P2Ps from benzene, acetone and Mn(AcO)3

[element109]

Thanks, i do understand now.

Well, i've been to the library to look up those "Linker" ref's from up above.
They don't have the J.Prakt.Chem. article from 1997, and Tet.Lett. 51,9917-26 (1995) doesn't exist, the pages only go to p.9566 .

I found in CA 77,151620 (1972):
CH3COCH3 and Mn(OAc)3 gives radical CH3COCH2* ; and this can add itself to C6H6. So, in AcOH at 70° there was formed 36% CH3COCH2Ph. Toluene reacted similarly and gave 30% tolylacetone and 7% PhCH2OAc. RR1C*COR radicals with R=alkyl and R1=H or alkyl did not add to C6H5 however, but recombined with themselves.

Anhydrous reagens and solubility apart, I understand that 7.8 grams of benzene, 53.6 grams of Mn(OAc)3 and 5.8 gr of CH3COCH3 reacts at 70° to give ~5.4 grams of P2P.
This all should be done in glacial AcOH as a solvent

One more thingie: tolylacetone is PhCH2CH2COCH3, right, isn't the amination product known to be active ?


e109

[PEYOTE]

Yes, on JACS 1971, 93, 524 the Authors use an alkene (should be 1-undecene) and compare the ratios of oxidation rxn using Mn(III), Ce(IV) and Cu(II) acetate.

[Rhodium]

element 109: The correct ref is Tetrahedron, vol 51, no 36, p 9917-9926 (1995).

[element109]

Chief, I'm very sorry, it was my mistake, i didn't know there was a difference between Tetrahedron and Tetrahedron Letters    until Sam told me.

Peyote: I've read that one too, wasn't the use of Cu(II) impractical because "the reversible interaction of Cu(II) with the radicals and thus represent a minimum value" (p.526,table I,note d)

It seems that SWIM is going to methylate 0.1Mol hydroquinone tomorrow, so we can see how promising this reaction is. He only needs to get ahold of 53.6gr of Mn(OAc)3, tho.
I wonder if the inert atmosphere is really needed in this rxn, the authors don't always use it.

e109

[encopo]

In the interest of those who don't have piles of
KMnO4 lying about, it might be of interest that
Manganese Oxide is available in huuuge amounts very
cheap at pottery supplies (SWIM picked up 250g of
Nickel Carbonate recently for $6 - there was a sale on).

Also, I expect many bees don't have too much carcinogenic
compounds (benzene) at their direct disposal, however
this could be easily synthesised from many other compounds.
I'll have a look into the reaction products of using
naphthalene as a substitution for benzene. This could
be useful for many people here, as a totally OTC synthesis
of P2P would be very interesting to say the least.
Don't mind me. I'm mentally ill.

[noche]

I`m a litle confused now. In the begining of the discusion it was claimed that the reaction would give 40% yeld wich would be somthing like 6 ml P2P from 15 ml benzene, 15 ml acetone and 1g Mn(AcO)3. Then it was latere concluted that 7.8 grams of benzene, 53.6 grams of Mn(OAc)3 and 5.8 gr of CH3COCH3 would give ~5.4 grams of P2P wich is about a 100 times as much Mn(AcO)3 as claimed in the begining. You can just tell me that it is still the firs ratios that is the right ones, anything else would be TO disapointing.

[Antoncho]

A Golden Rule #2 (#1 is UTFSE) - always read the whole thread bee4 posting anything into it!

Thus you can avoid being flamed.

You are currently being flamed.

Antoncho

[Prdy2GO]

Yes it is unbeleveabull shit hard to get benzene. What else may be used in it's place. Has anyone come up with an optimiced ratio yet? How are things going? I have had some success going from MnCL2 to MnAco3 with NA carbonate then acetic anhydred. Watch out it liks to foam up alot and for quite a while...
Hum did you get that?

[element109]

You can distill benzene from a 1:1 mixture of benzoic acid and calcium benzoate, if i remember correctly.

SWIM don't want no stinking benzene, he's got some p-dimethoxybenzene instead    but his working place is down so research is down for now too.  

e109

[halfapint]

The most direct and straightforward way to produce manganous acetate, is by the reduction (that's what it says here, folks) of KMnO4 with hydrogen peroxide in acetic acid. Reduction of potassium permanganate with hydrogen peroxide, except in sulfuric acid producing manganous sulfate, was given in one of my old textbooks as an example of the reducing ability of H2O2.

Well, I had no H2O2 at hand, so I used sodium perborate instead. I suspect any of the peroxide-generating oxidants, oxone or peroxicarbonate would serve as well, as of course would barium or sodium peroxide. I had fun, alternately turning acetic acid dark and clear, "black" and "white", by adding KMnO4 and NaBO3 respectively. This trial was just beecause I wanted to see it, but a little aliquot to which I added benzene and acetone seemed to do something to them, even without heating. No color showed up I would call "pink", but perhaps the manganic acetate only shows up with hot permanganate oxidation.

To prove I had manganous acetate, I titrated to basic with sodium carbonate, whereupon the carbonate precipitated, as in the manganese (III) acetate document at Rhodium's

https://www.thevespiary.org/rhodium/Rhodium/chemistry/manganous.acetate.html

so that's what it was. This is much more convenient than the roundabout method pursued by Antoncho, right?
a half a pints a half a pound a half a world a half a round
Sidearm n. Flask neck tube.

[Rhodium]

It sounds good - now if someone could just find a nice reference for that reaction with a suggested procedure, or that somebody would work out an optimized procedure from scratch...

[foxy2]

Hmmm

Manganous formate and acetate.   
Paltin, Edith; Grosu, Luminita; Selegeanu, Dinu. 
RO  51886  19690924  Patent  written in Romanian.
Abstract
The title compds. are prepd. directly from ores, which are treated with so lns. of org. acids in presence of a liq. oxidizer.  Thus, to 100 kg 4.44% soln. of HCO2H, 4 kg 33% perhydrol was added, re sulting a 1.3% H2O2 content.  This soln. was slowly added with stirring to 4 kg MnO2.  Oxygen evolution ended after 1 hr at 20° and the mixt. was worked up to give 95 - 99.9% pure (HCO2)2Mn crystals.  Similarly prepd. was Mn(OAc)2.


Refining of manganese acetate and cobalt acetate.    
Haas, Zdenek; Foniok, Alfred.   
Czech. (1974),CS  153278  19740515  Patent written in Czech.
Abstract
Cryst. Mn(AcO)2 and Co(AcO)2 were dissolved at 70° in 50% aq. EtOH contg. 7-10% HONH3OAc or (HONH3)2SO4 (on the wt. of alc.) and the soln. cooled to give 72-5% cryst. product in which the amt. of insol. material has dropped from 0.1 to 0.005% and the Fe content from 0.005 to 0.001%. 


Crystalline manganese acetate.   
Haas, Zdenek; Alfred, Foniok.   
Czech.(1974),CS  152911  19740415  Patent  written in Czech.
Abstract
Cryst. Mn(OAc)2 [638-38-0], useful as a highly active catalyst in polyester manuf., was prepd. by treating MnCO3 soln. with AcOH at 90° in the presence of a reducing agent, hydroxylamine sulfate [13973-61-0]. 


Study of the manganese acetate formation reaction.
Novak, A. M.; Abadzheva, R. N.; Bel'ferman, A. L.   
Zh. Prikl. Khim. (Leningrad)  (1977),  50(9),  2135.
Abstract
Mn(OAc)2 was prepd. by treating MnCO3 with HOAc in H2O in 1:5.5:36.0 ratio at 80° with high-speed stirring.
Make a Difference

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[Rhodium]

Foxy: Is it only people who speak incomprehensible languages who write articles/patents on the preparation of useful chemicals? I have seen that phenomenon over and over again.

[PolytheneSam]

One problem with US patents is that the attorney/patent agent writes them (they're applications first).  They typically have a degree in life sciences or other science (ie. computer science) and/or engineering and may also have a law degree.  They want to claim as much as possible and to do that the disclosure (the specification and drawings if any) has to be enabling (explains how to make and use the invention) therefore they make the specification as broad as possible which often makes the patent vague to some extent.  This seems to be more true with more recent US patents.  The more you read US patents the easier it gets to read them.  BTW, any employee of the USPTO cannot write patent applications or do any patent work other than what they do in the office.  Examiners can do amendments, but need the permission of the attorney/agent to enter them.
http://www.geocities.com/dritte123/PSPF.html

[halfapint]

Thread's too long. Starting a new one, to bee called "Acetate of Manganese",

Post 279306

(halfapint: "Acetate of Manganese", Novel Discourse).
a half a pints a half a pound a half a world a half a round
Sidearm n. Flask neck tube.

[PolytheneSam]

I didn't find these two UingTFSE.

Patent US3845116

Patent US3875224

http://www.geocities.com/dritte123/PSPF.html
The hardest thing to explain is the obvious