Sciencemadness Discussion Board

Methylenation of Toluene

ChemRaver - 13-12-2013 at 23:03

I was studying the following molecule
http://www.sigmaaldrich.com/catalog/product/aldrich/284548?l...

This is probably a very noobish question but could Toluene be considered a substituted Catechol?

Catechols, which are very similar in structure to Toluene can be Methylenated for instance by reacting with DCM(or DBM) in a basic environment.

For instance:
Quote:

Catechol (1,2-dihydroxybenzene) is reacted in a basic solution with dibromomethane(or dichloromethane) to 1,2-methylenedioxybenzene.


Could this also go:
Quote:

Toluene (Methylbenzene) is reacted in a basic solution with dibromomethane(or dichloromethane) to 3,4-(Methylenedioxy)toluene.


Perhaps I've oversimplifying the chemistry here, but this did strike me as curious, and it seems like it could be possible.

Paddywhacker - 14-12-2013 at 01:42

> Perhaps I've oversimplifying the chemistry here, ...

No, you are raving.

You can see, if you draw out your proposed reaction, that your product contains two oxygen atoms, but your starting materials contain none.

> This is probably a very noobish question but could Toluene be considered a substituted Catechol?

Not in any sense that a normal person would apply.

smaerd - 14-12-2013 at 06:06

It scares me that you (ChemRaver) recently made a post about using 300g of LAH for some type of reduction on an organic substrate. You display a lack of understanding pertaining to organic synthesis, even on a fundamental level. Yet you have claimed to have been doing chemistry for the past 3 years... Please learn the principals behind the reactions you day-dream, other-wise anything you end up attempting may be quite dangerous. Also, the way you have prompted your question is a bit bizarre... Most of the time when people ask a 'theoretical question' they propose why they think it should happen, rather then replacing a completely different reactant and a product name in a quoted sentence.

For example:
Quote:
Perhaps I've oversimplifying the chemistry here, but this did strike me as curious, and it seems like it could be possible.


Why does it 'seem' like it could be possible?

To iterate the answer to your question: no, there is no reason that I can see why any type of methylenation reaction would occur from what you propose.

ChemRaver - 14-12-2013 at 11:25

I was simply asking.... Give me a break. I never claimed to be an expert on this subject. I DID post this in the beginner section. Hence the reason I am asking here.

Could someone instead of criticizing me for trying to learn, actually point in the direction of understanding the mechanics of why the methylenation reaction of Catechol happens in the first place?

There clearly is some way for this 3,4-(Methylenedioxy)toluene molecule to be synthesized simply for the fact that it exists and is sold in bulk for a not much higher price than Toluene. I could easily go buy this from China if I really wanted to but I am interested in how it is synthesized. Forgive me for being curious.

Yes I am not an organic chemistry expert. You shouldn't feel smart for pointing that out. It should be obvious in the fact that I am posting this here. What other ways are there that a Methylenedioxy group can be added to toluene?

I've noticed that catechol' can be synthesized from Toluene. Catechols can be methylenated and apperently so can Toluene according to the above, real, molecule. My question is, if Toluene is not methylenated by the same mechanism, then by who is it methylenated?

[Edited on 14-12-2013 by ChemRaver]

hyfalcon - 14-12-2013 at 11:37

looking at the patents involving the 3,4-(Methylenedioxy) group and interesting substance pops up: piperonal

Now just what does that bring to mind?

TheChemiKid - 14-12-2013 at 12:04

Hint Hint
BLACK PEPPER

;)

Spoon-feeding complete


[Edited on 12-14-2013 by TheChemiKid]

ChemRaver - 14-12-2013 at 12:11

It is true this molecule is only a couple of reactions away from being Piperonal, though that doesn't change anything about the scenario.

I'm starting to get the feeling some of the people here know a lot more trolling than they do chemistry. If I was interested in making something out of this molecule(3,4-methylenedioxytoluene) I could get it from China and go from there. It's not illegal in any country. Clearly manipulating this molecule for my own purposes beyond that point is something I am not interested in. I am interested in figuring out how it can be synthesized.

I did exhausted searches of patents and was unable to find any mention of this molecule in particular, inspite of an abundance of 3,4-methylenedioxybenzaldehyde's (piperonal).

ChemRaver - 14-12-2013 at 12:38

Okay this thread can be closed.

I found out what I was asking is indeed possible since both catechol and toluene are benzene derivatives. Apparently the inferences I was drawing about how closely this molecules are related was correct. According to some patents this methylation of catechols by methylene chloride in the presence of a strong base applies not only to catechols but a great number of substituted benzene derivatives, which, toluene is. My inference seems to be correcta bout how closely these molecules are related. 1,2-methylenedioxybenzene in comparison to 3,4-methylenedioxytoluene.


[Edited on 14-12-2013 by ChemRaver]

DraconicAcid - 14-12-2013 at 12:39

Quote: Originally posted by ChemRaver  
I was simply asking.... Give me a break. I never claimed to be an expert on this subject. I DID post this in the beginner section. Hence the reason I am asking here.

Could someone instead of criticizing me for trying to learn, actually point in the direction of understanding the mechanics of why the methylenation reaction of Catechol happens in the first place?


Catechol is a phenol- it has hydroxyl groups on an aromatic ring. These can be deprotonated to give a phenolate anion, which can in turn react with an alkyl halide to be alkylated. Because catechol has two hydroxyls next to each other, they can both react with the same alkyl dihalide, giving you methylenation.

Toluene has the aromatic ring, but doesn't have any hydroxyls. It is much harder to deprotonate (can't be done in aqueous or alcoholic solution), and can't be alkylated the same way, let alone methylenated.

zed - 14-12-2013 at 13:27

You wanna know how the material is made. Inquire with the manufacturer. Generally, they are happy to tell a prospective purchaser about their products.

Otherwise, use the search engine. Go to Rhodium. Use Wiki. Some things are possible, and some things are not.

smaerd - 15-12-2013 at 05:33

Was I trolling or asking you if you had come up with a reason as to why the reaction you proposed was possible? I actually thought about it and couldn't see it. I'm sure there is a way from toluene to the target compound, it just isn't as you had proposed...

No your inference was not correct, which also means you do not realize why, which again means you should do some reading on organic chemistry. Hexamethylbenzene is also a substituted aromatic. That doesn't mean it will react the same way as catechol, benzoic acid, or aniline which are also substituted aromatics. Looks like DraconicAcid covered what you were asking.

It's not about being 'smart' and definitely not a trolling effort. It's about knowing what you're doing when you're dealing with chemicals, I.E. being a chemist. Learning how to propose questions in a constructive manner generally requires some preliminary knowledge on the subject. That's something that is encouraged even in the beginnings sub-forum. Go figure I look up the target compound and it's a drug precursor, explains everything including the user-name...

Fantasma4500 - 15-12-2013 at 09:38

wonder if people with general interest in chemistry are more prone to fall victim for SAD.. always such... short temper on SM in winther periods of what i understand..

smaerd - 15-12-2013 at 09:57

I'm just holding posters to the same level that was/is expected from me. Definitely not angry. New members tend to get these types of posts so that they learn ways to create constructive discourse rather then spoon-feeding and a lack of genuine interest in the subject matter that they inquire about. Normally posts similar to these result in a UTFSE or detritus type response. Suppose you're right, I haven't been terribly happy lately. Not due to the lack of sunshine though... I'll refrain from responding until the weather in my head subsides :P.

DraconicAcid - 15-12-2013 at 10:13

Quote: Originally posted by Antiswat  
wonder if people with general interest in chemistry are more prone to fall victim for SAD.. always such... short temper on SM in winther periods of what i understand..

If I'm feeling short-tempered, it's probably because I'm an academic, and it's exam time.

hyfalcon - 15-12-2013 at 11:20

I just have a thing about feeding cooks. If they want the knowledge, let them read and understand on their own. If they can't do it on their own, they don't need to be cooks in the first place.

turd - 15-12-2013 at 13:04

If only you had the same thing about feeding trolls.

For some reason this must be one of the most easily trolled forums. It's so weird because scientists are supposed to possess the ability of critical thinking. Seems like the "anti-cook" smugness interferes with that.

palico - 15-12-2013 at 14:03

Where the oxygen would come from ?