J. Philip Mason, Lewis I. Terry
J. Am. Chem. Soc., 1940, 62 (6), p 1622
DOI: 10.1021/ja01863a506
Publication Date: June 1940

Mmmmmmmm........ yummy P2P.... in bulk... Mmmmmmmmmmmmmmmmmm.. Delicious............ Stuff............

Free-Radical alkylation of Benzene with Acetone Catalyzed by Manganese(III)Acetate

Phenyl-2-Propanone can be made in a single step by a free-radical reaction between benzene and acetone. The reaction relies upon the special oxidative powers of manganese(III)acetate, a compound easily prepared from potassium permanganate. The yield is relatively low, and requires high dilution of the reactants, but this can be improved, and the reaction is also applicable for other substituted benzenes, as can be seen in the comprehensive Manganese(III)acetate catalyzed aromatic acetonylation document on this site.

around 40% yields.

http://www.erowid.org/archive/rhodium/chemistry/phenylacetone.html

I just have to point out, I dont know if you know? Benzene is some nasty shit, small exposures lead to a massive increase in the chance of contracting nasty shit like blood cancer. It was completely phased out in industry years ago for this reason, from wiki;

"The short term breathing of high levels of benzene can result in death, while low levels can cause drowsiness, dizziness, rapid heart rate, headaches, tremors, confusion, and unconsciousness. Eating or drinking foods containing high levels of benzene can cause vomiting, irritation of the stomach, dizziness, sleepiness, convulsions, and death.
The major effects of benzene are chronic (long-term) exposure through the blood. Benzene damages the bone marrow and can cause a decrease in red blood cells, leading to anemia. It can also cause excessive bleeding and depress the immune system, increasing the chance of infection.

Benzene causes leukemia and is associated with other blood cancers and pre-cancers of the blood.

 Benzene targets liver, kidney, lung, heart and the brain and can cause DNA strand breaks, chromosomal damage etc. Benzene causes cancer in both animals and humans. Benzene was first reported to induce cancer in humans in the 1920s. The chemical industry claims it wasn't until 1979 that the cancer inducing properties were determined "conclusively" in humans, despite many references to this fact in the medical literature. Industry exploited this "discrepancy" and tried to discredit animal studies which showed benzene caused cancer saying that they weren't relevant to humans. Benzene has been shown to cause cancer in both sexes of multiple species of laboratory animals exposed via various routes.[20][21]

One way of understanding the carcinogenic effects of benzene is by examining the products of biological oxidation. Pure benzene, for example, oxidizes in the body to produce an epoxide, benzene oxide, which is not excreted readily and can interact with DNA to produce harmful mutations.

Free-Radical alkylation of Benzene with Acetone Catalyzed by Manganese(III)Acetate

Phenyl-2-Propanone can be made in a single step by a free-radical reaction between benzene and acetone. The reaction relies upon the special oxidative powers of manganese(III)acetate, a compound easily prepared from potassium permanganate. The yield is relatively low, and requires high dilution of the reactants, but this can be improved, and the reaction is also applicable for other substituted benzenes, as can be seen in the comprehensive Manganese(III)acetate catalyzed aromatic acetonylation document on this site.

around 40% yields.

http://www.erowid.org/archive/rhodium/chemistry/phenylacetone.html


I just have to point out, I dont know if you know? Benzene is some nasty shit, small exposures lead to a massive increase in the chance of contracting nasty shit like blood cancer. It was completely phased out in industry years ago for this reason, from wiki;

"The short term breathing of high levels of benzene can result in death, while low levels can cause drowsiness, dizziness, rapid heart rate, headaches, tremors, confusion, and unconsciousness. Eating or drinking foods containing high levels of benzene can cause vomiting, irritation of the stomach, dizziness, sleepiness, convulsions, and death.
The major effects of benzene are chronic (long-term) exposure through the blood. Benzene damages the bone marrow and can cause a decrease in red blood cells, leading to anemia. It can also cause excessive bleeding and depress the immune system, increasing the chance of infection.

Benzene causes leukemia and is associated with other blood cancers and pre-cancers of the blood.

 Benzene targets liver, kidney, lung, heart and the brain and can cause DNA strand breaks, chromosomal damage etc. Benzene causes cancer in both animals and humans. Benzene was first reported to induce cancer in humans in the 1920s. The chemical industry claims it wasn't until 1979 that the cancer inducing properties were determined "conclusively" in humans, despite many references to this fact in the medical literature. Industry exploited this "discrepancy" and tried to discredit animal studies which showed benzene caused cancer saying that they weren't relevant to humans. Benzene has been shown to cause cancer in both sexes of multiple species of laboratory animals exposed via various routes.[20][21]

One way of understanding the carcinogenic effects of benzene is by examining the products of biological oxidation. Pure benzene, for example, oxidizes in the body to produce an epoxide, benzene oxide, which is not excreted readily and can interact with DNA to produce harmful mutations.

HOT MAMA. As soon as i get my equipment back i am going to try this reaction. Why haven't i seen this before? That is bizzare, i can't say i recall seeing this on that archive last time i saw it... It's definitely the way to go.. Thanks for posting that and bringing it to my attention. So nasty chloroacetone shit isn't even required.. well i'll be fucked... there you go huh... One tiny little question though.. Does this reaction really need to be carried out under an inert atmosphere? I Can't see how it does, what would decompose in a normal atmosphere? I mean i guess i'll just have to get a nitrogen tank and make a little chamber for it in to carry out the inert reaction. 40% Yields sound pretty yummy to me as well. Isn't phenylacetone such a nifty compound.. And who'd have thought you can make it without even using fridel-crafts and nasty HCI gas being evolved..

Plus i want somebody to clarify something for me here. It said the yield was 40% in the free radical reaction, but then it says that only 1.34grams of phenylacetone was recovered from 150ml benzene and 150ml of acetone. What the? That's not 40% !!!! Hmm.................

The yield is based on the amount of the manganese(III) acetate and not on the amount of the acetone and benzene. Because of two moles manganese(III) acetate is needed for one mole of P2P the yield is ok. Calculate it:)

The inert atmosphere is required but it states right there on the page quoted. That Helium is an alternative to argon or nitrogen, helium is very OTC just ring any party supply place and tell them you want to rent a tank of helium to fill balloons for an upcoming birthday party (then they will ask you how many bottles you need! lol)

"How easy is it to manufacture manganase(III) acetate?"

"Manganese(III) acetate can be made from any water-soluble manganese(II) salt, or from the corresponding acid soluble hydroxide (Mn(OH)2) and oxide (MnO) by precipitating it as the carbonate salt, and then boiling it in acetic acid to form manganese(II)acetate, which is finally oxidized to manganese(III)acetate by potassium permanganate. Potassium permanganate can also be used as a starting material itself, by reducing it with hexamine or formaldehyde solution. All manganese(II) salts are suceptible to oxidation to manganese(IV) by oxygen, so try to exclude air as conveniently possible from these compounds and their solutions."

http://www.erowid.org/archive/rhodium/chemistry/manganous.acetate.html

So it requires going to any decent gardening supply place buying a box of cheap Manganese Sulphate used as a trace element, you would also need glacial Acetic Acid to prepare manganese(II)Acetate then potassium permanganate to prepare Mn(III)Acetate and also would need it for the P2P reaction. Getting a cheap bottle of helium from a party supply place, then the reagents above is so much more easier than preparing and working with chloroacetone, anhydrous aluminum chloride etc.

This more active version of the aluminum chloride catalyst was posted on the Hive long ago:

Preparation of Radsiwanowski AlCl3. 144% of aluminum shavings (based on wt of benzene) was added to a flask containing anhydrous benzene, and anhydrous HCl gas was pass through for 3-4 hours at ordinary temperature. The formation of AlCl3 was accompanied by the evolution of bubbles of gas, the benzene grew dark, and the shavings were covered with a deposit of AlCl3. After standing overnight, the mixture was ready for the addition of other reaction components.

 

Haha to be quite frank i kinda lied when i said that. The only benzene i have ever seen in my life is a small distillate when i distilled NaOH and Sodium Benzoate together. I Meant ' theoretically ' have benzene sitting here. Which i do. I Have kg's of sodium benzoate and sodium hydroxide. Just need to get a god-damn distillation setup going, visit to the hardware store might not be quite a bad idea. Plumbing section. Some copper pipe pieces etc... Then you need some cooling/water pumping equipment for a distillation setup.. Through a metal-can. Thing about benzene is it's everywhere. In nature i mean. It is the backbone for almost everything.

However, isn't it what you put into your car everyday? I mean doesn't benzene constitute about 5% of modern gasoline blends?

It depends on the manufacturer, usually gasoline contains 0,2 to 6% of benzene, but I have no idea how can you get it out from that. It is not a good idea to make P2P from gasoline

Actually benzene is not a really expensive chemical (at us 1 liter is around 20 euro and this is reagent grade chemical).
The home made benzene has one problem: low yields and much power needed. We made long ago benzene from benzoic acid, We had a 10-15% yield and because of the heat the glass had broken what contained the benzoate/calcium hydroxide mixture, it wasn't a really successful experiment....

There is another method from PET bottles, but we never tried it (just thinking about the insoluble tar what will remain after the PET hmmmm......).

Yeah 1.4l from 2.5kg sodium benzoate isn't bad considering the cheapness of benzoates to begin with. I Think that i am going to carry out this reaction without a doubt but the bitch is obtaining that glassware. Nice big three-necked flask. I'd say the guy who performed that reaction worked at a lab supply warehouse or something to be honest. Considering that he uhh.. had all of the good bits.. So to speak. I Need to get my hands on some of that. I Have the money. Now it's about finding the god-damn supplier! So i can distill the benzene into masses of liters and carry out the god damn reaction to get my hands on some yummy and nice P2P !!!!!!

It depends on the manufacturer, usually gasoline contains 0,2 to 6% of benzene, but I have no idea how can you get it out from that. It is not a good idea to make P2P from gasoline

Haha i agree bro. I Wonder how though? Distilling it maybe? KABOOM. hehehe...