Mildronate
Hazard to Others
Posts: 428
Registered: 12-9-2009
Member Is Offline
Mood: Ruido sintetico
|
|
Alkylation with chloracetic acid
Is it posible benzene alkylation with monochloracetic acid by Fridel Craft to prepare phenylacetic acd
[Edited on 1-12-2010 by Mildronate]
Attachment: ph.tif (23kB)
This file has been downloaded 866 times
|
|
|
Rich_Insane
Hazard to Others
Posts: 371
Registered: 24-4-2009
Location: Portland, Oregon
Member Is Offline
Mood: alive
|
|
I think chloroacetone and AlCl3 will work better to yield phenylacetone. From there, I believe you can oxidize to phenylacetic acid. I don't think you
can attach the carboxyl group to the ring.
|
|
|
madscientist
National Hazard
Posts: 962
Registered: 19-5-2002
Location: American Midwest
Member Is Offline
Mood: pyrophoric
|
|
Sounds messy. Carboxylic acids can acylate aromatic rings as well. I'm betting on tar.
I weep at the sight of flaming acetic anhydride.
|
|
|
Nicodem
Super Moderator
Posts: 4230
Registered: 28-12-2004
Member Is Offline
Mood: No Mood
|
|
It is not possible. Under Friedel-Crafts reaction conditions, with a large excess of AlCl3 you could utmost obtain phenacyl chloride, but even this is
doubtful as FC acylations with free carboxylic acids tend to be very inefficient (except for some exceptions using catalysts other than AlCl3).
Quote: Originally posted by Rich_Insane  | | From there, I believe you can oxidize to phenylacetic acid. I don't think you can attach the carboxyl group to the ring. |
What kind of an oxidation method would give phenylacetic acid from phenylacetone? As far as I know, not even the haloform reaction would, just check
the pKa different between the methyl and methylene groups.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
|
|
|
Nicodem
|
Thread Moved
1-12-2010 at 16:19 |
DDTea
National Hazard
Posts: 940
Registered: 25-2-2003
Location: Freedomland
Member Is Offline
Mood: Degenerate
|
|
If you look at the mechanism by which Friedel-Crafts alkylation proceeds, a carbocation is formed:
R-Cl + AlCl3 --> R(+) + AlCl4(-)
If R-Cl is chloroacetic acid, you're going to be forming a primary carbocation adjacent to an electron withdrawing group (carboxyl). Not a very good
carbocation! Based on that, we can conclude this reaction would be highly unlikely.
"In the end the proud scientist or philosopher who cannot be bothered to make his thought accessible has no choice but to retire to the heights in
which dwell the Great Misunderstood and the Great Ignored, there to rail in Olympic superiority at the folly of mankind." - Reginald Kapp.
|
|
|
smuv
National Hazard
Posts: 842
Registered: 2-5-2007
Member Is Offline
Mood: Jingoistic
|
|
No it will go. Just not as you want. The product mixture will be very complex. The major theme though is that phenacylchloride will be produced,
which may either react at the carbonyl (2x) and at the halide. If you want more info about this kind of thing, a decent scientific library should
have a couple good reviews of the friedel-crafts reaction, most include info about using oxygen containing electrophiles (due to industrial interest).
In short this reaction has been studied, though I am not going to dig it up, because there is no way it will provide what you want.
[Edited on 12-3-2010 by smuv]
"Titanium tetrachloride…You sly temptress." --Walter Bishop
|
|
|
DDTea
National Hazard
Posts: 940
Registered: 25-2-2003
Location: Freedomland
Member Is Offline
Mood: Degenerate
|
|
| Quote: Originally posted by smuv | No it will go. Just not as you want. The product mixture will be very complex. The major theme though is that phenacylchloride will be produced,
which may either react at the carbonyl (2x) and at the halide. If you want more info about this kind of thing, a decent scientific library should
have a couple good reviews of the friedel-crafts reaction, most include info about using oxygen containing electrophiles (due to industrial interest).
In short this reaction has been studied, though I am not going to dig it up, because there is no way it will provide what you want.
[Edited on 12-3-2010 by smuv] |
Come on smuv, don't blue ball us!
I'm actually really interested in reading about that, even if the product is entirely different from the intended one at the beginning of this
thread.
"In the end the proud scientist or philosopher who cannot be bothered to make his thought accessible has no choice but to retire to the heights in
which dwell the Great Misunderstood and the Great Ignored, there to rail in Olympic superiority at the folly of mankind." - Reginald Kapp.
|
|
|
smuv
National Hazard
Posts: 842
Registered: 2-5-2007
Member Is Offline
Mood: Jingoistic
|
|
lol.
it is for sure mentioned in one or both of these books (they are both good to flip through though):
Friedel-Crafts chemistry,
by Olah, George A. 1927- Published 1973
Anhydrous aluminum chloride in organic chemistry,
by Thomas, Charles Allen, 1900- Published 1941
By my understanding of these reactions, the reaction should proceed, stepwise to 2,2,2-triphenyl(chloroethane). And then, go on to react at the
halide. The reaction would probably be done in refluxing benzene. DON'T think you can get say phenacyl chloride out of this or one of the steps
along the way. These reactions are very hard to control because the conditions are heterogeneous (although performing the reaction in nitrobenzene or
a nitroparafin can get around this).
You might have a shot getting phenylacetic acid from a friedel crafts of, BF3 (or any BX3) with fluoroacetic acid and benzene. But I think oxygen is
too small to allow that trick to work. Without a lit search, I can only think of indirect methods to get phenylacetic acid by firedel-crafts. For
example 2,2,2-trichloro(fluoroethane) with BF3 in benzene followed by hydrolysis of 2,2,2-(trichloroethyl)benzene to phenylacetic acid. It is
possible that TiCl4 or SnCl4 coordinate with halides in preference to oxygen (allowing the FC to produce phenylacetic acid from chloroacetic acid),
but I would have to lit search to find that (if you are so inclined look up the mechanism for formylations with dichloromethyl methyl ether).
p.s. this post is relying a lot on my memory over referred publications...grain of salt...
[Edited on 12-3-2010 by smuv]
[Edited on 12-3-2010 by smuv]
"Titanium tetrachloride…You sly temptress." --Walter Bishop
|
|
|
Rich_Insane
Hazard to Others
Posts: 371
Registered: 24-4-2009
Location: Portland, Oregon
Member Is Offline
Mood: alive
|
|
Sorry,
I meant one could prepare the aldehyde and oxidize to the carboxylic acid. I doubt one could prepare PAA efficiently using FC.
There's probably some theoretical pathways out there though.
|
|
|
ScienceSquirrel
International Hazard
Posts: 1863
Registered: 18-6-2008
Location: Brittany
Member Is Offline
Mood: Dogs are pets but cats are little furry humans with four feet and self determination! 
|
|
Easy ways to make an arylacetic acid is to start from the arene or the methyl arene.
The arene can be reacted with formaldehyde and a halogen acid to form the halomethyl arene, alternatively the methyl arene can be side chain
halogenated. This can converted to the Grignard or the lithium compound and then reacted with carbon dioxide to form the arylacetic acid.
Alternatively it can reacted with cyanide and then hydrolysed to form the acid.
The importance of arylacetic and more particularly 2 aryl propionic acids as drugs, plus the use of phenylacetic acid as a synthon has resulted in an
enormous effort at their synthesis.
Anyone who could do;
isobutylbenzene + 2-chloropropionic acid ----> Ibuprofen
would be flavour of the month at a lot of chemical companies and would get a big wodge!
|
|
|
Mildronate
Hazard to Others
Posts: 428
Registered: 12-9-2009
Member Is Offline
Mood: Ruido sintetico
|
|
But maybe I can make ester or salt of chloracetic acid and then alkylation?
|
|
|
Nicodem
Super Moderator
Posts: 4230
Registered: 28-12-2004
Member Is Offline
Mood: No Mood
|
|
Its been half a year and you still did not bother reading a single review article on Fridel-Crafts alkylations and acylations?
Alkyl carboxylates react just like carboxylic acids, except in that you also get the corresponding alkylbenzenes as side products to the aryl ketones.
Salts of carboxylic acids are bases. You need acid catalysis for the Fridel-Crafts reactions. Acids are quenched by bases, and vice versa.
|
|
|
azo
Hazard to Others
Posts: 163
Registered: 12-2-2008
Member Is Offline
Mood: No Mood
|
|
If the desired product is phenylacetic acid why would you go to all that trouble when everyone knows the hydrolisis of benzyl cyanide is the best way.
Or just as simple is to use the esters of phenylacetic acid
Then again theres nothing like taking 3 steps foward and 5 steps backwood is there.
regards azo
|
|
|
Mildronate
Hazard to Others
Posts: 428
Registered: 12-9-2009
Member Is Offline
Mood: Ruido sintetico
|
|
Maybe its not the best 
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
