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All 10 posts Subject: please criticize: route-toluene to DOM Please login to post Down

ning
(Hive Bee)
10-26-03 04:04
No 466803
      please criticize: route-toluene to DOM

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?

Lilienthal
(Moderator)
10-26-03 10:47
No 466837
User Picture       No links and refs, no answer...

No links and refs, no answer... But I really like the chloro-acetone part laugh

Rhodium
(Chief Bee)
10-26-03 14:03
No 466849
      Friedel-Crafts Alkylation with Chloroacetone

Step 1: Alkylate toluene with chloroacetone, to get p-toluacetone

It would be called p-Tolylacetone.

Using benzene/chloroacetone the yield is 32% P2P - https://www.rhodium.ws/chemistry/phenylacetone.html#chloroacetone

ning
(Hive Bee)
10-28-03 13:46
No 467259
      indeed

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.

Rhodium
(Chief Bee)
10-28-03 15:46
No 467291
User Picture       "plausible routes"

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 (Rhodium: "Dozens of routes to MDP2P", Novel Discourse)
Post 335214 (Rhodium: "MDP2P routes II", Novel Discourse)

ning
(Hive Bee)
10-29-03 17:33
No 467579
      That's the beauty of chemistry

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?

Rhodium
(Chief Bee)
10-29-03 19:30
No 467610
User Picture       1,2-Dihydroxybenzene methylenations

Here you have a few 1,2-dihydroxybenzene methylenations. (https://www.rhodium.ws/chemistry/methylenation.html#methylenation)

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.

ning
(Hive Bee)
10-29-03 21:11
No 467635
      indeed...

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 (https://www.rhodium.ws/chemistry/aromatic.nitration.html)
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 (https://www.rhodium.ws/chemistry/benzoquinone.html)
ning's favorite MnO2 will probably work here also, as the book said so, and ning believes everything ning reads. Especially on the net... wink

All you expert bees know how to take it from here (https://www.rhodium.ws/chemistry/stp.html)...

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.

Lego
(Hive Bee)
10-30-03 12:15
No 467780
User Picture       Nice ideas, but...

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.

The candle that burns twice as bright burns half as long

ning
(Hive Bee)
10-30-03 22:22
No 467869
      Ning will check this out

interesting. Ning would not expect this, as MnO2 is supposed to be rather selective and mild. Thanx Lego!

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	All 10 posts		Subject: please criticize: route-toluene to DOM		Please login to post		Down


		ning (Hive Bee) 10-26-03 04:04 No 466803				please criticize: route-toluene to DOM
						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?



		Lilienthal (Moderator) 10-26-03 10:47 No 466837				No links and refs, no answer...
						No links and refs, no answer... But I really like the chloro-acetone part



		Rhodium (Chief Bee) 10-26-03 14:03 No 466849				Friedel-Crafts Alkylation with Chloroacetone
						Step 1: Alkylate toluene with chloroacetone, to get p-toluacetone It would be called p-Tolylacetone. Using benzene/chloroacetone the yield is 32% P2P - https://www.rhodium.ws/chemistry/phenylacetone.html#chloroacetone



		ning (Hive Bee) 10-28-03 13:46 No 467259				indeed
						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.



		Rhodium (Chief Bee) 10-28-03 15:46 No 467291				"plausible routes"
						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 (Rhodium: "Dozens of routes to MDP2P", Novel Discourse) Post 335214 (Rhodium: "MDP2P routes II", Novel Discourse)



		ning (Hive Bee) 10-29-03 17:33 No 467579				That's the beauty of chemistry
						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?



		Rhodium (Chief Bee) 10-29-03 19:30 No 467610				1,2-Dihydroxybenzene methylenations
						Here you have a few 1,2-dihydroxybenzene methylenations. (https://www.rhodium.ws/chemistry/methylenation.html#methylenation) 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.



		ning (Hive Bee) 10-29-03 21:11 No 467635				indeed...
						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 (https://www.rhodium.ws/chemistry/aromatic.nitration.html) 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 (https://www.rhodium.ws/chemistry/benzoquinone.html) 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 (https://www.rhodium.ws/chemistry/stp.html)... 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.



		Lego (Hive Bee) 10-30-03 12:15 No 467780				Nice ideas, but...
						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. The candle that burns twice as bright burns half as long



		ning (Hive Bee) 10-30-03 22:22 No 467869				Ning will check this out
						interesting. Ning would not expect this, as MnO2 is supposed to be rather selective and mild. Thanx Lego!

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