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Here are
two hive threads on the subject:
quote:
IOC
(Stranger)
12-07-01 04:28
No 245275
Akabori run Bookmark
crap, at best 15% using 100 g BnZ, 40g l-alanine.
Heat to 140 seems best, extracted into H2o and evaperate, then
clean up.
would decarboxylation of a methylamino over the amino maybe improve
results?
How about a base and high bp solvent with C5H5N??
as suggested in tfse.
could some one please explain the reaction mechanics for the reaction:
,on heating BzH and DL-alanine directly; PhCH2NH2, PhCH(OH)CHPhNH2
(2 dl-compds.), AcH, and CO2 are formed.
Is this a condensation (no H2o) or a decarboxylation?
what conditions would be pref?
any ed imput would be great, cheers
jim
(Hive Bee)
12-07-01 05:53
No 245287
Re: Akabori run Bookmark
Give references.
Personnally I don't know of this reaction, and am wondering why you
would even attempt it? Get phenylalanine and decarboxylate
instead...
Aurelius
(Hive Bee)
12-07-01 10:15
No 245346
Re: Akabori run Bookmark
complicated rxn mechanism for just words. you'd have to look up the
actual article. (btw- your yeild will go up if you calculate
according to the converted benzaldehyde, and recover the rest for a
second go)
IOC
(Stranger)
12-08-01 01:33
No 245572
Re: Akabori run Bookmark
An otc way to PPA, what I,ve dug up so far
Synthesis of aminoalcohols by aldol condesation of aminoacids with
aromatic aldehydes.
The alanine is reduced via -COOH => -CH2-OH
Reaction between aromatic aldehydes and a-amino acids. I. New facts
on the Akabori reaction. Takagi, Eiichi. J. Pharm. Soc. Japan
(1951), 71 648-51. Journal written in Unavailable.
Abstract
The Akabori reaction (I) (C.A. 41, 3774g) on BzH and
dl-MeCH(NHMe)CO2H (II) with and without pyridine and removal of the
unreacted BzH by steam distn. gave dl-ephedrine and dl-y-ephedrine.
Similarly, direct heating of piperonal and II gave 2
dl-1-(3,4-methylenedioxyphenyl)-2-methylamino-1-propanols. A new
reaction (III), differing from I, takes place on heating BzH and
DL-alanine directly; PhCH2NH2, PhCH(OH)CHPhNH2 (2 dl-compds.), AcH,
and CO2 are formed. It is considered that the I-type reaction
occurs when the N of the amino acid is secondary and the III-type
reaction when it is primary.
Fester5 sites that direct heating of 20g N-methyl-alanine
with 50g Bnz at 150deg untill fizzing stops, produces
12g of a mixture 3g ephedrine and 9g pseudoephedrine isomers.
Reactant BRN 471223 benzaldehyde
1720250 DL-alanine
Product BRN 3196917 (1RS,2RS)-2-amino-1-phenyl-propan-1-ol
-------------------------
Reaction Details
Reaction Classification Preparation
Temperature 140 #65533;C
Other conditions Erwaermen des Reaktionsprodukts mit wss.-aethanol.
HCl
Ref. 1 2262852; Journal; Takagi et al.; YKKZAJ; Yakugaku Zasshi;
73; 1953; 1086; Chem.Abstr.; 1954; 12021;
As promised, here are some more refs on the interesting
condensation reaction between aromatic aldehydes and
glycine/alanine:
BER 25: 3445 (1892) + 52 :1734 ('19)
ANN. 284: 36 + 307: 84
JCS 1943 ('26) + 2600 ('22)
JACS 76: 1322 ('54)
J.PHARM.SOC.JAP. 67: 218 ('47)
Most of the articles are pretty old to say the least but they
contain some interesting stuff on the reaction we're interested in
here. I'm especially interested in the J.Pharm.Soc.Jap article, which
describes the preparation of a methylenedioxy-substituted
phenylserine. But the practical way to go is definitely as
mentioned in a certain patent, that is using a two-phase solvent
system. This prevents the benzylidene phenylserine from
crystallising and makes sure that the reaction mixture can be
stirred at all times.
After decarboxylation, these phenylserine derivates turn into amino
alcohols, the perfect substrates for aminoxazolines. By
substituting the benzaldehyde, a lot of phenylserine and amino
alcohol derivates can be made and thus a lotta aminoxazolines!
So with some 10x experiments with 20g alanine + 50g BnZ
a massive 15% return sux, any suggestions besides learn how to make
nitroethane?
java
(Hive Bee)
12-04-02 08:24
No 386214
Re: akabori: Bookmark
Did I read this correctly then one can then make ephedrine using
this method.......well have you tried it and what are the
conditions since I can't find the article ,,,anyone?
Akabori
Also known as Akabori-Momotani
Synthesis of aminoalcohols by aldol condesation of aminoacids with
aromatic aldehydes.
[image]
Bibliography
Akabori S., Momotani K., J. Chem. Soc. Japan, 1943, 64, 608; C. A.,
1947, 41, 3774
Dose K., Ber., 1957, 90, 1251.
Belikov V. M., Izv. AN SSSR. OHN, 1969, 2536.
This I was able to locate.
Rhodium
(Chief Bee)
12-04-02 08:53
No 386225
Akabori Bookmark
Yes, it's correect that you can make ephedrine very simply with the
Akabori reaction between Benzaldehyde and N-methylalanine. Ordinary
alanine would give phenylpropanolamine.
The only one of the above articles I could locate was J. Am. Chem.
Soc. 76, 1322 (1954) (https://www.rhodium.ws/pdf/akabori.phcho.glycine.pdf).
I doubt that the original reference has been retrieved as it is
written in Japanese, and "IOC" is not likely to answer
you either, as he hasn't been logged in since June.
quote:
dormouse
(Member)
04-22-00 02:13
No 108531
phenylpropanolamine from benzaldehyde and alanine -drone 342
Bookmark
the Hive BB
Novel Discourse
phenylpropanolamine from benzaldehyde and alanine
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Author Topic: phenylpropanolamine from benzaldehyde and alanine
drone 342
Member posted 10-15-98 09:18 AM
--------------------------------------------------------------------------------
Reactant BRN 471223 benzaldehyde
1720250 DL-alanine
Product BRN 3196917 (1RS,2RS)-2-amino-1-phenyl-propan-1-ol
-------------------------
Reaction Details
Reaction Classification Preparation
Temperature 140 #65533;C
Other conditions Erwaermen des Reaktionsprodukts mit wss.-aethanol.
HCl
Ref. 1 2262852; Journal; Takagi et al.; YKKZAJ; Yakugaku Zasshi;
73; 1953; 1086; Chem.Abstr.; 1954; 12021;
This informative post was brought to you by drone(tm) #342, who
reminds you: euphoria -- its what's for dinner.
-drone #342
Rhenium
Member posted 10-15-98 10:20 AM
--------------------------------------------------------------------------------
Drone,
I have a similar paper here, it's in Japanese and was published
around 1942. I can't read it, but the pictures suggest that they
reflux the two and get the PPA and CO2 produced. They have a little
picture of piperonal as well, but I can't figure out what they're
trying to do with it.
Take care,
Rhenium
beagle boy
unregistered posted 10-15-98 10:50 AM
--------------------------------------------------------------------------------
Shwing! I like what I hear. But I only hear the basic outline. Can
anyone (please) fill in the details. Like what solvent? How long a
reaction time? Japanese writing looks cool, but thats about all I
get out of it.
Labrat
Member posted 10-15-98 10:51 AM
--------------------------------------------------------------------------------
This is great and shit at the same time, great because it's one
beautiful method of making PPA from simple reagents, shit because
the article is in Japanese!
There are professional translators on the Net. How about paying one
to translate the experimental section of the two Yakugaku Zasshi
articles we have? If we share the costs, it won't be that
expensive. Lr/
drone 342
Member posted 10-15-98 03:38 PM
--------------------------------------------------------------------------------
I have a friend who's a Japanese native. The problem is she knows
nothing of chemistry. I sat down with her, and we went through the
Yakugaku Zasshi article from a while back, but they really didn't
say anything too intersting that I hadn't read elsewhere.
I could talk to her about translating the the two papers, but
you'll have to send me the second one, Rhenium. Hope you have a
scanner.
-drone #342
Cherrie Baby
Member posted 10-15-98 04:48 PM
--------------------------------------------------------------------------------
US patent 4501919 describes the reaction of glycine with
p-nitrobenzaldehyde (in a two phases: H2O-DCM with MeBu3NCl as a
PTC and concn. NaOH as a base, at 5-7#65533;C) to give
b-hydroxy,p-nitro-tyrosine.
What would happen if alanine were used in place of glycine? The
a-methyl analog?, which could be decarboxylated to
p-nitro-norephedrine? Your guess is as good as mine. This looks
like an interesting patent to explore as all the reagents are OTC.
It would work with other ring-substituents apart from nitro-, but I
only discovered the Chem. Abstract tonite [CA:102, 204296] and I've
not yet read the patent!
beagle boy
unregistered posted 10-15-98 08:48 PM
--------------------------------------------------------------------------------
Just checked that patent and saw that they were getting 70+% yield
of the #65533;-hydroxy phenylalanine derivative from this easy
procedure. And makes sense that alanine gives the alpha-methyl
derivative, which should be more readily decarboxylated, no?
So if just refluxing these cpds. in say, xylene, will decarboxylate
in good yields, this is one dandy scheme. Easy access to both
ethanolamines and propanolamines for that comprehensive aminorex
study.
Rhenium
Member posted 10-16-98 10:22 AM
--------------------------------------------------------------------------------
Drone : My friend with the scanner will be back in a couple of
days. I will try sending it to you after that. This could be a very
interesting procedure, hopefully the yields will be nice...
Take care,
Rhenium
Cherrie Baby
Member posted 10-16-98 05:56 PM
--------------------------------------------------------------------------------
beagle boy
In one of my references that quotes this they said that it was an
Aldol condensation between the aldehyde and the amine forming an
imine - which was subsequently hydroysised back to an amine, after
condensation with a further 1 mol of glycine. So it looks like a
different reaction mechanism to the one Drone's talking about -
theres only a slight possibility that it might work with alanine.
[I don't think so - I'm almost sorry I posted it - but it looked
good to me when I first saw it.
[no don't ask me I never thought that amines underwent Aldol
condensations either!]
beagle boy
unregistered posted 10-16-98 10:12 PM
--------------------------------------------------------------------------------
Cherrie:
I believe the patent you gave claims alanine could be used.
Checkitout: http://www.patents.ibm.com/cgi-bin/viewpat.cmd/US04501919__
Wierd amine aldol condensation, different from what I was thinking.
The question about decarboxylation remains, but I think these
serine derivatives should decarboxylate quite a bit easier than
tryptophan.
One downside to the above condesation is that the benzaldehyde
would have to be in twofold XS. The extra benzaldehyde is claimed
to be recovered for recycling after the reaction, but I'm not so
keen about letting precious aldehydes stir around in aq. NaOH and
then trying to recover them. Maybe the other route will turn out
better.
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#65533; Infopop Corporation (formerly Madrona Park, Inc.), 1998 -
1999.
Wouter
(Stranger)
01-28-03 17:40
No 402127
Full text journal of the akabori-momotani reaction Bookmark
Has any one the Full text journal of the akabori-momotani reaction?
Akabori S., Momotani K., J.Chem.Soc.Japan, (1943), 64, 608; C.A.,
(1947), 41, 3774
Is it possible to copy it and send it to me (wouter@chemist.com).
Please??
java
(Hive Bee)
01-28-03 18:24
No 402132
Re : Akabori..... Bookmark
This is all that is currently available....Akabori
Also known as Akabori-Momotani
Synthesis of aminoalcohols by aldol condesation of aminoacids with
aromatic aldehydes.
Bibliography
Akabori S., Momotani K., J. Chem. Soc. Japan, 1943, 64, 608; C. A.,
1947, 41, 3774
Dose K., Ber., 1957, 90, 1251.
Belikov V. M., Izv. AN SSSR. OHN, 1969, 2536.
although not available there is this at Rhodium's
place......................https://www.rhodium.ws/pdf/akabori.phcho.glycine.pdf.
this ofcourse combined with Rhegis's post Post 367468 (Regis:
"The most interesting CTH reaction ever documented?",
Novel Discourse)
makes for a nice package for the synthesis for
amphetamines.........java
Rhodium
(Chief Bee)
01-29-03 01:00
No 402201
Lots of threads on Akabori Bookmark
Post 122768 (dormouse: "Condensations of benzaldehyde and
alanine", Serious Chemistry)
Post 245275 (IOC: "Akabori run", Novel Discourse)
Post 278820 (ChemicalSolution: "alanine and Akabori???",
Chemistry Discourse)
Post 300434 (not existing)
Post 329052 (Aurelius: "Akabori-Momotani reaction",
Chemistry Discourse)
Well there you have it. This reaction is
turning out to be more and more realistic for everyone. SWIM is
predicting a comeback of 4-MAR  .
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