Author Topic: Yeah, I know I could reduce the benzaldehyde...  (Read 1301 times)

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phenethyl_man

  • Guest
Yeah, I know I could reduce the benzaldehyde...
« on: October 06, 2004, 07:16:00 AM »
Yeah, I know I could reduce the benzaldehyde but then I have to reformylate etc, and as you know I would rather just use this for other materials.

I tried that reduction of p-nitrotoluene with aluminum.  Yields are low and my residence got fumigated with toxic fumes so that route was abandoned.  The patent is very vague, do you know the reaction mechanism here?  I have a feeling it releases some not so friendly gases; at least with the aluminum foil I used.  The o-toluidine route seems like too much work; at least from toluene.  Nitration of toluene will give a mixture of ortho/para-nitrotoluene which would then have to be reduced, then subjected to those two reactions to finally arrive at toluhydroquinone (which I can just purchase anyway).

Basically, I have a bunch of hydroquinone and p-dimethoxybenzene lying around and want some 2,5-dimethoxytoluene.  :)

Formylation, reduction, and reformylation seems quite tedious.

I just don't see why Friedel-Crafts alkylation won't work.  And I don't understand why Shulgin uses a low-yielding acylation followed by reduction (PiHKAL: DOET, DOPR) to arrive at his alkylbenzenes when this seems feasible for a high yield of any alkylbenzene in just one rxn.


Saddam_Hussein

  • Guest
2-Hydroxy-5-methoxybenzaldehyde
« Reply #1 on: October 06, 2004, 08:04:00 AM »
It is also possible to reduce the -CHO of 2-hydroxy-5-methoxybenzaldehyde, a rather OTC substance (if you want). You can (m)ethylate and have a nice DOM precursor as well  :) . I used to have a procedure involving ethyl chloroformate doing the trick, but my pile of junk is rather immense.


hest

  • Guest
Acetylation/alkylation
« Reply #2 on: October 06, 2004, 09:35:00 AM »
Acetylation yeald a deactivated product, alkylatein an activated one. So the risk for more than one acetylation on the rin is low. The risk for more than one alkylation on the ring is high.
The Lewis accid used in the alkylation might cleawe the methoxyethers.
PErsonal I prefere bromination and the BuLi and RBr

phenethyl_man

  • Guest
Re: The Lewis accid used in the alkylation...
« Reply #3 on: October 07, 2004, 12:37:00 AM »

The Lewis accid used in the alkylation might cleawe the methoxyethers.




the Friedel-Crafts alkylation w/alcohols doesn't require a lewis acid..  I doubt AlCl3 would cleave the ethers anyhow as long as the solvent is right, otherwise bees wouldn't be having so many problems cleaving eugenol/vanillin's methoxy groups.


PErsonal I prefere bromination and the BuLi and RBr




you must like performing reactions at -70degC under an inert atmosphere and anhydrous conditions, eh?  not to mention the hassle obtaining butyllithium.


Saddam_Hussein - excuse my ignorance, but by what means is this aldehyde "OTC"?




Captain_America

  • Guest
Indirect Over-The-Counterness
« Reply #4 on: October 07, 2004, 12:50:00 AM »
Saddam_Hussein - excuse my ignorance, but by what means is this aldehyde "OTC"?

It meens you can make it from OTC chemicals;

Post 530676

(Captain_America: "OTC 2C-H", Methods Discourse)

demorol

  • Guest
You might want to read this post Post 530920 .
« Reply #5 on: October 07, 2004, 02:27:00 PM »
You might want to read this:

Post 530920

(Nicodem: "The best spices for DOM", Methods Discourse)
. Nicodem had quite an idea for OTC DOM synthesis.

phenethyl_man

  • Guest
well.. SWIM gave in and just ordered some more
« Reply #6 on: October 09, 2004, 09:31:00 AM »
well.. SWIM gave in and just ordered some more THQ anyhow, but here's a few more ideas for those interested:

starting from phenol:

ortho-methylate phenol with formaldehyde and base as described in

Patent US2401608

to obtain o-cresol; briefly discussed in this

Post 505367

(psyloxy: "H2O2 o-cresol to 2,5-dihydroxytoluene, 98%", Methods Discourse)


Patent IE904369

describes the preparation of toluhydroquinone from o-cresol.  o-cresol is acetylated (the patent states that even plain old acetic acid will work, though the examples only use acetyl chloride) to 4'-hydroxy-3'-methyl-acetophenone catalysed by HF.  The acetophenone is then oxidised to toluhydroquinone via alkaline H2O2.

I'm not familiar with the manipulation of acetophenone's to obtain phenylisopropylamines, but perhaps it would be a good idea to try methylating this, the target compound then being 4-methoxy-3-methylamphetamine.  Note this is like an iso-MMA, the substituents being reversed.  The combination of an alkyl (C1-C3) or halogen in the 3 or 4 positions, combined with at least one methoxyl group somewhere else on the ring seems to almost always lead to activity, probably a little lower than MMA in potency I would guess?

Back to STP; I'm somewhat confused here.  Wouldn't a simple oxidation of o-cresol with alkaline persulfate (elbs rxn) directly give toluhydroquinone..  or would the methyl group get oxidised?

I'm also wondering if that ortho-alkylation of phenols could be applied directly to hydroquinone to get toluhydroquinone, and if paraformaldehyde could be used in this process or if depolymerization or the use of formalin as in the patent would be necessary..

any thoughts?


psyloxy

  • Guest
Re: DOM precursors
« Reply #7 on: October 22, 2004, 07:58:00 AM »
Finally people start talking about my favorite topic, great ! ;D

Post 505784

(psyloxy: "K2S2O8 oxidation of o/m-cresol to toluhydrochinone", Methods Discourse)



I'm also wondering if that ortho-alkylation of phenols could be applied directly to hydroquinone to get toluhydroquinone, and if paraformaldehyde could be used in this process or if depolymerization or the use of formalin as in the patent would be necessary..



My thought here: rather use p-MeO-phenol than hydrochinone.

--psyloxy--


phenethyl_man

  • Guest
quite a coincidence, DOM is your favorite...
« Reply #8 on: October 24, 2004, 03:33:00 PM »
quite a coincidence, DOM is your favorite topic as well?  well, I guess I am no longer interested in this route cause I cheated and purchased a shitload of THQ.. I realized it is too inexpensive to justify this effort; from toluene would be nice thou, just for the satisfaction of accomplishing such a synth from OTC starting material..