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Author: Subject: Benzene --> benzaldehyde
roamingnome
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[*] posted on 27-10-2010 at 17:25
Benzene --> benzaldehyde



"Efficient synthesis of benzaldehyde by direct carbonylation of benzene in ionic liquids"

Catalysis Letters
Volume 107, Numbers 1-2, 123-125,

Please view Table 1 entry 6 on page 124

As good scientists that these men are, they preformed an experiment where they used AlCl3 alone with Carbon Monoxide and Benzene to achieve a 40% yield benzaldehyde

This appears to be an excellent approach for any experimenter.
remarkable if it can be confirmed.

Thank you for you time



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spirocycle
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[*] posted on 27-10-2010 at 17:57


how to get clean monoxide easily is the next question

also it says that they achieved
Quote:
with relatively high yield (up to 91%) and selectivity
(ca. 96%).


[Edited on 28-10-2010 by spirocycle]
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not_important
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[*] posted on 27-10-2010 at 18:10


A) There are existing threads on the general topic. Please attempt to find existing threads before starting new ones that make researching a topic more difficult.

B) 40 kg/cm2 CO pressure is not terrible, but not something many amateurs might not be able to do.

C) Best yields were with the highest AlCl3:ionic liquid ratios, with straight AlCl3 you need 1/2 mole AlCl3 per mole benzene. The AlCl3 complexes with the aldehyde, the traditional method of handling this is hydrolysis of the complex which results in the destruction of the chloride. Anhydrous AlCl3 of high quality is something not really easy to come by; some amateur attempts have had difficulty in obtaining the needed quality.

This general reaction, using AlCl3 or other metal halides, has been done before; there are examples in the patent records I believe; because of that I would not be surprised if the work referenced is correct or nearly so. It's just the difficulty of the two and a half bar dry CO pressure, plus large amounts of good grade AlCl3, that make it appear less accessible than the chlorination of toluene followed by fractionation and hydrolysis.
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spirocycle
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[*] posted on 27-10-2010 at 18:11


http://pubs.acs.org/doi/pdf/10.1021/cr980032t
this is the link to how they prepared their ionic liquid, if someone has access
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RiP057
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[*] posted on 27-10-2010 at 20:03


I thought vilsmeier hack was the way to go to make benzaldehydes???

simple DMF/POCl3 reaction with a reflux
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mnick12
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[*] posted on 27-10-2010 at 20:45


Well the vilsmeier-Haack reactions is often used for creating aldehydes, but it is not economic especially for a simple aldehyde like benzaldehyde phosphorus oxychloride is quite expensive and not readily aquired.
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Sandmeyer
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[*] posted on 28-10-2010 at 11:43


Quote: Originally posted by mnick12  
Well the vilsmeier-Haack reactions is often used for creating aldehydes, but it is not economic especially for a simple aldehyde like benzaldehyde phosphorus oxychloride is quite expensive and not readily aquired.


I don't think that is the reason, in fact Vilsmeier normally only works on electron rich aromatics hence formylation of benzene will not work this way.




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Methyl.Magic
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[*] posted on 28-10-2010 at 12:27


Benzene and CO :

If you are not dead by CO, cancer will take care of your death.
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RiP057
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[*] posted on 28-10-2010 at 16:35


benzene will readily undergo the vilsmeier hack just like it will undergo chlorination iodination nitration all of the above prefer electron donating substituents but will react with benzene easily just maybe longer reaction time....

POCl3 however is not easily gotten if you are an amateur chemist.... it is readily available from chem supplies just expensive to ship as it must be drop shipped, but if you buy any amount it is usually a substantial amount and unless you are making kilo quantities of benzaldehyde for unsavory purposes it does the job just fine and you arent exposing yourself to CO at what I heard was 2.5 ATM.
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entropy51
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[*] posted on 28-10-2010 at 16:57


Quote: Originally posted by Methyl.Magic  
Benzene and CO :

If you are not dead by CO, cancer will take care of your death.
My Organic Chem professor died last year at age 92. When I took his class in the 1970's he liked to joke about all the asbestos filters he stirred up in beakers from asbestos powder, and how he washed organic tars off his hands daily with benzene as a graduate student. Just say'n.
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not_important
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[*] posted on 28-10-2010 at 17:22


OTOH one of my chem profs recounted how many of his profs and fellow students that went into research (pure & applied) that died of cancer and various organ failures in middle age - rates far above the average for the population there. Asbestos isn't that much of a risk to workers in the field (or in the field pre-1970) especially compared to some of the other stuff.

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roamingnome
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[*] posted on 28-10-2010 at 18:19


Your right

all the reagents are toxic and take preparation.

CO can be made with Zn powder CaCo3
For AlCl3 your probably making Chlorine gas anyway so chlorinate toluene
Benzene seems to have a nice boiling point to work with but will benzaldehyde form azeotropes during work up anyway?

Hydrogenation of benzoic acid with H2 gas at 360 C over ZnO again seems friendly.
Ozonenation of styrene in methanol followed by hydrogen and lindlar's catalyst takes apparatus but doesn't it all.
And that Mn salt

Im just trying to put all the cards on the table

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[*] posted on 29-10-2010 at 06:25


Quote: Originally posted by RiP057  
benzene will readily undergo the vilsmeier hack just like it will undergo chlorination iodination nitration all of the above prefer electron donating substituents but will react with benzene easily just maybe longer reaction time....

When claiming things that seemingly make no sense, it is always good sense to provide a reference. So, please provide a reference describing a Vilsmeier–Haack formylation of benzene!
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RiP057
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[*] posted on 29-10-2010 at 12:49


will do going to do a search on beilstein after I shower.... I figure most people have access to something like that, but then again I guess most dont
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RiP057
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[*] posted on 29-10-2010 at 15:37


it would seem I am talking out of my arse, but in this journal article it was accomplished
Tetrahedron yr:1990 vol:46 iss:16 pg:5633 -5648
however the use of n-Bu-Li and t-BuOK were used to deprotonate the benzene ring... this article focuses on making deuterated benzaldehydes.... so I guess its done with extra reagents, but everyone else uses CO....
although this article uses hydrogen cyanide if you really want to kill yourself
Journal of the Chemical Society yr:1932 pg:2793 -2797

I guess in my past I worked on heterocycles which usually always have extra electron to push the reaction, and in my theoretical mind the reaction should be able to be accomplished just that the energy barrier for it is higher than what is supplied by the reflux.... then again just cause I cant find a reference doesnt mean it cant be done.... I guess you could try it for yourself and find out :)
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