Spoon Feed me NOW!

[Swede]

I cannot begin to describe how frustrating it is to have worked hard, become a degreed chemist, only to lose it all over the years. Literally, it drained from my brain. I know what you get when you mix NaOH and HCl, and touching acid=bad, and NO2 = death, but not much else anymore. Oh yes, Mercuric Chloride is also bad.

 

I have: Salicylic acid -

http://upload.wikimedia.org/wikipedia/commons/thumb/8/8e/Salicylic-acid-skeletal.svg/120px-Salicylic-acid-skeletal.svg.png

 

I want: 5-Sulfosalicylic acid -

http://upload.wikimedia.org/wikipedia/commons/thumb/9/97/Sulfosalicylic_acid.svg/200px-Sulfosalicylic_acid.svg.png

 

 

My primitive brain says "pour sulfuric acid on your salicylic acid, and like magic it will convert." My logical brain says "Don't be a dumb ass, that won't work. You no longer have a clue when it comes to organic chemistry. Go buy 500g for $50."

 

Googling "Synthesis of 5-Sulfosalycilic acid" yields jack. Any thoughts here? Please make fun of me, entertain yourselves in any way possible. I am off on a tangent that I'd like to resolve before beginning lead dioxide plating. The 5-SA is used to sequester iron in a plating bath.

 

Note the stalwart, brilliant young man in my Avatar - his test tube is full of 5-sulfosalicylic acid, yield 150%. How did he do it?

 

Obviously this is a partial joke, but I really would appreciate any comments on this obscure process. Organic was never my strong subject. And I still hold a grudge - the professor set up a crime scene (overdose) and gave each of us a few milligram sample of the "lethal drug." As we checked melting points, NMR, GC, etc, I could hear exclamations from the other guys as they ID'ed their sample. "WOW, mine's Cocaine" "Hydrocodone" "Holy Bat S**t, I've got pure morphine!"

 

My sample was sudafed. I was hacked and hated organic ever since.

Edited January 8, 2009 by Swede

[Mumbles]

The compound definately exists. And thus the magical reference:

 

MP - 120C

Sol - in Water, ethanol, and ether.

There is more on page 1050 of the concise encyclopedia chemistry by Eagleson

 

Hydroscopic, forms a dihydrate

 

Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, Salicylic Acid and Derivitives, pg 4.

 

"3.3. Ring-Substitution Reactions. In the introduction of a third group

into a disubstituted benzene, the position the group takes depends on the other

groups present. In the case of salicylic acid, the hydroxyl directs ortho- and para-,

and the carboxyl directs meta-substitution. The ortho–para director prevails

because unlike the meta director it activates the ring. Specifically, the electron-

donating hydroxyl group increases the electron density in the 3- and 5-positions.

The electron withdrawal nature of the carboxyl group decreases the

electron density around the 4- and 6-positions, which further enhances the

electron density of the 3- and 5-positions. As a rule, direct substitution occurs

more easily in the less sterically hindered 5-position with formation of only

small amounts of the 3-substituted and 3,5-disubstituted product. High yields

of the 3-substituted salicylic acid usually can only be prepared indirectly.

Direct halogenation of salicylic acid is generally carried out in glacial acetic

acid. As expected, the main product is the 5-halo-salicylic acid with small quantities

of the 3-halo and 3,5-dihalosalicylic acids.

Reaction with cold nitric acid results primarily in the formation of 5-

nitrosalicylic acid [96-97-9]. However, reaction with fuming nitric acid results

in decarboxylation as well as the formation of 2,4,6-trinitrophenol [88-89-1] (picric

acid). Sulfonation with chlorosulfonic acid at 160C yields 5-sulfosalicylic acid

[56507-30-3]. At higher temperatures (180C) and with an excess of chlorosulfonic

acid, 3,5-disulfosalicylic acid forms. Sulfonation with liquid sulfur trioxide in

tetrachloroethylene leads to a nearly quantitative yield of 5-sulfosalicylc acid (1).

Because salicylic acid contains the deactivating meta-directing carboxyl

group, Friedel-Crafts reactions are generally inhibited. This effect is somewhat

offset by the presence of the activating hydroxyl group. Salicylic acid reacts with

isobutyl or t-butyl alcohol in 80 wt % sulfuric acid at 75C to yield 5-t-butylsalicylic

acid [16094-31-8]. In the case of isobutyl alcohol, the intermediate carbonium

ion rearranges to (CH3)3C+."

 

 

The little circle for temperature didn't transfer over properly. I think I corrected them all. If you see an obcenely high temperatrue ending in an 8, just delete the 8 and you have the correct one.

 

Now. I'd imagine you could sulfonate it with just 98% sulfuric acid. Heat it to maybe 150 degrees for a while.

[Steps]

Mumbles is the undisputed master of the universe...

[tentacles]

Sulfonation with chlorosulfonic acid at 160C yields 5-sulfosalicylic acid

[56507-30-3]. At higher temperatures (180C) and with an excess of chlorosulfonic

acid, 3,5-disulfosalicylic acid forms. Sulfonation with liquid sulfur trioxide in

tetrachloroethylene leads to a nearly quantitative yield of 5-sulfosalicylc acid (1).

 

Lovely! You get to cook it in boiling tear gas! That'll be FUN, I'm sure. You could make your own chlorosulfonic acid if you've got some spare oleum -

"The industrial synthesis entails the reaction of hydrogen chloride with a solution of sulfur trioxide in sulfuric acid:

HCl + SO3 → ClSO2OH"

 

And other such lovlies as "ClSO2OH reacts violently with water to release HCl. Inhalation of ClSO2OH would generate HCl in the lungs, which is very dangerous."

 

I wonder if the sulfuric + H2SO4 + heat would work - is the salicylic acid or the product soluble in sulfuric?

Edited January 9, 2009 by tentacles

[Mumbles]

Yeah, I am pretty masterful.

 

No idea about solubility. You can make chlorosulfonic acid insitu without needing SO3 or HCl gas. You ONLY have to mix conc sulfuric acid (or oleum) with Thionyl chloride.

 

Googling "Synthesis of 5-Sulfosalycilic acid" yields jack. Any thoughts here? Please make fun of me, entertain yourselves in any way possible. I am off on a tangent that I'd like to resolve before beginning lead dioxide plating. The 5-SA is used to sequester iron in a plating bath.

 

Try spelling it 5-sulfosalicylic

[WarezWally]

Touching an acid isn't always bad, after all we do ingest dilute acetic acid, NO2 only equals death if you breath in a decent amount and instead of heading to hospital think nothing of it

 

The synthesis of 5-Sulfosalicylic acid looks to be a right bitch, is playing with hot sulphuric acid and processing the result worth saving $50?

[Swede]

You guys are awesome. Thanks Mumbles. I am slowly building my chemistry library back to what it should be. Back in college, I sold all the books because I was broke. Now, much regret.

 

I really did spell correctly when searching. One of the Google results actually read "Sulfosalicylic acid is easily synthesized by addding 50 grams..." and that was the end of the Google link. WOW! So I click on the link, and it's 404 city. And there was no Google cache! Argh!

 

It's probably easier to buy it, but just like the anode project I need to become a bit more knowledgeable, a bit less dependent. Also, in the last 3 months I cannot begin to add up the $$ I've spent. I've decided lab chemical sales are one of the biggest rip-offs in history. If I want to get rich, I'm going to sell chemicals. I understand some of them are ultra-pure, or ultra-rare; but I also have a feeling 55 gallon fiber drums of chems from China are repackaged into 500 gram bottles and the price is jacked up 3,000% at a minimum.

 

What we need is a chemical supplier (NOT like Sigma Aldrich or Cole Palmer) that sells a nice variety of chems that are NOT ACS, or 99.9999999% pure. A place that caters to people with a real budget rather than NASA or a university. There are not that many applications that call for those levels of purity, yet that is what the majority of offerings seem to be. And that also is one of the reasons I've been buying relatively cheap chems from the mining and recently the ceramics industry. Seattle pottery - 10 POUNDS of NaF. Cheap. What am I going to do with 10 lb sodium fluoride? But it was less $$ than 50 grams of the ultra-pure stuff. Got a boat-load of MnO2 as well, also dirt cheap.

Edited January 9, 2009 by Swede

[Mumbles]

Most of the prices are artificially inflated. Any real organization gets a huge discount.

 

I found another real good reference on google books, but the page the synthesis was on, of course was not part of the preview, and I don't have access to that book with my university literature access.

[Steps]

I've decided lab chemical sales are one of the biggest rip-offs in history. If I want to get rich, I'm going to sell chemicals. I understand some of them are ultra-pure, or ultra-rare; but I also have a feeling 55 gallon fiber drums of chems from China are repackaged into 500 gram bottles and the price is jacked up 3,000% at a minimum.

 

What we need is a chemical supplier (NOT like Sigma Aldrich or Cole Palmer) that sells a nice variety of chems that are NOT ACS, or 99.9999999% pure. A place that caters to people with a real budget rather than NASA or a university. There are not that many applications that call for those levels of purity, yet that is what the majority of offerings seem to be.

 

Damn right!

Though there are some nice chemical suppliers one place offered me Barium Nitrate $80 for 100g, another place offered me 25kg for 250. Only difference were bottles and the $80 one was a tiny bit more pure. But still I was outraged how some chemical companies think they can rip people off. I got this huge scheme to buy bulk chemicals from various wholesalers so that pyro's in need of chemicals would not get ripped off. Though as a lazy teenager i have very little money and all my saved money is going towards a delicious bag of LEGAL KCLO4 i found from a supplier.

 

Any who Swede good luck with your synthesis and purchases in the future, may the chemistry god grant you sales and good deals.

Edited January 9, 2009 by TheLummox

[andyboy]

It's the same in every business, the company where I used to work imported stuff like Sodium Benzoate, Ammonium Chloride and such for the food industry, paid someone to slap on their own stickers on top of the old one and sold it for a lot more, repacking in smaller containers was even more lucrative.

[crazyboy25]

Direct sulfonation with sulfuric acid won't work.

 

From powerlabs:

 

C7H4O2 + H2O ---> C6H6O + CO2

(Salicylic acid with heat source converts to phenol and carbon dioxide; (in presence of water from 98% H2SO4)

Or the formed phenol just sulfonates rapidly.

 

Removing of all Fe+ from a plating bath I see.

 

I hate organic chemistry but I'm hoping to learn something about it.

 

Yeah I recently found a supplier near me that carries all the good chemicals at good prices but it looks like the owner died recently and they went out of business. I sent them an email to see if someone else took over but it doesn't look good.

 

Scrounging, synthesizing and buying chems from eBay sucks, I'm looking for a supplier all the time.

 

You bought your SA? I made mine from aspirin I'm so cheap!

Edited January 10, 2009 by crazyboy25

[Swede]

My plate is too full to pursue this unless an easy synthesis pops up. It is also not too critical, as there are other means to sequester iron. In fact, there are enormous industries that exist solely to isolate metal ions in well water so the public can drink it and not go "ewww".

 

Crazyboy, there's a guy on eBay who sells a variety of useful chems ("Quartzpegmatite?" Something like that) and the SA was about $7/lb. I refuse to fall into the eBay paranoia trap, and if someone is selling a chemical that I want, and the price is right, I buy it. A lot of the chems come from the mining/refining industry, I believe, and don't have that ACS stench about them.

[Swany]

I agree with crazyboy and am thinking that the H2SO4 would decarboxylate that stuff and leave phenol, though perhaps you could coax it into not doing it... direct sulfonation may require a better sulfonating reagent. Well, experimental is king. Try it out.

 

EDIT: Well, not a better sulfonating agent per say... just a different one. One that is a bit more subtle. And, I do agree with mumbles electron density arguments. That 5 position wants it.

Edited January 11, 2009 by Swany

[Dez]

I'm no chemistry major (yet), but if the issue with direct sulphonation with sulphuric acid is that it will leave the phenol, how about turning the carboxyl into an ester?

 

Esterify with an alcohol, sulphonate the resulting ester, then... make the ester back into a carboxyl? Not sure how/if you can do that, I'd have to find my organic synthesis book...

 

The general idea would be to just protect the carboxyl group somehow.

[Swede]

Welcome Dez! Thank you for the thoughts. I never did pursue this, mainly because I decided to ignore any Fe ions in my plating bath for the time being, but with continued additions of cheap litharge to replenish the lead and neutralize the nitric acid that evolves, the Fe may possibly build and cause problems.

 

That is one of the problems with plating lead dioxide. Freshly-mixed electrolyte usually performs fine, but it apparently it does not age well, and eventually the plating becomes poor.

[Dez]

Now I'm curious as to if it would have worked... I'll have to find an excuse to try it!

 

Care to share more details about the plating bath, as in what it's used for, what goes in n out of it? I have a friend who works in a metalwork shop and he does everything from electroplating to etching to chemical colour treatments, I could ask him about it...

[Mumbles]

An ester wont be able to withstand the hot concentrated sulfuric acid. A certain pain relieving precursor still yields 4-phenol sulfonate. There are a few special things that will work. Some of the longer chain silyl esters, benzyl esters, there is one more that slips my mind. They of course require more difficult proceedures to remove.

[Dez]

I once used tert-butyldimethylsilane once to protect a the carbonyl group in cyclohexenone (forming a silyl ether)... Can't remember exactly what the reaction was (I think it was an aziridination), but it was easy enough to remove with a fairly good yield...

 

Don't know how a silyl ester would compare, but I found the silane fairly nice to work with.

[Mumbles]

Compared to ester hydrolysis, it's more complicated. You really only need to stir with a few equivalents of Tetrabutylammonium fluoride to remove damn near any silyl protecting group, possibly a trivial workup from there. The benzyl ester I believe requires hydrogenation, or perhaps DDQ. I remember something special happening with DDQ and some protecting group.

[Swede]

Dez, the plating is Lead Dioxide over a Ti mesh ruthenium-based MMO. The lead dioxide anodes in turn will produce perchlorate electrochemically. In the past, home-lab LD plating attempts usually end up failing for a number of reasons, and I wanted to see if I could come up with a process that works. The only other real alternative is platinum, and even that slowly disintegrates, making your homemade perchlorate expensive.

 

I blogged on it a bit if you are interested:

LD plating blog