4 (may be a 10 % could be enough) yields are 84-88 %.
It's what we have seen.
 
 
 
 
    LaBTop
(Daddy)
02-05-01 20:57
No 171287
      Re: Detailed Methods for Non-chemists . edit 6feb1  Bookmark   

METHYLAMINE.HCl salt production.

Ultraman (Member)01-30-00 00:27 No 123283
Questions about MeAm formation

Concerning H20 + Paraformaldehyde + Ammonium Chloride -> MeAm.HCL:
1. Is ALL MeAm produced during the 4-5 hour reaction period ? i.e. Is the reaction complete at this point ?
2. Is the rest of the distillation work after this 4-5 hour period just for seperation of the MeAm from the reaction by-products ?
3. If 2 is correct, then could one bypass further distillation and proceed directly to refluxing the contents of reaction flask in denatured alcohol to dissolve the MeAm and Buchner filter out Am.Cl. crystals, repeating several times until all Am.Cl. has been removed ?
4. Assuming that 1 and 2 are true, if the MeAm and Ammon.Cl. solution is left sitting in the flask after the 4-5 hour reaction period (say for a period of 48 hours), will the reaction reverse itself ? Will any other product formation occur ?

LaBTop (Moderator)01-30-00 14:08 No 123284
First, read ChemHacks long posts about the procedure,
Do you see the light allready after reading ChemHack?
Now follow Sploofer's advice and go to a Uni library and ask for Vogel's Textbook of Practical Organic Chemistry.
Read all about Methylamine Hydrochloride(from formalin) under Aliphatic Compounds.
You will see now that you use technical formaldehyde solution (formalin, 35-40 per cent. formaldehyde), AND not PARAFORMALDEHYDE (anhydrous!), which you only use to make trimethylamine,HCl at 160 C.
Dimethylamine you make at 115 C.
Methylamine you make at 104 C and you mix 2 parts by weight of formalin(ca. 35 % formaldehyde) with 1 part by weight of ammoniumchloride.
The method in Vogel is one page long in small typesetting. If you do it that way, you can't go wrong. READ IT!
250 g Ammoniumchloride(NH4Cl) + 500 g formalin 35-40% (HCHO) gives 100 g Methylamine,HCL. (CH3NH2,HCl)
Answers:
1.Yes, you can stop when no distilate is collected anymore.
2. No, it is a lot of recrystalisations to get the highest possible yield. AND to separate the ammonium chloride and the dimethylamine,HCl and the methyl formate and the methylal from the desired Methylamine,HCl.
3. No.
4. A lot of other product formation. You wanna watch TV inbetween? Some sexfilm? Tsktskstsk...  LT/

Ultraman (Member)01-31-00 02:35 No 123285
sexfilms?? naaa, not me. Savin my bones for glassware  .... besides, too busy looking out the window for cops.
LaBTop: I've searched the hell out of the hive and it seems as if most references indicate that Paraformaldehyde is de-polymeramizable (is that a word)- add to water to depolymerize it, and is usually dissolved by the time the solution reaches 55-60C. Have I been mis-informed ?
1. Werner in the JCS 844('18)
2. Sigma Product Information Sheet
P.S. I'd lock up that old copy of Vogels you got - seems to be priceless from what I've researched so far. The current edition doesn't mention a damn thing about MeAm recipes, or many other goodies.

LaBTop (Moderator) 01-31-00 05:21 No 123286
paraFormaldehyde can be seen f.e. as 3(HCHO)3 , a chain of formaldehyde molecules.
If you add water and warm it up, the chain will break up again into separate HCHO molecules, and you have formaline again.
So tell me, why you want to buy the more expensive para form, when you gonna mix it with water again? Quite unlogical thinking.
Formaline 35% (rest is water) is shit cheap.
Ok, just insured my Vogel for 10,000$, and am now typing the recipe out for you. In the mean time, say as loud as you can : Thank You, LT, 1000 times. LT/

LaBTop (Moderator) 01-31-00 06:23 No 123287
Vogel :  Methylamine Hydrochloride (from Formalin)
Place 250 g. of ammonium chloride and 500 g. of technical formaldehyde solution (formalin, 35-40% formaldehyde) in a 1-litre distilling flask : insert a thermometer dipping well into the liquid and attach a condenser for downward distillation. Heat the flask on a wire gauze or in an air bath slowly until the temperature reaches 104 degrees and maintain the temperature at this point until no more distillate is collected (4-5 hours) (note 1). Cool the contents of the flask rapidly to room temperature and filter off the ammonium chloride (ca. 62 g.) which separates rapidly, at the pump. Concentrate the filtrate to one half of the original volume on a water bath, when more ammonium chloride (ca. 19 g.) will crystallize out on cooling to room temperature. After filtration at the pump, evaporate on a water bath, until a crystalline scum forms on the surface of the hot solution. Allow to cool and filter off the methylamine hydrochloride (about 96 g.) (note 2). Concentrate again on a water bath and thus obtain a second crop (about 18 g.) of methylamine hydrochloride. Evaporate the mother liquid as far as possible on a water bath and leave it in a vacuum dissicator over sodium hydroxide pellets for 24 hours ; digest the semi solid residue with chloroform ( to remove the dimethylamine hydrochloride), filter off (note 2) the methylamine hydrochloride (about 20 g.) at the pump and wash it with a little chloroform. [ Upon concentrating the chloroform solution to about half the original bulk, about 27 g. of dimethylamine hydrochloride may be obtained : the mother liquor should be discarded.]. Purify the crude methylamine hydrochloride by placing it together with 250 ml. of absolute alcohol in a 500 ml. round-bottomed flask fitted with a reflux condenser carrying a cotton wool (or calcium chloride) guard tube. Heat the mixture to boiling for about half an hour, allow the undissolved material to settle and decant the clear solution. Cool the solution when pure methylamine hydrochloride will separate : filter (note 2) and use the filtrate for another extraction. Four or five extractions are required to extract all the methylamine hydrochloride. The yield of recrystallized material is about 100 g.

Notes.
(1) The distillate weights about 110 g. and contains methyl formate and methylal.
If it is placed in a flask provided with a reflux condenser and a solution of 25 g. of sodium hydroxide in 40 ml. water is added, the methyl formate is hydrolysed to sodium formate and the methylal separates on the surface. The latter may be removed, dried with anhydrous calcium chloride and distilled : about 30 g. of methylal, b.p. 37-42 degrees, are obtained. If the aqueous layer is evaporated to dryness, about 25 g. of sodium formate are isolated.
(2) The best method of drying the precipitate of methylamine hydrochloride is by centrifuging ( see it rev drone, that's why a centrifuge is handy in the lab ) ; the compound is hygroscopic.
-Vogel end-

Ultraman (Member) 01-31-00 10:04 No 123288
x 1000, hell make that  x 2000.
Would you mind scanning the whole novel and placing it out on the web somewhere ?
If you don't mind too much, back to a modification of my original question.... If formation of MeAm is complete after the 4-5 reaction period, then I assume it doesn't matter if you vac distill at this point to concentrate solution. There seems to be different opinions/techniques about applying vac after the reaction period around the hive. Seems if reaction is complete after 4-5 hours, then why not use vac to concentrate... it would just speed up the process, and keep temperatures down. Is there a disadvantage to it ? Product loss perhaps ? Thanks a mill LaBTop.

LaBTop (Moderator) 01-31-00 14:31 No 123289
I have a feeling that good old Birdie would have had the same idea, but ended up with a lot of bunk when he vacuumdistilled the whole batch after 4-5 hours, so he choosed for this method. If your still curious, devide all quantities by 10 and try it out. Could work, with perhaps only a small loss of yield, but practice will teach the truth. LT/

LaBTop (Moderator) 01-31-00 14:44 No 123290
Oh yeah, the centrifuging has of course the advantage that it can be done in a few minutes, while evapping off in open air or a open distillation system will turn your MeNH4 into a watery sludge.
You use a linen sack in a vedgetable centrifuge or something like that, the more speed, the drier. LT/

ChemHack (Member) 01-31-00 14:52 No 123291
The reason to use paraformaldehyde is if you can get it at the hardware store and the only formalin you can get without going to the chem supply shop is full of blue dye and purfume for portapotty use.
Paraformaldehyde justs lets you stay that much farther under the radar. Depends on the level of police control in your state.
Best way to deal with paraformaldehyde is not to dissolve it in water because that takes way too long.
Instead to dissolve it in concentrated (much stronger than from grocery store) ammonium hydroxide (blue printing solution) to make a solution of hexamine in water.
Then evap away some of the water and add Hydrodchloric Acid and procede from there. The HCl breaks the hexamine back into formaldehyde and ammonia. The ammonia reacts with the HCl to make ammonium chloride and you are right where you wanna be to start the rxn. Heat to 104C and go.


LaBTop (Moderator) 01-31-00 15:12 No 123292
Thanks, chemhack, good additional info.
In europe, you just say that you need the formaline for your hobby of preparation of dead animals you found along the highways.
In fact you use the para-form to rub on the inside of the skins, and the formaline to put them in glas jars. LT/

Ultraman (Member) 01-31-00 19:01 No 123293
Ok, just one more question about technique. See a lot a references (hive, Vogel, and elsewhere) using Chloroform to remove Di-MeAm before using Ethanol to remove further Amm. Cl. Why not do it the other way around ? ie purify with Ethanol 1st, then wash with Chloroform. Seems like this might use a little less Chloroform, which is more expensive and takes more work to obtain than the Ethanol.

LaBTop (Moderator) 02-01-00 10:40 No 123294
Same answer as 5 posts above.
Rule of thumb is allways removing the impurities first, then you don't have to worry about their influence on the rest of the procedure.
And it looks as if you'r the trial and error type, please, do first the proposed method, report back here, and THEN start experimenting with own ideas. This mixing up of good recipees with own ideas at forehand (without telling it), has caused a lot of misunderstanding on this board, you have to pull the truth out ,before you can see the obvious wrongdoing. This gave a lot of good advice/recipees a bad "press" at the start of experimenting by other members.(most of them with minimal chemistry background; strange thing is, however, they seem to have the best enthousiasm level).  LT/

Ultraman (Member) 02-01-00 10:47 No 123295
Point taken. Thanks for all the input guys. Will report back - hopefully with  results.

Starlite (Member) 02-01-00 13:28 No 123296
LaBTop: What's the date on your Vogel...I have a '57 and a '62 but they only give the acetamide process...pg # pleeezzeee, I may have to get another one! thx!

LaBTop (Moderator) 02-01-00 15:11 No 123297
First published 1948, Code Number: 85288. The Preface by Arthur I. Vogel is dated December 1946. LT/

Ultraman (Member) 02-01-00 22:32 No 123298
Where can the older editions be bought ?

LaBTop (Moderator) 02-02-00 03:39 No 123299
If you'r lucky, in a specialized second hand bookshop. You can't order them allready for a loooooong time anymore.
And you have to thoroughly search the shelves yourself in the chemistry or physics corner. You will find many more hidden treasures there. LT/

Ultraman (Member) 02-04-00 12:49 No 123300
Godzilla thought about the Bright Star Procedure for MeAm and this is what he suggested:
1. Followed BS instructions exactly. (Used Lab grade Paraformaldehyde, Lab grade AmCl)
2. Heat slowly - took one hour to reach 104. (Consider this Time=0.0 Hours)
3. Held at 104 for 5.5 hours. Used boiling stones and stirbar on slow.
4. At T=5.5 hours turned up heat. Attempted to vary stirbar speed to induce distallation and keep temperature at 110 or less. Note: 1st 125 ml came over while mother liquor was at 110 C. Next 75 ml came over at about 115 C. Last 25 ml came over between 115C-120C. (all temps are mother liquor)
5. At T=9.3 hours distillation got painfully slow, and was nervous about 120 C temp. There was approx 275 ml of stuff in recv flask. Took boiling flask off heat, poured into beaker and placed beaker in ice bath. Mother liquor was a very light golden yellow with a faint odor of fish. Sometimes it almost smelt like Oreo cookies, but that might just be the other shit trying to cover up all the funky smells.
6. In about 5 minutes AmCl crystals began to form. Started getting nervous that the whole beaker was going to become AmCl crystals and nothing else. It became very full of AmCl.
7. Poured beaker contents into vac buchner funnel and obtained approx. 250ml of very light golden yellow filtrate. Recovered 25.9 g of slightly moist AmCl.
8.At T=9.6 mother liquor was back at distil. Mother liquor temp was at 118 C, oil temp was at 137 C as distillate came over.
9. At T=11.0 125 ml had distilled. Mother liquor temp was now at 125 C. Turned on Vacuum.
10. Vacuumed away until no more distillation occured.
11. Product weighed 104.9 g before purification with SLX denatured Alcohol. Was a white-very light yellow mixture just a described by Bright Star. Very soggy, a small stick will stand up straight in it.
12. Poured boiling SLX into product, stirred vigoursly and vac. buchner filtered.
13. Recovered an additional 25.9 g of AmCl. (This AmCl smells slightly of fish and passes the 20ml/5g NaOH test, but I figure it is too pristine white to be MeAm. It is also more hygroscopic than the AmCl from the previous AmCl filtration.
14. Boiled away SLX/product until boiling ceased. Mixture was same color, but syrupy.
15. Poured mix into container and put in freezer.
16. After a while - checked mixture. It was a very frozen slush. Came out of container in one chunk.
17 Now have 99.4g of very wet, yellowish white product. It still looks like it is frozen, but is at room temp. The color reminds one of a yellow snow cone that someone has sucked all the flavor from.
18. Don't know what to do with it now, as no dessicator or centrifuge available.
How the hell do you make a centrifuge ?

LaBTop (Moderator) 02-04-00 09:26 No 123301
Go to a household store and get yourself a vedgetable centrifuge( a plastic wireframe basket within another solid plastic basket, with a lid on it and a handle, connected to a plastic gearbox in the lid.) You hang a peace of linen in the wireframe basket, fill your goodies in it, at the outside of the bottom, close the lid and start milling like a crazy coffeegrinder.
Your liquids go through the linen, your goodies are as good as dry. Hang your goodies in the linen in a widemouth glass bottle, with a bottom full of dry NaOH pellets, and close the bottle with a rubber/cork stop, which holds the linen. Eventually place the bottle now in a hot water bath, fix it, that it won't fall over.
A much faster method is to crunch your lump of goodies, put them in your destillation flask and set the oil on 75 C and put full vacuum on it, untill totally dry. You will see that at the end, suddenly the mass will turn into dryness.
Preferably use a Rotavap for it, but when not in your posession( sell the car, a good cook offers anything for a good "meal"!), use a fixed vacuum set-up.
The color indicates you still have contamination in it, probably sodium formate and methylal. You did not really read my Notes. And you still don't understand all the washings and what they do. Combine BS method with the knowledge I gave you, and the next time, please post the URL to BS method, I don't know what is meant. LT/

LaBTop (Moderator) 02-04-00 09:30 No 123302
For a reasonable cheap self to build Rotavap machine, see here: Post 123387 (EuroNovaice: "Destilling ketone in a alcohol/wather destilater? Pleace answere rigth now!!!", Newbee Forum)
LT/

Ultraman (Member) 02-04-00 19:59 No 123303
I read that chloroform dissolves di-MeAm. Does it also dissolve sodium formate and methylal, and leave our friend MeAm ?

LaBTop (Moderator) 02-05-00 15:05 No 123304
read first this:
""digest the semi solid residue with chloroform ( to remove the dimethylamine hydrochloride), filter off (note 2) the methylamine hydrochloride (about 20 g.) at the pump and wash it with a little chloroform.""
What does this teach us? That you can wash MeNH2 with chloroform, so it will not dissolve too well in it, otherwise another solvent would have been chosen.
n this:
""Purify the crude methylamine hydrochloride by placing it together with 250 ml. of absolute alcohol in a 500 ml. round-bottomed flask fitted with a reflux condenser carrying a cotton wool (or calcium chloride) guard tube. Heat the mixture to boiling for about half an hour, allow the undissolved material to settle and decant the clear solution. Cool the solution and then pure methylamine hydrochloride will separate : filter (note 2) and use the filtrate for another extraction. Four or five extractions are required to extract all the methylamine hydrochloride.""
What does this learn us? That you must do four or five extractions( in this case you could better talk about recrystallisations), with PURE (no water!)alcohol (ethanol or methanol or isopropyl alcohol etc.), to obtain PURE MeNH2. It's a bit of work, but:
Proceed please LT/

Ultraman (Member) 02-06-00 03:19 No 123305
You got it BIGTOP !!  I was hoping to squeak out of a little work by not having to reflux. Been there with the MeNH2 on previous attempts. Guess I'm just looking for the easy way out. Was hoping that the boiling SLX would be good enough.
Hey. Got the centrifuge today. It is one kick ass son of a bitch. You can either crank it by hand, or when you get tired, you can use your foot. I love it. Can't wait to try it out.
Also found an xcellent desicator. A mason jar with a big old rubber seal. What kind of linen do you prefer ?
Also, I know this is a stupid question, but I'm gonna ask anyway. How pure does MeNH2 have to be to make honey ?
Next time Godzilla and UMan try, we'll post it as a new topic as you suggested.
Damn, I'm really start to appreciate the work involved in org. chem labs !!
Take care and be good. And thanks for sharing your wealth of knowledge.
Over and Out. UMAN.

CHEMMAN (Member) 02-06-00 03:35 No 123306
Methylamine was my first ever chemical venture.I followed Vogels synth( library). It works fine Formalin and ammonium chloride.
When he says concentrate to half, you need a vacuum source preferably to distill half of the water away. When the vessel cools it will be ammonium chloride that falls out. It Liivess.

LaBTop (Moderator) 02-06-00 18:49 No 123307
""What kind of linen do you prefer ?""
Any fine woven pillow cover or T-shirt will do, Check in the wash-mark that no other sources than linen are used, must be 100%.
""How pure does MeNH2 have to be to make honey ?""
This is a hobby-horse of me: try to get your ingredients as pure as can get, so you don't have to ask here: what the hell went wrong?
Or start a thread on a good synth, saying that it don't work.(should add: for me!), because of lazy, slobby precursor purification. I get the chills when somebody proudly announced: and then I proceeded with my beautifull, RED coloured ketone( MDP2P, P2P), and the sucker don't even realises that when it's red, he should purify it first, it should be light YELLOW. How many times do I have to YELL that here........ LT/

LaBTop (Moderator) 02-06-00 18:53 No 123308
And you still did not post the BrightStar URL, so we all know then which syntheses you use, when we discuss it in this thread. LT/

Niels Bohr (Member) 02-06-00 22:01 No 123309
If you are having a problem finding formaldehyde solution, go to the pharmacy and ask the pharmacist for 37% formaldehyde solution. It is sold by the gallon for < $10. I got mine at Rite Aid - no questions asked.
Tell them that you are going to perserve fish, frog eggs, or pork rinds for fishing bait.
When you use the solution from the bottle, replace the leftover into a smaller bottle where the formaldehyde takes up the entire space in the bottle so as to exclude air, else it will polymerize into paraformaldehyde (white flakes in the solution). Keep at room temperature and do not refrigerate because it will accelerate this polymerization.

LaBTop (Moderator) 02-07-00 14:17 No 123310
Easier solution: buy such a opened wine bottle preserver thingy ( a small hand driven vacuum pump with a needle attached), and slam the needle through the rubber stopper you gonna use to close the bottle with formaline. Then pump all air out, and let the wine thingy sit there, or pull it out. And eventually close the minuscule opening with a greased plastic toothpick, only stuck in half deep.
Grease the sides of the rubber stopper with vacuum grease, not too much, but all around it. LT/

Ultraman (Member) 02-07-00 20:37 No 123311
Awww hell, sorry LaBTop. Thought you meant next time post as BS sythn on new thread. The synth is at:
http://lycaeum.org/~rhodium/chemistry/mdmasyn.txt

Ultraman (Member) 02-07-00 20:42 No 123312
CHEMMAN - Are you saying that after the flask is cooled for the 1st time, and AmCl crystal filtered - you put flask back on heat and applied vacuum ? To speed up subsequent distillations and keep temps lower I presume ? What was your yeild ? What was your starting amounts ?

Ultraman (Member) 02-07-00 20:59 No 123313
Continuing dream from post 02-04-2000 12:49 AM above:
19. Several Days later yellow mush was placed in coffee filter and allowed to drain overnight.
19.5 Remaining mush in coffee filter was washed with enough Chloroform to cover the mush and make if fairly liquid.
20. This was then brought to vac. buchner where a very sparkly crystilline and white crystals were left on the filter - approx 19 grams.
21. The yellow filtrate was washed again in Chloroform and an additions 1.5 grams were recovered - looked just like the 1st batch.
22. Crystals dissolved in 18 C deg SLX very easily.
23. Crystals passed delequesence test.
24. Crystals brought to centrifuge and then to the "dessicator".
Possible mistake - might should have tried recrystallizing stuff that drained from coffee filter. May have lost a little yeild, it was a significant amount of liquid - 25 to 50 ml (didn't measure)
QUESTION ABOUT centrifuge : Do ya cover the entire centrifuge in the linen and lay the crystals at the bottom without any further protection to keep them from flying around ?

Ultraman (Member) 02-07-00 21:04 No 123314
Thanks for the tip Neils. It just happened that Godzilla had some PARA buried in his backyard so UMAN thought he'd give it a whirl. Hoping to try the liquid stuff next round.

ChemHack (Member) 02-08-00 14:13 No 123315
quote:
---------------------------------------------------------------------------
"Also, I know this is a stupid question, but I'm gonna ask anyway. How pure does MeNH2 have to be to make honey ?"
---------------------------------------------------------------------------
The answer is that it depends on your method of amination.
# If you use the Al/Hg method it doesnt have to be very pure at all because it calls for a 300% of the of methylamine that is actually need. (amine:ketone approx 3:1).
# If your so called methylamine is 50% ammonium chloride then you are still have a 50% excess of methyamine (3:2 ratio).
# The ammonium chloride isn't very reactive with the Al/Hg method so you don't really have to worry about it making MDA before you get your MDMA.
# Now if you plan on using the cyno- amination instead of Al/Hg then it WILL matter.

ChemHack (Member) 02-08-00 14:15 No 123316
Oh yeah, a lot of that melted stuff prolly had some goodies. Oh well.

Niels Bohr (Member) 02-08-00 18:22 No 123317
In case anyone has not figured this out yet, ChemHack is the expert on this subject, so just do a keyword search on methylamine and his name and spend the day reading. Lots of good info - thanks ChemHack


WISDOMwillWIN
 
 
 
 
    LaBTop
(Daddy)
02-10-01 09:23
No 172622
      Re: Detailed Methods for Non-chemists . edit 6feb1  Bookmark   

DMF O2-Wacker : Safrole to MDP2P.

KrZ (Hallucinogenius) 11-07-00 11:31 No 67435
Let's look at the literature (LT/ : editted for readability) :

3.24g PdCl2
32.40g CuCl2.2H2O
324.36g Safrole
70mL H2O
500mL DMF (DiMethylFormamide)

Placed everything except the Safrole in a 4L reactor, stirred heavily exposed to atmosphere for 4 hours, till all compounds were dissolved.  Then added Safrole, and removed atmosphere with vacuum. Pressurized to 35 psi O2.
Pressure	                 Time after 	
drop (psi) Last Drop (minutes)
15 17
15 18
15 20
15 20
15 29
15 38
~4 30

Total O2 uptake ~94 psi. Repressurized to 35 psi after each drop.
Total Reaction Time: 172 Minutes

Added 500 mL 5% HCl to reacted solution.
Separated precipitated Ketone/Aldehyde.
Extracted the 5% HCl solution with 3x 100mL DCM and separated those, and pooled the 3 DCM/ketone extracts with the precipitated Ketone.
Clean up :
Washed pooled extracts  2x with 300mL Saturated Sodium Bicarbonate solution and separated pooled extracts each time.
Washed pooled extracts with 400mL distillated H2O and separated H2O.
Washed pooled extracts with 400mL Brine Solution (saturated NaCl) and separated again.
Dried extracts with 50g dry Na2SO4 for 45 minutes.
Filtered to Remove Na2SO4.
Vacuum distilled at ~2.0mm Hg to recover 311.22g PiperonylMethylKetone (MDP2P) fraction between 105-114C. 
There was an Isosafrole forerun, and a minimal high boilingpoint and thus polymerysized glop after 114C.
Molar % Yield: 81%


A confirmation of above procedure by Grouch :

Grouch (Old Hiver)02-05-01 10:58 No 171271
I just confirmed that the 35psi O2 DMF wacker works fine. 
I used a Nalgene 20L polypropylene carboy and I drilled a hole in the cap and used a threaded long stem tire valve with a nut and washer and rubber grommet.  I also used a 3'' stirbar and a Thermoline heavy duty stirrer that's rated to stir up to 132 litres.  I pressure tested the carboy to 50psi with scalding hot water and stirring for 5 hours and there was a bulge at the bottom but I'm guessing it could even hold much more psi.
Edit : Nalgene Carboy Warning!!
For those who saw the O2/DMF/CuCl/H2O/PdCl2/safrole thing in the 20L carboy, on the second try, right when the reaction was complete, I noticed after I picked up the carboy, a few ml's leaked out.  There were a lot of little cracks all around the bottom sides of the container so choose a better one. End Edit
 

Here's my data:

Inside the carboy I placed the following:
30g PdCl2
165g CuCl (not CuCl2)
669ml water
4600ml DMF

I stirred this thing uncapped for close to 3.5 hours then I added 3kg
safrole, then capped it and tightened the cap with a BoaConstrictor strap wrench from Canadian Tire, and pressurized it and purged it 3x with O2, and then I took it up to 36psi and started stirring.  I checked the psi every 20 minutes exactly and topped it back up to 36 psi:

time        drop in psi
0                 0
20min             10
40min 11    getting warm
60min 7
80min 12    getting hot
100 12.5  hot to the touch, but still touchable
120 12
140 9
160 8
180 5
200 4     still hot

After the reaction, I dumped it into my 22L sep funnel which is made from a 22L heavy walled SHOTT RoundBottomFlask, and then dumped in 5L of 5% HCl.  I allowed this to cool for a few hours.  When I returned, I let the crude ketone come out and there was already about 2750ml. 
I then extracted with:
3x1L DCM
The combined extracts and crude ketone was then washed with :
2x3L saturated sodium bicarbonate (528g/6L)
Skipped KrZ's water wash
1x4L saturated sodium chloride solution (1250g NaCl/4L)
Then I dried it with 551g sodium sulfate for 54 minutes
then evaporated the DCM to get 3124g crude ketone
then distilled to afford me with 2500g ketone (76% molar yield!!!)

  Grouch (Old Hiver) 02-06-01 01:48 No 171396
The way you shake it is by stoppering it and carefully lifting it out of the 'wooden chair with a 6" hole drilled in it' hacked stand, inverting it and resting the shoulder of it on one knee while taking the stopcock side and shaking/swirling it and venting it.  When finished, carefully put back, unplug and let settle.  The 22L flask was originally just a plain SHOTT RBF but modified by a glassblower with a joint on the neck and a stopcock at the bottom.

CuCl instead of CuCl2?  Reason not really important; you can use a little less and have less Cl- ions around.  Solubility may be different in different solvents, but I haven't checked.  I like the colors more using the CuCl left over from over two years ago back in the days of the 'balloon on top of the flask, ton of catalyst' Wacker.

Above procedure is pretty much EXACTLY the same as KrZ's post a long time back in a thread called 'o2 is shit' or something like that where people were, for wrong reasons, doubting the procedure.  The ONLY change is the CuCl and the scale and equipment used.  I copied it almost EXACTLY.

The reason for the erroneus pressure decrease at 60min was likely due to me not setting the stir speed as fast as the other times.  And NO, I wouldn't have used the word 'confirmed' if the reductive amination failed.

PS:  The wooden chair had to have been in your family's home and be a minimum of 43 years old and re-painted a few dozen times by your father, or none, ABSOLUTELY NONE, of the above procedure will work.



WISDOMwillWIN
 
 
 
 
    LaBTop
(Daddy)
02-13-01 02:19
No 173000
      Re: Detailed Methods for Non-chemists .edit 13feb1  Bookmark   

Detailed Methods for Non-chemists. edit 19feb2001
   
XII.MDMA via LEUCKART, SMALL TO HUGE SCALE.

http://rhodium.lycaeum.org/chemistry/leuckart.txt
Huge scale Leuckart MDMA manufacture by LaBTop.

http://rhodium.lycaeum.org/chemistry/mdp2p.leuckart.txt
MDMA via the Leuckart reaction

http://rhodium.lycaeum.org/chemistry/asarone.wacker.txt
TMA-2 from Calamus oil: Wacker Oxidation of asarone, followed by Leuckart amination


XIII. SAFROLE to MDMA, BRIGHT STAR SYNTHESIS

http://rhodium.lycaeum.org/chemistry/mdmasyn.txt
Complete MDMA Synthesis by Bright Star


XIV. RHODIUM's MULTIPLE PREPARATIONS of ISOSAFROLE

The latest findings of Rhodium for preparation of Isosafrole :

http://rhodium.lycaeum.org/chemistry/isomerizafrole.html

and the preparation of the Alumina/Sodium catalyst for nr 8 :

http://rhodium.lycaeum.org/chemistry/uspat3852305.html

Pay also attention to :
Safrole + 1-Butanol +4M KOH at conventional reflux for 15 minutes gives 99% Isosafrole in nr 4.

Nr 7, solventless PTC variation is covered under my Isosafrole writeup in this thread. LT/  WISDOMwillWIN

---------------------------------------------------------------------------
---------------------------------------------------------------------------

Here is that info how to make d- or l- isomers of your drugs.

Serious Chemistry :  MDMA chirality  All 22 posts

ChEss_Piece_Face (Stranger) 07-15-00 00:28 No 28995        
It occurred to me that MDMA is chiral, and most chiral pharmaceuticals have only one active isomer. For example, only the S isomer of ibuprofen is active, although the R isomer racemizes over time in the body. Pure S is therefore more potent and faster acting than a racemic mixture, which is what is usually sold OTC.
Does anyone know which isomer of MDMA is the active one, and has anyone toyed around with making enantiomerically pure MDMA?
I happened to notice the other day that Aldrich sells MDMA.HCl!!! It just so happens that they sell one of the pure isomers in addition to the mixture.
 
gaston (Hive Bee) 07-15-00 03:57 No 29040
The S isomer, as with methamphetamine: http://www.erowid.org/library/books_online/pihkal/pihkal109.shtml
     
JOESTALIN (Stranger) 07-17-00 07:02 No 29651
actually it is the R isomer of Extacy THAT IS THE active isomer as it was proven in a J. Pharm. CHem. article in 1984, and to obtain an optically pure isomer of E is about as expensive and time consuming as the synthesis itself with no increase in yield.
     
john_galt (Stranger) 07-17-00 13:11 No 29757
From what I read in PIHKaL, it is actually necessary for the desired effect of MDMA to consume the racemate.
"A penny saved is .72 pennies earned (after capital gains tax)"
-John Galt
     
JOESTALIN (Stranger) 07-19-00 05:45 No 30453
When was the last time someone ran into an illegal drug that was racemically pure, huh?
     
Rhodium (Chief Bee) 07-19-00 06:02 No 30464
Last weekend I saw a couple of guys snorting coke. Coke is pure l-cocaine.

john_galt (Newbee) 07-19-00 16:01No 30683
Don't be silly, dude, NONE of the popular synths for MDMA are enantioselective. They produce both enatiomers at equal rates, therefore, all of them produce the racemic modification. Resolution would involve recrystallization of a salt with 2 chiral centers of an enantiomerically pure acid(thus producing diastereomers with differing physical properties) or chromatography.
-John Galt
     
Rhodium (Chief Bee) 07-19-00 17:33 No 30705
None of the MDMA sytntheses, no, but I don't think anybody said that either.
     
JOESTALIN (Stranger) 07-20-00 10:03 No 30967
what I meant to say was no designer drugs and cocaine by definition isn't really illegal doctors still presribe and use it... i do mean use it
     
john_galt (Newbee) 07-20-00 13:33 No 31015
When someone insinuates that one never encounters a completely racemic drug, he is inevitably implying that there is some sort of enantiomeric excess. With the popular MDMA synths, this is impossible. I was just using basic theory to show that, indeed, *ALL* of the XTC that people consume IS racemic, as that is what the dude was asking.
-John Galt
     
ChEss_Piece_Face (Stranger) 07-20-00 20:44 No 31163
No, I wasn't asking if street ecstasy was racemic or not, I'm quite aware that it is. Rhod had it right, I was wondering if any curious bees had tried to isolate the active enantiomer. This could either be done as in J-G's post, or via ring closing, then opening rxns (you can get pseudoephedrine from ephed/pseudoephed racemate this way).
I guess no bees have gone there.
gaston - thanks for the link with relevant info. I've only been at this for a little while now, so I didn't even know PiHKAL was online!
     
LD_50 (Stranger) 07-21-00 03:54 No 31278
ok...we all seem to agree that the standard synth produces many enantiomers and as such is a racemic mixture.
and using a chiral "agent" would be usefull in seperating them into thier 2(?) diastereometric salts.
now if we had mdma as a mixture of the s and r forms in (aq.) soln. (R)-(-)-MDMA and (S)-(+)-MDMA....and used (+)-tartaric acid to this soln. this should precipitate out the (S)-(+)-MDMA from solution (by using molar equivelents of the +tartaric acid?equivelent to the amount of the different sterio isomers?).....then follow with (-)tartaric acid for the (R)-(+)MDMA
but,like in methamphetamine, this could compose as much as 50% of the total product...so we perhaps have a slight problem, for wasting half of the product for recemic purity is very unfortunate indeed...
So the problem seems to be converting the (S)MDMA to the prefered (R)MDMA after seperating the racemic mixture??????
now temperature during the synth to mdma is probably a big factor in determining if r or s isomers are produced and i have heard of using chiral catalists to get racemicaly pure products...anyone know if keeping the reactants in the Hg/Al amalgam process at a low temp might favor the (S) or (R) entomers?
     
Osmium (Moderator) 07-21-00 03:55 No 31279
There are stereo-specific syntheses which produce only the desired isomer.

LD_50 (Stranger) 07-21-00 04:17 No 31286
maybe not pre reaction--->(X)MDMA but maybe some kind of catalitic treatment to the (S) isomer after seperating them?
But this is not pharmacy 300...and it seems that the (S) isomer is active and not unpleasant...but is definatly less prefered than the (R) isomer....now if it was temperature dependant on what isomer was producduced in greatest quantity then tight controll of the reaction could produce fairly easy controll. I am wondering if having the reaction proceed at a low temperature(in coolant,methylene glycol etc<antifreez>, and a refrigerator coil @ 0 degrees centigrade might be better<but maybe very slow> it would be really nice to have a spectrophotometer at home.

phree_radikal (Stranger / Eraser) 09-29-00 18:23 No 55828
Firstly, there seems to be a descrepency between published articles on whether it's exclusively R or S... sources I read implied the S was active and the R not.
The significance of this, as I see it, is that 50% of the propanone is effectively sacrificed at the step of reductive amination. I'm not quite down with the mechanism yet but that's gotta be when chirality is introduced... if you know the mechanism (which some of you do, I'm sure), then you can predict the product distribution or whether it's entirely racemic (equal distribution).
What I wanna know is whether any one has a stereoselective synth for the active enantiomer?
Please, please, pretty please?

FarQ (Hive Bee) 09-29-00 22:32 No 55890
In my understanding of Shulgin's writings, is that while neither isomer is inactive, one produced more effect. Neither effect was as good as the synergictic effect of both together. So WTF you wanna seperate them or worry about stereo specific synthesese?

phree_radikal (Stranger / Eraser) 10-02-00 20:24 No 56743
So we can verify the research of others...
If it's true they're synergistic, then I'm not going to do more work for reduced effect. That's silly. But I am curious about which is which and what the difference in effect is.
I gotta feel it. p_r

LaBTop (Daddy) 10-11-00 11:06 No 59321
Here is some more in-depth info on the subject :

Ref.: 'Quasar' Research Monograph 22.
Absolute Configuration and Psychotomimetic Activity.
G.M.Anderson III, Gisela Braun, Ulrich Braun, David E. Nichols, and Alexander T. Shulgin.

This paper is 8 pages long, so I will highlight the most relevant pieces of it, relevant to the questions and answers (which are all not precise enough or even erronomous to fully understand the matter).

Exerpts:
Most of the known psychotomimetic agents have at least one chiral center within their structures but have been studied only as the racemic mixtures. All of those which have been studied in optically  active form are consistent in that the more potent isomer is the isomer with the absolute "R" configuration at the chiral center carrying the nitrogen that correspondents to the amino group of the phenethylamine moiety. (Follows a long list of isomers and their potency in humans).

Finally, the "R" (levo-rotatory) isomer of 3,4-methylenedioxyphenylisopropylamine (MDA) is reported to be three-fold more potent than its optical enantiomer (Marquardt 1978).
With MDMA this potency assignment is reversed !
"S"-MDMA is more effective as a CNS agent than is "R"-MDMA.

Amphetamine (a stimulant, not a psychotomimetic drug), on the other hand, has the "S" or dextro-rotatory form that is the more axtive. (+/- twice as more potent as the "R" isomer, Smith and Davis 1977).

The 3 chemical species : racemic MDMA, "R"-MDMA and "S"-MDMA, were evaluated in normal human subjects as their hydrochloric salts, orally.
Judged as -, +\-, +, ++, and +++. The data represented 35 clinical trials. (follows a plotted graph with 3 lines through data points. The "S"-line is the highest, a +++ at 120 mg dose, followed by the "dl"-line,racemic, a +++ at 160 mg, and the "R"-line with only one + at 200 mg).
It is concluded that the "R"-isomer only slightly interveres the effect in the racemic sample, compared to a pure "S" sample, in contrary to nearly all other psychotomimetic drugs.
Qualitatively, most of the sensory and interpretative properties reported for the racemate are seen in the "S" isomer, including the frequent physical toxocity manifestations of mydriasis and jaw-clenching. The "R"-isomer is free of both side effects, even at the highest doses assayed.
It must be concluded that (in contrast with the previous generality that the activity of racemic psychotomimetic compounds could be largely accounted for by their "R" isomers), with MDMA, the active optical isomer is the absolute "S"-isomer, with the configuration of dextro-amphetamine, so d-MDMA. **


As an answer to the last question,
one direct synthesis for the preparation of the two freebases "R"(-)MDMA and "S"(+)MDMA (with "R"-MDA as another possibility as an extra) is as follows :

MDP2P is coupled with "R"(-)benzylmethylamine [ "R"(-)CHNH2CH3 ], and the resulting Schiff base reduced with Raney Nickel.
Catalytic reduction of this "R,R" secondary base provides "R"-MDA (nice aint it, precisely the right, most active MDA isomer, keep that in mind!), (alpha)D= -24.7, agreeing with literature and bought sample from reliable source.
This base is formylated in methyl formate in a sealed tube, and the resulting formamide has a reversed rotation (alpha)D= +12.4 (in ethanol) and a m.p.=99-101.
Reduction of this amide in THF with LAH provides the desired "R"-MDMA, (alpha)D= -18.2, m.p.=181-183 as the HCl salt.

The "S"-isomer can be prepared in an exactly parallel manner (with "S"(+)CHNH2CH3 of course), with the primary amine showing (alpha)D= +25.3, the amide (alpha)D= -12.6, m.p.=101-102, and the final "S"-MDMA with (alpha)D= +17.2 and a m.p.=184-185.
Racemic MDMA m.p.=150-151.

"R" = levo
"S" = dextro
dl  = dextro/levo (racemic mix)


May I conclude for you all, the synthesis of specific isomers for MDMA is useless. The difference in effects felt for the "S" isomer and the racemic mix are neglectible !

The synthesis of the d-methamphetamine isomer however, compared to the racemic mix, dl-methamphetamine, is surely worth the trouble, it's effects are noticably different, especially the fucked up state connected with orally administering the dl racemic mix is smoothed down exessively.

The synthesis of "R"-MDA is also worth the trouble, find out yourself if you'r the investigating kind of person.


The synthesis of a racemic mix of dl-methamphetamine into the pure d-form has been posted by Spitball/Drone:
http://hive.lycaeum.org/ubb_board/Forum6/HTML/001137.html  Let's Go for the gold.. 05-27-99 11:00 AM :

15 g d-tartaric acid and 12 g dl-methamphetamine.HCl
300 ml Ethanol >98%.
Heat the ethanol to a boil. Slowly, add both d-tartaric acid (a whitish powder) and dl-methamphetamine till both totally dissolve, surplus heat needed when too slow, until boiling again.
Then put the closed flask in the freezer and see the crystal needles formed after a few hours.  That's d-methamphetaminebitartrate acid crystals. Filter the crystals off.
An acid/base extraction and then gassing of the freebase with HCl gas gives d-methamphetamine.**
LT/ : NO ! This procedure gives you the unwanted  l-methamphetamine !!!

And dwarfer gave us 2 patents explaining the matter a bit more elusive:
British patent nr. 508757
US patent nr. 2276508
Also look at the VillageIdiot pages:
http://www.angelfire.com/de/VillageIdiot/isomers.html
http://www.angelfire.com/de/VillageIdiot/racemateresolution.txt

Now, after reading the US patent, I must say, I've never seen a more unreccognisable form of english explanation before.
I understand that the above method is not the same as the one outlined in the British and US patent, indicating that with above method from Spittbal, you get l-methamphetamine.

TO DO IT RIGHT :

The British patent however is as follows, in simple understandable text:
85 Parts of racemic methamphetamine are introduced into a solution of 100 parts of d-tartaric acid in 1000 parts of methyl alcohol. After protracted(what's that?) standing, about 100 parts of the precipitated salt are aspirated off and extracted with hot ethyl alcohol.
Since the d-tartrate of dextro-rotary methamphetamine is readily soluble in both methyl and ethyl alcohol, whereas the d-tartrate of levo-rotary methamphetamine is sparingly soluble both in methyl alcohol and hot ethyl alcohol, an extremely simple separation of the d-tartrates of the optical antipodes of the base is effected.**

In my opinion that means that you must filter off the unwanted l-methamphetamine-d-tartrate crystals precipitated out of the solution, (better recrystalize a few times more by evaporating more solvent and cooling again, to obtain a pure solution of the d-form!) and add a strong base (KOH, NaOH) to the remaining solution until pH 13 to force the freebase d-methamphetamine-d-tartrate out as an oil. Then separate the oil from the solvents, and distillate to be sure, and then gas that clean oil with HCl gas to exactly pH 7 to get your d-methamphetamine.HCl salt. Filter and dry.

I hope this error has not given too much of trouble to experimentors in the past. They made then the wrong l-methamphetamine following those instructions.

Correct me if I'm wrong. LT/
---------------------------------------------------------------------------
WISDOMwillWIN   
     
 
     
buchiguy (Stranger) 10-12-00 14:03 No 59546
Cheers to Labtop! Thanks for clarifying that for my imaginary friends as they were ready to abandon the sodium borohydride reduction, speculating too much of the racemate being produced was weakening the product. If memory serves me correctly, you were partly responsible for that great post on the borohydride reduction to begin with. Definately one of the easiest reductions my imaginary friends have seen and the yields are great! Any suggestions for getting away from methylamine gas though? Stinks up the neighbourhood. My friends built a nice scrubber but doesn't completely do the job.

LaBTop (Daddy) 10-24-00 03:43 No 62904
"R"(-)benzylmethylamine [ "R"(-)CHNH2CH3 ], and "S"(+)CHNH2CH3 : can anybody close to chemical suppliers provide us with the prices of these chems, and tell us if you can order them at all ?

Did you really all miss the importance of this easy route to the most potent isomers of MDA and MDMA in pure form?
Expected some more reactions.
If these 2 isomers of benzylmethylamine are obtainable of course, or could be -easily- created in your garage !
The sources I have access to have no info on these compounds.
Psychokitty, do you have access ? Anybody ?
The rest of the steps is childsplay. LT/
---------------------------------------------------------------------------
WISDOMwillWIN

LaBTop (Daddy) 10-24-00 05:07 No 62922
Missed that last question from Buchiguy :

If you follow all the OnePot directions shattered over the board, and use some McGuiver techniques, you will virtually smell nothing.

Use a exhaust fan connected to a box with a in and out opening, with clothhangers in it, 5 to 10, and hang well wetted towels on them, alternating 5 cm above the bottom and the next one touching the bottom, so you create a labyrinth where the air is forced to follow a S-shaped route to the end of the box. The water in the towels will absorb all traces of MeAm gas escaping your setup, especially during the adding of the boro. The clean air will be exhausted out of your working space. Wash the towels periodically in lots of water and use rubber gloves for that.

You pump (gearpump in case of 100th of liters) your 10% MeAM/MeOH mix into your vessel, or syphon it in, this will also prevent any gas from escaping.

All open pipes must have washing bottles attached.
Adding boro in one with a funnel means you must have another pipe with a big ass washing bottle attached, filled with 10% HCL/water solution, to effectively kill all MeAm smells pushed out by the pressure, building up, when adding boro. And have another EMPTY washbottle in line before that one, to trap suckbacks, or you have WATER sucked in the reactionvessel when you loose pressure suddenly !
The rest of all your entrances to the vessel must be airtight !!!

While adding boro, you have the exhaust fan intake hose placed near to the funnel, so it takes away directly all fumes escaping there. Stopper the funnel loosely inbetween addings, or the stopper will pop out, caused by the pressure buildup.
 
Especially airtighten your big lid, which you use to climb in and clean the kettle afterwards, or the other use of this opening for taking out the 100 kg powder produced in the same kettle with a  big ass coal shuffle from SSteel(your 90 liter clean base with the 270 liter acetone, and then bubble HCl gas through, while mixing).
First shuffle the powder away from the valve tap opening in the center of the bottom, or that will be stucked with powder at the end. Then you open that valve for 2 seconds to clear the valve, close it again, remove the first bucket with some powder and acetone in it, and then open the valve a bit again to let the clear acetone slowly out, not disturbing the pile of powder inside the vessel, into several buckets, until no more acetone comes out, close the valve and start gold digging with your shuffle ! Have fun !

The last rests of powder you wash out with the acetone you decant off from the buckets where you shuffled the wet powder in (remember, the result of the crystallization is a big wet mass of toothpaste-like powder mass), and wash the powder, left in the kettle, out into the new bucket you placed under the big ball-valve in the bottom center.

At the end of the 36 hrs reaction,  after adding the 8 x volume of water and tapping your raw freebase, you add a lot of 20% NaOH or KOH solution to your lots of waste water, till pH 13, and then a lot of 33% HCl solution again till pH 7 or slightly lower. This will break up all hydrocarbons. You now have a non-MA smelling solution, it will have a slight perfume smell.
It's neutral, it will not be destructive to plant and animal life. LT/
---------------------------------------------------------------------------
WISDOMwillWIN

Acme (Hive Bee) 11-02-00 19:56 No 66110
Acme's route to "R"(-)benzylmethylamine : [ "R"(-)CHNH2CH3 ],

Starting with D-N-Boc-phenylalanine-OH.

React this with Ethylchloroformate, TEA (0 C, 5 min in THF), and diazomethane (as a 0.3M soln in ether), stir 20 min to get the diazoketone. Yield 100% easy chromatography (follow the yellow band).

Homologate this with AgClO4/THF/water(few drops) yield 100% (after adding some brine(sat.NaCl) to precipitate silver, filter over celite) chromatography 10% MeOH/DCM or EtOAC/Hex 0.5 OH.

Decarboxylate with NaOH, then TFA/DCM to remove the Boc. Voila! 
"R"(-)benzylmethylamine [ "R"(-)CHNH2CH3 ].
Use the naturally occurring (cheaper) L-N-Boc-phe-OH similarly to get the S form.


WISDOMwillWIN
 
 
 
 
    LaBTop
(Daddy)
02-18-01 08:39
No 174043
      Re: Detailed Methods for Non-chemists .  Bookmark   

Feb19 2001 :

THERE WILL BE NO MORE ADDITIONS BY ME TO THIS THREAD (or it get's too big and overloads the server access time)

THE UPCOMING INFO WILL BE PLACED IN A NEW THREAD !
That space is reserved for :

1. Alcoholic O2 Wackers (Successfull testruns in process).
An easy and fast OTC, small to big scale synthesis of MDP2P and friends.
Based on KrZ's many inputs.
2. DMSO O2 Wacker (Testruns in process).
Idem.
3. All Hydrogenation methods spelled out by KrZ, if we can get his cooperation to explain those methods to me, or to someone who can PM me again, so I can edit them for him in a readable fashion for less gifted members. (PM me?)
4. The rest of his non-Hydrogenation posts, idem.
5. Baalchemists improvements on Methyl_MAn's Nitromethane method.
6. CURBSHOT's nanoscale Meth method.
7. Aquagirls nanoscale Meth method.
8. Dwarfers ideas, sometimes too mystic to get a grip on, for me alone.
9. Ozbee's Sodium metal ether Birch.
10. PtO2 (also called PtOIV), Adams catalyst Hydrogenation by me and that dutch sculptor, for MDMA and MDEA.
11. A real life? working Safrole + H2SO4 route. I doubt it. See TS I+II.
12. Some of Uncle Fester's really working methods, yes,they do, most of them. Will need some input and improvements of our members.
13. Some links to the most valuable info on Worlock's, WizardX's, ChemGuy's, VillageIdiot's websites.
14. Some of Bankrobbers successfull testruns.
15. List of links to Rhodiums page's most easy procedures for beginning chemists and cooks.
16. Ymirs long forgotten excarvations of old text books.
17. A long list of Psychokitty's references to feasable methods, f.e. the Sodiumtriacetoxyborohydride and Titaniumisopropoxide reactions, and much more, he has lots of them. Let's combine them with a similar list from RefDrone and LaBRat! (Where are you guys, PM me ?)
18. Photo's, brochures, text from Hydrogenators and the appropriate technique's invalved.
19. An extensive 40 page long description how to make tablets, and all possible fillings, a pharmacological approach.
20. Lots of info on Evaporators, many unknown models to the Hive.
21. Mescaline analogs.
22. Testreports on d- and l- isomeric procedures.
23. Photo's and text of pillpresses.
24. How to make improvised equipment for small and huge scale methods, with photo's.
and
25. In another NEW thread, all REAL important computer based knowledge for SAFE and FAST browsing of the Hive and the Web.


And ANY other posts or threads or links or own NEW methods/procedures/inventions I forgot, which ANY of you feel they belong in here, and which you can send me by PM (Personal Message) or e-Mail.
Don't be shy, I appreciate ANY INPUT!
coollaughshocked
 
 
 
 
    LaBTop
(Daddy)
09-05-01 12:20
No 210291
      Re: Detailed Methods for Non-chemists .  Bookmark   

This is the latest buffered Performic write-up by me, use these guidelines, and it won't hurt to compare them to the earlier one somewhere there above.


To help everybody out in this somewhat chaotic 2 year long discussion on one of the most interesting subjects for most of the readers, I offer you the following effusion :


A correct timeline of the-Hive's development of the following high yielding procedure is as follows:

Ritter first posted on the young Hive, end of '98 a short, buffered Performic acid oxidation, and he used Na2CO3, Sodiumcarbonate as the buffer, and DCM as the solvent, then Beagle posted a similar procedure, and LaBTop posted a short one using NaHCO3, sodiumbicarbonate (a.k.a. baking soda or sodiumhydrogencarbonate) and DCE, where he mentioned that DCM could be used in practice with similar yield. Then Gyrogearloose reproduced that one in practice also, on medium scale, 500 g MDP2P, then LaBTop wrote in april 2000 a very extensive writeup from past practice in the sticky threads, where he advised to use a new find from Osmium to produce the precursing Isosafrole with Aliquat phase transfer catalyst in 5 minutes after the heating reached the boiling point of safrole.
Then Baalchemist got enthousiastic and reproduced in practice LaBTops extensive practical MDP2P write-up, and made a few small alterations during the following year.
Ritter as the last one posted again, from practice, saying there is no real difference between the use of sodiumbicarbonate and sodiumcarbonate as the buffer salt, and proved it with hard facts, so feel free to use either of these salts.
Now Rhodium included this procedure in short form in his latest write-up at his page.

LaBTop build all the latest info into his latest extensive write-up, with some important new additions for large scale production of MDP2P, which is mainly different compared to small or medium scale in producing performic acid portions only 1 hour before needed during the proces of adding it to the isosafrole/DCM, thus providing a constant supply of FRESH performic acid, no use of cooling when dripping the performic, and preheating the intermediate  and the 15% H2SO4  before adding them together, which seems rather unimportant, but will increase yield substantially, if also a good professional vacuum source is used, yield percentages between 80 and 90% can be reached! Thanks go to Baalchemist for the last two.
And now LaBTop provides you with the latest extensive write-up, because he knows that 90% of the members will manage to majestically misunderstand these ultrashort writeups, because of the nature of this board, 90% non chemists and 10% chemists.

* * * * * * * * * * * * * * * * * * * * * * * * *

For small, medium and large scale MDP2P ketone entrepeneurs, I would strongly advise to pay full attention to the following write-up.

See first Post 23325 (LaBTop: "Detailed Methods for Non-chemists Edit: IT'sDONE!", Methods Discourse), and Post 184407 (Ritter: "Re: Medium scale performic", Methods Discourse) to get a grip on the Hive's historic development leading to the following newest procedures to produce MDP2P ketone.

After that I advise instead of the messy and time consuming Aliquat procedure mentioned there, to follow the most simple, next procedure, to convert your safrole, vacuum distilled from minimal 85% Asian or Brazilian sassafras oil, to vacuum distilled Isosafrole, and then the LT buffered Performic acid oxidation procedure to produce MDP2P from it :

Here's first the conversion from Safrole to Isosafrole done by LaBTop, Osmiums simple route was followed, yields are ~95% without vacuum, ~99% with vacuum :

No vacuum:
Weight 130 kg distilled safrole and add 2% = 2.6 kg KOH grinded flakes or pellets >98%.
KOH flakes are in some countries 85%, the 15% rest is water, check it on the label.
Then heat up. At 100 C the eventual 15% water will start evaporating, or, when 98% KOH was used, only a small amount of water will come off.
This removal of water is critical to the reaction, water present when refluxing will totally stop all isomerization.
Add more heat until all water is evaporated. Then at last connect a reflux condenser vertical on your vessel and continue heating until the safrole starts boiling, without vacuum, reflux will be constant at circa 232 C until boiling stops, that means it has nearly all converted to higher boiling Iso.
Do NOT crank up the heat then, but disconnect heating and let cool to roomtemperature. Reaction takes roughly 3 hours for non vacuum. You now have ~95% Isosafrole which you use for the MDP2P conversion step. You could distillate it now, to get >99% Isosafrole, but that seems to be no option for the ones who choose for this approach, they probably have no vacuum source, and ~5% safrole will not really interfere with the MDP2P step.

Under vacuum :
Same as above, only boil off eventual water first with a normal condenser attached, so you can check for any water present, when eventual water stops condensing in the condenser, change horizontal condenser to a vertical reflux condenser, and keep heating (far under 200 C, boiling temperature depends on vacuum source.)
Vac reflux should be done overnight because of lower temp, reactions at lower temps take longer.
Start a vacuum reaction f.e. at 21:00 hr and next morning its done, all boiling has stopped and safrole is nearly quantitatively converted to isosafrole.
Then just distillate the now isosafrole out of reaction flask, dont distill it completely dry though, because you can add a next batch safrole to that little bit leftover {isosafrole/safrole + all the used KOH} again for a next run.
Just add at the next run 50 gram of new KOH to refresh a little.
Trying to wash reaction in a sep funnel for purifying is terrible: results in a terrible emulsion that's nearly impossible to break up and ends up in alot of LONG labor and endproduct loss.
Distilling is a must for best result. Don't worry about leftover safrole with O's Isosafrole vacuum route, usually all converts.
However, if a small amount leftover safrole is present, f.e. because you have no vacuum, it wont screw up the performic route.

Notes:
No CaO at all, 98-99% KOH only. Make sure the KOH are roughly grind-up solids, (not a liquid mix with water), where you sieved all powdered KOH out for an easier workup at the end, use a nylon insect-screen.
Add 1-2% of safrole weight KOH flakes and away you go. Make sure that there is no H2O present anymore when you start the actual reflux!. At atmospheric it runs quicker because of higher temp, ~3 hours.
Bring it to a reflux and hold it till refluxing stops. Then you know it has converted to the isosafrole which has a higher boiling point. Vac reflux is much longer, but if you're into yield maximalization, then thats the way you want to go. ~98-99% yield.

* * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * *

Here's first Baalchemist's write-up for LaBTops modified performic as he posted it lately, then the second part is scaled to what LT/ would do. This can be scaled up or down according to your wishes, may they always come true :

Baalchemist:

There is no need to pre-stir for more than 5-10 mins. In a nutshell; With stirring in 2L flask add in this order> 250g Iso, 76.9g Baking soda, 770ml DCM, let stir 5-10 mins. Begin dripping in performic solution (232.2g 35% H2O2, 384.5g 86% Formic acid) over a period of a couple hours. It should reflux slightly during addition,but not a hard reflux.Solution will turn from yellow to orange,keep stirring 24 hours,no less. Allow to sit and remove DCM layer,and extract top layer with a small amt. DCM. Evap DCM extracts, add orange syrup to 2768g 15% H2SO4 (preheated to 80c). Stir for 2 hours, no more. Let cool, 2 layers will form. Remove bottom layer, and extract top layer with some DCM, add this to bottom layer. Evap off DCM and proceed to vac distill ketone. Yield 190g+ Ketone ~76% w/w.    

============================



LaBTop's ultimate procedure :

( If you prefer a small scale procedure, just change ALL kg in grams, and liters in milliliters !! )


PERFORMIC ISOSAFROLE GLYCOLIZATION STEP:

In a 1600 liter vessel ( f.e. a second hand stainless steel milktank ), add, in this order (while heavy stirring anti-clockwise, (a must-have is a stirringmotor which can turn clock- and anti-clock wise (1), otherwise too much oxigen and other gasses from the air will be mixed in; you will notice no vortex, but a 1 cm high and quite wide bubble on top instead) :

first:  125    kg Isosafrole, distilled.
then:    38.45 kg Baking Soda, NaHCO3, SodiumHydrogenCarbonate 98%.
then:   385    liter DCM, CH2Cl2, DichloroMethane a.k.a. MethyleneChloride, 98%.
Totals to 681.28 kg (weight of 1 liter DCM is NOT 1 kg!).

The purpose of the baking soda is to buffer the pH of the reaction in such a way that it doesn't become too acidic, in which case the intermediate monoformyl glycol may undergo oxidative cleavage (and thus lessen the yield). Running the reaction at a higher pH than usual makes more of the epoxide (and thus risk of tar forming) and less of the actual glycol and will decrease yield quite notible. (both will of course form the ketone with 15% H2SO4).
 
Attach a reflux condenser & addition-funnel/container with a dripping valve to the 1600 L vessel. All other openings must be frantically closed with proper tape, or teflon seals, or the reflux will not work accordingly. Leaks will make bad smells.
Allow this to stir fast anti-clockwise while you prepare the first 25 liter portion of the total amount of performic mixture :

192.5 kg 86% Formic acid (preferably made by diluting 99% Formic acid)
118 kg 35% H2O2 (hydrogen peroxide), as FRESH as possible, don't use month's old stock.
This makes a total of 310.5 liter performic mixture.
 
To prevent such a big amount of performic mixture to get exothermic and too hot, while waiting all these many, many hours necessairy for dripping all of it in the Iso/BakingSoda/DCM mix :

Before adding parts of it to the 25 liter dripping container+drip-valve, only 25 (or even 10) liter portions are prepared each time with strong mixing while adding the two ingredients together, and kept in a freezer at around zero degrees Celsius, until needed. Don't cool too deep, it will slow the reaction rate when added to the dripping container and dripped in the vessel.
It means that you make during ~half a day, under strong stirring, twelve 25 liter portions and one 10.5 liter portion performic mix, one portion each time, when the dripping container is 4/5 empty.
Or even better thirty 10 liter portions and one 10.5 liter portion.
That way your performic mix is of a constant FRESH nature, which increases end-yield.

The performic acid portions should be prepared in advance (one hour, at room temp: the last 1/5 of the dripping container takes around 15 minutes to empty) to make sure the formic acid has reacted with the hydrogen peroxide (but don't let it stand overnight, or decomposition will occur).

Using DCM as the solvent is advantageous, as the reaction temperature can never exceed 40C (bp of DCM), and by keeping the reaction temperature that low minimizes side reactions.


When the 25 liter dripping container is 4/5 empty, refill it from a 25 or 10 liter portion from the freezer.
(If your Formic acid isnt 86%, then down to 77% will work, compensate with more H2O2, based on % of formic acid available.)
The Formic acid is only acting as a solvent in this reaction, it does not react.
Remember, the less performic in the dripping container, the slower the dripping goes, so adjust accordingly, watch the reflux rate AND the temperature, when one of these go too fast or high, close the drip-valve a little, until both reflux and temp are stable again.
The technically gifted can make a pressure-equalized dripping container.
 
Slowly, add the performic-mix drop/or smallstream-wise over a 6 to 12 hour period under constant fast mixer speeds.
If you add it too fast, the reaction will boil over, and contaminate everything.

Use a glass or SS pipe with wide internal diameter, attached to the drip-valve, properly sealed where it enters the top of the 1600 liter vessel, extended just under the fluidlevel, to drip the performic-mix directly into the mass of the fluid, and so prevent too much oxigen or other gasses to interfere with the reaction.
It will start to reflux a little, adjust addition rate so it doesnt reflux too hard.
Once all performic is added, it will have turned from a yellow to an orangejuice color.
 
Keep strongly stirring for 24 hrs total, no more, no less. (included dripping time). If you stir longer, sidereactions will kick in, lowering the end yield.

Note:
Remember, do NOT cool the whole reaction mix at all, let the reaction temperature be controlled by the dripping rate!
A good double check is the reflux rate, at no times, uncondensed vapours should leave the top of the reflux column! A bad smell indicates this.
End note.

 
Turn off the stirrer after these 24 hours, allow the two layers to settle.
Separate off the bottom layer (DCM), and extract the remaining top residue-layer 2 times with a small amount of DCM, and add these to the already separated main DCM body.
 
Take this combined portion to a 22 liter Rotavap or conventional distillation machine, distill off the DCM in 15 liter portions, and collect all the resulting orange syrup portions in a heating vessel and heat it up carefully, meaning don't overheat it, to 80 Celsius. All eventual residual DCM, (if any), will evap off (about 5-minutes).
You will be left with 183 kg monoformyl glycol, nearly quantitative, 100% yield.

Remove the residual fluids from the above procedure for eventual recovery of solvents and clean the 1600 liter vessel with hot, slightly soapy water and then cold water.

SULFURIC ACID HYDROLISIS STEP:

After the vessel cleaning, pre-heat (2) the 1600 liter vessel filled with 1384 kg 15% H2SO4 to 80 degrees Celsius.

NOTE:
Dilute 209.7 kg 99% H2SO4 with 1174.3 kg=liter distilled water for this amount of 15 % H2SO4.
Calculation of this amount:
15% / 99% = 0.1515% x 1384 kg total = 209.7 kg 99% H2SO4.
1384 kg 15% H2SO4 - 209.7 kg (99% H2SO4 + 1% water etc) = 1174.3 kg(=also liter) water.
209.7 kg (99% H2SO4 + 1% water etc) x 0.99= 207,6 kg 100% pure H2SO4/13.84= 15.00 % , always double check calculations. NO liters used in calculation here!
End NOTE

Then add all of the 80 Celsius preheated, distilled orange syrupy monoformyl glycol to the 80 Celsius hot 15 % H2SO4 portion in the 1600 liter vessel.
 
Connect a reflux-condenser on top of the 1600 liter vessel, and be sure there are no other open pipes or joints.
Keep the mixture between 75-80 Celsius for 2 hours, NO longer, or again sidereactions will kick in.

DISTILLATION STEP:
 
Switch off the heat, and allow to cool back to room temperature.
Flooding the reaction mix with some extra H2O prior to extraction helps improve yield because it facilitates separation and fastens cooling down.
It will seperate into 2 layers, the bottomlayer is raw MDP2P ketone, which you tap off through the bottom ballvalve.

Extract remaining top watery layer with small amounts of DCM (2x, a few liters), tap them off, then add all these DCM portions to already tapped off raw ketone bottom layer. When your last tapped DCM has the same color as when you poured it in, there is no more raw ketone to extract.

Then wash and separate this raw ketone 2x with sufficient 5% Sodiumbicarbonate/H2O mixture (a few to 10 liters at a time), to neutralize all residual acid. Check pH first with pH paper, then start adding bicarb until pH stays constant, or even goes up, when adding a bit 5% NaHCO3 again. Then all acid is neutralized.

Now place 15 liter portions in a 22 liter Rotavap or newest distillation machine, and vacuum distill the MDP2P ketone  which comes over between 155 and 165 Celsius and lower with the newest vacuumpump, it will begin to come over at circa 20 mBar vacuum and end at circa 1 mbar. A golden, honey coloured ketone will be obtained.
Clean the leftover tarry residue in your destillation flasks with acetone, a bit warm acetone will work faster.

Yield 76 % w/w, with a Rotavap, about 95 kg clean and pure MDP2P, ready for prefered method of amination.
Yield 85-90% with special distillation techniques, about 106.5 to 112.5 kg pure MDP2P.

Clean the leftover tarry residue in your destillation flasks with acetone, a bit warm acetone will work faster.

AND I DO NOT TELL THE OPPONENTS HERE WHAT THAT TECHNIQUE IS, and will be strongly pissed off when someone else does it openly here, we made their oppressive life already too easy.
We have PM's for that. And don't start PM'ing me to ask, only the few I trust to be able to do this can do that, the rest gets no answer. Yes, I'm a prick!
******************************************************************

NOTES:
1: Easy to construct with a stirrer shaft with a pulley on top, and the shaft leading through two ballbearings, one on top of the vessel, with an extra seal under it to seal the vessel airtight, and one at the bottom of the vessel, to keep the shaft+stirrer rigid. The motor has a pulley attached also, and the belt can then be attached to both pulleys normally, to stir clockwise, or in the form of a folded 8 to stir anti-clockwise. Motor must be tilted a little, to prevent the belt from scratching, when used in an 8 form.
You will be surprised what a 2-way stirrer motor costs, this is definitely cheaper to make yourself.
A 350 or 500 RPM motor+pulley and a SS-shaft+pulley with an outboardmotor SS-propellor attached is sufficient for all purposes. Instead of this expensive propellor you can design any other SS-mixerblade made by a machinist shop which will do the same job just as good, but will be much cheaper.

2: Heating such a 1600 liter vessel can be done in various ways, but the best is some sort of coiled-up hard-chromed copper pipe ( do NOT forget to hard-chrome the copper coils at a chroming-shop before ever using them in this kind of reactions, pure copper will solute in 15% sulferic acid and turn your solution to a nasty darkgreen color).
Place the coil, or coils, if your man-hole is too small for one big coil, at the bottom of the vessel and connect the ends outside the vessel to a convenient gear-pump and  heating vessel, silicone-oil filled, and electrically heated, with a connection to a thermostate, triggered by a thermometer at the bottom of the 1600 liter vessel. Make the passages through the vessel top airtight with silicone glue!
This way you are sure to not form hotspots.

Another easy method is to attach electrical heated car motor-oilpan heating pads to the outside of the bottom and eventually the sides of the 1600 liter vessel.
This method can be combined with the above one, to speed up heating, do not forget to stirr maximal when using heatpads.

30 August 2001 by LaBTop.

WISDOMwillWIN

WISDOMwillWIN
 
 
 
 
    LaBTop
(Daddy)
01-03-02 08:49
No 252179
      Re: Detailed Methods for Non-chemists .  Bookmark   

Ritter
(Master Whacker)
01-02-02 23:26
No 252122
         Re: 02 Wacker Help Please  
   
Someone told me that the IPA (isopropylalcohol) 02-Wacker has produced the most consistent yields of 2-propanone (xxx-ketone).  The secret is to warm the reactor to at least 40'Celsius to accelerate 02 absorption to a decent pace.  It has been observed that when this variation is run at room temp, absorption may completely cease long before even half the alkene has reacted-no matter how hard you mix it.  One mole of alkene absorbs over 80% theoretical oxygen in less than 6 hours using an initial pressure of 75psi.  It is very important to use some type of non-metallic  material for the rxn. vessel.  Many people here have wasted thousands of dollars worth the Pd salts over this mistake! 


WISDOMwillWIN
 
 
 
 
    LaBTop
(Daddy)
06-29-03 19:34
No 443314
      Hydrous One Pot Boro! AT LAST !  Bookmark   

See : Post 328680 (Barium: "A really wet reductive alkylation", Novel Discourse).
READ it CAREFULLY and INTENSLY, especially the PTC post!

This method should replace all Boro One Pot methods I have posted, for small to medium scale reductions. I mean: up to 1 to 2 kg endproducts.
Bigger scale production can also be done following this new, novel procedure from Barium.
ONLY in case you have access to methylamine gas in cylinders, your yield will be nearly quantitative if still using the old LaBTop One Pot Boro procedure.

Yours is the choice.

I'm very glad and proud that at last someone out of our own ranks, Barium, found the solution for an hydrous reduction with NaBH4 and 40% Methylamine.HCl salt solution in water.
Very clever, and found all by himself ! LT/

WISDOMwillWIN