Ohh you mean an ammonium salt of Alanine and PPA, 'Ate' used as a suffix denotes an ester so an Alaninate is an ester of alanine

Sorry for the terminology confusion, but the "ate" suffix can be used to denote a carboxylate salt as well (i.e sodium acetate, benzoate etc...). The ammonium salt you just mention would be an ammonium carboxylATE salt. Its not only used for esters.

I must say you have made me very happy with the info you have posted here.

not being into ice and more into the substituted amphets the info on the different substitutions giving
different yeilds is very welcome to me.

those yeilds though were for n-methyl alanine am I correct.

I wonder at a guess if you would have an idea of the differences if one was to use straight alanine
on say piperonal or maby even 2, 5 methoxy 4 methyl benzaldehyde.

this coupled with an easy birch is truly a killer

thankyou for the work you are doing.

interesting.

but did not cycloknight first use a dean stark trap and xylene as a solvent.

now I know that he had some probs with getting a great yeild due to formation of benzylamine due to the temp of
xylenes boiling not being anywhere near high enough to preform the reaction properly.

but .....

as you have posted here

"N-Methylalanine (2) with 6 equivalent aromatic aldehydes (4) with the non solvent 130?"

the temp only needs to be 130 with the n methyl veriaty

now if we have a look at cycloknights origonal try and take into account that were using n-methyl alanine instead of the
straight alanine that he used we may have a winner for at least mdma.

http://www.sciencemadness.org/talk/viewthread.php?tid=5979

Amino alcohol via Akabori, trial run


Recently I’ve been experimenting with the Akabori reaction, just curious to see if the process for making amino alcohols can be improved upon. I thought it would be quite an interesting amateur science experiment.
So far its been an interesting challenge !

The Akabori refers to the reaction between an aldehyde & amino acid to yield the corresponding amino alcohol.


For this run, the following chemicals were used:
83 g l-alanine (considerable excess)
40g benzaldehyde
250ml xylene as solvent (convenient & OTC)

The conventional low yielding approach is to simply heat benzaldehyde & l-alanine at 150-160 C until CO2 evolution ceases.
The objective with this variation is two fold: to keep the l-alanine in excess at all times by slowly dripping the aldehyde into the reaction mix, the idea being that this will increase yields wrt to consumed benzaldhyde, & to keep water out of the reaction.
When water gets into the reaction, by-products are immediately formed and the reaction mix will turn red (tar) quite quickly. The boiling temp of xylene is 139 C, therefore if water drips back into the boiling solution, the results can send foam as far as the condenser & beyond.
Foaming is another issue with this particular trial run, higher dilution is required, higher than what was used in this trial run. By the end of the reaction, due to tar formation, foaming was getting a bit out of control.

The reaction was maintained at high reflux to help flush out generated moisture, this was maintained for 1 hour before the aldehyde addition. To assist with this task, a DIY Dean Stark trap was hastily thrown together, to collect generated water and help keep it out of the mix.

and on with the pics baby

if you think so

my nick on SM is ephoton I have been in that thread since the start though no were near as intellengently as
cycloknight.

I belive he got a 25% yeild first go
and then only went up another 10 or so percent afterwards.

the extra aldehyde was just a high boiling point solvent to my knowlage and also to solve the problem of getting excess
aldehyde out of the NP as he had not read up on benzylchloride synths lugh and I were playing with I think.
We all used ethanol or IPA to get tol and xylene out
of benzaldehyde and benzylchloride.

also the major reason for using a NP solvent and dean stark trap is you dont end up with tar at the bottom of your
reaction.

you can reuse the piperonal that has not reacted.

still unfortunatly at the moment I am not in a position to test what I say so as they say put out or shut up so I guess I shall shut up.
I can not do the experiment yet.

I guess I shall have to wait till I can test these things my self.

well just for the sake of backing why I think this we see that cycloknight got a 10gram yeild out of 40 grams of aldehyde
and 83 grams of amino acid

and then when he uses the 2 to 1 ratio of aldehyde to amino acid he gets 35 g from 200g of aldehyde and 100 of amino acid.

but in the second try he was unable to recycle any aldehyde as it was turned to tar. thats like 165 grams waisted.
all becouse he did not use a dean stark trap and then brake the azeotrop of the aldehyde and solvent.
still then again he may just of he went awfully quite after that.


Update


The yield of PPA given in the previous reaction was no more than about 50% of the final crystallised product.

So far a few different variations on this reaction have been attempted.
As solvent, white spirits works quite well.
Reflux was maintained at 165 C while the aldehyde was slowly added. But the reaction time was still quite high, 4 hrs minimum.

Overall, its been found that the lower temperature variations appear to be producing a larger proportion of other amines, most notably benzyl amine.
The best approach to use for this reaction, is the conventional one (without solvent).
This yields a higher proportion of the desired amine, and is far less time consuming.

Until someone finds a way to minimise the unwanted amine by-products, this is how its done.

Conventional akabori run.

200 ml benzaldehyde
100g l-alanine

equipment required: distillation apparatus & oil bath, hotplate w/stirrer

Simply set up the equipment for distillation, generated by-products will distill out of the reaction as they form.
Finely ground alanine is first added, then the aldehyde.
It's essential to keep the stir bar spinning for the duration of this reaction.
Oil bath temperature is heated to 150-160 C and maintained at this temperature until the evolution of CO2 diminishes (>1.5 hrs).
The freebase is extracted with organic solvent and carefully washed with several ml of distilled water to remove most of the NaOH.
Solvent is evaporated. Residue double distilled under vacuum to yield 35 grams PPA freebase. Melting point ~50 C.
If a way can be found to efficiently extract the remaining PPA from the other distillation fractions, then any remaining PPA could be recovered.

Overall, this was far less work than the previous runs using solvent. Not too impractical for producing a little PPA if you happen have benzaldehyde lying around.

"I wonder at a guess if you would have an idea of the differences if one was to use straight alanine on say piperonal or maby even 2, 5 methoxy 4 methyl benzaldehyde."

According to the paper;

Abstract




Run 1 = Benzaldehyde                                             48%
Run 2 = 4-Bromobenzaldehyde                                  43%
Run 3 = 4-Nitrobenzaldehyde                                    45%
Run 4 = 4-Methylbenzaldehyde                                  55%
Run 5 = 4-Methoxybenzaldehyde                               83%
Run 6 = Piperonal  (3,4-Methylenedioxybenzaldehyde)  87%

They did not run 2,5-Methoxybenzaldehyde in the paper, but you can see from above it would do much better than Benzaldehyde. I would not be suprised if one reacheda yield of up to 90% with the 2,5-Methoxy derivative.

What is suggested ratio and instruction for N-methyl-L-alanine instead of alanine in Quantum Dude method(posted in SM)?
http://www.sciencemadness.org/talk/viewthread.php?tid=14326#pid185474

We should use 6 mole Benzaldehyde for every mole of N-methyl-l-alanine?
We should concentrate the aqueous phase extracts in the work-up?
We should reflux 3 hours mixture of 20% acetic acid in toluene and 15% HCl?(using 15% Hcl is necessary even if we use N-methyl-l-alanine)?
What about 1,2-diphenylethanolamine?(this will produce or not?)

i was thinking why not steam distill the whole mess after it is made basic to ph 8-9 after work-up this would satisfy any qeustions as to if there is any waste as the alanate salt.