DraconicAcid
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Cinnamic Acid
I've introduced a new experiment at my college, in which my students make cinnamic acid. Now I've got a whole bunch of it....what to do with it?
I'm planning on trying to make some esters, just to see how they smell (it won't surprise me if they smell like cinnamon, but you never know).
I made some copper(II) cinnamate the other day- nice blue solid (unsurprising). Nickel cinnamate is clearly soluble- playing with the solution never
gave anything but gummy nickel(II) hydroxide or a precipitate of cinnamic acid.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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thesmug
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Make cinnamaldehyde or sell it if you can. I know I would really like some cinnamic acid!
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DraconicAcid
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I'm not sure if I want the bother of shipping it internationally, but there's no point in turning it into cinnamaldehyde (that's what the students
make it from).
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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blogfast25
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DA:
How did you make it?
The esters may be surprisingly different in odour: see e.g. the esters of the real stinker butyric acid!
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DraconicAcid
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Chlorite oxidation of cinnamaldehyde. Quick, simple, and worked better than last year's attempt at oxidizing vanillin with silver oxide (most of the
students added too much water to wash the silver oxide into the flask, and could not get the acid out of solution).
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Töilet Plünger
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You could just recycle the cinnamic acid...can you use that as a lab for your students as well?
Why not make cinnamates of other metal salts?
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DraconicAcid
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| Quote: | | You could just recycle the cinnamic acid...can you use that as a lab for your students as well? |
We don't do much organic chemistry in this course, so probably not. (I am planning to recycle the adipic acid that they also make for a
recrystallization lab that a different class does- it recrystallizes quite nicely.)
| Quote: | | Why not make cinnamates of other metal salts? |
I intend to try...have to clean up the nickel attempt first....
[Edited on 7-4-2014 by DraconicAcid]
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AvBaeyer
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You could brominate it to get the isomeric dibromides and carry these on to phenylpropiolic acid using a basic dehydrohalogenation (KOH/ EtOH). You
could also dehydrobrominate/decarboxylate the dibromocinnamic acid to alpha-bromostyrene. If the isomeric cinnamic acid dibromides (erythro/threo) can
be separated in a student lab, they could test the differential reactivity of the isomers. Maybe too much but have fun.
AvB
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zed
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Could possibly perform the reverse aldol, by steam distilling benzaldehyde from the cinnamic acid in a basic NaOH solution. The procedure works with
cinnamaldehyde.
Could create the ester, oxidize the double bond via performic acid, then perform a hydrolyses that would yield phenylacetaldehyde.
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DraconicAcid
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Well, I found this: http://books.google.ca/books?id=8PI4AAAAMAAJ&dq=gmelin%2...
That described a number of cinnamate salts (if the link doesn't work, do a google search for "cinnamate of lead". One of the first hits will be
Gmelin's Hand Book of Chemistry, Volume 13, p 276), including manganese(II), which is supposed to be a yellow crystalline solid. I got a pale yellow
solid, but it started turning dark brown on exposure to air. I suspect the reaction
2 MnCin2 + O2 + 2 H2O --> 2 MnO2 + 4 HCin (where Cin = cinnamate) is responsible.
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DraconicAcid
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Weird. I searched for this thread four or five times, as I was *sure* I had started such a thread last year, but it never came up. My students made
another big crop of cinnamic acid, so I'm still looking for ideas. Methyl cinnamate worked, but was disappointingly odourless.
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Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Ozone
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I find that it smells a bit like a cross between feet and cinnamon. YMMV.
This is a great one that I've had a lot of fun with:
You could make poly(vinyl cinnamate): http://www.sigmaaldrich.com/catalog/product/aldrich/182648?l...
Perform the esterification of poly-vinyl alcohol with it. This works best by first making cinnamoyl chloride (with thionyl chloride (yeah, right) and
running the rxn in TEA or pyridine), but demo-grade results can be had via Fischer esterification in a non-aqueous high-boiling polar solvent such
that the resulting polymer precipitates.
Once you have poly-vinylcinnamate, you can, for example, cast films from DCM (or other suitable solvent), mask them off, and cross link the polymer
via UV light (272-360 nm is preferred for this photochemical [2+2] cycloaddition to truxillates, etc., but I've had good results with a 300nm
transilluminator...or, you could add a sensitizer).
Shows cyclobutane-type products: http://pubs.acs.org/doi/abs/10.1021/ma50002a019
This is cool because the un-reacted polymer is fluorescent blue under LWUV and the exposed material is green. This can make for a striking
demonstration.
O3
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zed
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There is also the possibility of converting that Cinnamic acid to Phenyacetic acid.
It isn't the most commonplace of pathways, and styrene or acetophenone are the more common feedstocks for producing Phenyacetic via the Willgerodt,
but Cinnamic Acid will do.
Performing the Willgerodt on an unsaturated acid, such as Cinnamic, produces a saturated acid, of one fewer carbon atoms. Phenylacetic acid.
Quite possibly, the Thioamide that is initially produced, can be reduced to Phenethylamine. Though I am at a loss as to what reducing agent might be
employed to achieve this transformation.
The question is, "Do you feel confident that you can conduct such an experiment, without releasing dangerous amounts H2S into the lab."
PS. Yup. It appears Thioamides can be reduced to Amines in a number of ways. Raney Nickel, Borohydride, and Aluminum Amalgam, among them.
[Edited on 13-5-2015 by zed]
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smaerd
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I like the ester idea! Then again I have a big interest in fragrance compounds.
Or make the ester then see if you can do a borohydride reduction of the alkene under luche conditions or cyanoborohydride. IIRC that reduction is
selective for a,b unsaturated carbonyls.
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DraconicAcid
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I checked the mp. of my methyl cinnamate, and it turned out to be 34.5-36 oC, which is pretty close to the literature of 36 oC. Putting a small
amount into a flask and shaking it up with hot water gave off a strawberry-ish smell....very synthetic smelling, though (expected).
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zed
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Ah. Wiki tells us that the P-Methoxy version of Ethyl-Cinnamate, may be a monoamine oxidase inhibitor. Sounds like a potentially deranged
experiment. Could you feed it to a rat, and then kill the rat by feeding it cheese? I know it is wrong to think this way, but I got dark yearnings
today.
Whoops. It occurs to me that you might be able to produce phenylacetaldehyde from your cinnamic acid. Yup! I'm pretty sure.
I'll go refresh my memory. But, make the ester, oxidize with peraformic acid (or) and hydrolyse the product. Presto! Mimics some physiological
processes. Wherein, a keto-acid really wants to decarboxylate, or become an amino acid.
[Edited on 16-5-2015 by zed]
[Edited on 16-5-2015 by zed]
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