Sciencemadness Discussion Board - TCP from Aspirin?

TCP from Aspirin?

YT2095 - 30-9-2006 at 05:10

given that This: http://www.sciencemadness.org/talk/viewthread.php?tid=389
thread was immensely helpfull with respect to TNP synthesis from aspirin.
A thought occured to me about an alteration during the procedure, would it be possible after the sulphonation stage of the ASA, to use NaCl or KCl instead on the KNO3, to make TCP instead?

it also is only slightly soluble in water apparently, and has a pink/white crystal color.

it would seem Logicaly possible imo, however I am somewhat of a newb to organic chem, and could just as easily found yet another way to make totaly useless black junk again.

I don`t actualy posses any Phenol, and the only other chems I have with any Similarity and Catechol, Hydroquinone, and methylbenzene.

if I can go the ASA route to phenolic compounds, that would be fantastic.

leaving the only other issue of making an Oxalate ester with these, but that`s for Much later.

Nicodem - 30-9-2006 at 06:51

TCP? I assume you mean 2,4,6-trichlorophenol?
But HCl is not a chlorine electrophile so it can not chlorinate phenols. Even if it would be, or if you would use Cl2 or some other chlorine electrophile, the intermediate chlorinated acetyl salicylic acids would not decarboxylate as easily like in the case of nitration (it could or it could not, depends on the conditions). Therefore you could also end with the mixture of regioisomers or, if the conditions to harsh, also with overchlorinated products.
But anyway, are you sure you want to produce any chlorinated phenols? They have a certain unhealthy stench that normal people generally avoid as far as possible.

not_important - 30-9-2006 at 07:39

Yes, you are better off just doing the aqueous halogenation of phenol. Manganese dioxide is a decent route to the free halogens, and can be mostly regenerated with Caa(OH)2 and air.

Oxalate ester of phenols?

YT2095 - 30-9-2006 at 08:21

well this is what I`m Ultimately after: http://www.chem.leeds.ac.uk/delights/texts/VV_exp_26_files/V...

I can make the TNP, the DNP will take more work, but using the guidlines that Rosco mentioned in his other thread, I MAY be able to halt the reaction when the DNP is the majority part of the synth product.

I don`t Have any phenol to use, only the chems similar that I listed.

Rosco Bodine - 30-9-2006 at 09:11

Perhaps you could completely reduce the picric acid
to triaminophenol and then chlorinate that to obtain the
trichlorophenol .

Trintrophenyl oxalate ( possible? ) might be worth looking at too as a possible reactant , or possibly some product of picryl chloride and oxalic acid or an oxalic acid ester .

[Edited on 30-9-2006 by Rosco Bodine]

YT2095 - 30-9-2006 at 09:18

wow, I honestly wouldn`t know where to begin with doing something like that, I`de just end up making Ammonium Picrate or something daft.
it sounds like a great idea, and I have 4g of PA that I could quite happily live without 3g of it (it`s such a potent dye that a gram is plenty for my needs).

my only worry is making something unpredictable, I can live with the danger or toxic side of things, it`s explosives that bother me, and it would be just my luck to come up with something really nasty by accident

Nicodem - 30-9-2006 at 09:46

Quote:

Originally posted by Rosco Bodine
Perhaps you could completely reduce the picric acid
to triaminophenol and then chlorinate that to obtain the
trichlorophenol .

Unfortunately it does not work this way. Organic chemistry is a bit more complex.

Quote:

Originally posted by YT2095
well this is what I`m Ultimately after: http://www.chem.leeds.ac.uk/delights/texts/VV_exp_26_files/V...

Are you sure you want to waste your time preparing phenol from Aspirin, chlorinating phenol and make your lab stench for years from chlorophenols only to realize that you don't have any oxalyl chloride for the last step?
If you want to prepare some 2,4,6-trichlorophenol just for the sake of it, then take the advice not_important gave you. It is not that dificult to prepare phenol from Aspirin and chlorinating phenol is easy. It can be done with sodium hypochlorite (chlorine bleach). Some form of a dioxine might form in the process (1,3,6,8-tetrachlorooxanthrene), especially if you are not careful in performing the reaction and in the isolation process. But since you said you can handle toxic compounds, I'm sure you will not get scared by this remote possibility.

YT2095 - 30-9-2006 at 10:04

Anthracene!

Hmm... that IS metioned also as another chemiluminescent material as the 9,10 (something) anthracene.
although I think something like this is well beyond me at the moment and may remain so for several years to come.

as for the NaOCl synth for the chlorinated phenol, will CaOCl serve the same purpose, I have the NaOCl, but only a 5% (at best) soln in the form of Chlorox bleach (the cheap stuff that hasn`t other crap in it).

Toxicicity at these levels I can handle quite safely too, although I would sooner avoid such things also, ANY potential danger that is unnecesary is just plain crazy to submit yourself to IMO.
that`s not to say a certain level isn`t inevitable with some persuits though, and certainly worth doing.

EDIT: on that site it`s writen as trichlorophenYL not OL, so I may be barking up the wrong tree here also unless it`s the same thing or a typo (and I doubt that).

[Edited on 30-9-2006 by YT2095]

Nicodem - 30-9-2006 at 10:37

Quote:

Originally posted by YT2095
Anthracene!

Who said anything about anthracene? I was talking about the dreaded oxanthrenes, also known as dibenzodioxines (this particular compound that can be formed is also called 1,3,6,8-tetrachlorodibenzo-p-dioxin).
I'm sure you heard about oxanthrenes before. Does the phrase "agent orange" ring any bells?

Quote:

I have the NaOCl, but only a 5% (at best) soln in the form of Chlorox bleach (the cheap stuff that hasn`t other crap in it).

The 5% solution is just of the perfect concentration for such use.

Quote:

EDIT: on that site it`s writen as trichlorophenYL not OL, so I may be barking up the wrong tree here also unless it`s the same thing or a typo (and I doubt that).

I highly recommend you to learn the IUPAC nomenclature. It is the No. 1 prerequisite for any dealing with organic chemistry. The No. 2 prerequisite is the literature search skills. The No. 3 prerequisite is the organic chemistry knowledge. All the rest is trivial, like handling with the glassware and things like that.

YT2095 - 6-10-2006 at 03:05

is there a way to speed up the autocatalytic degradation of ASA, to leave the pure salicylic acid behind, other than just keep the ASA moist and wait a few months?

I`m thinking this may be a better route towards TCP than the ASA and Sulphuric acid method.

YT2095 - 14-10-2006 at 05:51

*bump*

I Think I`ve found a way to isolate it, pure ASA in warm water, then add KOH until all dissolves (stiring well).
Then add HCl to ppt out the Salacylic acid. filter and wash as usual.

does this sound about right?

Trying to Synth Phenyl Oxalate, without Phenol, I need as many Phenol type precursors as I can get to UP my chances of experimental success.

S.C. Wack - 14-10-2006 at 15:28

"pure", "warm", and hydroxide is unnecessary. A solution of carbonate, a solution of aspirin tablets, and an acid is all you need. Do and see.

YT2095 - 15-10-2006 at 00:15

the reason for the pure ASA is that I didn`t wants any fillers/buffers caught in the final product, interesting about the carbonate though, I may try that next time if I run out, K2CO3`s less expensive than the hydroxide.

I`m quite surprised to note that the final Volume doesn`t look any less than the starting volume of the ASA, although the mass is less.

Thanks S.C. Wack

Mason_Grand_ANNdrews - 18-10-2006 at 10:18

I would guess you mean trichlorophenol, C6H5OH.
2,4,6-trichlorophenol
I don`t know the product is phenol when it treated with dilute KOH solution but
i think it can shurely oxidised. A reaction of phenol with sodium hydroxide will give
sodium phenolate.

I have a nice idea to trichloropehnol from phenol. Some iron powder will act as a catalyst
by the subtitution of the inner hydrogen atoms in benzene ring when more than one hydrogen
should be substituted. It should be easy to obtain 2,4,6-tribromophenol from phenol and
bromine but i don`t know it can work with chlorine and some derivates will form (tetra- and
pentachlorophenol). Phenol is hard soluble and i don`t know the chlorination will work without
a solvent, water may be. The synthesis can calculated by wight. A heated mix of 100 g phenol, 2 g of iron powder should give around 209,8 g trichlorophenol.
Maybe a little water will help, some hints will help.

YT2095 - 19-10-2006 at 00:18

through experimentation over the last few days, I find I`m strugling to even get Phenol in any usable amount beyond a vague aroma of it in a test tube.
the ASA to SA was only reasonably succesfull as when it`s heated to decomp, there is still a strong acetic smell, and when that`s driven off, I find most of the SA has sublimed and condensed further up the tube, and there`s only a faint hint of phenol.
after doing some reading on here in the Phenol based threads, there was a sugestion that from the SA stage you add NaOH to make sodium salicate, that will then decompose on heating giving off CO2 and leaving sodium phenolate, then HCl is added to that leaving NaCl and phenol.
needless to say, that failed here also.

the TCP( 2,4,6 trichlorophenol) isn`t that critical at the moment, as Phenyl Oxalate will work just as well for my purposes, of course, TCP would be nice to have as well, I fear it may be a little Too ambitious a project for me just yet.

Mason_Grand_ANNdrews - 20-10-2006 at 10:39

You mean it is to difficult, i dont think ?
Some practical issues, i hope it helps a little bit.
Phenol is somewhat soluble in diethylether but it have a bp of only 34,6°C and i don`t think you
can get trichlorophenol when the dissolved phenol is heated to 34 °C and
chlorine is bubbled through the solution, to many side reactions. A useful solvent is maybe carbon tetrachloride. I don`t know how it is soluble.
Prepare a mixture of 100 g phenol and 2 g iron in 1000 ml carbon tetrachloride in a large beaker, set the beaker to a hotplate heat the mixture to 70 °C and dryed chlorine is bubbled through solution until the weight of the solution is around 840 g (- weight of the beaker). Cool the mix and filter out the trichlorophenol, around 210 g. The iron is removed by dissolving the trichlorophenol in diethylether or EtOH, the solution is filtered and then the solvent is evaporated. I don`t know somewhat about the content of tetra-and pentachlorophenol in the syntheis.

I don`t know somewhat about the solubility of phenol in benzene, may be you can obatin two results in one step, 2,4,6-trichloropehnol and 1,3,5-trichlorobenzene (C6H3Cl3, 181,46 g/mol).
100 g phenol, 2 g iron in 186 g benzene should give around 193 g trichlorobenzene, 214 g trichlorophenol and 98 g benzene (derivates) when it chlorinated at 80 °C. Have someone a suggestion to the separation of the results and if this can work ?

I have found nothing what is useful to the synthesis of phenol from ASA, maybe later. I would guess you mean
ASA will give salycylic acid when is treated with dilute NaOH solution and HCl ? I don`t know that is right. I think it is sodium salycilate.

[Edited on 20-10-2006 by Mason_Grand_ANNdrews]

not_important - 20-10-2006 at 15:47

Quote:

Originally posted by Mason_Grand_ANNdrews
(snip)

I have a nice idea to trichloropehnol from phenol. Some iron powder will act as a catalyst
by the subtitution of the inner hydrogen atoms in benzene ring when more than one hydrogen
should be substituted. It should be easy to obtain 2,4,6-tribromophenol from phenol and
bromine but i don`t know it can work with chlorine and some derivates will form (tetra- and
pentachlorophenol). Phenol is hard soluble and i don`t know the chlorination will work without
a solvent, water may be. The synthesis can calculated by wight. A heated mix of 100 g phenol, 2 g of iron powder should give around 209,8 g trichlorophenol.
Maybe a little water will help, some hints will help.

Way too complicated, and overkill - do not need Fe or whatever catalyst. Chlorine and bromine will 2,4,6-trihalogenate phenols in water. This is used to form bromo-derivatives of phenols by putting a bit of the phenol in dilute HCl and adding bromine water.

(working from memory, might be worth downloading some of the old Ochem books inthe Library section to check)
For 2,4,6-TCP just mix phenol with about 5 times its volume of dilute HCl, warm slightly to get the phenol to form a solution, then bubble Cl2 through the mixture with stirring; TCP will precipitate out. Set up your chlorine generator to make 3 moles of Cl2 for every mole of phenol. Remember it's forming HCl, the solution will grow more acidic.

Filter off the TCP and wash with cold (ice) water. Recrystallise from boiling water or water+alcohol solution (it's really soluble in MeOH, EtOH, and acetone). Extra purification might be crystallisation from hot ligroin or similar hydrocarbon, or fractional freezing where impurities tend to remain in the liquid portion. There's got to be a number of references around for preparing it.

gil - 26-10-2006 at 08:07

salicilic acid? wart remover?

CuReUS - 23-1-2015 at 00:16

Quote: Originally posted by Nicodem

Quote:

Originally posted by Rosco Bodine
Perhaps you could completely reduce the picric acid
to triaminophenol and then chlorinate that to obtain the
trichlorophenol .

Unfortunately it does not work this way. Organic chemistry is a bit more complex

I think he meant converting the triaminophenol to trichlorophenol by diazotisation

but which reducing agent can be used for the reduction
using Metal/HCl might be risky as metal picrates are explosives but as the reduction will be carried out in aqueous medium,the picric acid will be moist so it will not be that unstable

Btw,what would you get If you reduced picric acid with 1 mole Sn/HCl and with 2 moles Sn/HCl. does the ortho NO₂ get reduced or the para ?

Chemosynthesis - 23-1-2015 at 23:51

Picramic acid, which is ortho. Plenty of references to old classics like Urbanski and Fundamentals of Dye Chemistry in this thread along with at least one member having tried the Fe/HCL reduction. I have seen weak metal picramate salts used in some kind of cosmetology product MSDS, so at least some are stable enough damp for commercial transport.

All this said, that thread was around three years prior to the OP's post in a section he had familiarity with, and probably should have found or referenced. The lit is even older.

CuReUS - 24-1-2015 at 00:58

Quote: Originally posted by Chemosynthesis

All this said, that thread was around three years prior to the OP's post in a section he had familiarity with, and probably should have found or referenced. The lit is even older.

if you are referring to me,then I am very sorry.I should have UTFSE'd earlier

here is that thread
http://www.sciencemadness.org/talk/viewthread.php?tid=433#pi...

but could someone explain why the ortho NO₂ will get reduced.shouldn't the para NO₂ get reduced more easily by Fe/HCl as it is less sterically hindered and also the ortho NO₂ are H-bonded with phenolic OH

Chemosynthesis - 24-1-2015 at 10:00

Quote: Originally posted by CuReUS

but could someone explain why the ortho NO₂ will get reduced.shouldn't the para NO₂ get reduced more easily by Fe/HCl as it is less sterically hindered and also the ortho NO₂ are H-bonded with phenolic OH

Not you, but the thread OP, who had a link to the energetic section and was obviously familiar with TNP and picric acid.

Thanks for linking to the thread. I meant to link it, but must have failed. That is exactly the one.

The reason I believe picramic acid is favored over 4-Amino-2,6-dinitrophenol is due to resonance. The phenol is an electron donating substituent, and the two proximate 2,6-nitro groups are a much stronger resonance form contributor due to the relative lack of charge separation versus the 4-nitro. This enhances their reducibility.
This is not explicitly stated in IJCB 48B(09) 1315-1318, but the authors do support my logic.

Also, the hydrogen bonding you mention is probably not taking into account the alkaline pH most of these reduction occur under. Another reduction is mentioned in The Chemistry of Dyestuffs: A Manual for Students of Chemistry and Dyeing (L. L. Lloyd), utilizing a transition metal and ammonia. I'm not sure how feasible a reduction would be with metal and formic acid, but one could look up pKa's and test it if inclined.

Hawkguy - 24-1-2015 at 11:52

You probably could get TCP after a lot of work. Base hydrolysis on Acetylsalicylic Acid would yield Salicylic Acid, which can be distilled to Phenol so you can do your business...

Hawkguy - 24-1-2015 at 11:54

For the record, distilling Phenol is terrible business an no fun. I'd recommend any other way to TCP you can find.

CuReUS - 25-1-2015 at 07:35

Quote: Originally posted by Chemosynthesis

The reason I believe picramic acid is favored over 4-Amino-2,6-dinitrophenol is due to resonance. The phenol is an electron donating substituent, and the two proximate 2,6-nitro groups are a much stronger resonance form contributor due to the relative lack of charge separation versus the 4-nitro. This enhances their reducibility.

if resonance is taken into account,the reaction must be under kinetic or thermodynamic influence.So can para NO₂ be reduced selectively at higher temperature ?
also will both the ortho NO₂ get reduced when 2 moles Fe/HCl is used or will one ortho and one para get reduced

Chemosynthesis - 27-1-2015 at 10:03

Quote: Originally posted by CuReUS

if resonance is taken into account,the reaction must be under kinetic or thermodynamic influence.

What? Only if there is an option between the two, meaning:
1. Two competing reaction paths must be present whereby path A has a thermodynamically more stable product, yet path B has a more thermodynamically stable intermediate.

2. The kinetic pathway must have an activation energy lower than that of the (other) bond enthalpies of the starting material.

Are either of these indicated from molecular mechanics or ab initio calculations, or is there any literature to suggest so?