Sciencemadness Discussion Board - Phenol from Domestically Available Chemicals

Phenol from Domestically Available Chemicals

ParadoxChem126 - 7-4-2013 at 21:19

I have not yet had a chance to try this synthesis, but I have come up with the procedure. Start by reacting a quantity of aspirin (acetylsalicylic acid) with saturated aqueous sodium hydroxide solution (crystal drain opener) until it is all dissolved. The aspirin may contain binders that do not dissolve, so simply filter the solution. The solution will consist of sodium salicylate and sodium acetate. Now, slowly add concentrated hydrochloric acid (hardware store muriatic acid) in small amounts. Keep adding HCl until no more salicylic acid precipitates out. Acetic acid will have formed as a byproduct, but it will stay in solution. Filter out the salicylic acid, wash it with water, and set it aside to dry.

Once the salicylic acid is dry, put 25g of it into a suitable round-bottom flask and clamp the flask to a ring stand. Now, heat the salicylic acid with a hot torch for 5-6 seconds at a time, pausing 10-15 seconds between heating sessions. Continue to heat and pause for a total of 10-15 minutes. During the heating, the salicylic acid will break down into phenol and carbon dioxide gas. After heating, allow the flask to cool to room temperature, and add 100ml of dichloromethane (distilled from paint stripper). Swirl the flask until all of the phenol is dissolved. Now set up for distillation and distill off the dichloromethane at 40 degrees Celsius. When all of the dichloromethane is removed, the residue in the boiling flask will be composed of phenol with a purity of 95 to 98%.

[Edited on 8-4-2013 by ParadoxChem126]

[Edited on 8-4-2013 by ParadoxChem126]

[Edited on 8-4-2013 by ParadoxChem126]

[Edited on 8-4-2013 by ParadoxChem126]

[Edited on 9-4-2013 by ParadoxChem126]

vmelkon - 8-4-2013 at 17:55

I think you could do a decarboxylation reaction with the salicyclic acid.

Heat solid salicyclic acid with solid NaOH to 500 °C or something like that. You should end with phenol and Na2CO3.

ParadoxChem126 - 8-4-2013 at 18:06

Well, if you heat the molten phenol to 500 degrees Celsius, won't it all instantly vaporize? Also, I would not want to mess with molten sodium hydroxide and phenol vapors...

Finnnicus - 8-4-2013 at 18:48

[Edited on 9-4-2013 by Finnnicus]

macckone - 8-4-2013 at 21:17

Certain throat sprays also contain phenol.
It might make an interesting work-up to isolate the phenol.
Chloraseptic

ParadoxChem126 - 8-4-2013 at 21:26

Yeah, but the ingredients list phenol as 1.4%. You would only be able to isolate a very small amount from the entire bottle. Still might be interesting to try…

elementcollector1 - 8-4-2013 at 21:36

Quote: Originally posted by vmelkon

I think you could do a decarboxylation reaction with the salicyclic acid.

Heat solid salicyclic acid with solid NaOH to 500 °C or something like that. You should end with phenol and Na2CO3.

I hope you have a steel container for that molten NaOH.
Isn't phenol deathly toxic?
I hope that decomposition of salicylic acid works - I'd love a good source of phenolphthalein.

macckone - 9-4-2013 at 06:59

Quote: Originally posted by ParadoxChem126

Yeah, but the ingredients list phenol as 1.4%. You would only be able to isolate a very small amount from the entire bottle. Still might be interesting to try…

That comes to about 2.4g per bottle.
If you want cheap go the benzene sulfonate route or cumene hydroperoxide method.

macckone - 9-4-2013 at 07:07

Quote: Originally posted by elementcollector1

Isn't phenol deathly toxic?

In large quantities, breathing hot phenol gas or getting hot phenol on your skin is inadvisable. Of course the same can be said for steam and boiling water. It is somewhat toxic but certainly not as toxic as hydrochloric acid. If exposed to vapor, seek medical attention. If you get it on your skin wash it off and seek medical attention if there is skin damage. If it is hot and you get it on your skin, it will cause severe burns. Small quantities are used as a throat medication, so I wouldn't freak out if I got a speck of dust on my arm. Of course, if you get a little sulphuric acid on your arm it will leave a mark.

Mailinmypocket - 9-4-2013 at 07:43

Quote: Originally posted by macckone

Quote: Originally posted by elementcollector1

Isn't phenol deathly toxic?

Actually a speck of phenol on your arm it is absorbed and will cause burns and blistering. It is quite toxic actually. More so than HCl...

ParadoxChem126 - 9-4-2013 at 13:55

Quote: Originally posted by elementcollector1

Quote: Originally posted by vmelkon

I think you could do a decarboxylation reaction with the salicyclic acid.

Heat solid salicyclic acid with solid NaOH to 500 °C or something like that. You should end with phenol and Na2CO3.

I hope you have a steel container for that molten NaOH.
Isn't phenol deathly toxic?
I hope that decomposition of salicylic acid works - I'd love a good source of phenolphthalein.

The decomposition of salicylic acid should work... Check out this website about phenol from salicylic acid.
http://books.google.com/books?id=y5mZrW1KB_AC&pg=PA129&a...

zed - 9-4-2013 at 17:34

http://www.youtube.com/watch?v=hlR3UWLyxEU

Don't know how difficult these chemicals are to acquire. But, in my day if you needed Phenol you either bought it outright, or made it from Aniline. Or, if you were a Chem student, you Nitrated Benzene, Reduced the Nitrobenzene it to Aniline.....Etc.

Aspirin seems like an interesting alternative.

ParadoxChem126 - 9-4-2013 at 18:45

Benzene and nitric acid are not easily accessible to me, so I've kind of ruled out the aniline approach. Also, I don't have a fume hood, and I don't want to mess with benzene without one.

chemcam - 10-4-2013 at 09:19

I can verify that the OP's procedure works, at least sort of, I have done it personally a while back with 2 failures and 1 success. I believe the failures took place because I do not have a Bunsen burner I was using a propane torch, held at a distance of course, so the heat applied was never consistent. I used chloroform in the place of DCM. I was thinking about doing a YouTube video since none exist on the topic but I haven't had a chance to improve the dependability.

ChemistryGhost - 10-4-2013 at 10:07

Maybe you could obtain cumene and try using the cumene process in a Hock rearrangement to obtain acetone and phenol. Acetone is always useful. :cool:

zed - 10-4-2013 at 16:57

Well, Benzene is a carcinogen.......eventually. A few minor exposures are unlikely to give you the big C... Everybody, used to get lots of Benzene exposure, all of the time. Most of us are just fine.

Aniline can also be prepared by the degradation of Benzamide. A material you could likely produce from Benzoic Acid, or Sodium Benzoate. These are materials that can be obtained cheaply, and in bulk.

[Edited on 11-4-2013 by zed]

vmelkon - 19-4-2013 at 13:35

Quote: Originally posted by ParadoxChem126

The decomposition of salicylic acid should work... Check out this website about phenol from salicylic acid.
http://books.google.com/books?id=y5mZrW1KB_AC&pg=PA129&a...

Wow, that is very simple. Just heat the salicyclic acid.
The text suggests to use methylene chloride (DCM, CH2Cl2) which I don't have but I guess other solvents would do the job as well.
In the USA, you can buy BBQ cleaner liquid and distill to get the CH2Cl2 out.

[Edited on 19-4-2013 by vmelkon]

ParadoxChem126 - 4-5-2013 at 21:24

I think that distilling it from paint stripper is cheaper.

[Edited on 5-5-2013 by ParadoxChem126]

BlackDragon2712 - 30-9-2013 at 18:09

Phenol, a quite toxic chemical but damn I love its smell xD!

I can confirm that the decarboxylation of salicylic acid does in fact work. The first minute after you put the flame out a strong smell of phenol is perceptible. Later I made the extraction using ethyl acetate and apparently it worked just fine. Recristalization was made later using water as the solvent. You can get very pure fenol from this method (pure enough as to what a home chemist can ask for)

I do apologize for not having any photograph of the other processes; this was actually taken by a friend of mine.

DJF90 - 30-9-2013 at 22:10

Theres a fairly detailed experimental over at Versuchschemie

macckone - 1-10-2013 at 11:45

Quote:

Actually a speck of phenol on your arm it is absorbed and will cause burns and blistering. It is quite toxic actually. More so than HCl...

Not true
HCl LD50 oral (human) 2.8mg/Kg
Phenol LD50 oral 270mg/Kg

Phenol is not as toxic as most of the stuff we take for granted.
If it were that toxic it wouldn't be in Chloraseptic.
Having said that, take reasonable precautions because it can be dangerous but then so can potassium chloride.

[Edited on 1-10-2013 by macckone]

MichiganMadScientist - 1-10-2013 at 12:37

So, is anyone here agreeing with the OP regarding producing the salicylic acid from aspirin tablets? Because honestly, producing phenol from aspirin tablets sounds way easier than the other methods mentioned here such as trying to screw around with benzene, etc. I understand there might be purity issues from binders in aspirin tablets, but at that, pure aspirin is itself a fairly simple synth. However, one has to come by acetic anhydride for that, and thus, simply generating the salicylic acid from aspirin tablets becomes a bit more desirable for me.

Also, the step involving the dichloromethane is simply a recrystallization, correct? One should have crude phenol simply from heating the salicylic acid, and this crude phenol should be solid once it cools to room temp?

[Edited on 1-10-2013 by MichiganMadScientist]

Random - 1-10-2013 at 13:55

I have found one study about chlrobenzoic acid synthesis from hypochlorite and benzoic acid and then probably hydroxybenzoic acids may be obtained from them with NaOH, they could be used instead of aspirin for decarboxylation.

DJF90 - 1-10-2013 at 14:30

@Macckone: Where did you get that data from? Its way off according to Sigma:

HCl (gas) LD50 Oral (Rabbit) 900 mg/kg

Phenol LD50 Oral (Rat) 410-650 mg/kg, LD50 Dermal (Rabbit) 630 mg/kg

Phenol is pretty nasty stuff. Its hepatotoxic (liver) and sufficiently volatile to cause concern. I've seen a bottle where half the contents were in the upper part of the bottle due to sublimation.

The crude phenol can be (vacuum) distilled to purify to an acceptable level (again, see the VC page).

[Edited on 1-10-2013 by DJF90]

bfesser - 2-10-2013 at 05:24

Quote: Originally posted by DJF90

Theres a fairly detailed experimental over at Versuchschemie

Provide the link, then.

Mailinmypocket - 2-10-2013 at 07:07

Phenol from salicylic acid in German but Google Translate does a fairly nice job of converting it to English.

Attachment: phenol.pdf (18kB)
This file has been downloaded 1273 times

CAUTION: Phenol is rapidly absorbed through skin, and from the stomach and lungs. Systemic toxicity can result from ingestion of solutions, or from inhalation or cutaneous absorption of solutions or vapor. This is characterized by an initial excitatory phase, rapidly progressing to fulminating CNS depression with coma. Potential symptoms of acute overexposure are steatorous breathing, mucous rales, froth at mouth and nose, frank pulmonary edema; cyanosis; tremor, convulsions, twitching; death due to respiratory failure. Characteristic odor of phenol on breath. Ingestion may cause burning of mouth and throat; white necrotic lesions in mouth, esophagus and stomach; abdominal pain. Direct contact may cause irritation of eyes, nose and throat; skin burns; dermatitis; ochronosis. Chronic exposure may result in vomiting, difficulty swallowing, excess salivation, diarrhea, anorexia, weight loss; headache, fainting, vertigo, mental disturbances; muscle aches and pain, weakness; damage to liver and kidney, dark urine. See NIOSH Pocket Guide to Chemical Hazards (DHHS/NIOSH 97-140, 1997) p 248; Clinical Toxicology of Commercial Products, R. E. Gosselin et al., Eds. (Williams & Wilkins, Baltimore, 5th ed., 1984) Section III, p344-348; Patty's Industrial Hygiene and Toxicology vol. 2B, G. D. Clayton, F. E. Clayton, Eds. (Wiley-Interscience, New York, 4th ed., 1994) p 1567-1584.

[Edited on 2-10-2013 by Mailinmypocket]

DJF90 - 2-10-2013 at 09:10

@bfesser: Don't be so lazy. I appreciate german may not be your first (or second) language but I don't speak it either and I managed. Theres some interesting stuff on there so its worth a browse and you'll pick up phrases etc as you go. Either that or you can use google translate like most other non-german speaking visitors

bfesser - 2-10-2013 at 09:52

Heh. I was under the impression that you were the one being lazy. I can read German fairly easily, and could find the link myself, but that's not really the point. The point is that you should have provided the link in the first place, rather than sending everyone else on an errand to see what you're referring to. Personally, few things annoy me more than when members mention the existence of a reference, then fail to provide it.

Since you, apparently, can't be arsed... here's the link [again, apparently]:
http://www.versuchschemie.de/ptopic,287006.html <img src="../scipics/_ext.png" />

[edit] Just saw Mailinmypocket's post...oh well.

[Edited on 2.10.13 by bfesser]

DJF90 - 2-10-2013 at 22:48

Ha thats a good one. I don't have time to go searching around for stuff on the behalf of others unless I have the page open in another window. It is not being lazy, I told you where the reference was and its up to you to go and get it, just like any other literature citation. Sure, "go see VC" is pretty vague but anyone with half decent searching skills would find the page in question with minimal effort.

And like I said, its worth looking for as theres a bumload of other decent experiments over there in the same subforum, most with decent pictures.

Fantasma4500 - 3-10-2013 at 09:33

i recall benzoic acid can be heated and condensed into phenol, chemcamtv told me he did it before, if im not entirely wrong i recall he used copper salts as catalyst for it..
benzoic acid is relatively easy to make and even easier to seperate..

sodium benzoate shouldnt be too hard to get a hold of, if this has HCl added while in solution benzoic acid will ppt. out as a white mass
its easily dried, but when its a dry powder you might want to pour it into whatever container youre gonna store it in, it stings alot, and is most likely quite toxic to inhale

basically..
sodium benzoate, add HCl, filter and dry out, heat and condense

im very very sure it was benzoic acid used for this, i could be wrong, but im quite sure it was..

bfesser - 3-10-2013 at 09:39

I could be mistaken (and likely am), but I was under the impression that copper(II) benzoate will decarboxylate to benzene under such conditions. I think you may be confusing benzoic and salicylic acids.

[edit] <a href="viewthread.php?tid=325">Benzene synthesis</a>

[Edited on 3.10.13 by bfesser]

mr.crow - 3-10-2013 at 10:48

Heating a flask with a torch seems kind of crude so I searched for a better method. I found an interesting Patent.

It uses molten benzoic acid as a solvent plus a benzoate salt as a catalyst.

A good experiment would be to mix benzoic acid, salicylic acid, and nickel carbonate in a distilling flask and heating with a mantle to 200C. The salicylic acid can also be constantly replenished.

MichiganMadScientist - 3-10-2013 at 18:00

So here's the deal. I completed the process suggested by the OP. Everything went very smoothly......and I feel I got a very good yield of the crude salicylic acid as a result of hydrolysis of aspirin. I then took the crude salicylic acid, and heated it in a beaker which was being covered by a watch glass. The white crude melted at a relatively low temp (my hotplate was only set on 2/9), and very nice large crystals then condensed near the top of the beaker.

My question is: is this phenol? Or did I just collect sublimmed salicylic acid crystals? The crystals don't have a super strong odor, and I'm still trying to think of other simple analytic tests I can perform. Any suggestions? Thanks.

[Edited on 4-10-2013 by MichiganMadScientist]

confused - 3-10-2013 at 18:35

if you have some phalic anhydride handy, you could convert it to phenolphalein and look for a colour change under acidic or basic conditions.

http://www.youtube.com/watch?v=lBIxBJMZD9Y

and it should react with sodium bicarbonate to form carbon dioxide gas
10 C6H5OH + 10 NaHCO3 = 10 C5H5Na + H20 + 20 CO2

MichiganMadScientist - 3-10-2013 at 18:49

I have no phalic anhydride available, so that test is a no go. I'll try the sodium bicarb test though....thanks for that.

I just tried comparing the solubility of my white crude (salicylic acid) with my mystery crystals. The mystery crystals seem to dissolve appreciably better in water than my crude salicylic acid......and this seems consistent with the fact that Phenol is significantly more water soluble than salicylic acid....

Magpie - 3-10-2013 at 18:54

Quote: Originally posted by MichiganMadScientist

My question is: is this phenol? Or did I just collect sublimmed salicylic acid crystals? The crystals don't have a super strong odor, and I'm still trying to think of other simple analytic tests I can perform. Any suggestions? Thanks.

Phenol has a strong and distinctive smell. But to answer your question there is a color test with FeCl3:

http://en.wikipedia.org/wiki/Ferric_chloride_test

MichiganMadScientist - 3-10-2013 at 19:20

Well, my mystery crystals don't have a very distinctive smell, so that's not encouraging. Also, I tried sodium bicarb test, and both my white crude and my mystery crystals produced outgassing upon the addition of sodium bicarb in the presence of water.....

And regrettably, I don't have any ferric chloride sitting around, so that test won't be possible for me...

confused - 3-10-2013 at 20:03

you can get ferric chloride as an etchent for printed circuit boards

also, you can make phthalic anhydride, but its kind of impractical if you're just making some to test for phenol

[Edited on 4-10-2013 by confused]

DJF90 - 3-10-2013 at 22:09

Sodium bicarbonate will not react with phenol, it is not a strong enough base. The fact your sublimate reacts with sodium bicarbonate indicates it is the acid, although there may be some phenol present. Ferric chloride test for phenols probably won't distinguish the two either as salicylic acid is also a phenol! Though you may have some luck if different coloured complexes are produced for the two compounds.

The easiest analytical work you could do is a melting point determination. That should give you a pretty good indication.

hames - 3-10-2013 at 23:50

hi guys,I've had about 3l of dirty 88% phenol solution lying around for a while and wish to purify it,its from the bottom of an old corroded 205l drum I found at work so its almost black. It absolutely reaks of phenol so I'm guessing its still quite potent,Im going to try a liquid/liquid extraction,I have a few solvents I can try with such as dichloromethane,ethyl acetate,methyl isobutyl ketone,methyl amyl ketone,D-40-D80 solvents,ethylene glycol monobutyl ether the ethylene glycol monomethyl ether,ethylene glycol monomethyl acetate and diethyl ether plus a few more hardware store types.I want to avoid distilling but if I have to I will if so what should I use to neutralise phenol vapours coming from the vacuum takeoff.
any general tips would be appreciated by those in the know.

jim

[Edited on 4-10-2013 by hames]

macckone - 14-10-2013 at 07:39

Quote: Originally posted by DJF90

@Macckone: Where did you get that data from? Its way off according to Sigma:

HCl (gas) LD50 Oral (Rabbit) 900 mg/kg

Phenol LD50 Oral (Rat) 410-650 mg/kg, LD50 Dermal (Rabbit) 630 mg/kg

Phenol is pretty nasty stuff. Its hepatotoxic (liver) and sufficiently volatile to cause concern. I've seen a bottle where half the contents were in the upper part of the bottle due to sublimation.

http://kni.caltech.edu/facilities/msds/HCl.pdf for LD50 man oral

I would trust actual LD50 oral man for liquid vs LD50 oral rabbit of gas for a practical. I am guessing they intubated a rabbit and pumped the gas straight into the rabbits stomach where HCl is less toxic. While the LD50 man was probably from medical records of people actually swallowing it and destroying their esophagus.

My figures for Phenol were more toxic than yours so not really in question there. But the reality is that phenol is not that toxic. A 100kg man (using my weight) would have to ingest 25g of the stuff to have a 50/50 chance of dying. I wouldn't do that but certainly quantities up to a gram are not going to kill a healthy adult although it may make you very very sick. People have swallowed a whole bottle of Chloraseptic (2.4g of phenol) without dying although I am sure there was lots of vomiting and an emergency room visit and maybe even an extended hospital stay.

For comparison purposes phenol is an order of magnitude more toxic than sodium chloride while sodium cyanide is two orders of magnitude more toxic than phenol. And tantalum chloride is an order of magnitude more toxic than phenol. So although it is toxic, it is not what one would think of as deadly toxic, nor is it a cumulative poison like tantalum or other heavy metals.

I really wish LD1 was commonly published for compounds because that is a base minimum of what can kill a person vs 50/50 chance of killing a person. Keeping in mind I don't advocate skipping safety precautions but the common perception of phenol as 'deadly toxic' is not really accurate. It is certainly toxic and it isn't a good idea to get it on your skin or breath the vapors, a small amount of exposure should not send you screaming to the hospital.

ORM-D is a very stringent definition of toxic and phenol just barely makes it using my figures and Using your figures it doesn't make it for oral ingestion.

Magpie - 14-10-2013 at 08:14

Why all the fuss about phenol toxicity - you are not planning on sticking your snoot in it are you?

In the old days phenol was commonly called carbolic acid and was widely used as a disinfectant in hospitals.

macckone - 14-10-2013 at 08:26

My point exactly, the stuff isn't good to ingest or get on your skin but taking reasonable precautions it is unlikely to kill you.

testimento - 13-2-2014 at 13:53

Has anyone researched this method:

http://www.greener-industry.org.uk/pages/phenol/8PhenolProdM...

Essentially benzoic acid can be made in liquid phase catalytic oxidation of toluene.

After that, benzoic acid would be catalytically decarboxylated at 240-249C(BP) to phenol and carbon dioxide over copper catalyst. I'm not perfectly sure is this at gas phase or liquid phase, but if it were the latter, it'd simply consist by mixing catalytic copper with benzoic acid and heating it up to that.

blogfast25 - 13-2-2014 at 14:14

Quote: Originally posted by Magpie

Why all the fuss about phenol toxicity - you are not planning on sticking your snoot in it are you?

In the old days phenol was commonly called carbolic acid and was widely used as a disinfectant in hospitals.

Thank G-d for a bit of common sense!

DraconicAcid - 13-2-2014 at 14:38

Quote: Originally posted by testimento

After that, benzoic acid would be catalytically decarboxylated at 240-249C(BP) to phenol and carbon dioxide over copper catalyst.

Er, you mean C₆H₅CO₂H -> C₆H₅OH + CO₂? There's an oxygen appearing from nowhere, there...

testimento - 13-2-2014 at 16:33

Sorry, forgot the N2O.

So the process would essentially go like this on a tabletop:

In first, one makes a distillation apparatus with dropper funnel filled with conc. ammonium nitrate solution. This drops onto the reactor heated strongly to instantly vaporize the water and cause the AN to turn into N2O. AN would cause mass detonation risk if heated in bulk and the gas generation speed would be very difficult to control. Gas and water steam are led through condenser and water is accumulated into the receiver. The N2O is led with pipe out of the receiver and it goes through desiccant trap to remove moisture, and is then lead through pipe. To this pipe is connected another reactor fitted with dropper funnel filled with anhydrous toluene. Toluene is dropped into the highly heated reactor to vaporize it, and both gases mix in the tubing and are then led into the main reactor. Metal tube reactor filled with ZnO impregnated silica gel is heated up to 450C, in where phenol is supposed to form in 35% yield at 99% selectivity. The outcome is lead into condenser column and is accumulated into flask and can be purified by fractional distillation to yield high purity phenol.

Should be a lot cheaper method than to mess up with salicylic acid.

[Edited on 14-2-2014 by testimento]