Cinnamic Acid and Cinnamaldehyde

[Shake]

I have been studying these lately, there is an alkene double bond just like isosafrole, there are several fairly simple routes for the epoxidation of either of these. I will post pictures below.

I searched this whole forum, this is the only cinnamic thread so im not covering old ground
This is in cinnamon 80%.. it is very common stuff

If Cinnamic acid was epoxidised, then reformed to a ketone structure with sulfuric (the same as in the peracid route to mdp2p), then if this worked up as though it was p2p, so a reductive amination via Al Hg amalgum, i want to know where the NH2 would land? i believe carbox acids are 'protected' i am thinking the amination will take place in the same way, then from the aminated product the key groups are fairly resistant to many elimination reactions like clemmensen or wolf kishner..

There are several methods of eliminating an aldehyde function, 1 method is to brominate, which will replace the aldehyde function and then react that with NaOH which will steal the bromine away leaving a carbon. there are simpler elimination methods i am sure you guys would know them

The key would be to be able to eliminate the aldehyde function with out destroying that double bond between the second and third carbon.. Most elimination reactions ive seen on cinnamic leave Phenyl Ethanol, so the double bonded carbon get sacrificed..

Anyone have ideas here?

the reagents used below arnt very OTC but its an example of the structure change

[Shake]

here is the reductive bromination

[Wizard X]

Or use this procedure http://www.orgsyn.org/orgsyn/pdfs/CV4P0771.pdf

Ph-CH2-CHO ==[CH3MgBr]==> Ph-CH2-CH=CH2

[Sedit]

You are very off on many levels Shake.

If Cinnamic acid was epoxidised, then reformed to a ketone structure with sulfuric (the same as in the peracid route to mdp2p), then if this worked up as though it was p2p, so a reductive amination via Al Hg amalgum, i want to know where the NH2 would land? i believe carbox acids are 'protected' i am thinking the amination will take place in the same way, then from the aminated product the key groups are fairly resistant to many elimination reactions like clemmensen or wolf kishner..


Epoxidise Cinnamic acid--->ketone--->amination-->> then what?

You will be left with Phenylalanine


There are several methods of eliminating an aldehyde function, 1 method is to brominate, which will replace the aldehyde function and then react that with NaOH which will steal the bromine away leaving a carbon. there are simpler elimination methods i am sure you guys would know them

I dont know of any means to directly brominate an aldahyde, there is the possibility of reduction to the alcohol followed with bromination but I don't really know of direct routes. Im sure they must exist but I dont know of any.



The key would be to be able to eliminate the aldehyde function with out destroying that double bond between the second and third carbon.. Most elimination reactions ive seen on cinnamic leave Phenyl Ethanol, so the double bonded carbon get sacrificed..

I already told you, Wolff-Kishner being an acid liable substate thats all your left with. It will leave you with Propenylbenzene
Anyone have ideas here?

the reagents used below arnt very OTC but its an example of the structure change

Also, Cinnamaldahyde is the primary compound in cinnamon oil.

[psychexplorer]

Careful, there are two common essential oils of cinnamon (C. verum) in commerce, with the term "cinnamon" being thrown around loosely among various members of the genus Cinnamonium.

The expensive bark oil is primarily cinnamaldehyde, whereas the cheap leaf oil is primarily eugenol.

The essential oil of cassia (C. aromaticum) is predominately cinnamaldehyde.

[lugh]

This is very old ground, this was discussed long ago on the Hive     Cinnamaldehyde can be reduced by aluminum isopropoxide using the Meerwin-Ponndorf reduction as in Ann 444 221 (1925) to cinnamyl alcohol    As far as cinnamyl alcohol:

http://www.erowid.org/archive/rhodium/chemistry/cinnamyl.txt

psychokitty said:

(This appears optional. According to the review, commercial zinc dust worked just fine when used in proceedure A.)

Commercial zinc dust (16 g., 325 mesh) was activated by stirring for 3-4 minutes with 100 ml of 2% hydrochloric acid. The zinc was immediately filtered under suction, washed to neutrality with water, and then washed with 50 ml of ethanol, 100 ml of acetone, and diethyl ether. The resulting powder was dried at 90 deg C under vacuum (10 minutes) and was used within 10 hours of preparation.

Procedure A:

Cinnamyl alcohol (1.30 mm) was dissolved in 75 ml of dry ether saturated with hydrogen chloride at 0 deg C. Activated zinc dust (5.0 g; 0.076 mol) was slowly added to the cooled mixture with vigorous stirring at a rate such that the temperature maintained below 5 deg C. The reaction was exothermic and considerable hydrogen evolution occurred. The reaction mixture was stirred for 1 hour at 0 deg C and then filtered. The filtrate was shaken with 500 ml of ice water and then washed to neutrality with aqueous sodium carbonate. The aqueous washings were dried over sodium sulfate and evaporated under vacuum. Chromotography of the residual oil over silica gel (Mallinckrodt, 100 mesh, 25 g) using benzene as eluant afforded 60% yield of allybenzene (4 parts) and propenylbenzene (1 part).

The above ratios seems a little steep for the average bee with the volume of solvent too great. A more practical method that is on a preparative scale can be found in Tetrahedron 27, 5081 (1971).

as far as the remainder, that should be obvious 

[Wizard X]

This is very old ground, this was discussed long ago on the Hive     Cinnamaldehyde can be reduced by aluminum isopropoxide using the Meerwin-Ponndorf reduction as in Ann 444 221 (1925) to cinnamyl alcohol.

Or Cinnamaldehyde to cinnamyl alcohol using this procedure. http://www.orgsyn.org/orgsyn/pdfs/CV1P0304.pdf

[Sedit]

You are mainly wrong in the way your viewing carboxylic acids. There is no =O or OH to eliminate on a carboxylic acid there is only a COOH. It is a resonance structure and behaves as a unified functional group. They are very difficult to remove while keeping the carbon in tacked.

This substance is a lost cause.

I have seen all those links already guys, how lazy u think i am?? i have spent hours and hours on this, most is learing as i go, so discussion saves me alot of effort.. i feel like we are giving up to easily on things........ If it cant be done then it  cant be done but i guess thats why im bringing it up.. takes so long to figure these things out on my own......

I see many old bees who have been there done that, and i have full respect.. but there are no young bees, no one is doing shit, they are just copying the old bees

I told you already what needs to be done, I was clear and precise. You have two options to eliminate the Aldahyde one is the Wolff Kirshner the other is the Clemmenson. With the Clemmenson you would have to protect the double bond first and I know of no one that has attempted this.

Im curious why you ask for our help.... get people that know for a fact how to handle this kindly share some information with you and in return you get snippy... Would you like Me, Lugh and Wizard X to stop answering to this post? Would that be better since it sounds like its hurting your pride? Are you under the impression that no one skilled in the arts has ever attempted this before?

[Sedit]

I first stated his methods would not work because if you look it up there are two very distinct chemicals with the same name, one is used in phamacuticals. Plus I was pretty convinced when he first showed up that he was just some kewl that stole Quantum dudes reseach from over at drug forumsand Twodogs name and wrapped it into a nice neat package to try to be... Kewl.

I am no genius. I did use to be but that was long ago, well over a decade. Life takes its toll on the mind and memory while reality takes it toll on ones soul and creativity, sometimes the happy ambishion of life fades quickly and you get left with the harsh reality that not everything is possible and people are not looking out for you the way you are looking out for them. My pessimism has its routes.

It boils down to not really whats possible but whats practical, One could build MDMA from Benzene but would it worth it at all? Back in the 60's if you told a cook there would be a one pot to meth they would have laughed at you and said... So... then proceeded to show you there commercial bought P2P, there commercial Methylamine, there aluminum foil and the giant reaction flask they produced there meth in. Its a different ball game now.

If you wish to tread down this path then by all means have at it. But you have the information you need to get there posted already in this thread. After the carbonyl elimination you would proceed just as you would with Isosafrole.

[Goldmember]

Thanks to the contributors in this thread and the O.P.!
Interested in all things allyl for the moment ,I recently reduced cinnamaldehyde to the alcohol very easily and in fair yield using a  modified(TWEEKED) DCDMH/protic acid promoted Meerwin-Ponndorf reduction as Lugh suggest. Next Psychokitty`s reduction was attempted with no luck(lack of skill,equipment coupled with a huge amount of rxn mess vs product).
I was going to try a few things next. Im going to have a go at working a route toward the alkyl halide using NBS,TCCA,DCDMH etc either as a direct reagent or as a means of producing the halo acids in situ.Then reduction using Activated aluminium,Zinc/Copper couple and zinc-acid to see which best does the job.(that Iron reduction should work also shouldnt it Wiz?)

The reason I post this is because I do all this purely to see if it can be done.More than enough Benzaldehyde has been made from this load of cinnamaldehyde to see my needs catered.
If it works ,I imagine this reaction scheme will be a lot simpler to pull of than any benzaldehyde route, and the amount of reagents halved.
The intended end application to all this is to  use it on alpha-methyl-1,3-benzodioxole-5-propanal .

So Shake you are not alone!
Having said all that, and after copping my fair share or bitch slaps to the head from better chemist than I(three of them posting in this thread) over the years for presenting them with long conveluted and most probably low yielding reactions, It stuck with me something CHI said a while back along the lines of "you  are better off optimising/tweaking an established method rather than trying to reinvent the wheel".

Oh and please any suggestions pertaining to what Im doing are more than welcome.

P.s, Shake, did you see the reference I requested in which the authors use OXONE in acetone  to oxidise cinnamaldehyde to a mixture of phenylacetic/benzoic acid in fair yield?
This was given a real quick shot and from the flask did the unmistakable odour of PAA eminate. On the to do list once a work up is wored out.

[Wizard X]

Then reduction using Activated aluminium,Zinc/Copper couple and zinc-acid to see which best does the job. (that Iron reduction should work also shouldnt it Wiz?)

Only for cinnamaldehyde to cinnamyl alcohol, -CHO => -CH2-OH using procedure. http://www.orgsyn.org/orgsyn/pdfs/CV1P0304.pdf

No for -CH2-OH to -CH3

[Shake]

Here is what aminated cinnamic acid would look like..

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

[Shake]

ill post some refs, here

none of those are leaving the carbon though..

[Methyl Man]

If you told a chemist in the 60s that meth will one day be made 1 pot in a soda bottle hed shun you

Back in the 60's if you told a cook there would be a one pot to meth they would have laughed at you

I'm WAY out of my depth to even enter this discussion, but I feel compelled... haven't I heard that there was a "Nazi method" in the 1940s/WWII whereby SS troops were cooking it up in their Stahlhelm helmets (the ultimate "one-pot" vessel)? Or is that a myth?

[The Lone Stranger]

As satan will i was just reading this . Hope it helps  ------>

"Nazi Speed cold cook? - the Hive BB - Crystal Meth - posted 08-25-1998 12:53 PM "

"Phather PhreeX
unregistered    posted 08-25-1998 01:35 PM            Reply w/Quote For the most part, its your basic run-of-the-mill mediaSpew ... see, this makes meth sound like some evil chemical made by evil kitchen cooks .. that 'recipie' they refer to is the Birch reduction of (pseudo)ephedrine using Lithium and Anhydrous Ammoina ... yes, you can, in fact, obtain lithium from batteries (there is a thread about it in this forum, I belive its called 'Obtaining Li from batteries') and yes, it can be done in a few hours ... the article says " no fume method " ROFL! if you live within a hundred yards (or so) of anyone with a working nose - its NOT a good idea to crack open that ammoina. Anyway, read up on the Birch reuction .. but don't think its as easy as the media makes it sound. "

"micifer
unregistered    posted 09-25-1998 06:08 PM            Reply w/Quote Materials needed:
pseudoephedrine
anhydrous ammonia
lithium (from camera batteries)
acetone
dry ice

Procedure:
The mixture is given a electric charge with the lithium battery. I'm not to sure how much of the ingrediants you need or how long the shock treatment is too be done.
But this is all the materails you need.
reficulL signing out. "

The thread goes on for two pages so unless someone wants it all i wont post the rest .

[Shake]

Styrylic Acid will work. it has 1 extra carbon.

Phenyl Pyruvic Acid looks interesting check that out.

[letters]

cinnamic acid (cinnamate) can be epoxidized and then rearranged/decarboxylated to give phenylacetaldehyde, which is unstable, but useful if you want plain phenethylamine. some info into this can be found by going through darzens condensation (homologation of carbonyls).

[reDEEMed]

i came here a month or so ago i did not even know what a methyl group was

Wow, are you fucking kiddin' me? That gives me hope, man. I'm familiar with most of you guys (from your posts of course, here and other places) including you and I would have never guessed you were that new to shit.

I'm glad I read that lol. I know I have the intelligence to learn this stuff (not to sound arrogant), but it's sometimes pretty daunting. I can tell the curve is starting to lean more towards the horizontal, but it's still pretty steep where I am now.  I can only hope one day that I can argue with sedit about my idea , or even you, or even half these guys. I'd say pat yourself on the back, man.

[Sedit]

Methods that most have used to attempt it with Phenylalanine have been faulty logic from the start due to a lack of understanding on the reaction mechanisms of the Kolbe electrolysis. I have seen divided cells, wrong solvents, wrong electrode materials, wrong potentials being used ect.

This however will not work in the case of Cinnamic acid since due to it being unsaturated you will more then likely get a cross between the Me* radical placing itself across the double bonds and the oxidized solvent molecule also doing the same leading to dimethylated products, Ethers and a variety of in between.

Transformation of the Pi bond into a Nitro group on the other hand could prove valuable since the alpha position will now be filled with an EWG increasing yields of the Kolbe dimmer to very respectable levels.

I would like to see the full reference of the Stainless steel electrodes since as I understand it Fe ions greatly decrease the yields of the Kolbe dimmer down to in some cases Undetectable levels. This is not so much an issue in non-aqueous environments but its still something to highly avoid in most cases. Glassy carbon has been found to be on par with Pt electrodes, understand this is not normal carbon however crucibles of Glassy carbon can be had for a much cheaper price then Pt electrodes of the same dimensions.

[hypnos]

i came here a month or so ago i did not even know what a methyl group was

  Yet you have been a member since August 2nd 2009? 

I know all of you guys, you dont know me.. i have studied your posts in old archives, it is truly an honor for me to personally to be here, few people who are interested n this field in the whole world get granted this, i know that.. there are only a few forums WD and whatever else i dont know im only here.. but that is the World Wide Web.. where the fuck are the other 40 million who like drugs? where are there forums??

 YEAH, Right.... there seems to be some 'conflicting info here'!

Im curious why you ask for our help.... get people that know for a fact how to handle this kindly share some information with you and in return you get snippy... Would you like Me, Lugh and Wizard X to stop answering to this post? Would that be better since it sounds like its hurting your pride? Are you under the impression that no one skilled in the arts has ever attempted this before?

  probably!

 All those ref's...what just found em via Google (scholar? maybe?)

 Hmmmmmmm? a 'bit Shakey' IMO