toluene+cl/oxychlorination via oxone thoughts

Ephoton · Fri Jul 15, 2005 6:21 am

potasium dichromate + table salt + sulfuric acid ---> chromylchloride

chromylchloride + toluene ---> benzaldehyde.

toluene + light + chlorine gas gives benzylchloride in around 6 hours
just reflux and bubble gas into solution when reflux temp hits that of benzylchloride
bingo.

toluene + hypochlorite + light gives benzylchloride just make sure you only heat it
over a water bath becouse over 105 C boom. other than that its safe as.

the sommelet rocks it works perfect just get some hexamine tablets and
your toluene benzylchloride mix and reflux (still try to boil most of the toluene off
before sommelet)
the chlorination if done with hypo can be done in normal glass bottles
the sommelet can be done in paint tins
and final steam distillation of product can be done straight out of the paint tin
just by adding water.

Ephoton · Sat Jul 16, 2005 6:14 pm

na no inert dude were talking experiance here Smile

even got yellow fruity crystals from the aldehyde after a little work.
BzCl is fucked shit trust me im not leading you astray.
probably find the acetonitrile is a cosolvent for both np toluene and Ca salt
sounds great but ive tried a lot of ways to aldehyde and the two best
ive come across are Chromyl Chloride (only wast if you pay more than your end
product is worth) or reflux toluene chlorine and light then sommelet.
trust me no inert gas wast of time. If your worried about impurities use bisulfite.
you only need inert or vacuum when you distill.
ive made heaps of this shit. never used it for the dark arts though but I knowz
how to make aldehyde.
get a reflux set with an input for chlorine use two fluro lights then begin.
with the sommelet you will have over 300 grams of aldehyde in a 1 litre setup
in under two days.
of course if you dont belive me Smile

ill talk to ya in 2 days and ya can tell me how
much aldehyde ya have hehe Smile

aldehyde is piss easy this way.
if you can change the solvent I would be in for your method though.
dont use MnO2 for a straight oxidation to aldehyde from toluene it sucks
takes ages to dry and make and ya could have made 10 times the aldehyde with
some simple lab work in the same time.
good luck Smile

Ephoton · Fri Aug 05, 2005 5:56 pm

a few interesting post I found while synthetikal was down Smile

synthetika

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Mood:
posted on 14-2-2005 at 02:14 AM

Toluene to Benzaldehyde

Hi all,
We too, are really interested in this particular subject,
We are now looking at some similar, and some new methods as well,

These pictures are just too good, They are sharp, and fruitfull with shit loads of needed, sometimes misunderstood info,

Syn

I believe that the persufate of Ammonia, works very well, having done it a few times, and the yields are very high

www.shroogle.org/synthetika

[Edited on 14-2-2005 by synthetika]

hmm this is interesting maby more research needed .....

I read a little down the page to find this which I checked and well
if your into this will know or look.

evil_lurker

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Mood:
posted on 20-4-2005 at 08:17 AM

Swim is working on a new route to Benzaldehyde which is completely OTC from patent US 4,146,582.

Ferrous-Copper Catalyst: Toluene (7.6 g.), water (35 ml.), ferrous sulphate (0.110 g.) heptahydrate, cupric acetate (0.072 g.) and methanol (8 ml.) are placed in a 250 ml. reactor.

Sodium persulphate (47.05 g.) in an aqueous-methanol solution of sodium persulphate is added slowly to the mixture which is maintained at 70.degree. C., in an atmosphere of nitrogen and under agitation.

The organic phase is separated after two hours and the aqueous phase is extracted with ethyl ether.

The combined organic phases are distilled to afford 8.29 g. (95% yield) of very pure benzaldehyde (compared against a pure sample).

If this works it will be sooooo easy. The cupric acetate can be made by reacting a 1:2 molar ratio of dissolved copper sulfate (aka septic line root killer) and sodium bicarbonate. The sodium bicarbonate is dissolved in about 2 liters of water and placed in a 5 gallon bucket. The CuSO4 is dissolved in about 2-3 liters of water and then slooowly poured into the bucket. The stuff is allowed to sit over night while the Copper Carbonate Cu03 precipitates. The next day the stuff is washed with water by filling up the bucket and again allowed to sit. The water is decanted the day after and again washed. After several washes, the Cu03 is then filtered out and a wad about the size of a pancake is placed onto a pizza pan sitting on a hot stove eye. The heat breaks down the Cu03 into copper oxide, Cu0. The resulting finely ground Cu0 is then placed into a stainless steel pot of boiling vinegar. The Cupric Acetate which is formed is thus decanted into a separate dish and then slowly evaporated.

The Iron Sulfate is prepared by again taking CuSO4 and dissolving it in water. Some unsoaped steel wool is placed in the vessel, and the CuS04 is allowed to react. Copper precipitates as metal out of the solution and the iron sulfate is left as a green coloring in the water. The iron sulfate is decanted off and dried similarly to the way the cupric acetate was.

The sodium persulfate is obtained at a pool supply store as a shock treatment. If the sodium persulfate is unavailable, it can possibly be substituted with oxone or potassium persulfate and ajusted for weight.

To make the benzaldehyde, the ingredients are thrown in a pressure cooker large enough to hold many times the original formula. The pressure cooker has been adapted in a manner to take out the pressure relief plumbing to fit it with a paint stirrer, and the safety relief is removed and equipped with a rubber grommet and thermometer. While nitrogen atnosphere would be nice, it probably would not be necessary unless one's goal was to minimize over oxidation of the toluene into benzoic acid.

After the reaction the contents of the pressure cooker are handled according to patent.

so ive been thinking that a catylized ammonium persulfate direct oxidation
would probably be the easiest highest yeilding (OTC) route from toluene to
benzaldehyde in the domestic market.

I looked further into this and it is very probable I have a few pdf's on the subject
from sciencemadness and other places on the web.

personaly im not a pressure man.
so I stick to my original formulars.

I have been thinking of trying the H2SO4 route
with persulfate this I belive will need to be cooled rather
than heated. (Im not sure on this as I am finding it hard to find
info on this route)
probably needs an organic acid as solvent or one of thouse funky
bi polars that dont react with acids.

hopfully this will not produce a piranha bath Smile

MiNdBaBY · Mon Sep 12, 2005 7:05 am

Ephoton:

...potasium dichromate + table salt + sulfuric acid ---> chromylchloride...
What a waste of reagents, especially the Cr2K2O7!

If you're after Benzaldehye, use that sulfuric in an electro cell, with some N2H8SO4 and MnSO4. The ammonium is $5 for 20lb bags OTC for garden use (i.e. fertilizer), while the Mn is also available for the same use though MUCH harder to find/source. Ref. the MAA thread.

This one really got my goat and actually invoked me responding..
"toluene + light + chlorine gas gives benzylchloride in around 6 hours
just reflux and bubble gas into solution when reflux temp hits that of benzylchloride
bingo."

ROFLMAO,
So, Mr. Theoretical Ephoton, you've never synthed BzCl I see..
You'll note that BzCl's bp is 179 while Tolly's is 110.. Let me tell you what happens with the procedure you stated, before you ever make any BzCl, your boiling flask will have emptied it's tolly content into your distillate flask, real fucking funny it is!
As I've done it! Took about one minute in my case to empty 1/2 gallon of tolly out of my boiling flask into the distillate flask, with Gaseous Cl2 escaping out the distillate flask.. It was one of those, 'fuck!' moments, that I' didn't find too comical.. lol

And actually that was a month ago, during my attempts at developing a continuous running industrial type BzCl production with tolly being supplied via pump, lol, all I ended up with was Cl2 gas escaping out of the distillate flask and litterally pouring off the condensor, not dripping, I didn't find it comical! Though I laugh at it now..

"dont use MnO2 for a straight oxidation to aldehyde from toluene it sucks"
As for this, I again re-emphasize, try an electro cell, god the amount of energy you 'might' have exerted in your previous aldehyde production to date, makes me roll in laughter.. Nothing but a huge waste of time & precursors.. Sad really.. Smile

Moral of this post?
Use an electro cell for your aldehyde production; and
I have yet to find any way to distill off or continuously produce BzCl via the UV chlorination of tolly, due to the dog damn BP's of each, and mind you I've really put some work into such, very dissapointting to MiNd.

Otherwise, I hope you try the electro cells and good luck with the rest of your chemistry my brother (or sister).. Smile

MiNd,

bio · Working Bee

..........Took about one minute in my case to empty 1/2 gallon of tolly out of my boiling flask into the distillate flask, with Gaseous Cl2 escaping out the distillate flask.......
......a continuous running industrial type BzCl production with tolly being supplied via pump, lol, all I ended up with was Cl2 gas escaping out of the distillate flask and litterally pouring off the condensor, not dripping, .........

I'm not sure what the setup is for this but seems it should be possible by using some sort of variable reflux along with slow distillation of the unreacted PhMe. Reflux rate could be adjusted simply by cooling water water flow but would take some time to stabilize. Maybe if the chlorine rate was slowed down with maybe 80-90% reflux then make up with the pump.

Or am I missing something here?

primathon · modified

Congratulations! 10,000th post!

Edit: well almost we're at 9099, it will get there !..................../java

Ephoton · Wed Sep 14, 2005 2:25 pm

what the fuck havent been here for a wial Smile

reciving flask in a reflux ha yep I did spew all of that wonderfull stingy shit
into my reciver wial doing a reflux with out a distilattion head.
your method I will have alook at and thankyou for showing me it.
so wial you are emphisising my none practical knowlage rethink how you do a
reflux with gas input (might even stray towords a two neck flask and a condensor)

wait for it ....... bucket amalgum spewed into reciver leaving spoiled goods .
yep yep yep I own up.

MiNdBaBY · Thu Sep 15, 2005 5:37 am

Wonderful advice ep,
"rethink how you do a reflux with gas input (might even stray towords a two neck flask and a condensor)"

However, honestly, MiNd doesn't care for having to often replace lab glass, due to various reasons including breakage, or such being filled with impossible to remove Ca from a hypo chlorination, or the salt remnants from an Ammonium & hyrdroxide gas production, etc..

But even more importantly to MiNd, oddball that he is, just builds plenty of DIY, and improvised things, for the fun and challenge of such..

MiNds rubber stoppers and PE tubing, opposed to 2/3 neck flasks and glass tubing, works just fine.. Smile

Is far more otc, and far less costly, and far more versatile..

All in all, have fun Ep.. And don't do anything MiNd wouldn't, lol..

loki · guinea pig

i would think that a claisen adapter would be just as good.

people sometimes forget that people did chemistry without ground glass joints commonly until the 60s. rubber gets a carbonised coating which is pretty much inert.

bio · Working Bee

I hate rubber stoppers but sometimes they are a necessary evil.

Getting the hardest neoprene ones and boiling in 20-30% NaOH conditions them somewhat for better survival. Distilling hydrocarbons for example swells them badly without conditioning and they won't "carbonize" under these temperatures.

Is there a way to "pre-carbonize" rubber stoppers that you have ever heard of?