the correct road to amphetamine

[dextro]

hi bees !
after spending several days (and nights) with TFSE swid
brought back 4 methods from the jungle of routes and methods:

1.)Raney/Urushibara   (looks good on the paper)
2.)LAH     (seems to be not state of the art)
3.)Al/Hg   (poisonous, but wtf...)
4.)Pd/C-GAA-HC00NH4, direct from the p2np  (doubtfuly)
   
NaBH4 is not available, overhead stirrer is not the problem.
But swid can`t try each route, he only wants to find a confidential bee which can say: "this is the right way for a newbee"
the rest of the way home can swid then walk alone.  
 
hope there is an answer possible without flaming

thx, dex

[dextro]

o.k. after weeks of research swim will try the LAH method.
now he has to decide to work with THF or ether.

after reaction and workup is done, the freebase is dissolved in THF, is it possible to drip H2SO4 in the THF to make the salt or must the THF distilled off before? 

thx

[java]

Read here and get your answer....

Post 459611 (missing)

(Rhodium: "Reduction of Phenylalanine to Phenylalaninol", Stimulants)

Post 459300 (missing)

(tpower9s2003: "DL-Phenylalanine--->PEA--->Dl-amphetamine?", Stimulants)

Post 516647 (missing)

(java: "Phenylalanine  to amphetamine continuation.....", Serious Chemistry)

[Lestat]

If you aren't used to working with LiAlH4, then I REALLY wouldn't use it as my first cook, it is extremely pyrophoric, and with shitloads of THF/ether around, pyrophoric materials are generally a bad thing

I would bee worried about your safety if you were to try the LAH method, I haven't worked with it myself, but I have seen what it is like, and it is fucking scary!

[dextro]

swims route is: start with p2np, then red. via LAH in  dried THF.

TFSE found nothing about refluxing time and temp. any suggestions for him?

[dextro]

the addition of the THF/p2np solution to the LAH/THF solution takes 2 hours.

then refluxing for additional 6 hours ?

is this o.k. or too long?

[Rhodium]

Definitely not too long - you can even reflux for 12-24 hours with no ill effects.

[dextro]

9,5 g LAH in 250ml dried THF and 13,1 g p2np in 100ml dried THF are refluxed for 6 hours. everything fine so far.

cooled to RT, then 9,5ml Water are added dropwise to kill remaining LAH. But when the first drop hits the surface of the LAH the solution solidified at this point.
result: after the complete addition of the water, the whole solution in the flask solidified to a foamy, bubbling mass, which was impossible to stir.  IS THIS NORMAL? next rxn swid will try a IPA/THF solution at this point. ADVICE IS NEEDED!
thought swid has already fucked up now, but proceeded with the addition of 9,5ml 15%NaOH and the additional 50ml THF. > shaked the flask like hell and the whole thing liquified again. additional 28,5ml water but there was no fizzing, SO THIS WAS NONSENSE? but swid read it so.
THF was distilled of by vacu. gave me 10ml golden oil, but the smell of this was not as expected (not this typical amine like amphe. smell). WAT IS THE RIGHT SMELL AT THIS POINT?
dissolved this in same ammount toluene (bad idea) next time swid will try it with IPA or Ether. but i wanted to do a water wash of the oil (REDUNDANTLY ?), for this reason swid decided for toluol
then 95% H2SO4 was added dropwise. IS IT BETTER TO DISSOLVE THE ACID IN ETHANOL OR IPA 50:50 OR SO?  after a little fizzing a white mass formed in the toluene, next drop, same result.
white mass was filtered off. again H2SO4, filtered again
till no more white is build after addition of acid.
after drying swid received ca. 3g.
snorted 30mg, not so bad. BUT HELP IS NEEDED at some points (where the letters are BIG) so dex is waiting for some helpful advice.

thx again

[WizardX]

Dextro: Have a look at this!

PREPARATION OF ENANTIOMERICALLY PURE a-N,N-DIBENZYLAMINO ALDEHYDES: S-2-(N,N-DIBENZYLAMINO)-3-PHENYLPROPANAL

http://www.orgsyn.org/orgsyn/prep.asp?prep=v76p0110

Hydrogenation of the aldehyde on the S-2-(N,N-DIBENZYLAMINO)-3-PHENYLPROPANAL to a -CH3 group gives S-2-(N,N-DIBENZYLAMINO)-PHENYLPROPANE, aka S-2-(N,N-DIBENZYLAMINO) amphetamine.

Now, removing the N,N-DIBENZYL to aford the -NH2 is a tough one.

Maybe using CH3I instead of benzyl bromide in part "A" will give the N,N-DIMETHYLAMINO  ??

Another possiblity is to reduce the end product of "B" with HI/P to the S-2-(N,N-DIBENZYLAMINO) amphetamine. Since the amino on the S-2-(N,N-DIBENZYLAMINO) is protected then cyclozation is eliminated.

[dextro]

did another rxn with ether and this way it is much easyer and faster with more yield, cause the solvent must not distilled off. dripped h2so direkt in the ether/amin solution and saw a nice snow storm. thats the way.

PLEASE: can someone discribe the typ. smell of the freebase oil ? swim thougt it was like flowers but the feebase what he dreamed smells not like flowers. hm ?

[WizardX]

P2NP, C6H5CH2CH(-NO2)-CH3, reduced to amphetamine with LAH. Freebase amphetamine oil has a amine odour (fishy) with a acrid burning taste.

Test using Marquis Reagent

Amphetamine:    orange => brown (blue)      
Methamphetamine: orange => brown (blue)      
Ephedrine:    yellow-yellow brown (purple)   
Phenmetrazine:    green (blue)      

Add 9 mls of concentrated sulphuric acid and 1 ml of 40 % formaldehyde solution.
OR
Add 10 mls of concentrated sulphuric acid and 10 drops of 40 % formaldehyde solution.
The colour takes about 15-30 minutes at room temperature to develop.

[wareami]

WizardX: I could be wrong...but you may want to double check those ratios.
I just crossreferenced using the CRC and that didn't help as I think it refers to 100% formaldehyde solution since no %age was given.
So I googled and came up with shulgin's ratio
His gives 2 drops of 40% formaldehyde and 3 milliliters of concentrated sulfuric acid for marquis reagent.

All the references I've seen converting drops to ml= 18-20drops per 1ml.
Does that sound right?
My personal measures also came up with 20drops exactly per 1ml.
Maybe my dropper is smaller than yours OUCH that hurt!
Even if shulgins is inaccurate...the two example ratios you provided don't look right to me.
Making the second one you provided 10drops more acidic.
Again I could be wrong with the drops.

http://www.cognitiveliberty.org/shulgin/adsarchive/marquis.htm

[Ascension]

Shulgin says the original testing agent was 2 drops 40%  formaldehyde and 3 mls of sulfuric acid but this was the original procedure from 1896. Im sure its been refined a bit since then.

[WizardX]

Wareami: Both shulgin's ratio and mine are correct. They both work. The 2 drops of 40% formaldehyde and 3 milliliters of concentrated sulfuric acid ratio will maybe give a faster colour development?

A lab pipette drop is approx 1/10 of a ml.

[wareami]

Dextro and Bees: I realize this deals more with nonmenclature than the topic at hand.
So please forgive the intrusion and hijacking of this thread.

WizardX:
Cool deal WizardX!
Thank you for the clarification.

I also noticed that my pipettes dropped more liquid per drop than an ordinary household eyedropper.
I guess these type discrepencies lend themselves to inconsistancy between clandestine kitchen/household chemistry and real life lab professional chemistry.
Believe it or not...depending on the procedure, this can spell the difference between success and failure where accuracy is a must.

As much I felt I was being too anal and/or picky in the above post.
(in other words "I wasn't trying to get the DROP on Ya"   )
I also knew that your expertise in labwork would help us all arrive at an understanding to diminish the margin to err in all areas...not just this one.
Thank You! And thank you as well for describing what may be encountered in more/less concentrate marquis solution.

For reagants used as organic indicators, the importance is that the color shows.
Unless in extreme "weaker/stronger" marquis solution,
"weaker/stronger"=time for color to appear
       =hue/tint of color indication

Now Ibee is more inclined to make a note of the "drop" source whenever he uses drops in write-ups from now on.
ie...eyedropper, pipette, blood...sweat...tears...Mr.Johnso......errr uhhh Nevermind[YIKES!]
Thanx again!

http://www.peteducation.com/category_summary.cfm?cls=0&Cat=1305

Also...see

http://www.newton.dep.anl.gov/askasci/chem00/chem00578.htm

Looky what I found!(*see pipetters below*)

•adjustable 20-200 or 10-100µl eppendorf pipette with yellow tips

Now as with anything chemistry related I didn't expect to find anything but an accurate definition surrounding Pipettes and PIE-Petters !
So here ya have it.

PIPETTES AND PIPETTERS

PIPETTES: There are three kinds of pipettes:
1. TD (to deliver) pipettes which deliver the final volume someplace before the tip (no rings marked on the top of the pipette;
2. TD pipettes which deliver the final volume to the tip and are designed to be blown out (marked with two double rings at the top of the pipette;
3. TC (to contain) pipettes which deliver the final volume by touching the tip of the pipette to the side of the beaker or flask which will leave a drop of solution in the pipette.
TC pipettes are rare. Volume is measured at the bottom of the meniscus.

PIPETTERS: Rainin Pipetman Pipetters are available in four sizes;
P10 (measures 1-10 ul),
P20 (measures 1-20 ul),
P100 (measures 10-100 ul)
and P1000 (measures 100-1000 ul).
P10, P20 and P200 require a small (usually yellow or white) pipette tip.
P1000 requires a larger blue tip.
NEVER pipette without a tip.
To get the required volume, set the pipette by using the threaded wheels at the top of the pipette and reading the amount in the window, depress the plunger to the first stop, insert the tip in the solution, slowly release the plunger. To transfer the liquid, press the plunger to the first stop, wait 1 sec., depress the plunger to the second stop to expel the last drop. NEVER tilt the pipetter upside down when there is fluid in the tip.

For P10, P20 and P200 pipetters, the red digits on the dial indicate tenths and hundredths of microliters.

For P1000 pipetters, the red digits on top indicate milliliters. In all cases, the black digits are m l (microliters).

Tips for accurate pipetting:
It's not necessary to put any pressure on the first stop. If you do, you will actually pipette a few extra m l of fluid.

http://fp.bio.utk.edu/mycology/Techniques/mt-calculations.htm

Ya gotta love this MindExpanding place!