P2Ps from benzene, acetone and Mn(AcO)3

[Rhodium]

Yes, but what was the rationale for the hexamine? And is the equation for the KMnO4 oxidation of Mn(II) to Mn(III) correct?

[Prdy2GO]

Rhodium:
I am interested in the convertion as well. Swil is in a posistion right now to do a few experiments with about a Kilo of Manganese(II)chloride anhydrous MnCl2 in hand and willing to try anything. What shall we try first?
Rdy2go
...
..
.
 
Hum did you get that?

[Rhodium]

Precipitate the MnCO3 with carbonate, dry it and record the yield. See if it is quantitative.
Make the Mn(OAc)2, dry, and record the yield.
Make the Mn(OAc)3, and record the yield of both the formed triacetate and the brown precipitated MnO2, so we can see if the reaction needs tweaking.

[PEYOTE]

Hey, see my

Post 214788

(PEYOTE: "Re: P2Ps from benzene, acetone and Mn(AcO)3", Novel Discourse), some post ago.

Or visit:

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

I've written these things some time ago.

[uemura]

Another way from Mn(II)-acetate to waterfree Mn(III)-acetate is to dissolve the Mn(II)-acetate in Acetanhydrid (AA) which is unfortunately even more difficult to get than Kaliumpermanganat! Carpe Diem

[Prdy2GO]

could you please post this reference. I canot read it?
Thanks
Hum did you get that?

[element109]

Check USP 4,011,239

they say Mn(III)acetate  is made by dissolving any manganese oxide in acetic acid.

e109

[PolytheneSam]

In US patent 4,011,239 see column 20 (page 11 of the images) last paragraph (lines 43+), column 21 (page 12) down to about line 32 and column 23.  A lot of useful info in the patent.
In column 23 it also says

Alternatively, the isolated manganous acetate may be dissolved in acetic acid and the solution electrolyzed, using a carbon or other suitable anode, to form manganic acetate, the resulting electrolyzed solution being directly usable in a free radical reaction. Where the manganous acetate is already in solution in acetic acid, no preliminary isolation step is necessary as such solution may be charged to the electrolysis cell and electrolyzed.

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

[obituary]

does anybody here a suggested procedure to run?  this is very interesting and if at all possible obit would like to try running some experimental trials.

[Rhodium]

Obit: What more do you want? The preparation of Mn(III)acetate seems pretty straightforward, and so does the condensation.

[obituary]

sorry- missed the first portion (forgot about the first part of the thread)
sincere apologies

suggestions on anything are still welcome though.

[PEYOTE]

Hi guyz. I've mumbled and mumbled and I think.... referring to:

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 etc etc etc

on Antoncho

Post 205055

(Antoncho: "P2Ps from benzene, acetone and Mn(AcO)3", Novel Discourse).....

.... if I use an aniline or an N-monosubstituted aniline (also this possibly substituted) instead of benzene, is it possible to make a substituted indole, and open a way for new DMT and related synthesis?

I'll email a possible explanation to Antoncho, if he'll want.
 

[element109]

I was thinking, suppose someone has 20 grams of 2,5-dimethoxybenzene, obviously the best choice here (yield-wise) and is willing to do an experiment.
Is there anyone that has a clue on the total yield here, because i don't seem to understand. If 20gr will give only a sub-gram amount of the corresponding P2P i don't think it's worth the effort.
What's the best we can do here ?

e109

[PEYOTE]

suppose someone has 20 grams of 2,5-dimethoxybenzene

Ehm, 2,5-dimethoxybenzene? How can someone have 20 g of 2,5-dimethoxybenzene? Ah.... 20 g of 1,4-dimethoxybenzene, or para-dimethoxybenzene !

However, the TOTAL THEORETICAL POSSIBLE YIELD from 20 grams of 1,4-diMeO-Bz to 2,5-dimethoxy-P2P is about 28,12 grams



Just A Toch Of Mojo Hand

[obituary]

is the product worth tasting? (after amination obviously)
and what solvent would be best?  just straight acetone in a large excess?

[Rhodium]

2,5-dimethoxyamphetamine is not good in itself, but it can be brominated to give DOB for example (and chlorinated, iodinated, nitrated etc).

[PEYOTE]

Extracts from JACS, 51, (1969), 143-144

Procedure #1:

In a 5-l., 4-necked round-bottom flask fitted with a stirrer, condenser and a thermometer, 428.7 g of Mn(OAc)₂ . 4H₂O in 3 l of GAA was heated to 110°C. Ground KMnO₄ (68.2 g) was added in small portions through the condenser over a 20 min. period, while the temperature was mantained at 110°C. The rxn mixture was heated an additional 20 min., cooled, poured into water (750 mL), and left to crystallize overnight. The solid was filtered off, washed with ether and air dried. Yield: 486 g (82%)

Procedure #2: (FOR THE ANHYDROUS PRODUCT)

A mixture of Mn(NO₃)₂ . 6H₂O (60 g) and Ac₂O (225 mL) was stirred vigorously in a 4-l. beaker and heated cautiously until the cloudy mixture suddenly turned clear. The heating was stopped and a vigorous rxn followed during which there was a copious evolution of NO₂. The product was allowed to crystallize overnight, filtered, washed with Ac₂O, and dried over P₂O₅. The Mn(OAc)₃ anhydrous thus obtained titrated as 90-98% Mn(OAc)₃. Yield: 70-90%.

[element109]

I'm sorry... of course it's 1,4-dimethoxybenzene.

Then how comes one gets only 134mgs of P2P from 15mls of benzene and calls it 40% yield. I don't seem to understand this.

e109

[Rhodium]

They calculate the yield on the basis of added Mn(III)acetate, and not on the added amount of acetone and benzene.

[Antoncho]

Note too that two molecules of the Mn comp'd are needed to make one P2P molecule. Also note that Mn(AcO)3 molecule is almost two times heavier than P2P.

That's why    - yes, it's pretty dissappointing.



Now an idea/a question for everybody interested.

BTW, in one of the patents dedicated to this issue this salt was prep'd in situ. However, Ac2O was then used to dehydrate the rxn mixtr - it was stated that for the condensation the conditions must bee unhydrous, and  water is obviously a product of KMnO4 rxn w/Mn(AcO)2/AcOH. So it is pretty seductive to suggest that maybee some more common dehydrating agent like Na2SO4 could bee used instead, and a pretty concentrated solution of MnAcO3 could bee thus obtained through a series of MnAcO2/KMnO4 rxns followed each time by dehydration and filtering (MnAcO3 is hydrolized by water, so you can't just do a bunch at a time).
For this - just to bee sure - we would only need to know how much Mn triacetate can bee dissolved in a given quantity of GAA.
Can anyone find this out? I know a couple of bees here who have access to real good chem. libraries  

Antoncho