Author Topic: please criticize: route-toluene to DOM  (Read 1063 times)

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  • Guest
please criticize: route-toluene to DOM
« on: October 25, 2003, 09:04:00 PM »
Sorry for all the posting lately, but ning has much on the mind involving benzenes. Ning sees beehive-like tesselating benzene rings while sleeping! Maybee that's why it's called the hive? 1 mole of phenethylamines might very well look like an infinite beehive if one could see them??
The second route. If it works, may good psychedelics saturate the market in obscene quantities. *makes bow of respect to the gods & buddhas*

Step 1: Alkylate toluene with chloroacetone, to get p-toluacetone (is this a valid name?)
This step is the hard one. Ning does not know how much o-toluacetone would be produced, but ning hopes that the bulk of the acetone will push the balance to something reasonable. Also, ning does not know how the two isomers would be separated. But anyway *handwaves problem away*

Step 2: Iodate ring with I2-NaNO3 method. In situ hydroxylate. Recover iodine. Yielding 2,5 dihydroxy 4 methyl p2p

Step 3: methylate. 2,5 dimethoxy 4 Me P2P.
Alternately, use NaOMe to directly replace those iodines to get here. Same same, maybe higher yield, more otc, etc.

Step 4: Aminate. Reduce.
By the standard methods.

Step 5: Bioassay. Flood market. Render drug laws obsolete.

Or something in that order.
How's it sound?


  • Guest
No links and refs, no answer...
« Reply #1 on: October 26, 2003, 02:47:00 AM »
No links and refs, no answer... But I really like the chloro-acetone part  ;D


  • Guest
Friedel-Crafts Alkylation with Chloroacetone
« Reply #2 on: October 26, 2003, 06:03:00 AM »
Step 1: Alkylate toluene with chloroacetone, to get p-toluacetone

It would be called p-Tolylacetone.

Using benzene/chloroacetone the yield is 32% P2P -


  • Guest
« Reply #3 on: October 28, 2003, 05:46:00 AM »
Yeah, that's where ning got the idea...
As for refs??!! come on, rhodium's page and a standard O-chem textbook, guys! None of this is earth shatteringly new or exotic stuff! You want a ref for nitration of substituted bezene? really? Then ning will have to go find one, obviously. The reduction of nitro to amino is also std, Zn or Fe in HCl. No papers, just an old O-chem book.
Oxidation of aniline to quinone is nothing new, and ning has seen similar reactions with a beilstein search. MnO2 in H2SO4. Not much more is known by ning. Ning is asking for criticism of idea because ning is not a chem expert. If ning had all the papers, there would be little to ask. In fact, ning doesn't know why Sr. L assumes ning has a secret stash of world-shaking scientific literature that ning refuses to release. Ning doesn't. Ning has some papers ning will type as soon as the demands of PHYSICAL REALITY permit. Ning has only the best wishes for the hive, and works hard to further the knowledge and shared power of the hive. Ning promises not to be stingy, and asks the same from you, Sr. L.


  • Guest
"plausible routes"
« Reply #4 on: October 28, 2003, 07:46:00 AM »
One can easily draw up thousands of "plausible routes" to a target compound, but such ideas aren't worth anything until the precise details are worked out, as in presenting the procedural details with yields, workup, boiling points, melting points, recrystallization solvents etc.

See the following posts, as you probably can understand the two images I posted are not of much use if you don't have access to the actual procedures on my page:

Post 335195 (missing)

(Rhodium: "Dozens of routes to MDP2P", Novel Discourse)

Post 335214 (missing)

(Rhodium: "MDP2P routes II", Novel Discourse)


  • Guest
That's the beauty of chemistry
« Reply #5 on: October 29, 2003, 09:33:00 AM »
and the bee's art, ne? The possibilities are such that bees at large can never be stopped--always move-counter move. We have our own little scientific community, and despite all the danger and risk, progress is made.
It's truly heartwarming.

Actually, ning was just wondering about how that dihydroxybenzaldehyde got to become piperonal(?)...where was that one?

Ning was just thinking last night that if one dehydrated formic acid with diHObzhyd., then reduced in acidic solution, (aldehyde to alcohol, -H2O), one could form the MeDiO bridge thingy...of course, that second step maybe wouldn't work with the benzaldehyde...maybe with an allyl though. Or just a subst. benzene? Or benzal chloride?
.... a chopped up penny (post 1982) for these thoughts?


  • Guest
1,2-Dihydroxybenzene methylenations
« Reply #6 on: October 29, 2003, 11:30:00 AM »
Here you have a few

1,2-dihydroxybenzene methylenations.


Unfortunately, the only method of creating that bridge is to use a dihalomethane and a base, you cannot make a formaldehyde acetal with 1,2-dihydroxybenzenes like you can with alcohols, as phenols do not react like aliphatic alcohols.

This is one of the reasons why it is necessary to go through the literature to see what kind of reactions are actually possible in practice, and not what seems good on paper. A few hours in the library often saves many days of work in the lab.


  • Guest
« Reply #7 on: October 29, 2003, 01:11:00 PM »
why, at the rate ning has been spending time in the library, ning might not even have to go to the lab...

Upon rethinking, and mild what-we-all-hope-is-sucess in the lab, ning has rethought the beginning of this synth, and thought it to be better this way:

step 1:

toluene nitration a la rhodium

if this step has the claimed 84% ortho selectivity, we're in business.

Step 2: reduction of o-nitrotoluene to o-aminotoluene
this is well covered, thinks ning. Zinc dust, iron dust, HCl, rhodium has something on it, etc.

Step 3:

oxidation of o-aminotoluene to o-toluquinone

ning's favorite MnO2 will probably work here also, as the book said so, and ning believes everything ning reads. Especially on the net... ;)

All you expert bees know how to

take it from here


The advantage of this method is:
1. from toluene, it might bee higher yielding than trying to get the p-nitrotoluene out from mixed nitration isomers. 84%, wow...
Or at least, it could be easier to separate isomers by just using the cleanup between procedures to weed them out.


  • Guest
Nice ideas, but...
« Reply #8 on: October 30, 2003, 04:15:00 AM »
Dear Ning!

Lego really likes your enthusiasm and your ideas, but there are still some problems.

The oxidation of 2-aminotoluene with MnO2/H2SO4 will yield not only the desired methylbenzoquinone but also the methyl-group will be oxidized to the aldehyde or even to the benzoic acid. See

Post 208702

(Antoncho: "The easiest synth of benzaldehyde from toluene", Chemistry Discourse)

MnO2 is OTC, not only in batteries. It is used and sold as a pigment for oil paintings. The puritiy is only technical but for oxidation of such a simple molecule it should work.


  • Guest
Ning will check this out
« Reply #9 on: October 30, 2003, 02:22:00 PM »
interesting. Ning would not expect this, as MnO2 is supposed to be rather selective and mild. Thanx Lego!