Sciencemadness Discussion Board

p-toluenesulonyl chloride advice

Renaissance Man - 28-11-2010 at 19:53

I was able to find what looks like a good sources for sulfonyl chlorides on ebay. They stock mainly garden variety lab chemicals, a good sign for legitimacy. The toluene and benzene derivatives are priced at 37 and 57 USD respectively. I have a few questions about what I should do, I have looked all around but I haven't been able to find much, and some of the questions require a more human input.

Should I be worried about having a squad of swat guys kicking in my door? The benzene derivative does not appear to be watched. I am just not sure how much TsCl is, it might just be something that got grandfathered in.

Are there any behavioral differences between the two?

What do you think some good bases to work with might be? I can't really get a hold of any pyridine.

Could a reaction be done in such a way not to damage an amine moeity? this reaction is used to form a protecting group for the amine in other reactions, but If possible I would not like it to eat up all of my reagent only to have to reduce the amine again. (could the sulfonamine be reduced by acid catalyzed hydrolysis to form a salt?)

The benzene derivative is ~ 110% the efficiency of its bulkier toluene, but the former's price is 150% of the latter. I would go with Benzene sulfonyl chloride if it would raise fewer eyebrows and is just as effective chemically; But if neither one would be a concern to the authorities or if they were both just as bad why not save the $20 and go with what is more commonly used in the literature?



Sorry for assaulting you with all these questions. I just haven't been able to dig up enough information on this stuff.

Paddywhacker - 28-11-2010 at 20:04

Stick to the one that is used. That way if it doesn't work then you won't be left wondering if your substitution was at fault or not.

As for bases, the same source, unless I miss my guess, sells triethylene diamine (DABCO) in 500g lots at a very reasonable price.

Renaissance Man - 28-11-2010 at 21:13

Quote: Originally posted by Paddywhacker  
Stick to the one that is used. That way if it doesn't work then you won't be left wondering if your substitution was at fault or not.

As for bases, the same source, unless I miss my guess, sells triethylene diamine (DABCO) in 500g lots at a very reasonable price.


Thanks, I completely passed over the DABCO. I can't believe I missed that.

Well they are both used, they are just a methyl group apart I would expect that they would behave almost identically, my real issue is if that holds true then where do I choose the trade off between economics or anonymity.

Nicodem - 29-11-2010 at 10:38

Quote: Originally posted by Renaissance Man  
Should I be worried about having a squad of swat guys kicking in my door? The benzene derivative does not appear to be watched. I am just not sure how much TsCl is, it might just be something that got grandfathered in.

Benzene- and toluenesulfonyl chlorides being watched? I don't know anything about the legislation of your country, also because you never told what country it is, but I find it odd that such trivial chemicals would be "watched" and unimaginable why they would be.
Quote:
Are there any behavioral differences between the two?

Of course. They have different physical and spectroscopic properties. Though their chemical properties only differ in reaction kinetics if used as electrophiles. But if used as substrates for electrophilic or radical reactions, then their chemistry is very different.
Quote:
What do you think some good bases to work with might be? I can't really get a hold of any pyridine.

Impossible to properly answer as you forgot to describe what reaction they will be used for. Besides, if used as reagents they give different products, so obviously they can not be substituted for each other if what you are after is a specific reaction product.
Quote:
Could a reaction be done in such a way not to damage an amine moeity? this reaction is used to form a protecting group for the amine in other reactions, but If possible I would not like it to eat up all of my reagent only to have to reduce the amine again. (could the sulfonamine be reduced by acid catalyzed hydrolysis to form a salt?)

Both reagents react with free primary and secondary amines or anilines. Sulfonamides or aliphatic amines can not be easily hydrolysed, if at all. The N-deprotection requires reductive cleavage. On the other hand, sulfanilides can be hydrolysed, at least as far as I remember.

Renaissance Man - 12-12-2010 at 10:59

I had read that Tosyl chloride was useful for converting alcohols to a alkyl chlorides through a tosylate intermediate that is cleaved. I know that the p-toluene sulfonic acid is on the list (I must have recalled incorrectly that the acid halide was) but I would think that being so similar, and probably much more useful than the acid that it would be looked as well. And I don't think that they have it on there to stop bootleggers of penicillin. ;)

But as far as using them as reagents I was under the impression that they would behave fairly similarly, I mean the difference between a reaction intermediate with a phenyl vs methylphenyl group is pretty small especially if you are going to cleave it off immediately, or at least that was my thought. Of course there could be some funky steric hindrance or problems with ortho directing side reactions, but I would not expect it

I am in the US, who else would have such preposterous laws?

I was also vaguely considering buying some hydrazine hydrochloride but I think that would raise far more red flags than Tosyl chloride.

497 - 6-4-2011 at 16:08

A possible alternative route to sulfonyl chlorides from OTC materials could go as follows:
Chloramine-T to toluenesulfonamide by reaction with sulfites, etc.
Then microwave acid hydrolysis of toluenesulfonamide to toluenesulfonic acid in dil. H2SO4. Ref
Then chlorination of toluenesulfonic acid with TCCA. I didn't know this was even possible until now. Ref
Looks reasonably easy and very OTC. At least easier than the diazotization route mentioned above..
If someone has access to the full references and can post them I would appreciate it..

smuv - 6-4-2011 at 16:37

That's TCT (sym-trichlorotriazine) not TCCA (trichloro-isocyanuric acid).

497 - 6-4-2011 at 18:02

Shit. No wonder i was surprised.

smuv - 6-4-2011 at 18:23

lol. You don't know how many people have made this mistake.