Author Topic: P-BENZOQUINONE; synthesis, appearance and problems (Read 271 times)

Oerlikon · « **on:** July 30, 2010, 12:15:15 AM »

Hi,

I obtained every possible chemical needed for some good summer expect this bitch...

Firstly I made it with acetaminophen/aqua regia method.
After re-crystallization I got really nice and (probably) pure crystals
with very distinctive, almost nice, but harsh smell.

Next I obtained some hydroquinone and I2.
Since isporopily is hard to find here I used denat. ethanol.
I followed erowid document and failed miserably. Or at least I think so...
No nice looking yellow christals,only some ugly smelly brown perticipate.
I dissolved these crystals in DCM and washed them with water.
Didn't helped much, but you could clearly see distinctive yellow
product on the walls of the baker. Now I will try to recrystallize them from the
supersaturated ethanol solution.
Main problem is that reaction and yellow crystals had totally different smell,
extremely unpleasant smell of acid with burnt plastic that really hurt when you smell it.
Is this also p-benzoquinone?!

After that I did procedure involving K2Cr2O7, getting some green creamy stuff with
same bad smell. Dissolving it in DCM and washing it with water really helped.
Upon re-crystallization from ethanol I got insanely large yellow crystals,
again, with this unbearable toxic smell.

My question is it normal that 2 identical pure products can have such different smell
only because they were made by different method!?
This might be funny to some, but what is the "right" smell of very pure p-benzoquinone!?
One distinctive and not as bad you have after acetaminophen/aqua regia method or
unbearable toxic suffocating burnt-plastic stink you got after I2/H2O2 or K2Cr2O7 method?!

Second, how do you separate I2 from p-benzoquinone
when they both dissolve in non-polar solvents and they both sublime!?

Any detailed info on this synth. with use of water or ethanol instead of
isopropyl alcohol would be great!

Sorry if this thread has been worked over but I failed to find it with search engine...

Thanks!

Vesp · « **Reply #1 on:** July 30, 2010, 12:40:57 AM »

Quote

Firstly I made it with acetaminophen/aqua regia method.
After re-crystallization I got really nice and (probably) pure crystals
with very distinctive, almost nice, but harsh smell.

I did not know it was as simple as mixing aqua regia and acetominophen together -- If you feel like giving more info on how this reaction turned out, I would be interested in hearing it. It seems like there is some discussion on it here also: http://www.sciencemadness.org/talk/viewthread.php?tid=8250

Also I am not sure if you saw this or not -- and honestly i don't know if it is of any use since I didn't bother to read it other than slightly skimming it - but this might be useful for this conversation as well.... http://www.sciencemadness.org/talk/viewthread.php?tid=14232

Oerlikon · « **Reply #2 on:** July 30, 2010, 11:45:29 AM »

Damn you are fast!

Guy who started this thread is my friend I work with on project,we both need this thing but for the different use.I will post full procedure of acetaminophen/aqua regia during the
day,it is simple,it works,gives very pure product but it is allso rather expensive and long procedure to get enuogh acetaminophen.Jield is decent(cca 50% mass of acetaminophen) but reaction MUST be done outside or in foome hood!If someone could do it and compare product to the I2/H2O2 method it would be great!

NeilPatrickHarris · « **Reply #3 on:** July 30, 2010, 02:55:24 PM »

search for Bond_DoubleBond's Hive post "big breakthough for benzo bees" or something along those lines, hydroquinone/i2/h2o2 give a mustard yellow product that stings the eyes like chlorine when you're near it and also smells bad. Just reflux the reaction and there's no need to do it outside at all, it isn't until you dry the benzoquinone that it becomes unbearable to be around. With proper technique you can probably get the canary yellow that people talk about. The main problem is people only get partial oxidation so they get the quinhydrone intermediate (hydroquinone/benzoquinone complex) that looks like metallic gold flakes. The i2 is very hard to remove but IPA will indeed remove it, washing with ice cold IPA and re-x'ing in IPA will help. But yeah that i2 stains the hell out of everything and can be a little difficult to remove from the product.

Moriarty posted a quinone solubility chart somewhere on here so if you can't use IPA then look at his chart under p-benzoquinone and find another solvent with similar solubility that is inert. I think water has a similar solubility as IPA to these quinone products but consult that chart, i'm not 100% sure on that.

Other routes such as spiceboy's may not yield yellow benzoquinone, spice has always said his benzo was green. swim has never seen green, only yellow and orangish (due to a tiny bit of residual i2)

Oerlikon · « **Reply #4 on:** July 30, 2010, 04:13:24 PM »

I done Spice method ang get green goo,I tought I screwed something up but then I dissolved it in little DCM and washed it with straight water 2 times.
Water pulled most crap out and I got nice long yellow chrystalls.
Now they are rechristalising from the EtOH and they are insanely hughe!
Both,reaction,sollution and dry product had unbareable toxic smell while p-benzo i got from acetaminophen has border-line nice smell with only little irritation.
Christals from both methods look same but smell totaly different!
If you could give me straight link I would be VERY thankfull!

Oerlikon · « **Reply #5 on:** July 30, 2010, 10:45:47 PM »

As I promised....

p-benzoquinone from acetaminophen, step-by-step:

Buy some acetaminophen containing tablets with least additional chemicals,
search for pills containing only microcrystalline cellulose and acetaminophen.
Use methanol or ethanol to dissolve them completely.
SWIM use 120ml of ethanol for 40 500mg pills, heat it and stir vigorously until everything dissolves,
don’t crush them so you know when they are really dissolved.
Methanol works better, but DMF is far the best.
Filter warm solution of acetaminophen in alcohol and let the filtrate evaporate.
Scrap the dry crystals and weight out 15g.

Prepare 33ml of 65% HNO3 and 100ml of concentrated HCl, put them both in the freezer.(SEPARATELY!)
IMPORTANT!!! Use biggest glass baker you can find and do reaction outside or in the fume hood!
Put inside that baker 100ml of HCl and 15g of acetaminophen and let it stir while you are making ice bath.
Put the glass in the ice bath and add 33ml of HNO3 at once.
The colder the batter, you don't need to measure temperature, just get sure it is very cold.
After few minutes of stirring you and color change, violent exothermic reaction will began.
A lot of foam and extremely toxic gas will be present, just be sure to stir properly,both liquid and foam,
keep it as cold as possible and avoid deadly gasses.
After some time reaction will settle but keep stirring at least 1h, or until no more foam and gas is liberated.
Now flood this with 300ml of water and give it a little stir.Vacuum filter puffy p-benzo with very distinctive yellow color and smell.
Press filter cake to get rid of most water and than dissolve it in 200ml of ethanol.
Heat the alcohol gently with stirring unit everything is dissolved.(you will get black solution, this is OK)

Let this supersaturated solution covered at room temperature at least 12h and than put it in the freezer for few hours to get
as much crystals as you can.(you can put it in the fridge,but christals will be hard, ugly and impure)
Filter your nice and big yellow p-benzo crystals with vacuum and was it with little bit of cold alchohol.
Dry it in the big baker with hair dryer and constant stirring. It is dry when no more lumps are forming and
product does not stick to the walls of baker. Wear gloves and gas-mask since fumes are very irritating and toxic.

Vesp · « **Reply #6 on:** July 31, 2010, 01:15:17 AM »

Thank you.
That is as simple as I had hoped. Much better way to make it than I've done in the past - assuming no nitro compounds are formed, or other bizarre oxidation products.

Oerlikon · « **Reply #7 on:** July 31, 2010, 12:40:04 PM »

As long as you keep temperature at some normal range(less than 60°C) and STIR, STIR, STIR
only minor retarded product will occur. Recrystallization from EtOH will get rid of all the crap.
Recrystallized product is almost analytically pure and has pretty much different smell than one you get
from hydroquinone oxidation. Don't bother extracting what was left in the mother liquor, it is mostly chloranil and no more than 2-5% of total p-benzo.
Actually this whole procedure is modified procedure of chloranil synthesis, only difference being lower temperature.

Organic molecules are hardly nitrated by the HCl/HNO3 but that is not problem with H2SO4/HNO3.
You will more likely get something chlorated instead of nitrated if you don't stir and keep temp. low.

NOTICE,if you don’t get baker FULL of foam after the vigorous reaction you most likely screwed up.
Remember 100ml of conc.(30-37%) HCl and 33ml of 65% NHO3,not the opposite as my friend did by mistake!

If you don't have HNO3 you can use any nitrate from alkali metal or alkaline earth metal, just don't use NH4NO3.

Now I need some help on finding;
"Bond_DoubleBond's Hive post "big breakthough for benzo bees" or something along those lines"
I searched for it whole night but no cusses.

Can anyone help?!

I found some I2/H2O2 synth that involves refluxing for short period (5 min) instead of 5-6h reaction.
(This document used to be part of thevespiary but I managed to get only Google backup)

This sounds un-plausible and dumb since author doesn't even mention temperature of reflux.
I am pretty sure you will waste most of the reactants to get acetone from IPA or
acetaldehyde/acetic acid from EtOH if you overshoot temperature.

Vesp · « **Reply #8 on:** July 31, 2010, 05:22:53 PM »

Here: http://127.0.0.1/rhodium/Rhodium/hive/hiveboard/methods/000473279.html

A bit tricky to find, but have a look at the other threads too: http://127.0.0.1/rhodium/Rhodium/hive/hiveboard/wwwthreadspl.htm
and
http://127.0.0.1/rhodium/

I hope that helps.

NeilPatrickHarris · « **Reply #9 on:** July 31, 2010, 07:35:45 PM »

Quote from: Vesp on July 31, 2010, 05:22:53 PM

Here: http://127.0.0.1/rhodium/Rhodium/hive/hiveboard/methods/000473279.html

this absolutely works as advertised

Oerlikon · « **Reply #10 on:** July 31, 2010, 08:51:42 PM »

Hope this works with EtOH or acetone!
Since IPA is probably becomes acetone in this process that should be plausible.
if reactants are soluble enough in it.
This is the most helpful forum ever, many thanks!
Will report you as soon as I try it!

Oerlikon · « **Reply #11 on:** August 01, 2010, 09:01:45 PM »

IT WORKS in EtOH!!!

Quantum Dude · « **Reply #12 on:** August 02, 2010, 02:10:24 AM »

Quote from: Oerlikon on July 30, 2010, 10:45:47 PM

As I promised....

p-benzoquinone from acetaminophen, step-by-step:

Buy some acetaminophen containing tablets with least additional chemicals,
search for pills containing only microcrystalline cellulose and acetaminophen.
Use methanol or ethanol to dissolve them completely.
SWIM use 120ml of ethanol for 40 500mg pills, heat it and stir vigorously until everything dissolves,
don’t crush them so you know when they are really dissolved.
Methanol works better, but DMF is far the best.
Filter warm solution of acetaminophen in alcohol and let the filtrate evaporate.
Scrap the dry crystals and weight out 15g.

Prepare 33ml of 65% HNO3 and 100ml of concentrated HCl, put them both in the freezer.(SEPARATELY!)
IMPORTANT!!! Use biggest glass baker you can find and do reaction outside or in the fume hood!
Put inside that baker 100ml of HCl and 15g of acetaminophen and let it stir while you are making ice bath.
Put the glass in the ice bath and add 33ml of HNO3 at once.
The colder the batter, you don't need to measure temperature, just get sure it is very cold.
After few minutes of stirring you and color change, violent exothermic reaction will began.
A lot of foam and extremely toxic gas will be present, just be sure to stir properly,both liquid and foam,
keep it as cold as possible and avoid deadly gasses.
After some time reaction will settle but keep stirring at least 1h, or until no more foam and gas is liberated.
Now flood this with 300ml of water and give it a little stir.Vacuum filter puffy p-benzo with very distinctive yellow color and smell.
Press filter cake to get rid of most water and than dissolve it in 200ml of ethanol.
Heat the alcohol gently with stirring unit everything is dissolved.(you will get black solution, this is OK)

Let this supersaturated solution covered at room temperature at least 12h and than put it in the freezer for few hours to get
as much crystals as you can.(you can put it in the fridge,but christals will be hard, ugly and impure)
Filter your nice and big yellow p-benzo crystals with vacuum and was it with little bit of cold alchohol.
Dry it in the big baker with hair dryer and constant stirring. It is dry when no more lumps are forming and
product does not stick to the walls of baker. Wear gloves and gas-mask since fumes are very irritating and toxic.

This is a copy/paste protocol posted at Versuchschemie.de. I happen to know that you tried to pass this work as your own at drugs-forums too (lots of pointers are showing it is you such as the use of the same typos like ''baker''). Always give a reference and credit to the work youre posting about otherwise it looks like plagiarism.
Also,
1.Acetaminophen is soluble in hot water but not in cold water. A much better, and economical, way of extracting it is by dissolving the ground pills in hot water, filter while hot and leave the filtrate in the fridge overnight. Acetaminophen crystals will precipitate out of the solution and can be filtered and washed easily.

2. You seem to ''borrow'' a lot of initial parameters from the original versuchschemie.de writeup but at the same time ''skip'' the most crucial part, wheres the yield ? Also how come youre not adressing the fact that the final product is contaminated with chloranil ?

EDIT: Nevermind part-2, I saw you were talking about it in your previous posts.

Oerlikon · « **Reply #13 on:** August 03, 2010, 10:22:59 AM »

I never said I invented this method...
This is pretty standard and well known old experiment we did on coledge,
only thing I borrowed from versuchtchemie.de is ammount of solvent (but better one) and acetaminophen.
I culd mention it,but since this is well known procedure,most members here don't read Germam and I didn't just "copy paste" I didn't found it necesary.

Other than that,extraction with hot water is pain in the ass,and you lost more acetaminophen than you save on solvent.Far best solvent for price/solubility ratio is MeOH.

Quantum Dude · « **Reply #14 on:** August 03, 2010, 12:39:11 PM »

Quote from: Oerlikon on August 03, 2010, 10:22:59 AM

I never said I invented this method...
This is pretty standard and well known old experiment we did on coledge,
only thing I borrowed from versuchtchemie.de is ammount of solvent (but better one) and acetaminophen.
I culd mention it,but since this is well known procedure,most members here don't read Germam and I didn't just "copy paste" I didn't found it necesary.

Its 2010, dont you know how to post a URL ? You should mention it, especially since you are using the same ratios and protocol. The link was provided to you in that SM thread you started, so its pretty easy to figure out you discovered the procedure in that thread where you posted your results for your first attempt. So you knew about this back in college hey ?

http://www.sciencemadness.org/talk/viewthread.php?tid=8250&page=2#pid182495

Quote from: Oerlikon on August 03, 2010, 10:22:59 AM

Other than that,extraction with hot water is pain in the ass,and you lost more acetaminophen than you save on solvent.Far best solvent for price/solubility ratio is MeOH.

Bullshit, maybe you do not know how to properly isolate a compound by exploiting its solubility properties but that does not make the technique inferior for the less. Just dont use friggin liters of water to extract a few pills and youll have a quantitative yield.

Oerlikon · « **Reply #15 on:** August 03, 2010, 01:51:16 PM »

Procedure was made to demonstrate how different temperature with same reactants gives different products. Assistant did the experiment and we just watched, I didn't memorized name of reactants nor products (but chloranil) since I didn't know how important this chemical is.Will give you exact references for source when I find them.
Never the less,versuchtchemie.de helped a lot with reactants ratio,will post link in future according to your instructions.
If I made something new feel free to use my procedure as much as you want.
I don't take credits,others didn't know anything abbout this so I just wanted to contribute,thats all.

And yes,I tried with water but this is not for unpatient people like me!

It does work but it is too damn slow and if you oversaturate solution too much
you can lost quite a lot.
Will post chart of solubility in different solvents when I find it,with URL of course...

Author Topic: P-BENZOQUINONE; synthesis, appearance and problems (Read 271 times)

Oerlikon

P-BENZOQUINONE; synthesis, appearance and problems

Vesp

Re: P-BENZOQUINONE; synthesis, appearance and problems

Oerlikon

Re: P-BENZOQUINONE; synthesis, appearance and problems

NeilPatrickHarris

Re: P-BENZOQUINONE; synthesis, appearance and problems

Oerlikon

Re: P-BENZOQUINONE; synthesis, appearance and problems

Oerlikon

Re: P-BENZOQUINONE; synthesis, appearance and problems

Vesp

Re: P-BENZOQUINONE; synthesis, appearance and problems

Oerlikon

Re: P-BENZOQUINONE; synthesis, appearance and problems

Vesp

Re: P-BENZOQUINONE; synthesis, appearance and problems

NeilPatrickHarris

Re: P-BENZOQUINONE; synthesis, appearance and problems

Oerlikon

Re: P-BENZOQUINONE; synthesis, appearance and problems

Oerlikon

Re: P-BENZOQUINONE; synthesis, appearance and problems

Quantum Dude

Re: P-BENZOQUINONE; synthesis, appearance and problems

Oerlikon

Re: P-BENZOQUINONE; synthesis, appearance and problems

Quantum Dude

Re: P-BENZOQUINONE; synthesis, appearance and problems

Oerlikon

Re: P-BENZOQUINONE; synthesis, appearance and problems