Author Topic: P2Ps from benzene, acetone and Mn(AcO)3  (Read 20740 times)

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Antoncho

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P2Ps from benzene, acetone and Mn(AcO)3
« on: August 16, 2001, 02:33:00 AM »
This is another synthesis from "the Russian Hive" - hyperlab.org. It describes prepn of P2P from nothing else but benzene, acetone and Mn(CH3COO)3. The latter is easily prepared from KMnO4(see below). As far as the search engine goes, it hasn't been covered here at all (xcept for one unanswered post in Aquisition where some stranger asks where to buy manganese triacetate  ::) )

Here's the deal:



15 ml benzene, 15 ml acetone, 25 ml AcOH and 5 mmol(1,01 g) Mn(AcO)3 are boiled under N2 atmosphere until the color of the soln changes from dark brown Mn(AcO)3 to pink Mn(AcO)2 - approx. 1,5 h. The rxn mixtr is diluted w/40 ml ether, washed w/25 ml water and 2x25 ml 5% NaHCO3, the org layer is dried and evap'd to yield 40% P2P (134 mg)





Now, as you can see the yield is not that great - but, hey, who cares for acetone, what is more important the benzene/acetone to Mn(AcO)3 ratio is huge. Well, i can only say that the above procedure (as i have some good reasons to believe) bears rather analytic than preparative approach and the amt of Mn(AcO)3 undoubtedly can be scaled up significantly, but the exact answer is still to be found.

Although SWIM didn't succeed w/this rxn the 1st and the only one thus far time he tried it (see the experimental details below) there can be no doubt that it works as i've personally read two articles dedicated to studying its mechanism. It works even better w/substituted benzenes: for anisole the yield is 74% (in 45 min), unfortunately a mixture of isomers is formed of which ortho- predominates. Para-dimethoxybenzene is even more activated than anisole and completely symmetric, it seems to bee ideal for this rxn, don't you think so, bees? 8)

The rxn also runs w/naphtalene (selectively forming 1-acetonylnaphtalene), furan, sylvan, pyridine, thiophene (all forming alpha-acetonyl compds), chloro- and cyano-benzene, toluene (forming a mxtr of isomers) and, beyond a shadow of a doubt, a whole lot of other aromatics which opens so many roads to new, untasted yet compounds - (which, coincidentally, are currently being discussed in Serious Discourse/Fluoroamph. thread) - that it is even scary. Just needs to be made to work  ;D  :)  ;D  

The mechanism of the rxn is as follows: first a ÑÍ2=Ñ(ÑH3)-Î-Ìn(3)-ÀãÍ complex is formed, which then falls apart w/simultaneous cleavage of Mn-O bond, acetonyl combines w/aromatic nucleus (the limiting step) and the resulting adduct radical is rapidly reduced w/another Mn(AcO)3 molecule.
Well, with that said let me finally get to the preparation of Mn(AcO)3 - i'll skip the abstract and just tell you guys what SWIM did, from the beginning to the end.




KMnO4 is reduced w/hexamine and HCl to MnCl2, precip'd as the carbonate, converted to Mn(AcO)2 and oxidized w/KMnO4 in boiling GAA to Mn(AcO)3.


15 g KMnO4 was dissolved in some hot water and combined w/a soln of 15 g camping fuel (SWIM used hexamine cause he had it at hand - any ammonium salt will do just fine). Nothing happened. Then conc HCl was added in portions w/swirling until mixtr acidic. As he did it,  the mxtr gradually turned completely clear and the stench of formaldehyde became almost unbearable  ::) . Then SWIM put the soln in a 5 liter jar and mixed it w/a molar excess of saturated NaHCO3 (you can calculate it if you want - SWIM just took a large xcess). White precipitate (MnCO3) forms. The jar was filled w/water to wash it. DO NOT use NaOH for precip'ing manganese - Mn(OH)2 instantly oxidizes when exposed to air, and the carbonate is pretty stable.

When all settled, the water was decanted into another jar (to collect the still remaining suspended MnCO3 later) and the precip't washed in the same manner once again, MnCO3 in the other jar washed later too. Then all combined, water decanted off, precip't vac. filtered, DO NOT DRY IT - there's no need for that, and it WILL oxidize somewhat during drying. Just scrape it off the filter and dump into some GAA. Now, guess what, there was no fizzling and bubbling at this stage as SWIM expected, in fact, to dissolve all the MnCO3 it took a 2 hour reflux. At this stage the soln was a pleasant pink color, just as it should have been.

The GAA was boiled off overnight at 130 C in an oil bath and when SWIM woke up he found that the bottom of the flask was covered w/some white (not pink) crystals - well, he thought, that must be unhydrous Mn(AcO)2 (the pink stuff is a tetrahydrate) - and so it turned out to be. SWIM dosn't remember the exact weight (uhhhh... 21 g?) but the yield was quantative.

Now SWIM went on to dissolving his salt in GAA, 250 ml (SWIM thought you'd have to 1st evap. GAA and then dissolve in it again as the former one has water in it - but he was wrong as you'll see. Well, he needed to weigh it anyway. Just skip this evap'n/dissolution step, it's probably not needed) - the shit doesn't dissolve! even w/reflux! Probably, SWIM thought, the unhydrous stuff doesn't, so he added a theoretical amt  of water, well, a little more in fact, about 7 ml to the mxtr and w/some boiling most of it went in the soln, some was still left at the bottom - it was OK, as it turned.

To this boiling soln SWIM added about 5,4 g (~1/4 molar equivalent) of KMnO4, in, say, 6 portions. During and after each addition the mxtr was vigorously stirred w/a glass rod. The KMnO4 must be prior to that ground as fine as possible - it's not hard at all. The mxtr turned dark and opaque. Boiling was continued for some 10 min, then the flask put into the fridge (16 C) and 3 ml water added to it to induce crystallization. The walls of the flask were periodically furiously scratched (on the in-side :) ) w/a glass rod and after like 10 hours - voila! - a heavy crop of dark brown, as they should be, crystals precipitated. (If it doesn't, you can add 3 ml more water to it and w/some scratching it'll happen in an hour).

The mxtr was filtered, the mother liquor still very dark (put 3 ml water into it and let stand for a week - all of your prouct will crystallize and the liquor will turn colorless, this time the crystals will be not dark brown, but of rust/cinnamon powder color, just like the dry stuff), crystals sucked as dry as possible and dried for ~3 days in a dessicator over CaO (SWIM doesn't have one so he designed one from a saucepan, a couple of plates, plastic bag and a heavy hammer :) ) Dry Mn(AcO)3 is a very-very fine rust colored powder, it's unbelieveable how much it increases in volume comparing to the initial KMnO4! Still the weight is consistent - SWIM got about 22 g from the 1st crop, and the 2nd one is still in the flask, probably  will be ~5-7 g - the original article states the yield of 85%, fits w/SWIM's result perfectly.




OK bees i gotta go now, tomorrow i'll post the details of SWIM's  P2P fuckup and maybe someone will tell me what was the reason (frankly speaking, i think it was his fucken carelessness and dirty reagents)

Hope this one will draw some attention :)  :)  :)  Is it that my posts are too long that no one answers them? ;D  Eagerly awaitng your ideas and opinions,

Antoncho

Rhodium

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Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #1 on: August 16, 2001, 04:27:00 AM »
This is GREAT! This synthesis has been covered in Fester's book earlier, but it was ridiculed, because with the price of Mn(III)Acetate ($500 for 250g), it would be cheaper to buy meth on the street. Now with a preparation of that using simple reagents, this could actually be of use! Thanks Antoncho!

But - The mechanism of the rxn is as follows: first a ÑÍ2=Ñ(ÑH3)-Î-Ìn(3)-ÀãÍ complex is formed - this cannot be read with my font. Could you rewrite that using non-kyrillic characters?

I believe the refs for this rxn is Chemical Abstracts 77, 151620 (1972), JACS 93, 524-527 (1971) and Bulletin of the Academy of Science of the USSR 21(7) 1626 (1972).

Antoncho

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #2 on: August 16, 2001, 08:20:00 AM »
a) thank you , chief, thanks and thanks and thanks a lot for your praise :):):)

b) yesss', it's "The mechanism of the rxn is as follows: first a CH2=C(CH3)-O-Mn(3)-ArH complex is formed "... et cetera. Always forget there are some shortcuts from the cyrillic keyboard to the chemical nomenclature  :)

c) now comes the time for the details on the final experiment.



To a soln of 120 ml benzene, 80 ml acetone (both fucken tech grade - yess', i'know, the amt of the impurities in them, multiplied by their _huge_ quantities... and the other stuff... you wouldn't believe how vague is the borderline between "chem. pure" and "tech grade" in the FUCKCKCKEN, in this fucken, fucken country is!! - i should have distilled them ANYWAY, shouldn't i?  and 150 ml GAA there was added 10 g Mn(AcO)3, w/out any stirring (turned to be fine) and the mxtr brought to a boil for ~ 1,5 h. By the end of that period (y'know, i actually think that it stayed dark brown for an hour and then suddenly beecame pink in a matter of like 15-20 min's) the mxtr diluted w/500 ml H2O, the aq layer extr'd w/80 ml more benzene (yellowed quite considerably),  the org. layers washed w / aNaHCO3 and combined and washed w/a bisulfite reagent.

The latter was prep'd from : 5g Na2SO3 ; 1/2 mol. eq. CH3COOH; denat. alcohol - all quite in accordance w/ the Eleusis method, xept NaHSO3 is prep'd in situ w/Na2SO3 and CH3COOH. Do you think it makes a difference? My comrades :) have isolated P2P this way many times...

And - ALAS - the bisulfite wash yielded naught but some vagueness in the aq. layer, which didn't even .... ahhhhhh....  i'm more of a curious chemist than a desperate speedhead, yes, but..... it's very disappointing. Oh... Fuck it. Currently, it's evaporating on  a 125 C oil bath.





Now that the fucken brew is finally evap'd i want to tell you that:

a) there IS a 1 ml (just as there should have been) of an unevaporated liquid in the evap's basseign.

b) Can there be a possibility that the bisulfite agent doesn't work all the time - i have a goood, real good reason to believe this  - ESPECIALLY  when the concentration of the product is less than ...

c) i'm so fucken unexperienced in making a bisulfite!! please, ANY help!!! Very, very appreciated!

Oh, meeen. Bees!

Antoncho

lugh

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #3 on: August 16, 2001, 09:24:00 AM »
Usually, one isolates the organic product before attempting to make the bisulfite addition product. Some impurities interfere with the reaction, unfortunately. Have you looked at:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/eleusis/bisulfite.html

? It's a pretty good guide :)

Rhodium

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Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #4 on: August 16, 2001, 11:14:00 AM »
For workup, I would dilute with a lot of water like you say you did, then extract that into any non-polar solvent, wash the combined organic layers with water, aq NaHCO3, and finally with a saturated NaCl solution. Then I would dry the organic layer over MgSO4, and vacuum distill (preferably with a column, but you can do without). After the benzene has distilled over, the P2P should come next, and what's left in the boiling flask is just crap.

I think that bisulfite purification is killing yields considerably and that the procedure is way overrated.

WizardX

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Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #5 on: August 23, 2001, 08:54:00 PM »
The Mn(CH3COO)3 can be made electrochemically and can be regenerated insitu during the reaction of the P2P synthesis.

obituary

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Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #6 on: August 23, 2001, 09:25:00 PM »
hey Rhodium, this looks like it could be a new link to add to your site- when you get time of course.

Rhodium

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #7 on: August 24, 2001, 01:27:00 AM »
Of course. I have a 5 MB directory on my HD with very good stuff to upload already, I just want it to be nicely edited first. I just need the time to do it. If I hadn't so much to do out in the ordinary world, the Hive and my page could easily be a full-time job. I also have 10-20 kilograms of copied references I could do something nice with, if I had the time to scan and OCR it...

I am in favor of cloning. I really need a spare Rhodium to do all this for me... I have a lot of things that just need to be typed up from refs, interested people can contact me, And I'll send you scanned TIFFs for you to convert into ASCII. I can then do the editing/HTML myself.

Antoncho

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #8 on: August 25, 2001, 07:11:00 AM »
Dear WizardX!

Are you sure that it can be electrochemically made? If so, do you know the precise cond's (like voltage and temp) ?

If this worked, it would bee a real breakthrough in meth production! ;)  Not that i'm in favor of increased meth consumption >:(  - i consider it to bee a dangerous and addictive drug. But i'm reaaly more interested in chemistry than in drugs, so... Would you mind sharing your thoughts on the subj?...

Antoncho

PolytheneSam

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Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #9 on: August 25, 2001, 04:40:00 PM »
I'd be interested in that too (electrochemical process for Mn(III)acetate).  I looked at every patent in 205/440 at www.uspto.gov and didn't find it.  I also looked at the classification manual at class 205 and 423 and can't seem to find a good home for it.  I did find some interesting patents while searching and doing keyword searches:

3546082 electrolytic process for Pd acetate, regeneration of Wacker catalysts

3969405  which includes the lines:


Among the metal compounds capable of oxidizing hydrocarbon or other organic substances, the cobalt (III) and manganese (III) salts of carboxylic acids are preferred. They are powerful oxidizers; they are satisfactorily soluble in such organic solvents; and they are easily produced by known methods. From these points of view, the cobalt (III) and manganese (III) salts of fatty acids containing from 2 to 10 atoms of carbon, and preferably their acetates, are particularly satisfactory. For example, cobalt (III) acetate may be produced by co-oxidation of cobalt (II) acetate with acetaldehyde in acetic acid in the presence of oxygen. Manganese (III) acetate may be produced by oxidation of manganese (II) acetate with potassium permanganate in acetic acid. The cobalt (III) and manganese (III) salts of the other fatty acids can be produced in analogous manner or by exchange reaction between these and cobalt (III) acetate.




4297520  anisaldehyde from p-methoxytoluene


http://www.geocities.com/dritte123/PSPF.html

PrimoPyro

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Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #10 on: August 25, 2001, 05:51:00 PM »
Would it be safe to assume that one could substitute methylene-dioxy-benzene for benzene, achieving MDP-2P respectively? Or would the MD interfere with this reaction? I would love this to be true, but i haven't the slightest clue if it would make a difference. I certainly hope not...
And if it would react, Id think that isomerism would be a problem, also. Any thoughts?


Of COURSE we don't know what we're doing! That's why it's called research!  (boom...)     :)

WizardX

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #11 on: August 26, 2001, 07:41:00 PM »
I'll put some ref's together, and I'm doing a major upgrade at my Wizard X site with 10 new XFiles.

WizardX

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #12 on: August 26, 2001, 07:48:00 PM »
Antoncho: Yes, it will be a major breakthrough in meth production, you can even make PAA, phenylacetic acid.
But, I can see the narcs at this site posing as user-bees quickly jumping on this.

Antoncho

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #13 on: August 27, 2001, 09:02:00 AM »

Yes, it will be a major breakthrough in meth production, you can even make PAA, phenylacetic acid




Dear WizardX! I too have been thinking of what other things may bee used in this rxn instead of acetone. As i understand it, acetone is suitable because =O draws electrons from a-carbons, making them easily deprotonated.

If so, then why not use acetaldehyde? If it worked, it could bee an awesome route to all the 2C-...'s: 2,5-dimethoxybenzene (or -phenylmercaptan - see my thread in Novel discourse) ---> 2,5-dimethoxyphenylacetaldehyde ---> (Leuckart) 2C-H.

What do the bees think about this?

Antoncho


Osmium

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Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #14 on: August 27, 2001, 10:55:00 AM »
> acetone is suitable because =O draws electrons from
> a-carbons, making them easily deprotonated.

Ever heard of keto/enol-tautomerism?

Osmium

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #15 on: August 28, 2001, 12:53:00 PM »
Oooops, sorry, brainfart on my part. Somehow I thought the equilibrium would be completely on the side of the enolate.

WizardX

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #16 on: August 28, 2001, 08:07:00 PM »
From memory,(without having my Spellbook with me), the mechanism is.....

CH3COOH ==>> .CH2COOH Radical generated by Mn(AcO)3

.CH2COOH + C6H6 ==>> C6H5CH2COOH

PolytheneSam

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #17 on: September 01, 2001, 12:20:00 PM »
Here's some more US patents relating to the Mn(OOCCH3)3 process.

4011239 olefins + ketones, etc.
3927077
3860612

4,230,893:
4-Hydroxy-3-methoxyphenylacetone, an intermediate for methyldopa, has been prepared from reacting two moles of guaiacol and one mole of a 2-alkoxy propanol followed by basic elimination to form the enol ether of 4-hydroxy-3-methoxy phenyl acetone. The enol ether is subsequently converted to 4-hydroxy-3-methoxy phenyl acetone upon treatment with a strong acid.



http://www.geocities.com/dritte123/PSPF.html

Prdy2GO

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #18 on: September 17, 2001, 09:39:00 PM »
In response to:
"interested people can contact me, And I'll send you scanned TIFFs for you to convert into ASCII. I can then do the editing myself."

I am very intrested in helping out I have state of the art OCR SW and if you like I can give you a place to ftp the files to?
Thanks

Quote


Hum did you get that?

PEYOTE

  • Guest
Re: P2Ps from benzene, acetone and Mn(AcO)3
« Reply #19 on: September 18, 2001, 08:00:00 AM »
Can be used this reaction for Mn(Ac)3:

4Mn(Ac)2 · 4H2O + KMnO4 + 8HAc > 5Mn(Ac)3 · 2H2O + KAc + 10H2O

Instead of boiling Mn(Ac)2 in GAA ?

Ref:

http://www.dissociative.h1.ru/chemic/otdreakt/%CCn%28%D1%CD3%D102%293.htm