Author Topic: Biosynth: Homebrewing Ephedrine  (Read 32358 times)

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Organikum

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answers
« Reply #80 on: January 29, 2004, 05:16:00 PM »
- Acetaldehyde works as a hydrogen acceptor - it is essential for good yields.
- Too much acetaldehyde as benzaldehyde kills the yeast.
- The yeast "cycles" through phases of high PDC activity and lower activity. The monitoring of these cycles is high tech and warrants not the efforts IMHO.
- Ethylalcohol may be added to suppress the benzaldehyde -> benzylalcohol transformation, about 10% to 15% is ok, more may disable or even kill the yeast.
- The benzaldehyde -> L-PAC transformation is depenedent on MANY factors not only PDC activity - yeasts with lots of PDC in a highly active state dont give the best results.

Do we know the amount of yeast that is required for developing enough of it in a specific time for a given quantity of benzaldehyde feedstock? An estimate?



Thats covered in my posts I linked to before.

The acetaldehyde added is NOT converted to L-PAC, only the acetaldehyde which is made in situ from the pyruvate is converted to L-PAC. This is not acetaldehyde in a pure form but a kind of nascent acetaldehyde compound.
It works without the addition of acetaldhyde with lowered yields.

The process which is used in the production of heaps of ephedrine to lowest prices in China and India is described in my former posts. No need to make it overly complicated.

Get yourself a nice b-dehyde synth and an acetaldehyde synth - thats the problem to solve. The biosynth is easy.




nightshade

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Phenylacetic acid
« Reply #81 on: February 07, 2004, 06:28:00 PM »
Does anyone have information concerning US patent #5,420,022
phenylacetic acid from yeast and phenylalanine. How much phenylalanine is added to the brew, and how does one extract the phenylacetic acid from the brew? Can nutrasweet be used as more of it can be dissolved in water,so it is easier to mix?

Methodman

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I think,not positive,but I think you need to...
« Reply #82 on: February 14, 2004, 04:44:00 AM »

Nicodem

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Anybody cares for R-PAC...
« Reply #83 on: March 06, 2004, 04:32:00 PM »
...well, that -OH is obsolete anyway.

Patent CA2414742

: Microbial Production Of R-Phenylacetylcarbinol By Biotransformation Of Benzaldehyde By Filamentous Fungi
Abstract: Process for the production of R-phenylacetylcarbinol by biotransformation of benzaldehyde by filamentous fungi.

Just some investigations of R-PAC production by filamentous fungi selected from the group of Rhizopus, Neurospora, Polyporus, Fusarium, Monilia, Paecilomyces, Mucor.


Organikum

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Its the same. l -(laevo)- phenylacetylcarbinol
« Reply #84 on: March 08, 2004, 01:18:00 PM »
Its the same.

l -(laevo)- phenylacetylcarbinol is identical with  R-Phenylacetylcarbinol.

So many compounds but much more names - oh Babylon, oh Babylon  ;D .

S we have the funny fact arising that:
l-PAC = L-PAC (whats wrong but often used anyways) = R-PAC
This doesnt matter anyways as "phneylacetylcarbinol is the wrong name also - a mistake made by the discoverers Neuberg and Hirsch.
Look above there are all names (known to me) listed.


Nicodem

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L-PAC to CATs in one step?
« Reply #85 on: March 08, 2004, 02:03:00 PM »
Thanks for the correction Organikum. I already figured that out, but it was too late to edit the post. Yes, it is just a different nomenclature, but I always mix up those R,S/D,L nomenclatures if I don’t think enough about stereochemistry and I almost never think :P .

Well, sometimes I do think but the results of such an irresponsible activity might be wrong 8) . Did anybody ever considered the following transformation:

Similar mechanisms are already known for alpha-hydroxy-ketones, especially in the heterocyclic chemistry. Here we have one more driving force to push the equilibrium on the right: the conjugation of the enamine and latter of the carbonyl double bond with the benzene ring. One additional push would be to eliminate the water that forms during the enamine formation. Azeotropic distillation with a Dean-Stark trap would be a little hard to acomplish due to the volatility of dimethylamine, diethylamine, methylethylamine etc. N,N-dimethylcathinone is a relatively good stimulant, isn't it? And it is much more straightforward for the kitchen chemist than reduction to ephedrine and so on.


Organikum

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You want it easy AND good?
« Reply #86 on: March 08, 2004, 03:52:00 PM »
You want it easy AND good?


Go:
benzaldehyde + bakers yeast = l-PAC
l-PAC (crude extract from the biosynth is ok) + NH3 = imine *
imine + Al/Hg = l-norephedrine
l-norephedrine + KOCN = carbamyl
carbamyl + HCl = "XYZ"  surprise, surprise what can this bee....?  ;D

* hydroxyphenylacetones form stable imines, so the formation of the same in advance before reduction is possible and advantegous regarding yields which are bad if the reductive amination is done one-step as usual.


roger2003

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Industrial Biotransformation
« Reply #87 on: March 08, 2004, 05:07:00 PM »
Very interesting book (5 MB)

Industrial Biotransformations:
A Collection of Processes by Andreas Liese (Author), Karsten Seelbach (Author), Christian Wandrey (Author)
 

http://www.amazon.com/exec/obidos/tg/detail/-/3527300945/qid=1078761717/sr=1-1/ref=sr_1_1/102-0732881-5495322?v=glance&s=books




Organikum

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?????????
« Reply #88 on: March 09, 2004, 01:07:00 AM »
You wanted to say 150$$ I guess.

Thats a joke, there are hundreds of interesting books at amazon, you know?
Thousands probably.

weird.


roger2003

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Books
« Reply #89 on: March 09, 2004, 10:16:00 AM »

elfspice

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pyruvic acid
« Reply #90 on: April 09, 2004, 05:37:00 AM »
I did a little research on pyruvic acid and discovered that it's right under our noses - well, when we're making our dinner it can make the eyes water... yes ONIONS! sorry if that was known to the reader... Pyruvic acid is produced during the decomposition of sugars (glucose i think) and it can reduce quite readily to lactic acid.

so all you need is a source of pyruvate decarboxylase, and with a few experiments one should find that a particular set of conditions is conducive to the PDC reacting with the pyruvic acid in such a way as to increase the chances of this decarboxylation occurring in proximity to the benzaldehyde so that one gets maximum transformation.

Or better still, is there a way to make benzaldehyde and pyruvic acid join together the right way without using an enzyme?

Pyruvic acid could probably be easily sublimation purified out of extract from onion - subzero alcohol extraction would extract solid pyruvic acid into the alcohol and then the material boiled off and the fraction boiling at 165 degrees distilled, and then sublimed onto a dry ice cooled dewar type condenser as it solidifies at 11.8°C.

This might be useful information for the biosynthesis process, as pyruvic acid probably doesn't have a very long lifespan in actively brewing warm vat... maybe it could be added with a dripping funnel thingy? I'm sure it wouldn't cost much to get a few litres of pyruvic acid from the supermarket...  ;)

Nicodem

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Pyruvic acid could probably be easily ...
« Reply #91 on: April 09, 2004, 10:12:00 AM »
Pyruvic acid could probably be easily sublimation purified out of extract from onion

Are you serious?
You can make pyruvic acid with the dry distillation of tartaric acid which is OTC and cheap (at least where I live). I don't remember the exact procedure but I'm sure it is as easy as it can get (maybe some sulphuric acid has to be added or something like that).


elfspice

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pyruvic acid (again)
« Reply #92 on: April 09, 2004, 12:31:00 PM »
the question is, would it help to add it? It is naturally formed as a part of the yeast's metabolism, (and virtually any organism that uses sugars to provide energy) but is the rate of production equal the rate of PDC production? If PDC was being produced in excess to the proportion of pyruvic acid, we could probably squeeze more out of it (?) If not, the whole line of thought is worthless... unless we can get PDC out of yeast somehow perhaps, or if it is commercially available. or... maybe there's some way to make pyruvic acid useful here somehow (chlorinate it and react with benzyl chloride perhaps?)

(just looking at molecules) oh i see decarboxylate tartaric acid one time and remove one hydrogen (or add an oxygen) and you get *tada* pyruvic acid.


I've been trying to nut out how exactly the PDC goes about joining these things together and what i've figured out is this: The pyruvic acid decarboxylates, and the free carbon bond remaining of what used to be pyruvic acid reacts with the aldehyde, which bonds by saturating the carbon with the acetaldehyde which is lacking a hydrogen (which is floating around from the decarboxylation), and the hydrogen goes onto the now single-bonded oxygen at the first carbon on the now phenylacetylcarbinol.

If one created reaction conditions of pyruvate decarboxylating in the presence of benzaldehyde, it doesn't make any difference how it is done so long as the process allows the freshly decarboxylated pyruvic acid take up the carbon bond. or am i missing some vital point here? The stereoselectivity is inherent in this reaction because of the way it reacts via the production of an aldehyde with an extra proton on the carbon with the aldehyde on it, because the keto group has some kind of interaction with the oxygen with a free electron. I think in this case we always want the OH and keto group to end up opposite each other, and i suspect that is exactly what they do. One could imagine that there would be some kind of interaction leading to a fairly predictable bonding formation.

Tricky thing is, how do we get the pyruvic acid to decarboxylate with benzaldehyde around? perhaps a high boiling ketone? pressure (*ducks flamethrower blasts*) ? *wince* ... ooh, maybe something simple like a natural organic ketone, eg carvone or something similar... That would dissolve the benzaldehyde well enough but the determining factor for the best ketone solvent/matrix/decarboxylation catalyst would be good solubility of pyruvic acid.

Organikum

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No. Pyruvic acid or molasses or even plain...
« Reply #93 on: April 09, 2004, 01:14:00 PM »
No. Pyruvic acid or molasses or even plain sugar makes no real difference. Molasses is even better for the nutrients it contains.

But pyruvic acid may be useful in another way.
- pyruvic acid and diluted H2SO4 gives acetaldehyde.

The biosynthesis is absolutely no problem. Acetaldehyde and benzaldehyde are the limiting factors here.

For the biosynth:
- permanent ph control and adjustment is essential.


roger2003

  • Guest
Acetaldehyde
« Reply #94 on: April 09, 2004, 03:59:00 PM »
- pyruvic acid and diluted H2SO4 gives acetaldehyde.

Any references ?


nightshade

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bio brew tryptophan->tryptophol.
« Reply #95 on: April 09, 2004, 06:29:00 PM »
bio brew tryptophan->tryptophol.
bio brew phenylalanine ->phenyl acetic acid.
now to do this can one use the same set up as is used for L-pac,I read that patent for phenyl acetic acid production but was wondering if it could be brewed more like beer as with the L-pac?

BOS

  • Guest
Here is a good Pyruvic acid patent.
« Reply #96 on: April 09, 2004, 10:09:00 PM »
Here is a good Pyruvic acid patent.
Claimed 90% yield from cream of tartar and h2so4

Patent US4136111


elfspice

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correction
« Reply #97 on: April 10, 2004, 06:23:00 AM »
if only it made phenylacetic acid... no sorry, biobrew is gonna turn the material into phenylethanol or maybe phenylacetaldehyde (i'm fairly sure it's the alcohol)

phenylethanol is not going to be an easy way to start if one wants to end up with an amphetamine, since the amine has to go on there but it needs another methyl group after it as well...

nightshade

  • Guest
phenylethanol can changed to phenyl acetic...
« Reply #98 on: April 10, 2004, 06:29:00 PM »
phenylethanol can changed to phenyl acetic acid then ran through a tube furnace to get p2p right? what is needed to change phenylethanol to phenyl acetic acid? in patent 5420022 it seems they were producing phenyl acetic acid,the beer brewing set up would be somewhat different than their set up so maybe the the main product would be phenyl ethanol.so can I get more feed back on this, thank you.

elfspice

  • Guest
oxidation of course
« Reply #99 on: April 10, 2004, 11:53:00 PM »
phenylethanol probably oxidises to it's carboxylic acid equivalent via some means, ordinary ethanol certainly seems to. This requires some kind of bio-catalysing normally, i think, you can't just let ever clear sit open and expect it to oxidise, a lot of water is needed. Probably you just brew it up, then don't stop until the thing gets really acidic and full of acetic acid. I would think the same oxidation would occur, but then i can't be sure cos phenylethyl alcohol is a lot bigger.

If there's a way to make phenylacetic acid, then couldn't tryptophol also be turned into indoleacetic acid?