Phloroglucinol Synthesis

[Marck]

I searched around for a while to find a proper method to obtain phloroglucinol (1,3,5-trihydroxibenzene) but i can't found somewhat to a useful synthesis. The stuff is sells for around $20 per pound from chemical suppliers. I was thinking about this for some time and i have compiled this short synthesis which contains two steps. If you have 1,3,5-trichlorobenzene, you can prepare 1,3,5-triaminobenzene and then 1,3,5-trihydroxybenzene from that. You need a littel ammonia equipment.

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Step 1: Preparation of 1,3,5-triaminobenzene, C6H3(NH3)3
Prepare a solution of 146 ml anhydrous ethyl alkohol and 10 g of powdered
1,3,5-trichlorobenzene in a 1000 mL round-bottomed flask. Cool the flask
to 10 °C and slowly bubble anhydrous ammonia into the solution for 8-10
minutes. After that, the solution is gently heated to 78 degree C and careful refluxed for 30 minutes. Then the ethyl alkohol is evaporated and the obtained mass is washed with 3 - 5% hydrochloric acid. The mixture is stirred for a while and the solid mass is collected by evaporating the liquid. The collected pieces are grinded with a motar to a fine powder to use the crystals in the next step. To purify the crystals, dissolve them in enough carbon tetrachloride, the solution is filtered, the liqiud is evaporated and the purifyed product is then collected.
Yield is about 6,7 g.

Step 2: Preparation of 1,3,5-trihydroxybenzene, C6H3(OH)3
Place 28,1 mL of 96-100% sulfuric acid to a 500 mL round-bottomed flask and careful dilute the acid with 232 mL of water. Prepare a second solution of 13,1 g of sodium nitrite in 62 mL water in a 100 mL beaker and the obtained product prepared above is stirred to the dilute sulfuric acid. Slowly the second mixture is combined to the first and the flask is gently heated to 50 degree C for 60 minutes. The solution is then concetrated much as possible to evaporate the water. Add enough sodium chloride until it becomes saturated, extract the solution several times with ethyl ether, combine the extracts and filter the solution. Add a small amount of sodium sulfate to the solution and let it stand for a few hours. Filter the solution again and the ethyl ether is then evaporated. The pieces are collected and dissolved in enough anhydrous ethyl alkohol, the solution is filtered and the ethyl alkohol is evaporated to collect the pices of anhydrous phloroglucinol.
Yield is about 2 g.

Anyone that have something useful to this, please comment on this. I have a
variety of nice suggestions to similar compounds and i hope i came up with it
it the next few days.

[nbk2000]

Phloroglucinol.

This phloroglucinol can serve as the starting material for synthesis of 1,3,5-trinitro-2,4,6-triaminobenzene (TATB), which is an important thermally stable energetic material used by the U.S. military. TATB possesses a higher density and detonation velocity relative to TNT. TATB is characterized by reduced shock sensitivity and increased thermal stability relative to the high explosives hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).

The Draths route to phloroglucinol stands in stark contrast to the current manufacture of phloroglucinol from 2,4,6-trinitrotoluene (TNT) by a route involving an oxidation utilizing Na2Cr2O7. Beyond the explosion hazard, environmentally problematic and carcinogenic chromates are generated along with other salts as waste streams during synthesis of phloroglucinol from TNT.

Beyond synthesis of TATB, phloroglucinol can be exploited for the synthesis of resorcinol. Draths has developed a high-yielding route to resorcinol involving catalytic hydrogenation of phloroglucinol. Resorcinol is widely used in novalac resins, which are used in adhesive applications ranging from plywood to tires. There may also be commercial opportunities for replacing resorcinol with phloroglucinol in novolac resins. Phloroglucinol-based novolac resins would likely have a more highly cross-linked structure and have been predicted to cure almost instantaneously at room temperature.


When posting a synthesis, you need to state what the chemical is useful for (and it'd better be E&W related), and whether or not the synthesis is something you made up, or if it's something you got out of a journal. If you got it out of a journal, we need to know which one, with year, volume, and page.

There was someone banned from here just a short while ago for doing this very same thing...posting a synth with no uses and no clarification on whether it was his own synthesis or from a journal.

I've highlighted some of your grammatical errors. Please correct them.

Also, considering how inexpensive the chemical is ($20/pound), it's rather silly to bother with making it. Though, of course, be prepared to make everything yourself, since you never know when it'll become an 'evil' chemical and be banned.

[megalomania]

Phloroglucinol is one of the new precursor compounds on my website, alas the synth has been relegated to a lower priority. I have it listed in the synth of trinitrophloroglucinol: http://www.roguesci.org/megalomania/explo/trinitrophloroglucinol.html

[Marck]

This synthesis was developed by me. Seems possible that it can be prepared from 1,3,5-trimethylbenzene. I have no sources which provides a similar
procedure like that. Might such a process can be used specific to obtain
1,3,5-triaminobenzene and this have a little importance.

1,3,5-Triaminobenzene:
C6H3(NH2)3
Molmass: ~123,16 g/mol

I have started a search over the web and in sigma-aldrich to find more about
the compound. This stuff is not to get. I don`t know the calculated quantity
of EtOH in the process is sufficient to dissolve the trichlorobenzene. May be it is possible to use THF, p-dioxane or acetonitrile.

Excuse me for some spelling errors in the topic, I will correct them.

[megalomania]

Possible, maybe, but all the theory in the world is useless (and is in fact technically hypothesis) without experimentation. There are other websites for theory…

[nbk2000]

It seems about every week or so that I have to ban someone who keeps posting 1+1 chemistry synthesis 'procedures', after failing to provide citations or sources. :rolleyes:

Silly rabbits, don't they ever learn?