Gm I apologize for my recent change in disposition. in reference to what interests you.
"
The essential oil of cassia (C. aromaticum) is predominately cinnamaldehyde"
    Correct, and kgs of this are available at your local friendly Vietnamese grocery store
   Steam distils easily, yeilds, of course vary, on many factors,,but at least here is a Cheap and accessable Source of the oil you wish to utilise
 Hyppy

Ps. Its actually Cassia Bark they sell, I know the stuff around IS C.Aromaticum.     And it looks like foot long,inch thick, rough textured cinnamon sticks, break a bit off and you can instantly smell cinnamon.

Here is what aminated cinnamic acid would look like..

The only hurdle, probably impossible, is a decarboxylatoin, while leaving the carbon..

.....reduce the carboxylic acid to the alcohol with NaBH4 in ethanol once converted to the ester , or use the `nickle/NaBH4 for the direct reduction to the alcohol....halogenate  then dehalogenate using the zinc acetate method mentioned in the cinnemaldehyde  bromination thread.....java

Note: This reminds me of phenylalanine with the amine group methylated....so all the info available for the reduction of phenylalanine to amph can be used to get meth.....

Okay, so... idea.

[the electron-deficient alcohol] N-acetylethanolamine adds across the [highly activated alkene] cinnamaldehyde to form an ether at the benzylic carbon... then hypochlorite oxidizes the amide to a chloramine. The chloramine [electrophilic nitrogen atom] adds to the [nucleophilic carbon atom] aldehyde enolate [under strong base] to produce an N-acetylmorpholine. Wolff-Kishner reduction produces N-acetylphenmetrazine.

Of course I'm not sure how to isolate the intermediates... but hey. N-acetyl can of course be replaced with other acyl groups; in particular formyl and methoxycarbonyl are easier to deprotect.

To be honest I'm not sure why someone would try to make an amphetamine out of cinnamaldehyde unless you had a massive amount just sitting around for no reason and nothing else to do... but phenmetrazine is a hard target, so if the above works.

Quote

On the topic of cinnamyl alcohol: it can be produced easily by grinding cinnamaldehyde with NaOH and distilling - the theoretical yield is 50%, but it's a cheap and easy way to do it.

You sure about that? Where or how is the reduction taking place,or are you thinking cinnamic acid (which dont look right either)?
At best, doesnt what youve described just retro-aldol to a small amount of benzaldehyde,after the majority of cinnamaldehyde distills over ? Any references to share?

The theoretical yield of 50% should really give this one away. It's a simple disproportionation! Get me my dharma stick.

bonk

http://its.goofyti.me/u/http://en.wikipedia.org/wiki/Cannizzaro_reaction

Of course, cinnamyl alcohol is notable for little else but being even more useless than cinnamaldehyde... some people never learn.

perhaps becoz it's an accessable starting point when others cant be found

Ugh.

Reduction to phenylpropionaldehyde can be achieved with hydrazine and peroxide (see "reductions with diimide"). 3-phenyl-2-bromophenylpropionaldehyde is next (bromine). Wolff-Kishner (to phenylisopropylbromide) and then amination (honey!).

A big pain. Why not Akabori?

Quote from: Assyl Fartrate on June 13, 2012, 08:27:14 AM

On the topic of cinnamyl alcohol: it can be produced easily by grinding cinnamaldehyde with NaOH and distilling - the theoretical yield is 50%, but it's a cheap and easy way to do it.

Bullshit. The Cannizzaro reaction is limited to aldehydes lacking alpha hydrogen. Treating cinnamaldehyde with sodium hydroxide will mostly yield benzaldehyde, as an hydrolysis product, and aldol condensation by-products.

Thankyou ^ Now wheres that spicy Dharma stick? Double bonk... Lol.

Actually, there is a Chinese reference out there that claims this can be put into effect with the help of microwaves, but simply grinding and heating wont work.

Cinnamic and piperic-type aldehydes are not enolizable and will not undergo aldol addition. Nucleophilic conjugate addition of OH- to the double bond is possible and can result in retro-aldol stuff. However, it does not occur when dry bases are used.

For practical purposes cinnamaldehyde does indeed "lack an alpha hydrogen", and this is why it is so hard to substitute the alpha position thereof.

http://its.goofyti.me/u/http://en.cnki.com.cn/Article_en/CJFDTOTAL-NXSH200701007.htm

Though, personally, I would prefer benzaldehyde to cinnamyl alcohol. You can actually do useful things with benzaldehyde, whereas cinnamyl alcohol is a waste of time. HCl in dry ether? You've gotta be kidding me!

http://its.goofyti.me/u/http://scholar.google.com/scholar?hl=en&q=nitrodecarboxylation+of+cinnamic+acid

That nitrostyrene will hydrolyse to PAA.

Quote from: atara on June 15, 2012, 12:06:53 AM

However, for practical purposes cinnamaldehyde does indeed "lack an alpha hydrogen", and this is why it is so hard to substitute the alpha position thereof. Degradation to benzaldehyde sounds better than any other idea this thread has produced thusfar.

1. No, it doesnt lack an alpha proton.  I agree that the proton in alpha position to the aldehyde functional group might have a different acidic nature due to obvious shielding, but it is still considered as an alpha proton.

2. Hydrolysis  in beta position to yield benzaldehyde is actually the favored pathway, lots of information available about that already.

I edited my post. Sorry. ataraposts are often works in progress. The completed post makes more sense. Though it is true that the phrase "for practical purposes" is a sophisticated form of lying.

Quote from: Quantum Dude on June 14, 2012, 08:25:44 PM

Quote from: Assyl Fartrate on June 13, 2012, 08:27:14 AM

On the topic of cinnamyl alcohol: it can be produced easily by grinding cinnamaldehyde with NaOH and distilling - the theoretical yield is 50%, but it's a cheap and easy way to do it.

Bullshit. The Cannizzaro reaction is limited to aldehydes lacking alpha hydrogen. Treating cinnamaldehyde with sodium hydroxide will mostly yield benzaldehyde, as an hydrolysis product, and aldol condensation by-products.

Thankyou ^ Now wheres that spicy Dharma stick? Double bonk... Lol.

Actually, there is a Chinese reference out there that claims this can be put into effect with the help of microwaves, but simply grinding and heating wont work.

Are you talking to me QD? If so there is some confusion ,as what you have said backs up exactly what I said upper thread. I was nodding in support.

Atara just posted the Chinese reference I was talking about. In another report it was suggested disproportion occurs,then Michael addition and subsequent retro-aldol back to benzaldehyde.
Semantics when talking of practical purposes. My original dispute was based on practical experience using a large excess of well baked  NaOH ground fine. Indeed a small portion of benzaldehyde was produced ,along with most likely benzoic acid/ benzyl alcohol and a whole lot of un-reacted cinnamaldehyde .

Ill request the two microwave papers.

REDUCTION OF CARBONYL COMPOUNDS TO THE CORRESPONDING ALCOHOLS WITH ISOPROPANOL ON DEHYDRATED ALUMINA UNDER MICROWAVE IRRADIATION

The reduction of different types of aldehydes and ketones were performed in the presence of isopropylalcohol (as solvent and hydride source) under microwave irradiation. It is proved that dehydrated Woelm chromatographic alumina supported KOH catalyses these transformations. Regioselectivity was observed in the reduction of cinnamaldehyde and chemoselectivity was observed in the reduction of carbonyl in the presence of nitro group.

http://www.adichemistry.com/organic/namedreactions/cannizzaro/cannizzaro-1.html
http://www.organic-chemistry.org/namedreactions/cannizzaro-reaction.shtm

Benzaldehyde can be synthesized from cinnamaldehyde obtained from the oil of cinnamon by refluxing in aqueous/alcoholic solution between 90 °C and 150 °C with a base (most commonly sodium carbonate or bicarbonate) for 5 to 80 hours, followed by distillation of the formed benzaldehyde. This reaction also yields acetaldehyde.


Cannizzaro reaction of the cinnamon aldehyde under solvent - free condition through grinding was studied. The catalytic ability of KOH, NaOH, Na2CO3 and NaAc were examined, and founded that the NaOH is the best catalyst. Then the factors of the effects reaction are investigated. The results show that optimum conditions with 2:3 molar ratio of NaOH and cinnamon aldehyde; the reaction time is within 5 min. under about 30 oC;the conversion ratio of the cinnamon aldehyde is 95% , the yield of cinnamon acid is 93% and cinnamon alcohol is 88. 5%. This facile new method is effectively, fast, and low cost.

Im sitting here thinking "How can they be microwaving the mix for 5 mins whilst keeping the temp below 30 deg??"
Damn I gotta get my head out of my arse. This isnt even the paper I was talking about,although I think it is from the same journal.
This is much better. Nice find Atara!
Excuse my inability to read/take in information very well. Ill shut up now, even though Im still a bit dubious about their results.