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Author: Subject: Amino alcohol via Akabori, trial run
roamingnome
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[*] posted on 10-2-2007 at 11:47


ill try to be a breif as possible here

first, the comment about the benzylamine was a joke becuase who really wants that stuff.. hahha not funny

second i took just today some of the post reaction mixture thats has been sitting in a box

pH 9.63
UV/VIS absorbances at critical wavelengths
325nm- 4.23
335nm- 4.3
415nm 2.1
290nm 3.2

Benzylamine check at 260 nm only .77

so i might have some shiff base knocking around in equlibrium with some other forms....

i didnt though fully grasp carbanion addition so i went to decarboxylate prematurly and am considering the above tests as "observational recon missions" I am physically loosing sleep not having pure almond esseance to continue these expirments.

altering my research queries to Pyridoxal 5-Phosphate
i have found a wealth of quality information about this topic almost precisly! and am massing it in my little "octopus garden" of a thread under vitaminB6
its just a matter of time now
------------------------------------------------------------------

AKABORI fans and biotransformation fans
should love the up and coming possibility of the protien

8-amino-7oxopelargonate synthase

it binds alanine, forms a carbanion, adds a carbon-carbon bond, and it even decarboxylates it for you!! now thats a biotransformation.....
scientists are spawning it up right now in E-Coli
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jon
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[*] posted on 10-2-2007 at 16:53


when CO2 comes off then you have the carbanion i have the japanesse papers with the diagrams of the mechanism the shiff's base forms, then some electron juggling CO2 comes off and the carbanion is formed. i'll have to shoot you those papers you'll see, those chincks are smart.
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comfort_develops
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[*] posted on 13-4-2007 at 13:29


Somebody tried this reaction 2 times and really likes it.

But some questions:

Is it possible to do this reaction with Valine, instead of Alanine? Would the product be of intresst (if possible)?

Arent there any possible reactions with other aldehydes/amino Acids?
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roamingnome
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[*] posted on 14-4-2007 at 09:01
the north west passage


Well did you use some type of base to facilitate the adding of the aldehyde to C-H acid of alanine? Or is 20% yield your idea of a good time.

Valine’s C-H acid might form the anion easier, but its bulkier. The bioactivity is left for you to test

While simply doing the whole synth with benzaldehyde will probably be the best, since you can possiblity recover half of it back.
Functional group surfaces are becoming more common.
The google patent
American Chemical Society, Mar. 3, 1998, vol. 31, No. 22, p. 7618-7626.
Example 1

I searched around for threads that use Acrolein to learn that simply decomposing glycerin will form this noxious gas. Despite that, depositing this on a large glass surface with aldehyde groups sticking up might become surprisingly simple.

http://www.diss.fu-berlin.de/2005/271/Chapter2.pdf
or maybye not


Then alanine is poured on the surface to create Schiff base linkages.
Dehydrate
Then base, probably NaMethoxide creates a carbanion
Then benzaldehyde adds, possibly with stereo selectivity
The surface is then treating with dilute acid to severe the Schiff base linkages
The surface hopfully can be used a number of times.
We can decarboxylate later after reality catches up.

[Edited on 14-4-2007 by roamingnome]
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jon
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[*] posted on 14-4-2007 at 16:54


man you really go out to left field on this, did you ever do a tlc chromatogram of your dmso expiriment?

[Edited on 15-4-2007 by jon]
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gambler
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[*] posted on 17-4-2007 at 19:30


Look i have read the whole thread and still have a few questions (maybe foolish) that is irrelevant.

Firstly,

How is the DIY deakin stark trap created. Please point me in the direction of appropriate refrences if you wish.

Secondly, this procedure seems simple enough, is there any other notes that people who have performed this can give me....

Thirdly, I would greatly like some refrences in regards to the Akabori reaction.. However, there is an appropriate forum for this.

Thanks in advance]
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[*] posted on 17-4-2007 at 20:26


Finally,

With benzaldehyde ever difficult to acquire, for the amateur is it best to

- Order bitter almond oil from ebay
- Cinammon conversion
- Toulene oxidisation
- Do what roamingone suggested and just buy essence..

However, am still confused by what roamingone wrote as to if he ever arrived at P2P or not..

Thanks
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roamingnome
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[*] posted on 18-4-2007 at 09:16


jon: the ball was hit deep into left field its going going.. bounces fowl off the pole…

it mainly is just theoretical banter, but double bonds can bind to silicon and forming an aldehyde surface would surly be cool, if it could be done with ease…
http://hamers.chem.wisc.edu/papers/pdf/hamers_jjap.pdf

this link which wasn’t working this morning explains it real nice. also sorry but "real life" has prevented all real chemistry for now, drat....

Gambler:
I hope no one minds me saying that as far as benzylaldehyde, hilski and predecessors have shown that oxidation of toluene is a most viable option. Soon juice will be run into a cell, OTC stuff is well a gamble…
Further more, in this thread I can not tell I lie, I have interest in the amino alcohol for certain cyclic urea studies…. But I have ZERO if 2% interest in p2p for any reason…. Using styrene is interesting for some reason, but not in this thread dude…

Astrum, fromthe hive supposly used a base in this reaction, but the sucker ran off to university before posting results...
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gambler
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[*] posted on 23-4-2007 at 20:30


So how is a DIY deakin-stark trap constructed?

And is this necessary for reaction to complete?
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tupence_hapeny
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[*] posted on 24-4-2007 at 00:42


look at the reaction procedures for producing phenylserine, the structure of which is here:

http://www.anaspec.com/products/product.asp?id=26317

(Disregard the fmoc/boc protecting group).

This is essentially what you want to make, is it not? Albeit with a methyl group where the carbonyl group is at the end?

Anyhow, phenylserine is produced by reacting glycine with benzaldehyde, in the presence of NaOH - which is essentially the same mechanism as that which you are asking about - the condensation of an aromatic aldehyde with an amino acid (aka the Akabori reaction)?

As fuck all information exists (in English at least) as regards the reaction between alanine and benzaldehyde, the reaction of a simple amino acid with benzaldehyde may offer some insight.

http://pubs.acs.org/cgi-bin/abstract.cgi/joceah/1973/38/i17/...

http://studentsupport.syr.edu/upload/Tracey-Ann%20Samuels%20...

I am not certain that this reaction is able to be directly translated to the reaction between alanine and benzaldehyde, however and given the structural similarity, it might very well work.;)

tup

[Edited on 24-4-2007 by tupence_hapeny]

Attachment: Process for the Production of B-Phenylserine (US Patent 4605759-1).pdf (321kB)
This file has been downloaded 966 times





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roamingnome
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[*] posted on 24-4-2007 at 09:42
its just alanine


Enantioselective alkylation of alanine-derived imines using quaternary ammonium catalysts
Lygo, Barry; Crosby, John; Peterson, Justine, A.
Tetrahedron Letters 40(49): 8671-8674, 1999
Abstract
Application of N-anthracenylmethyl dihydrocinchonidinium bromide as a catalyst for the enantioselective alkylation of a series of alanine-derived imines is reported. Using solid K2CO3/KOH as the stochiometric base such alkylations can be achieved with enantiomeric excesses up to 87% allowing rapid access to alpha,alpha-dialkyl-alpha-amino acid esters.


i just read all the references ive been collecting because it was all i could do at the time....
the fancy catalyst probably isnt required or could be replaced with something simple like tryptophan aminoacid.

at this point though, were just running in circles its time to get the beakers wet....

removing water from this reaction to drive it to completion etc, might be acheived with things like MgSO4
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jon
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[*] posted on 24-4-2007 at 13:37


does'nt bitter almond oil contain triglycerides as well, meaning you would have to purify it to get uselful benzaldehyde.
regarding the foreign articles the chem beritche article on reaction of amino acids with bennzaldehde here:

http://www.erowid.org/archive/rhodium/pdf/akabori-1957.pdf

can be translated with OCR software Claro scan2text I found is useful for converting to text form which can then be pasted into babelfish to translate but the trial versions only let you do one page so my strategy is to download adobe distiller from limewire of some such p2p software sharing program, and convert the pdf into seperate single page PDF's and the translate each page one at a time.
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tupence_hapeny
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[*] posted on 15-5-2007 at 04:44


Jon,

If I can post the sucker it will be here in separate pages very soon.

tup




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jon
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[*] posted on 17-5-2007 at 14:05


yes it's got a lot of useful information in it, you can go to downloads.com (c-net) and get claro "scan2text"
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[*] posted on 3-12-2007 at 20:37


I was searching high and low for n-methylalanine references but nothing -- I did find this one patent - but not too sure this is the correct compound needed

http://www.freepatentsonline.com/5587506.html

more info on it would be welcomed or even a better route...

I also found this -- much easier route

http://www.sciencemadness.org/talk/viewthread.php?action=att...

[Edited on 4-12-2007 by jimmyboy]
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[*] posted on 4-12-2007 at 08:37


Refrence Information



Catalytic Decarboxylation of alpha-Amino-Acids
KLAUS DOSE
Nature vol.179, 734 - 735, 1957

.
Abstract
NON-enzymatic decarboxylation of alpha-amino-acids was tried many years ago by heating them above 200° C., often dissolved or dispersed in an inert solvent too. As the reactions are always exotherm, heating is only required to reach the rather high energies of activation. The way in which Nature lowers these energies by enzymatic reactions has been frequently discussed. The formation of a Schiff's base between an alpha-amino-acid and pyridoxal-phosphate as the proved prosthetic group of most of the decarboxylases is postulated by many authors, and the easiness of their decarboxylation may be understood with the help of the electronic theory of valence.


----------------------------------------------------------------------------------

THE DECARBOXYLATION OF AMINO ACIDS, PROTEINS,
AND PEPTIDES BY N-BROMOSUCCINIMIDE

EMMETT W. CHAPPELLE AND J. MURRAY LUCK


http://www.4shared.com/file/31147254/a39727cc/THE_DECARBOXYL...



[Edited on 4-12-2007 by solo]

Attachment: Catalytic Decarboxylation of alpha-Amino-Acids.pdf (457kB)
This file has been downloaded 1002 times





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jon
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[*] posted on 13-12-2007 at 14:19


the reaction don't go that way first the benzaldehyde condenses on the alanine decarboxylation takes place and then another mole of benzaldehyde adds to the decarboylated carbanion look it up yourself it's those japanesse articles with diagrams.
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[*] posted on 22-12-2007 at 07:54


there a clearly two mechanistic pathways

jon eludes to the one that decarboxlation happens leaving room for a simultaneous alkalation

alternitivly, you can form a carbanion by abstacting the H from the C-H acid with strong base. The russians suggest the KOH/DMSO system is strong enough
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jon
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[*] posted on 22-12-2007 at 18:20


nope it won't work you need 2-bromopropionic acid, that's in org. synthesis you can look it up online.
you can bromonate it just like you can brominate a ketone because of tautomerism. it is done in ether. you would get a diamine using what you proposed.
I've given the serine route a thought but after some research I concluded it may or may not be possble because of the steric factors involved with alanine the carbon bearing the alpha hydrogen is substituted in alanine in the case of glycine it is not.

[Edited on 23-12-2007 by jon]
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manimal
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[*] posted on 15-1-2008 at 17:44


How about decarboxylating the phenylserine derivative by heating in sulfuric acid to 200C, or would that destroy the amino alcohol?
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[*] posted on 18-1-2008 at 00:26


Could this reaction be sucsesfully done without haveing proper glassware ?

And couldent boiling chips be used instead of having to use a Mag/hotplat stirrer ?, Thats how they did it way back before Hoplate/stirrer's come around !

And is a dean stark trap essiential for water removal ?, Or could something getto be created ?
:(




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[*] posted on 18-1-2008 at 18:50


The more I come back to this thread the more CycloKnight is awesome.

For right now you may just want to keep saving money on your car insurance and save up for the dean stark trap :P

Or you can help solve my problems for me

Just ten minutes ago, literally, my hands are black with graphite…
I was performing small test tube reactions to conserve stock

Powdered alanine, benzlaldehyde bisulfite adduct, graphite, and Microwave chemistry.

Very interesting stuff. Sure I didn’t add decraboxylating solvent catalysts like
N-methylpyrrolidone. But after adding K2CO3 base with a small bit of water to make a poultice, the post reaction methanol extraction has some translucent brown organics it it. Whereas without the base the methanol extraction was disappointingly clear. A few days ago without the graphite its even less good and smells like an old fart….

the point is im having fun and theres alot of ground to cover
Seriously Geko do you even have 50mls of benzlaldehyde to waste with a getto dean stark trap.






In other news ive found 4 anhydrous methods for deprotecting a bisulfite adduct. Only two are handy but notice the iron in both methods here.


http://www.ics-ir.org/jics/vol3/n1/articles/jicsv3n1r9.pdf
Deprotection Method of Aryl Aldehyde Bisulfite Adducts with Recoverable
[BPy]FeCl4 as a New Ionic Liquid Catalyst

http://www.ingentaconnect.com/content/ben/loc/2006/00000003/...
Selective Deprotection of Bisulfite Addition Products by FeCl3•6H2O and Fe(NO3)3•9H2O Supported on Silica Gel Under Solvent-Free Conditions
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Geko127
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[*] posted on 27-1-2008 at 17:37


That still dident answer gekos question .

Couldent boiling chips Or a fishtank bubbler be used instead of a hot plate stirrer.:D




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[*] posted on 12-2-2008 at 05:46


And why cant the reaction sludge be based directly :(
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[*] posted on 12-2-2008 at 05:57


tar.gz I belive.



e3500 console login: root
bash-2.05#

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