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All 16 posts   Subject: Failed Birch - Why?   Please login to post   Down

 
    Xavl2
(Hive Bee)
11-12-04 01:38
No 541133
      Failed Birch - Why?     

The basic set-up:
* 250mL of anhydrous ammonia was condensed in a reaction vessel in dry ice from a tank with excess fumes pumped into HCl through a number of fume/moisture suck back traps.

* The vessel was placed on a magnetic stirrer and 0.8g of Li (one AA battery) was dissolved in the ammonia added via a funnel in the reacttion vessel stopper to prevent moisture condensation on the inside.

* 2g of freebase suzy dissolved in 75mL of toluene was poured in followed by a slow addition of the rest of 6g of suzy.

* The blue was not going away - the mix was allowed to stir for 15min first and then for another unexpected hour as swim had an emergency to attend to.

* After this ammonia was taken off stirrer and allowed to evaporate bubbling through HCl. This took a good 2 hours. It was blue all the way until it was all gone.

Results:
Product was extracted with toluene, filtered/washed, added to a layer of water and small amount of HCl was dripped. The water was separated evaporated to leave white crystals that smoked up and tasted like Suzy!!!

The rest of the toluene was evaporated to see if there was meth oil, but only produced very smelly wet (from some meth oil?) crystals that stunk like some kind of medicine and not susy freebase (so some reaction happened?).

Note1: When suzy was extracted, a tad too much heat was added after freebasing to push suzy into toluene to be extracted and some of it burnt. So the initial feedstock of suzy was yellow but smelled like freebase suzy so swim thought it would be ok.

Note2: Suzy was stored for 5 weeks before use in a dark cold place. Does suzy freebase go off/break down?

Any comments very appreciated. By the way, swims setup produced no smell at all from start to finish since the system was 100% enclosed - about the only thing swim can be proud of in this instance :)
 
 
 
 
    jboogie
(Hive Bee)
11-12-04 06:09
No 541167
User Picture 
      i think...     

your ratios are way off. a "psudeo-birch" (no pun intended) should bee more like 2 parts Li to 1 part freebase. the hcl will require even more Li.

2g of freebase suzy dissolved in 75mL of toluene was poured in followed by a slow addition of the rest of 6g of suzy.
why didnt you dissolve all the freebase in the np first? did you just dump in the powder after the addition of the first bit in NP? anyways, that would bee a total of 8 gr. of freebase...

The vessel was placed on a magnetic stirrer and 0.8g of Li (one AA battery) was dissolved in the ammonia added via a funnel in the reacttion vessel stopper to prevent moisture condensation on the inside.

and not even a full gram of L1!! what the fuck! so your "reaction" is 1 part (im beeing fair by even calling that one part) Li and 8 parts of freebase. Subpar...
This is why its so important to UTFSE before you waste your time and money. you probably coulda ended up w/some good shit if you learned to research your reaction first. there may have been enough Li to reduce half a gram... better luck next timelaugh.

Don't you think if I had something intelligent to say, it would bee in my post?
 
 
 
 
    Xavl2
(Hive Bee)
11-12-04 08:11
No 541186
      Hmmm... Correct swime if swim is wrong but the     

Hmmm...

Correct swime if swim is wrong but the reduction part of the reaction goes something like this:

Suzy + 2e- -> MA.

Hence for every mole of suzy, 2 moles of lithium is required.

Moles of Suzy used = 8g/165 = 0.48

Mass of lithium = 0.48 x 2 x 6.94 = 0.7g

Swim actually used a slight excess of 8g of suzy that's why swim added 0.8g of lithium.

Any other ideas?

One of swim's theories is over-reduction due to a long cook. Anyone know what the over reduced base smells like?

The other one is that suzy got ruined during extraction or broke down after 5 weeks of storage.
 
 
 
 
    maj
(Hive Bee)
11-12-04 12:38
No 541220
User Picture 
      Why would you use a np solvent to administer...     

Why would you use a np solvent to administer into your anhydrous ammonia.  The reaction was stopped with this addition.  Birch with will reduce alchols.  However I beleive the toluene actually 'quenched'  your reaction.  Thus not reduceding your ephedrine to methamphetamine.  But to hey Suzy.  Might be clean enought for ya to do RP/i reaction or hypo.  You cannot over cook a birch you run the reaction till it is done.

I took the one less traveled by,And that has made all the difference.
 
 
 
 
    Organikum
(Wonderful Personality)
11-12-04 14:44
No 541238
      You have no hydrogen source in your reaction...     

You have no hydrogen source in your reaction scheme.
You have to use either the HCl salt of pseudoephedrine or an alcohol (anhydrous, so take IPA or methylalcohol, dry!)
But using the HCl salt is better and easier.

I am not sure about the toluene at all. I GUESS it doesnt matter, but I would leave it away.

A hydrogen source is needed, In the RP/I the HI provides it, in the Birch the HCl of pseudo.HCl or an alcohol when the freebase used. I cant remember to have heard that toluene can be used instead.

Use the HCl salt. Toss it in all at once when you have the blue. Stirring is usually a good idea, but on the small scale you are working a gently swirling of the flask will suffice (DONT SHAKE!), dont forget the gloves though. smile


Hope this helps
/ORG

I cant spell, I bad look, the only thing about me is I know how to cook......
 
 
 
 
    dwarfer
(esoteric)
11-12-04 23:09
No 541295
User Picture 
      Orgy is right     


You have no hydrogen source in your reaction scheme.
You have to use either the HCl salt of pseudoephedrine
or an alcohol (anhydrous,
so take IPA or methylalcohol, dry!)
But using the HCl salt is better and easier.




laugh  (inside joke, huh Orge??)


1 red-headed bat will handle 7 to 8 grams
of fake:
 but if there ain't no hydrogen around
it's not going to work:

and if I recall, theoretically, Li can reduce
toluene to something you don't want:

so don't use it until the blue is gone.

To bad about that search engine's apparently not working
on your end of the 'net..smile


dwarfer
 
 
 
 
    Xavl2
(Hive Bee)
11-13-04 02:40
No 541319
      Ok, swim has used search engine extensivelly...     

Ok, swim has used search engine extensivelly and has never seen anything that would suggest toluene gets reduced to anything or that an extra hydrogen source is needed as in the HI reductions. Can someone write in full ALL reactions that occur during a birch please?

May swim attact everyone's attention to this article:
https://www.rhodium.ws/chemistry/birch.pseudo.html

The article goes to explain in detail how the writer and his associates have reduced pseudo freebase to meth in a birch reaction by dissolving lithium in ammonia adding a preaddition toluene with freebase dissolved in it and then adding solid freebase so meth freebase goes straight into toluene. The guy sounds very knowledgeable and is obviously very familiar with the work of Eulesius and Fester which again gave him more credibility in swim's eyes.

Another article describes freebase addition in THF.
https://www.rhodium.ws/chemistry/birch.reduction.html
Reference: From Ely & McGarth J Forensic Sci 35, 720-3 (1990)

Someone in swims neck of the woods just empties same amount of ammonia as there is of toluene with freebase, chucks lithium in and dumps toluene in and watches the whole thing bubble away and then gets at least a semi-decent product out of it considering freebase wasn't cleaned that well, nothing is measured and so forth.
 
 
 
 
    WizardX
(Wizard Master)
11-13-04 04:27
No 541328
User Picture 
      Birch     

maj states...


However I beleive the toluene actually 'quenched'  your reaction.  Thus not reduceding your ephedrine to methamphetamine.




Correct!

Use the ephedrine in the freebase form that has been dried azeotropically. Ephedrine forms a hydrate with water. Eg. Ephedrine. 1/2 H2O

Add anhydrous ephedrine (sold form) to your NH3/Li.

All these solvents form azeotropes with water @ 760 mmHg.

Example. CHCl3 Trichloromethane forms an azeotrope with water @ 56.1 oC.

CHCl3 Trichloromethane 56.1
CH2O2 Formic acid 107.2
CH3NO2 Nitromethane 83.6
CS2 Carbon disulfide 42.6
C2H3N Acetonitrile 76.5
C2H5NO2 Nitroethane 87.2
C2H6O Ethanol 78.2
C4H8O2 Ethyl acetate 70.4
C4H10O 1-Butanol 92.7
C4H10O 2-Butanol 87
C5H5N Pyridine 93.6
C5H11N Piperidine 92.8
C5H12 Pentane 34.6
C6H5Cl Chlorobenzene 90.2
C6H6 Benzene 69.3
C6H6O Phenol 99.5
C6H10 Cyclohexene 70.8
C6H12 Cyclohexane 69.5
C6H14 Hexane 61.6
C7H8 Toluene 84.1
C7H16 Heptane 79.2
C8H10 1,3-Dimethylbenzene 92
C8H10 Ethylbenzene 92
C8H18 Octane 89.6
C8H18O Dibutyl ether 92.9

 
 
 
 
    Xavl2
(Hive Bee)
11-13-04 04:30
No 541330
      Ok, dug up are equations from TFSE written by...     

Ok, dug up are equations from TFSE written by chemguy 4 or 5 years back:

"It is really some what difficult to write out in text form but I will attempt. 

a)  Li (or any alkali metal) + NH3 (or other sutable solvent)  --> Li(+) + e(-) (the solvated electron) + NH3

b)  C6H5-CHOH-CH(NHCH3)-CH3  +  2 e(-)  --> 1,4-( - )-C6H5-CHOH-CH(NHCH3)-CH3  [or the 2,5- it doesn't matter]

c)  1,4-( - )-C6H5-CHOH-CH(NHCH3)-CH3  +  2 Li(+)  -->  4-( Li )-C6H5=CH-CH(NHCH3)-CH3  + LiOH

d)  H2O (or any proton donor)  +  4-(Li)-C6H5=CH-CH(NHCH3)-CH3  --> LiOH  +  4-(H)-C6H5=CH-CH(NHCH3)-CH3

e)  4-(H)-C6H5=CH-CH(NHCH3)-CH3  --{tauterization (sp?)}--> C6H5-CH2-CH(NHCH3)-CH3"


So ok, swim is a moron and it should have been obvious that the H has to come from somewhere. In the post mentioned above https://www.rhodium.ws/chemistry/birch.pseudo.html, the guys doing it quenches the reaction with water in the end, so that's where the proton comes from I guess.

Swim will attempt next either a water addition to the blue after 15 min of stirring or dripping suzy dissolved in MeOH into the blue untill blue is gone. More lithium may be added if more MeOH with freebase remains.

Any comments?
 
 
 
 
    Xavl2
(Hive Bee)
11-13-04 05:24
No 541337
      WizardX: as much as swim agrees with you, swim     

WizardX: as much as swim agrees with you, swim doesn't think that was the problem since the solution remained blue till the end, so there were plenty of electrons to go around.

Swim obviously completelly ommited the hydrogen source needed to replace the OH group on the susy. Swim has read many a post instructing to "quench" the reaction with water however never realised that the quenching process actually supplies the needed hydrogen to complete the methamphetamine as stated by the above equations.

Swim heard and read of many using toluene as the solvent to add suzy in, but obviously addition of H2O or ice cubes supplies the needed proton to make MA.

Is swim's logic correct?
 
 
 
 
    Jacked
(Ancient Alchemist Delux)
11-13-04 07:22
No 541346
      reply     

I'm not sure but I would think the reduction is complete before water is introduced.. Swim has used methods that does not use water at all.
 Li is capable of reducing 3 steps were Na is only capable of reducing 1 and that is all that is required for this reaction meaning to much Li can over reduce you gear to crap.
 The amount of Na or Li needed to reduce the freebase is 2 moles for every 1 mole of pseudo, If your going to run the HCl then add an extra mole to your calculations making it 3 to 1.
 Freebase in a supersaturated alcohol solution that has been sitting in the freezer to chill is the best approach in terms of a substance coming into contact with NH3. It is more forgiving already being so cold. Even if the H did not come from the alcohol it provides less energy to stabilize it in the NH3 than if it was at room temp.
 Sense freebase does have traces of water in it seems to me that it is carrying its own H donor. Water will reduce too using some of the Na's reducing power so if a little more Na is used one could overcome any problems using freebase with no alcohol. (from what I understand anyway) Too much water overwhelms the reaction and shorts it out but small amounts are reduced without you even knowing it. Moist conditions can shorten reaction times because the reduction power is being used up by the water as well as the pseudo. It would be hard to judge and using Li would make that decision even more critical than if one was using Na.

Tighten Up!  (UH)
 
 
 
 
    Xavl2
(Hive Bee)
11-13-04 08:03
No 541348
      Hmmm... swim thinks the fact the suzy has...     

Hmmm... swim thinks the fact the suzy has water traces in BEFORE it is reduced to the intermidiates in the equation above doesn't help since this water trace is also reduced and the hydrogen simply escapes. However, if anyhydrous conditions are kept until the initial reduction of suzy is complete and then water is added, the hydrogen will be readily absorbed to produce MA.

Jacked: from what I gather you believe my suzy got over-reduced? What does over-reduced stuff smell/taste when smoked like?
 
 
 
 
    Jacked
(Ancient Alchemist Delux)
11-13-04 08:40
No 541351
      reply     

I was only speculating about that. When Swim first started doing birches he used freebase with Na and never quenched the reaction. It quenched itself. Then Toluene was added and extraction was carried out followed by very good results. No H donor was added at the time because Swim didn't know any better. Swim was experienced in Rp/I2 reactions and was very familiar with an end product of high quality, in other words he knew the difference between a partly unreduced product and not.. After Mr. clean laid out the birch from a to z swim changed a few things not even then realizing what is being stated above until just a little while ago..
 As far as over reduced gear Swim has not seen any but from what he understands can be a white fine powder that does not crystallize or at least crystallize like we are use to seeing. Kind of like a talc powder. Judging from your amount of Li to starter I don't think it is an over reduction problem.
 Does it have a sweet after taste? This is typical of under reduced gear, it will stay in an oil form after heating longer than normal as well.
 It's very hard to trouble shoot such a small reaction but I would say if the NH3 stayed blue then the toluene was holding the material to be reduced and not letting it come into contact with the melted Li at all. The toluene was even blocking any moisture from the air that could use some of the Li's reducing power. If you were to dissolve the Li in the NH3 in a separate container it would act just like you described. It hast to come into contact with something to reduce so its energy can bleed off. IMHO

Tighten Up!  (UH)
 
 
 
 
    Xavl2
(Hive Bee)
11-13-04 09:12
No 541352
      Only a small amount of end product was ...     

Only a small amount of end product was converted to a salt that had the fairly distinct fruity sweet taste when smoked indicating unreduced suzy swim guesses. The rest of toluene was evaporated to produce wet crystals with a distinct medicinal odor not much like suzy freebase.

Swim will use suzy dissolved in MeOH next time. The plan is to add this to condensed NH3, then throw Li strips in whiel stirring until blue sets in indicating nothing more to reduce. Any experience with this approach?
 
 
 
 
    Jacked
(Ancient Alchemist Delux)
11-13-04 09:17
No 541353
      reply     

One more possibility that comes into mind is poly80 or polys of different weights that might have made it through the cleaning process and blocking a reduction but that is pure speculation as well. I don't know if the poly is capable of reducing but if it did it would be using some of the allotted Li up before the pseudo could use it.. Again pure speculation, I wish I could be of more help but my chem background is 90% common sense reduction by elimination. LOL

Tighten Up!  (UH)
 
 
 
 
    WizardX
(Wizard Master)
11-13-04 09:39
No 541355
User Picture 
      Birch     

Use dry O2 free solvents like Tetrahydrofuran or Diethyl ether.

Tetrahydrofuran was dried and made oxygen-free by boiling over sodium/benzophenone ketyl under argon, and distilling just before use.

In this birch reduction http://www.orgsyn.org/orgsyn/prep.asp?prep=cv7p0249 they add the sodium to the liquid NH3/tetrahydrofuran/o-anisic acid mixture until the blue persisted.

You can try this; liquid NH3/tetrahydrofuran/anhydrous ephedrine.

Also have a look at part A on this http://www.orgsyn.org/orgsyn/prep.asp?prep=cv6p0731

Because your solution was still blue this means that there was an excesss of Li still unreacted. Not adding an alcohol or water will leave unreacted Li and the benzyl radical on the ephedrine to couple together and react in an undesired manner.
 
 

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