Author Topic: little yields on al/hg reductive amination in methanol+nitro and hcl gassing (Read 411 times)

sassa · « **on:** June 01, 2010, 07:18:30 PM »

Hi all there.I was having problems with the yields with this procedure.I follow exactly the methylman´s bible,no too much problems with the steps,but ever get 5-8 grams salt from 25 grams of ketone.I allways use lab grade chemicals,reflux set up,...all the neede,but seems there it´s a problem on a step that at this day i havn´t found yet.I hope you can tell me what you think.

I have 3-4 hypothesis about where i´m lossing so many product:

1.i distill the ketone with an lab pump that only makes come out the ketone from 190-210 ºC.i know it´s very high,but it´s the best vacuum source can get at this moment.i´m planing get a stronger vacumm pump shortly.The resulting ketone it´s correct on color,odor,and the yields it´s only little less from expected.it´s possible some of my distilled ketone it´s wrong because too high temperature?i think it isn´t but i have to question it.

2. when i´m in the toluene washes i never folow a order.Sometimes beging with water,others with bicarbonate,because information sources seems to not agree with the order.i usually start with water,then bicarbonate,then brine,...and IMPORTANT:always i see too much clouds on the water layers that don´t return to the toluene.in most cases the onterfaces never broke,with a toluene layer plenty ,in the worst cases, of bubles-emulsion.I,m really think my problem it´s here,my freebase it is losting here.
It´s possible that my solutions are not enough saturated???i take the amount from a practucal organic chemistry book:

320 gr Nacl on 1 litre H20.
85 gr bicarbonate on 1 litre H20:

It´s posibble the freebase it´s migrating to the aqueous layer because the not enough saturated solutions. i never distilled the toluene to see hoe much freebase it´s on it,so i can confirm the problem it´s here.

3.when i´m gassing i used the Sulfuric over Nacl wet with hcl and fractionating colums packed with Cacl:on the first chances,no crystals obtained because i supposed to much hcl on the toluene,so i saw clouds but quickly the clouds dissapear.supposed to a to low Ph.
Then,with more experience,i gas smart,only few seconds andand then little 10 second wait.repeated again...This method brings me crystals(more exactly puffy-dust mdma),but when i weight after the acetone wash,the weight it´s only 5-7 grams froms 25 grams ketone.

i usually recrystallize it on boiling methano.Not to purify..only to get really crystals:i disolve on minimunt amount of boiling methanol,and the let it evaporate at ambient temperature to get nice big orange-translucid mdma crystals.I have seen there are more strong on effect where taken than mdma dust direct from the gassing.

i wonder with the titrate method,but never get results.Tried 2 timesand never got crystals or dust.
i really wish to use the titrate method because it´s clean,easy and secure,..but seems not to work on my case.

Any suggestions will be very very very very usefull to me!!thank´s

Naf1 · « **Reply #1 on:** June 01, 2010, 08:33:09 PM »

I would suggest testing your MD-P2P (to make sure) with TLC before you proceed, you can substitute TLC plates for filter paper (Whatman is good). Once they are done you can develop them like so;

Quote

3,4-Methylenedioxyphenyl-2-propanone (MD-P2P)

Characterstics;

Viscous liquid with an anise-like odour.

Identification;

A. Marquis Test (Test 1)

1. Place a small drop of the suspeced material on a spot plate.
2. Add one drop of reagent 1a.
3. Add three drops of reagent 1b.
Result

Orange-Brown colour indicates the possible presence of 3,4-methylenedioxypheny-2-propanone (MD-P2P).

Similar or other colours may occur in the presence of other controlled and non-controlled drugs precursors.

B. Gallic Acid Test (Test 14)

1. Place one drop of the suspected material in a test tube.
2. Add one drop of reagent 14.
Result

Brown colour indicates the possible presence of 3,4-methylenedioxyphenyl-2-propanone (MD-P2P).

Remarks

Similar or other colors may occur in the presence of other controlled and non controlled drug precursors.

http://www.unodc.org/pdf/publications/st-nar-13-rev1.pdf

Marquis reagent can be bought freely at places like;
http://www.ez-test.com.au/
http://www.dancesafe.org/documents/druginfo/testingkits.php

also it is easy to make! Gallic acid is also easily acquired, but you only really need one of them. Add the color reagent of choice to a small spray bottle and spray onto your TLC plate to develop it this will quickly determine how pure the MD-P2P actually is.

But from reading your post it would seem all your reagents are all good, in which case the gassing would be my prime suspect. I direct you towards Gonzos write up from the rhodium archive;

Quote

"A standard NaCl/H2SO4 generator for HCl gas was set up, with a fractionating column packed with CaCl2 (Damp-Rid from Home Depot) as a drying tube. A gas dispersion tube with a porous glass disc was attached to the drying tube, and the H2SO4 was started dripping.

Gas began to come out of the dispersion tube, which I immersed in the toluene filtrate. Absolutely nothing had happened after several minutes and I was convinced I had totally fucked up. Then a wisp here and there of white material started to appear, and within 30 seconds there were giant clouds of puffy MDMA HCl cascading out of solution. I nearly shit my pants.

The solution was so cloudy that I couldn't tell if any more crystals were precipitating, so I decided to stop. The beaker was covered and put in the freezer for half an hour. When cold, it was filtered with vacuum in a Buchner, then dried on a mirror under a light bulb (for heat) and weighed. There was a total of 8.26 g.

Then I set up to gas the toluene again. And lo and behold there was another massive precipitation of crystals. The toluene was chilled and filtered and the filtrate dried, yielding another 4.72 g!

Set up to gas again... it just keeps on coming. I give the crystals some time to settle, and now there really doesn't seem to be any more coming out of solution. Chill, filter and dry. This time there was 6.61 g more!"

http://orgchembase.com/archive/Rhodium/chemistry/clandestine/gonzo/index.htm

So as you can see it can take a while in certain circumstances, several minutes of gassing before anything at all happened.

"i wonder with the titrate method,but never get results.Tried 2 timesand never got crystals or dust.
i really wish to use the titrate method because it´s clean,easy and secure,..but seems not to work on my case."

The titrate method is excellent to see exactly how much you have in there, but I dont like the sounds of titrate method! Which would indicate a neutral solution is the endpoint, whereas you want to treat it with an acidic solution which lowers the pH and protonates your product resulting in an ionic bond; a salt(so acidify would be a more appropriate term to use). To do that you make a 10% HCl solution with water adding that to the toluene in 100ml portions, and stir vigorously for several minutes then separate and add another fresh portion, and start evaporating the 10% HCl solutions to recover your salt. It takes a long time to evaporate but you will know for future exactly how much you should pull from that gassing.

btw; Washing the toluene is irrelevant whether the bicarb goes first, or plain water (does not matter).

sassa · « **Reply #2 on:** June 01, 2010, 10:55:00 PM »

thank´s a lot Naf1 for the quickly answer.
I have made time ago the markis with sulfuric and formaldehide to test my first product.Totally black in 2 seconds.The salt i ´m getting it´s very pure (i want toi believe.)
   Testing the ketone it´s a good idea(more work...),but like i said the odor,color,smell, seems to be ok to me.Really probably not the best purity of ketone ,but i asume it would to be good,because on my first small batches(4 gr ketone), i have got the expected for a novice (3 gr. salt).The problems come when went o to bigger batches.
   Really ,i think too ,the problem it´s on the gassing step.I know very well,almost memorized,the articule you have post from Gonzo.In fact,i think was found that on Rhodium ,and the day after,begins to look after all i needed.Read that article,saw that pictures,...put me for real on the way to go.i thought...man...it´s real possible!.
   i´m now gassing with Hcl over Cacl,and putting a little wrap with calcium chloride before the gas out-let.
the problem it´s:
   how to gas?? ...on the surface of the toluene....on the bottom....moving the pasteur pipette on circles,let the pipette stay fixed,..i have saw that these parametres affected the way and the time when the clouds and the crystals begins to apear..
   Many times,i end the gassing procces with normal puffy product,sufficient for me but not the expected yields from 25 gr ketone.
But like i said,on 4 gr ketone batches the results are good.,.But many times ended with 500 ml of a strong acid toulene.i tested PH several times when gassing,but seems to stay on PH 8-6 a good time,but in moment go to 3-2 ,with me sitting on the chair like a stupid thinking:i´m fucked again,all the work of today spent.I´ve read about letting the toluene stay away to get the ph up,but again,and after too many hours,with ph 7,the missing salt doesn´t precipitate.
   Several times tried to recover the frebase from the acid toluene...thinking sometimes there was water too on the solution and then the crystals be not able to precipitate.Boiled the toluene completely ,and only see few drops of brown paste-liquid(freebase???)
on the bottom.
   I was thinking too why people took the work of filtering the result of the amination with alumminium to get the solution clean,then evaporate methanol(or isopropanol),..etc...make the A/B extraction,...etc... and then,... comes Methylman´s saying you can hit it directly with toluene to get the mdma freebase of the viscous solution.
I always thought it was very extrange nobody discovered that before Methyl´s man...It´s possible to be true no freebase distillation needed, but no A/B extraction seemed too much easy and beatifull to be true.IN fact,...really the Methyl´s methods works "right from the text".An 20 ml excesive impure freebase it´s able to crystallize totally?it´s strange...
   All i was looking for it´s for a secure crystalization method.No mater how strange or complicate,only a method that works on most batches.
And sure,on my next Al/Hg nitro ,i´m going to make the work of filtering the sluge across celite powder,and get the mdma freebase by then do the A/B extraction.With the freebase on my hands,i can assay diferent crystallization methods with small amounts and see what works better before try bigger batches.
I´m tired of losting whole batches with the dude on what the hell the problem resides??

   i need to work hardly!.read you this days again.Thank,s a lot guys.

Naf1 · « **Reply #3 on:** June 01, 2010, 11:59:33 PM »

If you were to use normal filter paper to do TLC on a small sample the Marquis will color for the by products also. So you can determine purity by seeing how many spots appear, and what proportions they are in. Then you can see if that part is good or not, MD-P2P is strong smelling and will overpower anything else so even at 50% conc the solution will smell only of MD-P2P.

You bubble the gas in from the bottom in a gentle stirring motion, and the bubbles rise to the top.

"Several times tried to recover the frebase from the acid toluene...thinking sometimes there was water too on the solution and then the crystals can not precipitate.Boil the toluene completely a only see few drops of brown paste-liquids(freebase???)"

Ohh that sounds unfortunately correct if you mean after gassing you tried to collect it, as if there is any water present it will scorch your product. If that is the case treating the toluene with 10% HCl instead of gassing should be done first to determine what yield is actually in there. Then can be gassed in later runs knowing how much you need to collect.

drone1240 · « **Reply #4 on:** June 02, 2010, 12:08:09 AM »

Quote from: sassa on June 01, 2010, 07:18:30 PM

Any suggestions will be very very very very usefull to me!!thank´s

Salutos y bienvenidos Sassa! Me gusta te conozo. Glad you like the site. If you scroll down on the main topics section "Drug synth and extcract" there is a thread named freebase crystallization. It is a good read from a number of folk and IMHO you will find it interesting to say the lease.

http://127.0.0.1/talk/index.php/topic,875.0.html

sassa · « **Reply #5 on:** June 02, 2010, 05:25:41 AM »

i have spent all night reading

i´m tired but plenty of good news for my holidays

   One thing Naf1:i don´t know if i´m understanding you about what you say.

"Ohh that sounds unfortunately correct if you mean after gassing you tried to collect it, as if there is any water present it will scorch your product. If that is the case treating the toluene with 10% HCl instead of gassing should be done first to determine what yield is actually in there. Then can be gassed in later runs knowing how much you need to collect."

   Sorry about my english.Here on Earth it´s not usual people talk well on english...on no language almost...
  i understand that like...when i have the toluene washed...i dry it(or seems not to be neccesary with this method??),...then i swirl it with 100 ml 10% hcl...so then...the mdma will go into the water layer(not on crystals form of course)...then take this water layer and evaporate it completly to get the crystals,...and repeat several times??? this is what are you trying to explain to me?.....
   Sorry,i know i sound like a Mexican De Niro....

   If a have got the correct meaning of your tecnique,...i think it´s way better than gassing to get the crystalls.
Please confirm that... to try it on my next visit to the white room.

   I have been reading long this night the crystallization post.
   Seems to be the way to go really.
   I really thinking now that my problem it´s on bad dried toulene(1 hour over MgSo4) plus water going into the solution on the end of the gassing.This explains the quickly lost of crystals when it was allready formed.

   I´m going to sleep now a little.

   PD:like i have read on a post,...to me...looking at crystals forming or cascading from a soltion...it´s a very "sexy" thing.
   Sincerelly,gratefull of see more people like me exist!

Naf1 · « **Reply #6 on:** June 02, 2010, 10:26:00 PM »

Dont worry about your english, you are not the only non-native english speaker here. And it is not that bad anyway...

"i understand that like...when i have the toluene washed...i dry it(or seems not to be neccesary with this method??),...then i swirl it with 100 ml 10% hcl...so then...the mdma will go into the water layer(not on crystals form of course)...then take this water layer and evaporate it completly to get the crystals,...and repeat several times??? this is what are you trying to explain to me?....."

Thats the right technique you dont have to worry about drying the toluene as you stated, you will actually see the MDMA go into the 10% HCl ; 90% water layer as clear streaks. Obviously it is going to take some time to evaporate that aqueous solution. But it is a good way to see exactly how much you should be getting, also if you plan to put the water with the goods in it on a hotplate and heat to 50-60*C and leave it to evaporate overnight or whatever. You may get some more scorching by heating it to too high a temperature in solution in the presence of 10% HCl which as it evaporates away becomes stronger conc and hotter(I have scorched at around 60-70*C in a strong 10-15% HCl, as the solution evaporates about half of the acid would be around 25% and as there is less water it will get hotter on the hotplate so ends up like 30% at 80*C), so if you are going to use fairly strong heat. Adding some bi-carb (sodium bicarbonate) will make sure it does not scorch by lowering the concentration of HCl available (you would not want to exceed pH 6 with the bi-carb). Any base will do but bi-carb is very gentle, and as you said you repeat several times until no more salt forms (about 3 or 4 pulls). The first couple of pulls will have the biggest yield so you can repeat as many times as want and just leave to evaporate at room temperature, as the first couple can be heated and should keep you busy while the others evaporate(you only really need to do this procedure once, as when you have done it you will then know exactly how much 10% HCl you will need in future and wont need to do several pulls and can just add it all at once.) What I have said makes sense if you think about how HCl gas burns MDMA if the solvent is wet, for example; using dry HCl into dry solvent the time the HCl ions and MDMA have in contact is very minimal. As soon as the first HCl gets near a molecule of free MDMA it reacts very quickly, as the salt forming reaction (protonation of the nitrogen, forming an ionic bond) is much more energetically favorable than any other reaction between MDMA free base and HCl so will happen quickly and specifically. By obviously transferring a proton to the basic nitrogen producing a HCl salt that has nowhere to go so drops out of solution where it waits to be filtered out. Whereas with wet solvent and partially wet gas, the free MDMA still reacts with the first HCl it bumps into and forms a salt but then dissolves into the water present. That water will contain a very high concentration of HCl as it will dissolve the gas also, the the MDMA salt is then exposed to very high concentration of excess HCl ions in solution with it which unlike the first molecule of HCl where protonation is favored, now HCl ions are available to react elsewhere via less favorable paths in very high conc. HCl (effectively burning the molecule, which is the same effect as heating too hard with 10-15% HCl). Also make sure you do neutralize with some sort of base at least a little, as when you evaporate 10% HCl it produces small to moderate amounts of HCl gas and in a small room is enough to start corroding metal, and burn your chest, eyes and throat ect. not nice.

Naf1 · « **Reply #7 on:** June 03, 2010, 08:57:26 AM »

The bi-carb was not the best idea, as NaCl will form. Ammonia would be good. (sorry bad day)......

sassa · « **Reply #8 on:** June 03, 2010, 10:51:27 AM »

thank´s for all Naf1,you are a "bright star" on the darkness

I´m not a hurry man,so i will let evaporate the water at ambiente temperature to assure no hcl scorching anything of the goods.
i will post with my results.
I will test of course like you said the ketone.I usually discart the first ml. of the distillation coming over until the liquid comes totally green-yellow to confirm no-little isosafrole it´s there.
Great method extend the product on a filter paper and spray with the markis.Really a very good method to estime impurities and how much.i will post with results on that too.
At this time i´m running out of ketone,so need to go again with the Benzo-wacker.so will take days to see the results.
Thank´s a lot again.Like said,...i´m felt at home since the beginning

marakov · « **Reply #9 on:** June 04, 2010, 01:10:56 AM »

Quote from: sassa on June 01, 2010, 07:18:30 PM

Hi all there.I was having problems with the yields with this procedure.I follow exactly the methylman´s bible,no too much problems with the steps,but ever get 5-8 grams salt from 25 grams of ketone.I allways use lab grade chemicals,reflux set up,...all the neede,but seems there it´s a problem on a step that at this day i havn´t found yet.I hope you can tell me what you think.

I have 3-4 hypothesis about where i´m lossing so many product:

1.i distill the ketone with an lab pump that only makes come out the ketone from 190-210 ºC.i know it´s very high,but it´s the best vacuum source can get at this moment.i´m planing get a stronger vacumm pump shortly.The resulting ketone it´s correct on color,odor,and the yields it´s only little less from expected.it´s possible some of my distilled ketone it´s wrong because too high temperature?i think it isn´t but i have to question it.

2. when i´m in the toluene washes i never folow a order.Sometimes beging with water,others with bicarbonate,because information sources seems to not agree with the order.i usually start with water,then bicarbonate,then brine,...and IMPORTANT:always i see too much clouds on the water layers that don´t return to the toluene.in most cases the onterfaces never broke,with a toluene layer plenty ,in the worst cases, of bubles-emulsion.I,m really think my problem it´s here,my freebase it is losting here.
It´s possible that my solutions are not enough saturated???i take the amount from a practucal organic chemistry book:

320 gr Nacl on 1 litre H20.
85 gr bicarbonate on 1 litre H20:

It´s posibble the freebase it´s migrating to the aqueous layer because the not enough saturated solutions. i never distilled the toluene to see hoe much freebase it´s on it,so i can confirm the problem it´s here.

3.when i´m gassing i used the Sulfuric over Nacl wet with hcl and fractionating colums packed with Cacl:on the first chances,no crystals obtained because i supposed to much hcl on the toluene,so i saw clouds but quickly the clouds dissapear.supposed to a to low Ph.
Then,with more experience,i gas smart,only few seconds andand then little 10 second wait.repeated again...This method brings me crystals(more exactly puffy-dust mdma),but when i weight after the acetone wash,the weight it´s only 5-7 grams froms 25 grams ketone.

i usually recrystallize it on boiling methano.Not to purify..only to get really crystals:i disolve on minimunt amount of boiling methanol,and the let it evaporate at ambient temperature to get nice big orange-translucid mdma crystals.I have seen there are more strong on effect where taken than mdma dust direct from the gassing.

i wonder with the titrate method,but never get results.Tried 2 timesand never got crystals or dust.
i really wish to use the titrate method because it´s clean,easy and secure,..but seems not to work on my case.

Any suggestions will be very very very very usefull to me!!thank´s

1) You are polymerising the ketone due to stress from high heat and not low enough vacuum. Use NaCl at appropriate time to drag out ketone.
2) This is wrong. Read Rhodium's Archive to see how it should be done. Memorise it. All have.
I have and I don't have anything to do with reductive aminations at present time.
I am not being rude but I am trying to help. I must stop now and others can continue from where I left off. I apologise.

NeilPatrickHarris · « **Reply #10 on:** June 06, 2010, 05:56:53 AM »

i've read that one shouldn't let the ketone exceed 180C so definitely get a stronger vac or check for leaks

the problem is not your h2o washes

maybe next time do the reaction, do the workup and washes, the vac distill the freebase (get a stronger vac) that way you can have a look at the isolated oils that come over in different fractions. how much is unreacted ketone? how much is freebase? that way you know exactly where it's going. now if you vac distill and get only a small amount of unreacted ketone and small amount of freebase then you know you're losing a good bit of it somewhere in your work-up (extractions and washes)

sassa · « **Reply #11 on:** June 23, 2010, 12:16:23 AM »

Proved the extractions with 10%HCL and evaporate water and the yields were the expected(not with nitromethane,with methylamine directly).
Seems 99% the problem was on the crystallization with Gassing.I was scorching the goods at the final of the gassing run,problably with some little water involved.Seems necesary to take care about to get a TOTAL DRY hcl gas.I was using HCL over CaCl.Supossed to be dry directly from the flask

Now works fine and with the exected results.The ketone seems to be not a problem too.Maked more with same method,same temperatures,...and yielding the correct product and the expected yields.
.TAkes 2 days

,but worked really well and easy!.I saw and ventilator near the water makes things way better than put the water on 40ªC.With strong air evaporates really quickly and seems the movement not affect to crystal formation(was afraid about that).The crystals were like the ones from Re-crystalization on methanol:Good enough little shards.And directly fom the toluene.
Of course it´s not the purest product.but workd fine....

Naf1 · « **Reply #12 on:** June 23, 2010, 12:31:56 AM »

Just another example, of the conditions having to be very dry when gassing. Otherwise the little bit of water causes big problems, whereas a dilute aqueous solution will do much less damage.

If you dont think the conditions are completely dry, there are many other techniques to use. A couple being;

A simple and convenient way of converting freebase material to the hydrochloride
Quantum Dude
http://127.0.0.1/talk/index.php/topic,713.0.html

or as previously mentioned by Drone

Crystals for dummies
Locked (DS)
http://127.0.0.1/talk/index.php/topic,875.0.html

Good stuff sassa!

sassa · « **Reply #13 on:** June 29, 2010, 09:47:26 PM »

Hi all!
I have a few questions that are directed specially to Naf1

,(others are wellcome of course) due to the fact that his advices have been of great help to me, with the result of incredible increase in my performances and efficiency of the process about AL/HG reductive amination and post crystallization.
Like said,i´m crystallizing now with the 10% hcl extraction and evaporation with ventilator.Rude,but to me,it´s the easiest and most secure method i found at this moment to crystallize,and have the dude about why it isn´t used by most of the people.Like said,only put the hcl+mdma solution on a big crystal pan,put the ventilator near,...and 2 days after ...voila!Little pink-brown shards.
But i supose that there will have to be any inconvenient with this tecnique.My questions are about that an more:
1. Is the final product really good to consume after the acetone washes?i was afraid some water soluble nasty things can go on little amounts and fix over the mdma when it is dried?posible some residual methylamine ? i have had to make like 5 washes with water and 1 with brine to take of any traces of methylamine smell coming from the toluene I consume my product and don´t want to eat nothing but mdma.Really have done it yet

.No problem.
2. i have noticed diferences about odor from the final product respect the recovered by gassing:Recovered by gassing,the product smells well to raw sasafras-safrol.After the acetone washes the smell it´s way less but it´s there.With water evaporation,absoluty no smell comes,but the product it´s a little more brown(talking about crystal form no puffy) and with a very little stink to hcl.That was the first time,when i heated the pan to something about 50ºC.I´m evaporation now my finall batch(a big one

),i will only use strong air to evaporate.Supose to reduce that little stink and get not too brown finall product.
What do you think it´s the best way to go after the salt gets hard?i´m now washing with acetone two times only.No recrystallization.Do you think it´s necesary with this tecnique?
3. i was afraid about mercury and methylamine contamination

.Made 5 washes with big amounts of water to assure get ride of any trace on that nasty mercury.POsible to contain amounts because i´m working with the water layer and not the toluene layer?

4. If i want to recover the freebase from the toluene to prove other crystallizations methods,can i distill of all the toluene after water washes and use that freebase as is,or need to make an A/B extration?Really would be interesting to me get the product on the freebase form to experiment.Need to said that i make the AL/Hg for 5 hours,the basify with Naoh and the extract with toulene,and finally wash water 4-5X and saturated NAcl once.

5. About neutralizing the hcl+mdma solution before evaporating,you said to use amonia(posible use commercial cleaning Amonia 5-10 % solution to make that?don´t worry about any salt precipited?.Sorry about my chemistry knowlegment(i´m from the biological world),

I know are lots of questions...but from the work come gradually more and more to me.I´m really now very at home with the tecnique and only need to experiment more with crystals!

Thank´s for all and allways it´s a pleassure to make this site the first internet visit of the day to learn more and more....and more.BYE!!

Naf1 · « **Reply #14 on:** June 30, 2010, 05:57:20 AM »

Quote

Thank´s for all and allways it´s a pleassure to make this site the first internet visit of the day to learn more and more....and more.

I am glad you found this site also, it is a pleasure to have good members!

Quote

put the ventilator near,...and 2 days after ...voila!Little pink-brown shards.

You ideally want all white, the brown would indicate (to me personally) that when the solution was evaporating it either got too hot or the conc of the hcl got to high. You also indicated this was the case "Supose to reduce that little stink and get not too brown finall product." so yield is suffering the browner it gets! A solution would be to drop down to maybe 6-8% HCl this will mean you need to use even more acid solution (so will take longer to evaporate). I also use this method as it avoids the use of nasty HCl gas, and is fine unless you are in a hurry.

Quote

If i want to recover the freebase from the toluene to prove other crystallizations methods

I hope you choose a more gentle ion to make the salt with, this will be a great test. For example tartaric acid and citric acid solutions are very gentle and still form salts in the same way. An acidic solution is used to treat the freebase in toluene.

Questions;

1.
Quote
posible some residual methylamine

No! once you base the solution to extract into toluene, any methylamine present will end up straight up your nostrils! It will gas off straight away. The pink color worries me moreso, recrystallization will remove that.
2.
Quote
"i have noticed diferences about odor from the final product respect the recovered by gassing:Recovered by gassing,the product smells well to raw sasafras-safrol.After the acetone washes the smell it´s way less but it´s there.With water evaporation,absoluty no smell comes,but the product it´s a little more brown(talking about crystal form no puffy) and with a very little stink to hcl.That was the first time,when i heated the pan to something about 50ºC.I´m evaporation now my finall batch(a big one Wink),i will only use strong air to evaporate.Supose to reduce that little stink and get not too brown finall product."

Yes we established you where 'burning' the MDMA when gassing with too much moisture present, the products of this degradation where most probably safrole or similar type compounds. Then when evaporating the yields are much higher and the smell of those products the super high conc acid causes are not there! When gassing if a little amount of water is present it absorbs the HCl gas until it is a very high concentration, then if this dissolves the salt.......damage happens! When evaporating the concentration is controlled, but obviously a little scorching is taking place leaving a slightly brown product. Which means yield can go up again! using a less concentrated acid! And no brown should result!
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i was afraid about mercury and methylamine contamination

GOOD! But like you were doing, washing the toluene extract with plenty of water. And making sure you give it vigorous stirring will remove the mercury compounds present. The MDMA will not bring any over with it!

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If i want to recover the freebase from the toluene to prove other crystallizations methods,can i distill of all the toluene after water washes and use that freebase as is,or need to make an A/B extration?Really would be interesting to me get the product on the freebase form to experiment.Need to said that i make the AL/Hg for 5 hours,the basify with Naoh and the extract with toulene,and finally wash water 4-5X and saturated NAcl once.

Yes, you can reduce the toluene like you said which will leave an oil. A quicker way would be to use the 10% HCl to extract it after washing with water. Then base the HCl extract with NaOH, after the fizzing stops when adding it. Oil beads (hopefully golden, but probably red/pink) will start forming on the bottom and get bigger until their own phase forms! You can just carefully decant the water off the top, then add more (washing it) then decant again and fill up again ect. Then decant the water and either separate the phases or add an acidic solution to make the salt (or whatever you want with your free base).

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About neutralizing the hcl+mdma solution before evaporating,you said to use amonia(posible use commercial cleaning Amonia 5-10 % solution to make that?don´t worry about any salt precipited?.Sorry about my chemistry knowlegment(i´m from the biological world),

I should not have added that, I was having a really bad week. And after writing my general procedure (what you are having luck with), I had a brain wave and thought I could remove those nasty fumes produced by simply neutralizing a little (thereby also making sure it does not scorch the product). Great in theory, and after documenting my actual procedure I should not have added it like that. I said "you could also" and was not clear that was a spur of the moment thought. And once I though about it, I slapped my forehead and said why did I write that? As ammonia will make 'ammonium chloride' precipitate with your product, sodium bicarb will make NaCl if you neutralize you need to keep going and make the free base and wash the solution as it will make salts (sorry about that).

It was a lot of questions I hope I ended up getting them all!

sassa · « **Reply #15 on:** June 30, 2010, 08:07:57 PM »

Thank´s for your time Naf1.really have answered all my question and in the best way:clean,direct,and both practical and theorycal.The best!

I have at this moment evaporating my last batch(a big one),using that Roundbottom write-up Al/Hg on full amounts.Have to say that this times the crystals are growing really well and are bigger than all i have seen.Big romboedric 1 cm shards.I suposse too that my first obtained product was brown because i heated that batch to 50ºC because was hurry about seeing the results.This last one,only with strong air for evaporating,are resulting on 1 cm big total transparent shards.Great!
I feel that at this moment i have nothing to adjust.Really a great improvement.Thanks!

Now,i´m way interested,like said on another post,on a real good reductive amination to get MDA. with not too much rare chemicals.Much more information about trusty experience synthetizind mdma than mda,and that´s makes me afraid about the real result.
After reading much,the only method i could afford at this time wouldn be sodium cyanoborohydride without Nitrogene atmosphere,because i supossed it would be easy to get(a baby nitogene tank),but it isn´t to me.Read it´s posible without N2,only have to adjust Ph while the 1,5 days it takes long to finish.I have friends that would do that for me

Naf1,have you any advice about a trusty way to get a few grams of mda to prove that compound?i´m really interested on that.Any information would be great!

And last,i have lots of curiosity about the exact composition of "street mdma".Like said on another post,i have noticed the diferent high that produces in relation with pure home mdma.To me:
"STREET MDMA":more speedier,more urge to talk,dance,more euphoria.Little better to me.
"PURE HOME MDMA":more rolling,more in the way to close eyes and relaxing,more loving(great).The last time consumed home mdma,i was with a 2 friends and taked strong doses,.The third friend( a big man),told us that we were mantained a dialog 2 hours with questions and answers that havn´t any relation bettwen.He said it was like the last scenes of "Fear an Loathing in Las vegas".

???Of course i only remember flashes from the first trip hour.And to me it isn´t the perfect mdma trip to me,but of course it´s interesting.Really stoning at good doses.
Naf,have you any idea about the the aditional components that make that street mdma more speedier,euphoric..?Have read about mda,caffeine,ephedrine,amphetamine,meth...but never get i trusty answer about that.
Thank´s again for all and have to say ever it´s a pleasure to read your post.Bye!

Author Topic: little yields on al/hg reductive amination in methanol+nitro and hcl gassing (Read 411 times)

sassa

little yields on al/hg reductive amination in methanol+nitro and hcl gassing

Naf1

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drone1240

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sassa

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Naf1

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sassa

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sassa

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Naf1

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sassa

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