06-05-00 10:40
No 13991
Here they are, with minor changes from older versions for greater accuracy.
======================================
Methyl Man's MeOH version of the benzoquinone wacker
Materials:
400mL MeOH (methanol)
50mL distilled H2O
150g p-Benzoquinone
2g palladium (II) chloride (PdCl2)
178g safrole
DCM (methylene chloride; dichloromethane)
NaCl (non-iodized table salt)
Sodium bicarbonate (baking soda)
5% NaOH
HCl (hydrochloric acid, from muriatic acid)
Magnesium sulfate drying agent (epsom salts baked in 400°F oven for an hour)
Method:
1. In a 2L flask fitted with a reflux condenser and addition funnel place 400ml MeOH, 50ml dH2O, 150g p-Benzoquinone and 2g PdCl2 and leave to stir for a minimum of 60 minutes. Note that a recent improvement has been discussed which involves stirring the PdCl2 in the solvent (MeOH in this case) for several hours before adding the water and benzoquinone. It is likely that this does enhance yields a bit by ensuring maximum efficiency of the PdCl2’s catalytic action. Either way will work well, however. If you let the PdCl2 stir alone for a while, when you then add the water and benzoquinone, let them stir for an hour as well before beginning the next step so as to ensure complete dissolution of the benzoquinone.
2. Place 178g safrole mixed with a bit of MeOH in an addition funnel.
3. Add safrole dropwise from the addition funnel over 60 minutes or more. However, when the addition is about 80% finished, apply low heat just sufficient to start a mild reflux (cold water through the condenser).
4. After the safrole addition is complete, leave mixture stirring and refluxing for 8 hours. (If you must stop at this point and resume another day, be sure to put the mixture in the freezer, sealed well. The raw ketone decomposes unless stored at freezer temperatures.)
5. Filter out the solids present in the mixture, which are hydroquinone (the degradation product of the benzoquinone) and PdCl2. This can be done by vacuum filtration or by simple gravity filtration with coffee filters. Many prefer gravity filtration with this synthesis because the solids produced in this reaction are very fine and are problematic to filter with vacuum. Don’t try to recycle the PdCl2, as it is too difficult to separate from the hydroquinone to be worthwhile.
6. Flood mixture with 1.7L 3N (~10%) HCl. (Here's the quick math: add 500mL of 31% HCl [muriatic acid] to 1150mL H2O to get 1.65L ~10% HCl—close enough for this purpose.)
7. Extract flooded mixture with 3 portions of DCM (1 x 500mL, 1 x 250mL, 1 x 100mL) in a large separatory funnel. The desired raw product, MDP-2-P (“ketone”), migrates into the DCM as an oil. Separate the DCM/ketone layers and combine them.
(Note: when you first hit it with the DCM you will probably observe a bit of scum which will float on top of the water layer, which will work its way down during these three extractions to appear as a blob of spongy semi-solid interface. It’s actually very mobile and easy to work around; simply avoid allowing it into your DCM separations. The same thing will happen in your washes in steps 10, 11 and 12 below, but by then you will be quite the pro at working with it.)
8. Extract water layer with a final small amount of DCM.
9. Add this final small DCM extraction to the combined oil/DCM solution from step 8.
10. Wash the ketone/DCM solution with saturated sodium bicarbonate in water twice (500mL each wash).
11. Wash the ketone/DCM solution with saturated NaCl 3 times (400-500mL each wash).
(Note: as you do these bicarb and salt water washes, you should be seeing the ketone/DCM solution getting progressively more greenish colored; this is visible in the film of solution that runs down the inner surface of the sep funnel).
12. Wash the ketone/DCM solution 3 times with 500mL 5% NaOH (500mL each wash). If you did step 5, you will have a very easy separation.
(Note: you should also see a very noticeable color change upon doing the first of these three washes wherein the ketone/DCM layer becomes a strange, thick reddish-brown, almost orange color. This happens as the NaOH pulls the majority of the solvated hydroquinone into its layer, cleaning the ketone. The NaOH layer in the first wash will be very dark brown, almost black in fact. The next two will be a far lighter, watery, orangy color.)
13. Dry the ketone/DCM solution with ~50g magnesium sulfate.
14. Distill off the DCM using mild heat on a water bath and ice-cold water through the condenser. This will take several hours.
15. Add 50mL of high-oleic safflower oil (no additives!!) to the ketone oil as a buffer to prevent the ketone from scorching in the distilling flask.
16. Vacuum distill the ketone/buffer oil mixture. This also will take a few hours, but probably not as long as distilling the DCM off did.
17. At 100 to 140°C (wherever your particular vacuum dictates), a minor amount of safrole might come over. If your safrole-to-ketone conversion was good, there should only be a very small amount. If it is only a few drops to a milliliter or two, you can leave it in, and not change/clean receiving flasks. If you are a stickler for purity, discard it. It will not harm anything later if you leave it in. But if it’s more than a couple of milliliters, get rid of it.
18. At anywhere from 25 to 40°C above the temperature your safrole usually comes over with the same vacuum, the ketone should begin coming over. You should get about 100 to 120g ketone. The color of the ketone coming over will likely be a pale, fluorescent-looking greenish yellow. In fact it looks not unlike anti-freeze—a similar “neon green.” You can stop distilling when the rate of ketone coming over has slowed to an agonizing one drop per 90 seconds or so. At this point there is so little left that it is probably not worth your time to wait for a drop per 1.5 minutes (it’s not worth mine anyway).
19. Immediately store your precious fluid in the freezer in an airtight sealed flask or bottle. Happy cooking!
---------------------------------
The MeNO2-Al-Hg reductive amination according to Methyl Man
Since the appearance of Ritter's writeup of this method in Total Synthesis II, much discussion has taken place about it but, it has sometimes seemed, little has been clarified. This is due in large measure to the sensitivity of this reaction to even the most minor changes in its many variables. With this writeup, I hope to provide a clearer view of the method and to allow others to benefit from the hard-won experience of someone (not me) whom we'll call Mr. A. Ritter's original writeup, while inspiring, lacked details about the many nuances that, once understood, allow the amateur chemist to really understand this reaction's dynamics. Thus I have tried with this writeup to help the neophyte who has only physical observations and scant written material to guide him (although I suspect and hope that it may even help a few more seasoned cooks as well).
The first thing I'd like you to look at is the array of interrelating variables in this reaction that make it so delicate. They are as follows:
1) the thickness/type of the aluminum
2) the consistency (i.e. flat, ground, etc.)
3) the amount of HgCl2 used in relation to the amount of aluminum
4) the addition rate of the MeNO2/MDP-2-P
5) the size of the reaction vessel in relation to the scale of the reaction
6) the ability to effectively stir the reaction
7) the coldness of the water through the reflux condenser (yes, even that!)
The above factors are sort of submitted in an order of importance (#1 being most important), but in reality they are all inextricably related. I observed firsthand the trials and tribulations of Mr. A as he struggled to match up the correct combination of ratios and conditions that would allow a smooth, consistent reaction and predictable results every time. Finally, after lots of frustration, confusion, losses, and---in the end---a revelation, the perfect set of elements was hit upon and recorded.
The scale Mr. A chooses to perform this reaction on is half-scale to the scale in the Ritter writeup, which was 55g aluminum and 50g MDP-2-P. Therefore this writeup will illustrate the reaction on a scale of 27.5g aluminum and 25g MDP-2-P. The subject found for his own personal reasons that this smaller scale was much easier to manage (not the least of which is that even with a huge 4-liter separatory funnel, at this smaller scale it gets pretty filled up!). There's no doubt that the original larger scale can be successfully applied, although it would require adjustments in the glassware capacity, stirring method, and probably other elements.
MATERIALS and APPARATUS:
? 27.5g Reynolds Wrap Heavy Duty aluminum foil
? 25g MDP-2-P
? 20 mL MeNO2 of 99+% purity
? 750 mL MeOH + 50 mL more for addition funnel + additional small amounts that will be needed later to thin the mixture
? 400mg HgCl2
? 2-liter 2-neck flat bottom flask
? reflux condenser (400mm preferable)
? 250mL or 500mL addition or separatory funnel
? cooling setup (bucket, water pump, tubing, 1 large bag ice)
METHOD:
1. Weigh 27.5g of Reynolds Wrap Heavy Duty aluminum foil (NOTE: it HAS to be Reynolds and it MUST be the heavy duty stuff) and then tear it by hand or cut it with scissors into small rectangles approximately 1" by .75". Settle down with this task with a good CD or TV show because it is tedious and may take about 1.5 to 2 hours.
2. With a coffee grinder, "grind" these pieces of foil for durations of about 10 seconds. Fill the coffee grinder only loosely (about two thirds full---don't stuff it! That will adversely change the consistency of the ground foil). It will probably take about 4 to 5 "loads" in your grinder to do the whole amount of foil, depending on the size of your grinder. (In actuality, the foil does not get "ground," but rather, each individual piece just gets compacted and compressed. If it is compressed too heavily, the inner surfaces of the foil nuggets may be rendered inaccessible to the Hg/MeOH solution, changing the timing of the amalgamation and maybe even causing an incomplete or failed reaction.) When properly done, the foil should be in gnarled little nuggets about the size of long-grain rice grains and should look really tight and small. The smaller, the better for good stirring.
3. Place a 3" stirbar in your 2L flat bottom flask and onto your stirplate. Add the foil nuggets to the flask and then proceed to set up your glass, support and clamps so that the reflux condenser and addition/sep funnel are securely affixed and your flask is well-centered on the stirplate (this will be critical when you begin to attempt stirring!). Also, prepare your cooling, i.e. attach the inflow and outflow tubes to the reflux condenser.
4. Carefully add the 400mg HgCl2 to 750mL MeOH to a tightly sealable bottle and shake to dissolve all HgCl2. Set this solution aside.
5. Combine the 25g MDP-2-P, 20mL MeNO2, and 50mL MeOH and pour them into the addition/sep funnel. Rinse your beaker (or whatever you used) with a tiny bit of additional MeOH to get the residual ketone and add it to this MDP-2-P/MeNO2/MeOH solution.
6. Very slowly and carefully (w/gloves, glasses, long sleeves and a Hail Mary if you're Catholic), using a large funnel, pour the HgCl2/MeOH solution from step 4 down the condenser.
7. Turn the stirring on full blast for a 5-second burst to intimately mix the solution and the foil. If you have prepared the foil as described above, it will easily stir. Give it a few more 5-second stirs over the next few minutes. I believe that doing this really helps facilitate the amalgamation process that is about to occur.
8. After about 5 minutes or so, you will begin to see bubbles popping up on the surface of the MeOH solution. At first they will be tiny, like champagne bubbles. Then after a few minutes you will see them joined by larger bubbles closer to the size of those seen in boiling water. It is around this same time that the appearance of the aluminum will change from its normal shiny silver color and start to take on a dull gray look, accompanied by a gray cloudy look that begins forming in the MeOH. This is the magic moment when you want to begin dripping in your MDP-2-P/MeNO2/MeOH mixture. Set a drip rate of approximately 2 drops per second at this point and no faster. You can speed it up a bit later to accelerate the reaction if desired.
9. Place about 3 lbs ice into your bucket. When you can feel exothermic warmth begin by feeling the outside of the flask, quickly add about 2.5 liters water to the bucket (or an appropriate amount to make very ice-heavy ice water) and plug in the pump.
10. While monitoring the growing intensity of the bubbling amalgamation, turn on/off the stirring intermittently as you did earlier. This time it is to assure distribution of the added ketone/nitromethane in the reaction flask but also because the amalgamation seems to gain its vital momentum more effectively if given some significant blocks of time (meaning about 30 seconds at a time) in between "stirring bursts." When the reaction is clearly starting to get vigorous and hot, crank the stirring to 10 and leave it on.
NOTE: This is where you can take advantage of Mr. A's trial and error regarding this reaction's parameters. If you used the kind of foil specified, prepared it as specified, used no more than the specified 400mg HgCl2, and used a 2-liter and NOT a smaller flask, you can breathe easy knowing that the reaction is going to hum along nicely but will not get out of control, and will result in perfectly processed aluminum amalgam sludge. You may think that a 2-liter flask is oversized for this reaction, but that is precisely the point. The extra headroom in the glass provides a nice zone of "breathing room" for the reaction and facilitates good refluxing. I've seen this reaction get out of hand in a 1000mL flask, and it isn't pretty, believe me. Use the 2-liter.
11. As the reaction progresses only a few minutes after the addition was started, you will observe that the aluminum is breaking up fairly rapidly. This is good, as long as you have the ketone/nitro mixture dripping in at a good rate of about 2 drops per second. But be careful with the addition rate at this point, as a rate that is much faster than this could easily send the reaction into overdrive (not good). Your reflux should be unnervingly vigorous as the amalgamation really starts to pick up speed, with the MeOH dripping really fast down out of the condenser. I know it's hard to believe, but this is what you want, this is good. I'm telling you, LOTS of trial and error came before this writeup. Trust me. You will also see sludge already starting to settle at the bottom and forming a ring on the glass around the top surface of the spinning mess. The consistency will get thicker by the minute. Add more ice to your bucket as needed.
12. At this point you can sort of control the reaction rate by slowing down or speeding up the addition rate a bit. Of course the reaction is already barreling along, so you won't want to speed it up much. The concept here is that you want the addition of the ketone/nitromethane to be paced neck-and-neck, as it were, with the breakdown of the foil as it amalgamates and gets turned into sludge. In other words, you have to watch those two things and sort of adjust the addition so that they proceed at approximately the same rate. It's tricky, and imprecise, but with a little experience and intuition you'll get the hang of it. Sure, you could be lazy and just leave the addition at a steady 2 drops per second the whole time, but if the amalgamation peters out way before your addition is finished, and you find yourself adding your beautiful ketone to impotent sludge, don't cry to me. The addition should take about 40-45 minutes in total, and as it's finishing, the state of the aluminum should be about 95% broken down. In fact the reaction should by now (~45 minutes after addition was started) look like a really thick, steely-gray chowder with only minor small slivers of undissolved aluminum visible if any at all. You will probably even need to add an extra 20-30mL of MeOH down the condenser at this point (or before) to help it keep stirring effectively. This is no problem.
A note about color at this point is helpful too. Comparing successful reactions to failed ones, I have observed that there is a distinctive color to the mixture early on that indicates healthy amalgamation and foretells a successful run. At a point maybe 30 minutes or so post-addition, the reaction takes on a color that I would describe as being "light steely gray with blue overtones." It is a hard thing to describe shades of gray, but I will try. It is a light shade, akin to the color of common gray sweat pants, but like I say with a very slight suggestion of a blue hue in there as well. This is in contrast to what I saw in failures resulting from using too thick of aluminum and not enough HgCl2, where a dark metallic gray with definite green overtones (from unreacted ketone) was noted.
NOTE: Another point I would like to make about the timing of the addition against the breakdown of the aluminum is that Mr. A found that there was a definite "spike" curve to the amalgamation reaction which was easily observed by watching the reflux rate. That is to say, there is a peak that it builds up to and then comes down from. At this scale, and using the exact materials described herein, that buildup to peak and subsequent slowdown occurs over approximately 25 minutes or so---very fast. So at only about 20-25 minutes after you first started feeling the amalgamation heating up, it will have slowed to a reflux of about 2 drops per second, after having been at a peak with a reflux rate so furious it is a stream, not drops. At one hour and 15 minutes after you first started the addition, the reflux will have slowed to a very calm 1 drop per 2 seconds or so. Finally, when...
A) the reflux has slowed to almost no reflux at all
B) if you stop the stirring you do not see any small bubbles anymore
C) no "uneaten" aluminum is visible and the solution is a thick, uniform gray soup,
...the reaction has essentially finished. It will reach this state at about one hour 45 minutes to two hours after addition was started. Nevertheless, you will leave it stirring happily for a total of three hours after the addition was finished to assure that the reaction has run its full course and the conversions that you desire have had ample time to take place. In fact you should add a bit of external heat at the point where the addition has finished and the reflux slows down dramatically, because I’ve found that if one doesn’t, there might be a bit of aluminum that refuses to break down all the way which results in the later extraction being messier and much more of a hassle. One reason I bring this all up is that there has been lots of talk about how this reaction needs 8 hours or 24 hours or even 36 hours to run! But those time frames apply only in cases where much thicker aluminum is used, and/or in variations using methylamine and not nitromethane. Mr. A was never successful in using thicker aluminum, and doesn't want to be! Why would someone want to make a reaction take any more time than it needs? Beats me! I'm mystified! The approach illustrated in this writeup optimizes this reaction to finish in 3 hours 45 minutes from beginning to end, and it probably doesn't even need that much time.
13. If you chose to apply external heat, turn it off at about 30 minutes before the targeted finish time. Otherwise you will have to wait an extra 30 minutes (at least) for it to cool for the next steps.
14. When finish time has arrived, dismantle your setup, set aside your reaction flask, and make 750 mL of a 35% NaOH solution (750 mL H2O + 262.5g NaOH) and let it cool to room temp or below (safety glasses!).
15. Into a separatory funnel no smaller than 2000mL capacity, pour your beautiful gray reaction mixture, being very careful to KEEP THE STIRBAR FROM FALLING IN to the sep funnel and breaking it (that would be ugly). If your mixture is really thick, you may need to add small amounts of MeOH to thin it to a pourable consistency. This is perfectly fine. Wash the final residue out of the reaction flask with a few mLs of MeOH and add it to the funnel also.
16. Slowly pour the NaOH solution into the sep funnel (gloves and glasses! no excuses!). That's right, don't dump it in wholesale. Basifying should be a gentle process. If you bully those molecules they may decide they're being disrespected and choose not to cooperate. Adding the NaOH will cause the mixture to warm up a bit as the very last bits of the aluminum are dissolved, which is fine. Swirl it a couple times and give it about 10 minutes to cool down to something closer to ambient temperature. That yummy stinky methylamine smell tells you that the reaction was successful.
17. When the mixture in the sep funnel has cooled down, extract it once with 400mL toluene followed by once with 100mL toluene. These are the critical moments for your yield now, so you be sure to shake long and hard (at least 3 minutes) during these extractions (I don't have to tell you to vent do I?!). The toluene/product layer will of course be on top since toluene floats on water. Also, be sure to give the separations ample time to happen (at least 15 minutes); it is easy to tell when it's okay to separate because the interface of small toluene bubbles finally resolves and you have a nice clean line between the layers. If you like, do as Mr. A does and finish off with a final small extraction of 50-60 mL toluene just to get the last of the stuff.
NOTE: Your extractions will contain a tiny amount of the base/metal/garbage from the bottom layer; this is inevitable but easily worked around in this way: when you have collected your combined toluene/product extractions in a bottle, chill that bottle in the freezer for 30 minutes or so. When cold, the garbage gets a lot less mobile and it is easy to decant the toluene away from it. Just be vigilant while pouring the last 50 mL or so and avoid letting that glob of crap rejoin the toluene. Yeah, you will lose the very last 2 or 3 mL, but that's life. Alternatively, you could filter it through a paper towel, but you will still lose the same amount when the towel absorbs it. Just get over it and move on!
18. If you haven't already, drain the garbage layer out of your sep funnel into a storage bottle or something, and wash the garbage residue out your sep funnel with water.
19. Wash the toluene/product 4 times (or more) in your sep funnel with 400 or 500mL H2O and a final time with 500mL of a saturated NaCl solution to remove any traces of solvated HgCl2.
20. Dry your toluene/product solution with 30g of your favorite drying agent (MgSO4 recommended) in an acetone-cleaned, heat-dried bottle for no less than 45 minutes (Mr. A is superstitious so he lets it sit for an hour). Shake it a few times during this period.
21. Filter the solution and gas it with that good ol' HCl bubbler setup. Be smart and use just enough muriatic (31% HCl) to wet the salt but not enough to make any puddles, and put a wad of drying agent wrapped in tissue paper in line somehow between the reaction flask and the tube leading to your pipette end. Weep with joy as a bumper crop of white precipitate crashes out of solution.
Expected yield: approximately 20-21.5g raw odoriferous product that will purify via careful recrystallization to 17-18g of beautiful snow-white MDMA! Ain't life grand?
~~~"There's a methyl to my madness"~~~
(Newbee)
06-05-00 15:17
No 14099
Yes, it's used in drag racing...Nitromethane.
Or buy it from a chem supplier, since you can get it already extremely pure for pretty cheap, and less hassle.
(Newbee)
06-06-00 10:49
No 14447
Hey MM have you tried this reaction with racing nitromethane?
What grades does it come in and can you just add more racing nitro and less methanol?
Thank-you
THE BUDWIZARD
(Hive Bee)
06-06-00 23:32
No 14733
Like MM's post says, just find 20 mL MeNO2 of 99+% purity. (Whatever you may find it) Just follow the procedure as written and you'll be fine.
(Newbee)
06-07-00 07:29
No 14916
Sit down in the front, I can't see the stage!
THE BUDWIZARD
(Stranger)
06-07-00 19:27
No 15159
(Hive Bee)
06-08-00 01:05
No 15275
(Newbee)
06-08-00 06:02
No 15428
Hmm, I wonder if nitric acid + methanol...nope!
(Stranger)
06-09-00 20:43
No 16100
I couldnt follow this part:
8. Extract water layer with a final small amount of DCM.
9. Add this final small DCM extraction to the combined oil/DCM solution from step 8.
Maybe Im just being stupid. Youre extracting the ketone from the aquious layer with DCM (bottom layer). After the 3rd DCM wash the organic layer is removed and the aqueous layer remains, sitting there in the sep funnel.
Now, do I add a "final small amount" of dcm to this aqueous layer, shake and then drain the new tiny organic layer from the sep funnel? Then I combine it with the oil/dcm mixture from step 8, right? But this is the oil/dcm mixture from step 8!
I know Im just flawed in my reading, but can someone please straighten me out. Im worried I dont have what it takes!!
everyone says she has good taste, so I would love to nibble on her ear- HoneySuckle
(Stranger)
06-14-00 20:16
No 17560
Any problem with substituing Xylene in place of Tolulene?
(Newbee)
07-23-00 05:53
No 32094
So is rhodium going to put this up on his page or what? The amination is up there, but i dont think the oxidation is.
with enough soap, one could blow up just about anything- HoneySuckle
(Hive Bee)
07-23-00 23:03
No 32417
Its under : "Benzoquinone wacker with methanol solvent"
(Stranger)
08-02-00 20:56
No 36037
Hey Methyl>Just wanted to give thanks for the nitro route. SWIM has had unstoppable successes.Varying in the 60-80% yield range,now usually 80. Unbelievable contribution IMO.
(Hive Bee)
08-04-00 07:37
No 36593
Anyone have comments on useing Hg2Cl2? Did it work and what were the yeilds, ect.
"Vote Libertarian"
(Stranger)
08-05-00 07:13
No 36998
MM you are a legend , both of these procedures are unfuckable! They are remarkably easy and consistant , perfect for the small scale producer. I salute you!!!!!
(Stranger)
08-06-00 17:08
No 37444
watwak and baalchemist, I thank you for your kind words but honestly, I just rewrote things that were already in existence, throwing in a little bit of neurotic detail. In no way am I an innovator in this area. I simply know how to write with clarity.
But hell, if you say I'm a legend, then I'm a legend!! AHH ha ha ha ha!! Top o the world, ma!! Drug kingpin!! Yee ha!
~~~"There's a methyl to my madness"~~~
(Newbee)
08-07-00 18:00
No 37937
Hi MM, Your nitro method uses 25ml md-p2p what amount would you recomend for p2p ?
Seagulls do not wear sandals
(Newbee)
08-08-00 00:44
No 38125
Wouldn't have a clue Harry, never seen the stuff before and don't like what it makes.
~~~"There's a methyl to my madness"~~~
(Newbee)
08-09-00 08:19
No 38618
Fine MM, I respect your views.
Seagulls do not wear sandals
(Stranger)
08-09-00 18:20
No 38787
Are there any alternative solvents which may be used for the MeNo2 amalgamation? Perhaps IPA or DMF?
(Hive Bee)
08-09-00 21:26
No 38829
Check Rhodiums page under "Osmium's variation of the Al/Hg reductive amination of MDP2P" concerning EtOH and IPA.
(Hive Bee)
08-11-00 17:34
No 39573
mm,
great write up! drx has done the benzo with formamide but not with meoh. 1 question is the heating absolutely necessary when the reaction is 80% complete? swim thought that this was an exothermic reaction after 4 1/2 hours, does the meoh use over mdf or formamide make for the heat requirement or could dr x just let it go for an hour or two more?
thanks in advance!
frost
(Hive Bee)
09-06-00 15:20
No 49428
Can the Toluene/product layer be extracted using aqueous HCL and dh20, like instead of gassing? You know , like in methead's speed synth? Or is that route only OK for Speed? And does gassing give you better yields than extracting with aqueous HCL & dh2o?
!
(Stranger)
04-05-01 13:02
No 182427
sup,
In step #19 of the amination, u state the following:
19. Wash the toluene/product 4 times (or more) in your sep funnel with 400 or 500mL H2O and a final time with 500mL of a saturated NaCl solution to remove any traces of solvated HgCl2.
Can you bee a little more specific about the "saturated NaCl solution? Maybe how you made it, %'s, etc.
Also, after the "spike" you say that a little heat can be added but stopped 30 mins prior to finishing. How much heat?
I'm out.
(Stranger)
04-05-01 13:24
No 182433
Thanx MadMax,
That makes perfect sense. Any suggestions on locale of NaCl?
Any precautions that need to be taken?
Later
(Hive Bee)
04-05-01 13:55
No 182444
NaCl, also known as sodium chloride, can only be found in the center of black holes. It has unique anti-gravimetric tachyonic wavelet properties that can cause inverse subspace distortions, so be sure to wear saftey glasses.
marijuana is the flame, heroin is the fuse, LSD is the bomb!
(Stranger)
04-05-01 14:38
No 182450
Gee thanx yellowjacket,
alot of useful info could have been spewed by you in those 3-4 sentences but NO....gotta be a smartass huh? Hey, i'm just a squirrel tryin to get a nut, that's all. At least MadMax knows what time it is.
Later,
(Hive Bee)
04-05-01 14:52
No 182453
But yellowjacket, once you get the NaCl in the center of the blackhole, how are you supposed to get back to your lab? Or for that matter, back to your kitchen table to put some on your chicken or something. I guess I should bring my plasma spraying transmogrifier so I can warp back to planet "shoot me in the head if someone asks me what NaCl is." Just a thought, though, I really have no idea how to get back with the salt. :(
I like to cook!
(Stranger)
04-05-01 16:46
No 182486
BWahahahahahhah! someone give that guy a nobel prize for figuring out how to navigate singularities. That's assuming he can make it back to this saltless planet.
(Hive Bee)
04-05-01 23:06
No 182545
jinx:
yea...no additives. In my experience, pickling salts usually has no additives.
And add enough heat so that the meoh mixture is mildly refluxing when the addition is 80% finished. My mother has done it with really no heat, and the only drawback is a horrible mess during the extractions. Lots of al will stay un-broken down (if thats a word) if you do not reflux (use heat).
Good Luck!
If some of us were not so far ahead, the rest of you would not be so far behind!
(Hive Bee)
04-06-01 01:38
No 182562
When you add the methanol + nitro to the ketone (preaddn) is the soln almost colorless? New ketone was aqua marine rather than greenish yellow. It almost had a blue tone to it in addn to the green.
Upon basifying does the soln turn yellow/green?
The last time did this reaction failed (same thing happened as did to noj; used photostore PdCl2 suspected problem)
This time using Laboratory grade PdCl2 so hope this fixes it.
Obviously am a bit skeptical since never had success. Will post results though in a few hours.
(Stranger)
04-06-01 02:03
No 182566
Just trying to make sure I'm clear on this one. Someone else has asked this already but as I am still in my reading and learning phase, I need to be sure I understand.
......
7. Extract flooded mixture with 3 portions of DCM (1 x 500mL, 1 x 250mL, 1 x 100mL) in a large separatory funnel. The desired raw product, MDP-2-P (“ketone”), migrates into the DCM as an oil. Separate the DCM/ketone layers and combine them.
(Note: when you first hit it with the DCM you will probably observe a bit of scum which will float on top of the water layer, which will work its way down during these three extractions to appear as a blob of spongy semi-solid interface. It’s actually very mobile and easy to work around; simply avoid allowing it into your DCM separations. The same thing will happen in your washes in steps 10, 11 and 12 below, but by then you will be quite the pro at working with it.)
8. Extract water layer with a final small amount of DCM.
9. Add this final small DCM extraction to the combined oil/DCM solution from step 8.
......
Step 8. How can you extract the water with DCM when DCM extracts oils. Should that be "extract with a final small amount of DCM" ? Whats this about the water layer ? As I understand it, presumably you could wash the water layer of all its ketone goodness with the DCM, but whats the point in keeping the washed water layer ? Why do we all of a sudden want some of the water layer ? Also on step 9, should that be corrected to "Add it to the combined extractions from Step 7" (and not 8) ?
please can someone clarify this for me.
muchas gracias
(Hive Bee)
04-06-01 09:47
No 182575
You are thinking too hard buddy. You are extracting stuff out of the water. it doesn't make any sense to extract water from an aqueous layer. and jinx/saltman, i am sorry for giving you some help before. If you have to ask these types of questions, you will hurt yourself in your lab. You are also going to waste quite a bit of your money. MDMA is a relatively simple synthesis. And for you weasil (sorry, nothing bad to say yet), was your ketone blue before addition. Blue ketone seems to be made when the sassy is not distilled properly. and after the almagation you basify and it turns yellow? wierd. Does your ketone smell like lemon lime kool aid with a hint of latex?
Information is Not Knowledge
(Hive Bee)
04-06-01 10:20
No 182581
Wusup, basically I doubted you dudes but you’re sheet backed up with decent references so I think that something else must be to blame. Basically someone had yielded methanolic Benzo yields of ketone. Threw the first one out because amalgamation was identical to what noj was complaining about. Anyway on the second lot of ketone trying to follow MM to the T cept using thicker foil. NXt day tried extracting with toluene but toluene is greenish/silver. Know you will say all ketone didn’t react but it was in the flask right from the start so wood af had nuff time. Serious problem aight. This didn’t clear after washing with water (starting to think fuck washing this shit). Noticed white crystalline mass between layers but this was excluded from extract. (Know what you are thinking but how can Xtals form if product ha not been gassed yet). After gassing and adding HCl no product is visible. WTF?. One time is bad enough but spending 2K I expect yield just like you wood. Sorry to report shit, but you would be feeling like me if you did same ting. If you saw mw do this now you would accept that could not have done wrong ting ya, represent. Either photo shop Benzo or NaOH drain cleaner to blame now. I have been through the pain shed my tears. But now my evil is purer than ever so I am ready to synth killer reaction. Will order 40% MeAm soln despite what u say, will do OS version. If Ketone is pure then expect KILLER yields, for real. No interference. Yes no fear, I am tragically saddened by this madness. Toluene was put in screw top bottle and 35% HCl was added. This was placed in Freezer and still no Xtals!. How many times did other guyz fail before success. If I kill someone for my pain then this shit will bee worth whilw, so that is my aim. Flatliners be'ach. By the way is there any way someone can extract eh goods from the water wahed aluminium mess. If so I would like to know.
(Stranger)
04-06-01 11:46
No 182597
sup,
Hey pric.... oops!(spric), there's no need to bee like that. Would you rather newbees ask no questions and make tons of assumptions on the threads that we read. Dude, bees ask questions, they learn to make honey.....not asking is how bees hurt themselves. I've asked some seemingly dumb questions i'm sure we all have , but only in the search for knowledge. I played pro ball for 6 yrs, chemistry was not top of the list in college (beer and bitches ranked alittle higher), so bare with me if some questions seem elementary. It's all the wonderful input and knowledge that i have gained at the Hive that keeps me coming back, obviously for you it's something different. Not all of us where born with the know-how from birth, some of us have to learn BY ASKING FUCKING QUESTIONS. besides, if it weren't for the better half telling me to get a hobby(hehehehe), this would've been avoided. I would prefer to watch my portfolio drop another $300,000 than to read one more post with an "expert" doggin on a newbee for asking a damn question!
Most everyone knows where the search engine is and how to use it, it's just that most of the shit is buried in a bunch of jibber-jabber, why do u think the same questions keep coming up? All you're doing by flaming fools is discouraging them from posting. That seems more dangerous than anything IMHO.
(Hive Bee)
04-06-01 11:49
No 182601
Weasil:
I have experienced blueish (or dark green) ketone before and have got to the end with fine results. As spric says, I think the weird color is a product of not distilling the safrole well enough. I know I told you this before, bro, but for me it was the sassafras. bad sassafras. And, from what I have been told, so was noj's. He got a little sample of REAL sassafras from a source who knew it was REAL from his own attempts and all of a sudden, his reaction worked. So, ask him. If you have the tone dude, even with semi-bad benzo, you should at least get some product. I have used dirt brown benzo and still got great results.
Also, in my experience, when the toulene is dis-colored and not foggy white...your fucked. Its bad tone, or not tone at all. I have experienced this many times. Your toulene should be foggy white even during the washes, up until you dry it with mag sulfate. After you filter the mag sulfate, toulene should be clear as day. (i don't know why, but it is, at least, in my experiences)
Of course, I am not sure if you have the same problem as I initially did (bad sassafras), but I'll tell you that it was the last fuckin thing I changed (success finally!), which really pissed me off because by that point I had wasted mega $$ and tons of chems. I thought it was this and that...and it was the sassafras. The al/hg is very forgiving so when you talk about bad benzo and pdcl2 or bad NaOH...I think you just trying to fix the wrong problems. Just for the fuck of it man, I would try a different batch of sassafras. But its up to you, of course.
Good Luck.
If some of us were not so far ahead, the rest of you would not be so far behind!
(Hive Bee)
04-06-01 11:51
No 182602
Chill kidd, you r new to this game. The hive is about pain. If you are not feeling pain yet then have not done uyet nearly enuff reasesrch. Comeback and ask questions when you have becone nasty.
(Stranger)
04-07-01 10:54
No 182697
right I'm fucking nasty. If I'm not missing something then why doesn't MM just say to do four extractions at Step 7 instead of saying do three, then to do another one again but telling to "extract the water layer". Remember I havn't seen a fucking RB flask yet so I'm getting this all straight in my head while I wait for the shit to come together.
later
(Hive Bee)
04-07-01 17:26
No 182794
I did not assume I was an expert. I failed at first too, and it makes you feel really pissed off. What I said is the fucking truth. When you are done with your frat party, you may realize that this shit can be physically dangerous. Even a 2L flask full of solvent can make quite a bonfire. Once you get sulfuric acid in your eye, I will bee willing to accept all of the shit you spew. It's like all of those cooks without any chemistry experience with those burn marks all over their body, or maybee you have never met any. When you ask a question that elementary, you set yourself up for the jokes. I've been flamed for fucking posting a zinc borohydride reduction that I never myself tried, so get used to it you salty dog.
And from one pric to another, good luck.
Oh yeah, if it was your benzo, that is that the benzo is complete shit, you will get about 5% of the expected yield. If you are worried about your NaOH, go to the hardware store and buy a bag of caustic soda for you septic tank, it is of decent purity and a 50lb bag costs thirty bucks.
Information is Not Knowledge
(Hive Bee / Eraser)
04-11-01 03:15
No 183426
Most of the time failures newbee failures are due to lack of comprehension of the functions of each step. Which is no surprise as most are not chemists. Thats why its important to understand everything 100% before going at it. Baal studied this shit for over a year before going at it, for personal & public safety. Success 1st time around, but couldnt crystallize shit for 6 mos. Ended up with a big damn jar of E-base, and a head full of frustration. Put chemistry away for 3 mos,studied,came back and crystallized that jar of base. Patience & persistance are ones best tools, if chemistry's your bag. Things are very relative with chemistry lack of knowledge=big economic losses
(Hive Bee)
04-11-01 07:28
No 183459
I swear all the guidelines have been followed though which really beats me...I'm mystified!
When did failure finally become success though? Did it take switching chemicals to something a little less over-the-counter or did you need to carefully revise you’re practical methods? Now that you are competent you can churn out the crystals what tips do you have for newbees? Does the initial investment repay itself or is that a debt that cannot be recovered? I know these questions will yield different answers from different bees but nearly all bees have failed on their first attempt regardless of their prep work. In foundation organic lab I follow the course handbook and I nearly always get crystals despite not doing nearly as much research into the synth as have done in the hive. This is what makes matters puzzling. Have not a clue where went wrong. If photoshit so crap why is it recommended?
This time post amalgation still orange (4th time). This time difference is it smells of ammonia!
(Hive Bee)
04-11-01 08:38
No 183483
Toluene extracted goodies from the mixture. During 1st water wash white crystals ppt in water layer thst float upwards into lower tolly layer. Think eh? Tolly still orangy. Must get to the bottom of this.
And did. Nothing but junk. Only crystals that have been formed here are NaCl.
(Hive Bee)
04-11-01 09:22
No 183498
I'm not sure i understand what u are saying here.
The crystals you are talking about fell out after gasing or after washing?
(Hive Bee)
04-11-01 10:09
No 183527
Yes, I don't understand this either. To be honest...I don't think anyone does [this is where you have a laugh at my expense]. Crystals ppt out during water wsa hof orange toluene. Water is yellow coloured? Guess this must have something to do with impurities.
(Hive Bee)
04-11-01 10:23
No 183530
Yes, this will stop when you start using pure ketone. Just throw away any precipitate during washing! It may contain Hg! Go on with the washes (some water, 1 or 2 conc NaCl). The toluene layer will never get colorless. Gas. If there are crystals, they will be red. Wash with lots of acetone or recrystalise with IPA/Acetone to get snow white crystals.
(Hive Bee)
04-13-01 23:28
No 184045
Excuse me, bro...Mr. Hydro, but the toulene certainly does get colorless, on my world, at least. Clear as the clearest water I have ever seen as a matter of fact.
Anyway, thats just in my experience.
You need an oil change. But, your car will probably die before you give it one.
If some of us were not so far ahead, the rest of you would not be so far behind!
(Hive Bee)
04-14-01 03:55
No 184074
Yes, in my world it will get clear too, given that you start out with reasonably pure ketone. Actually it will be pretty clear from the start.
IMO weasil is using dirty ketone and gets lots of organic shit. You cant wash that out with water. Still, there should be lots of good stuff in the toluene layer (if he did use ketone at all), the Al/Hg is pretty forgiving...
weasil: try dissolving the ketone in DCM, wash multiple times with water and Na2CO3 solution and distill again. Check the temperature.
(Hive Addict)
04-14-01 09:32
No 184110
(if he did use ketone at all)
Yes, often, when I see people complaining that their amination/gassing didn't produce any product, I wonder if they even had any ketone to start with. This is why I recommend the bisulphite test to verify that you possibly have a ketone.
Some people say; why bother with bisulfite, just aminate but bisulfite is easier than Al/Hg/Nitro especially for people who are working in a back room with almost no equipment or experience.
(Hive Bee)
04-14-01 11:12
No 184125
I can't understand why no ketone => good PdCl2 + Benzo and Safrole were used. MM's synth was followed to the key with the only modifications being the ommitting of the filtering and the first two sets of washes. Yeah, in hindsite should'nt have taken shortcuts. Collected fraction 20C+ what safrole came over at. Use of vigrex was necessary though so could'nt collect richest part of the fraction. So yeah impure ketone maybe, but is a bit of safrole enough to completely fuck things up this bad?
ACcidently added entire impure ketone to baking soda for bisuphite addn (have to run up and down three flights of stairs so shit just happens nomatter what). Will continue to do test and see what happens.
Dumped that ketone and am now phyched up to do a third batch overnight and am now distilling the last of my sassafras. OKay am pissed off about wasting hundreds in chems and hours of time but that is life. Am gonna follow MM with no compromises. I can do this shit without any paper infront of me I know it so well. Weasil is gonna die once he finds success.
(Hive Bee / Eraser)
04-14-01 14:02
No 184155
Over the years many bees have had the same problem with the wacker,theres no guarantee that it will produce ketone for reasons unknown. Toluene layer in these parts is always clear/colorless. If there is color(green/yellow), then an A/B is absolutely necessary to avoid the red oil BS(which is ketone/hcl mutant). After all your Al reacts, look at reactions overall color, if you see green/yellow toss some more Al in. This may help in some instances,but not all, again ketone purity plays a big part along with addition timing.
(Hive Bee)
04-14-01 14:46
No 184168
Weird, aint it? How some people can have success first time even with sloppy procedure, while others can do the reaction with the upmost care and fail. I would say this is something unique to clandestine chemistry and blame it on the chemicals themselves. Believe me I know all about acetone competing side reactions and the like so I am careful like one should be. Now this time will be attempting this at this level. If it does'nt work there will be no alternative than to buy from alternative sources.
(Hive Bee)
04-14-01 18:15
No 184194
Just a note if you want to mess with some sodium bisulfite, Any spa or pool place will sell you a pound or two of pH/alkalinity decreaser for a few bucks, which is 94% sodium bisulfite. REal easy way to get the qualitative yes or no. I think it is impossible to screw up an amalgamation with clean reagents. Shitty, shit shitty runs should still give you a few grams vitamin E. It will work one day, just wait, and you will get very excited, like a 5 year old kid on christmas eve.
good shit will blow the jam out your toes and make your boogers go south for the winter.
(Hive Addict)
04-14-01 18:23
No 184197
Any spa or pool place will sell you a pound or two of pH/alkalinity decreaser for a few bucks, which is 94% sodium bisulfite
Really? I would have guessed that it would be much more likely to be bisulfate than bisulfite.
(Hive Bee)
04-16-01 20:50
No 184606
oops, you know what I meant
good shit will blow the jam out your toes and make your boogers go south for the winter.
(Hive Bee)
04-17-01 05:02
No 184697
Well the first batch of ketone was extremly pale yellow when using photograde PdCl2. For this batch 3 washes with NaOH (10%) is recommended. Don't even bother filtering. I hate taking a long time on this because surely the ketone would decompose if one were to heat this for a prolonged amount of time. Hell, I even feel the need for a rotovapp olready. My 2nd hand Leybold Divac is certainly capable of doing it's job and is well respected compared to some of the junk sold at auctions. Check the blue tone in the Nasa. Someone I don't know said they got a lighter tone with the same colour on their 2nd run after discarding the forerun ~20mls prior to the fraction that was collected 20C+ the temp of the safrole.
(Stoni's sexual toy)
04-18-01 06:20
No 184953
Well in my opinion that colour is definitely yellow, even when distilled twice with vigreux columns.
I never experienced any other colour than that.
(Hive Bee)
04-18-01 14:56
No 185087
Tone, in its purest form, is certainly yellow. Although, in my mothers house, after watching her do benzo after benzo, I have seen colors ranging from yellow, to yellow with green undertones, and to a forest green color, which is the most recent. And this tone has worked absolutely fine with no problems.
If some of us were not so far ahead, the rest of you would not be so far behind!
(Stranger)
04-30-01 13:14
No 188172
Hi everyone, this is Dr Gonzo, I am making one of my twice-yearly appearances and after this post I'm afraid I have to go away again.
I have a couple updates regarding Methyl Man's amalgam and my photo essay that appears on Rhodium's page. First, as my client got better with this technique (and double-distilled the ketone), he brought his yields up to 21.0 g of the hydrochloride from 25.0 g of ketone. He maintains his opinion that for the MDMA-producing hobbyist (as opposed to the professional cook) the slightly less-than-perfect yield of the nitromethane Al/Hg is easily offset by the simplicity of the reaction, the unwatched reagents needed, and the good chance of success.
Also, my client asked a friend to do an NMR of some MDMA HCl he had produced with this method. The workup for this batch was a xylene extraction from the reaction mixture, double bicarbonate wash, double NaCl wash, double water wash, dry the approx. 800 mL xylene extraction with MgSO4, then carefully gas, filtering out precipitated crystals often and continuing to gas. Then a final xylene wash of the filtered crystals. Friend was extremely impressed with the purity and estimated it at being 99.5% or better. Any impurities were tiny, tiny peaks on the NMR spectrum, almost not there at all.
I'll probably email Rhodium and ask him to update the essay, and I'll see if I can get the NMR spectrum added too. Keep up the great work, everyone!