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Author Topic: 3C-E Discussion  (Read 173 times)

Happyman

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3C-E Discussion
« on: April 17, 2012, 07:34:39 PM »
Hi guys, here is a doodle I came up with at the thing I do. I'm sorry that it is so crude, but all the reactions are ones we know and love. I really want everyones input on it. Thanks.

embezzler

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Re: 3C-E Discussion
« Reply #1 on: April 17, 2012, 08:55:52 PM »
what are your proposed conditions for the first step? I imagine HBr is capable of interfering with both the alcohol and the C=O group easily enough? Is the Meta position a likely spot for bromine addition?


Got Refs?
« Last Edit: April 17, 2012, 09:04:24 PM by embezzler »
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pyramid

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Re: 3C-E Discussion
« Reply #2 on: April 17, 2012, 09:12:45 PM »
Moreover what are your conditions for ALL steps? Reference for the methoxylation working with LiOMe?

You don't need Br2 or HBr for the bromination, you can just use a bromide salt in AcOH with some H2SO4/H2O2 or similar. Search for this information.

Ethylation can be done with quant yield with EtI/ K2CO3/DMF stirring RT for 3-4days. Ethyl bromide can probably be used if you add some KI.

Condensation may work alright with iPrNH2 (OTC) in iPrOH at RT for a while or at reflux, or ethylenediamine in iPrOH with some excess AcOH at reflux. Well there are other catalysts maybe MeNH2.OAc can give a good yield too, you have to try.

You have a few options obviously for the reduction.

Polonium

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Re: 3C-E Discussion
« Reply #3 on: April 17, 2012, 09:33:38 PM »
Hi Happyman, the scheme looks about right to my untrained eyes. The first two steps are simply the conversion of vanillin to syringaldehyde which is well documented (http://www.erowid.org/archive/rhodium/chemistry/345-tmba.html). I like the proposed use of LiMeO, It is potentially a more OTC alkoxide than NaMeO considering the wide availability of Li batteries. Unfortunately they only contain small amounts (circa 0.75g) of Li metal IIRC. I don't see any issues with the substitution but this is something that will need to be confirmed experimental.

The ethylation should work without issue. Shulgin uses the same route from the syringaldehyde to the nitrostyrene in his entry on 3C-E in PiHKAL (http://www.erowid.org/library/books_online/pihkal/pihkal025.shtml)

The final steps just involved reducing the nitropropene by whatever means is accessible to you.

I like that you have done some work on this. Next time it would probably be best to upload the image to your post as an attachment. It will resize your photos automatically and ensure that the image won't disappear if the link breaks. Finally be sure to remove all metadata from any images you upload. They can be very revealing. It is very easy for you GPS coordinates to be embedded unknowingly in a photo upload from a phone such as a Samsung Galaxy SII! For example an Anonymous hacker was identified from a naked picture of his girlfriend that had her GPS coordinates embedded in it. (http://www.ibtimes.co.uk/articles/327325/20120412/anonymous-hackers-unmasked-girlfriend-s-semi-naked.htm)

dream0n

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Re: 3C-E Discussion
« Reply #4 on: April 17, 2012, 10:05:56 PM »
/ Hey there, sweet phone it is quite durable for a phone.
I think using the conditions referenced above in pihkal and rhodium, it should work fine.  I don't see why it would fail in any way/

off to bigger and better things - don't worry I will visit from time to time

embezzler

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Re: 3C-E Discussion
« Reply #5 on: April 17, 2012, 11:15:36 PM »
Where is HBr mentioned in the linked Rhodium archive and under what conditions is this recommended? I see Br2 in methanol. No mention of HBr?

IIRC Organikum posted a method for the preparation of sodium ethoxide from sodium hydroxide and methanol. An unusual one at that.

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Polonium

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Re: 3C-E Discussion
« Reply #6 on: April 18, 2012, 12:14:45 AM »
There is no reference to HBr in the bromination of vanillin. In the produce outlined at http://www.erowid.org/archive/rhodium/chemistry/345-tmba.html  elemental bromine is simply stirred with vanillin in methanol for one hour.

If liquid Br2 is difficult for you to handle you could also use elemental iodine. The procedure in http://www.erowid.org/archive/rhodium/chemistry/iodovanillin.html involves the addition of NaI and I2 to an aq. solution of vanillin. I assume the NaI is just required to ensure all the I2 goes into solution as the NaI3.NaI complex. This should also be somewhat more efficient, due to iodine being a better leaving group. The Br2 method seems to have >85% yields anyways. Just presenting the options!

embezzler

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Re: 3C-E Discussion
« Reply #7 on: April 18, 2012, 05:35:47 AM »
Hey Polonium, It's not really your method I was questioning as such. The OP has HBr listed with elemental Bromine as a reactant in their first step which I would like to see evidence (or reason) for?


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Happyman

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Re: 3C-E Discussion
« Reply #8 on: April 18, 2012, 08:11:55 AM »
Sorry for all the confusion, the HBr is a completely separate rxn. Unfortunately, I seem to have misplaced the refs for it making the likelihood that it is a complete fabrication of my imagination that much higher. Also, as dream0n pointed out, I am not infront of a computer, which I would like to use as an excuse for not posting refs XD.

embezzler

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Re: 3C-E Discussion
« Reply #9 on: April 18, 2012, 11:15:23 AM »
OK I found the BromoVanillin via HBr and Br2 reference at erowid in mmda.mescaline synthesis. Low temperatures seem to be the key to this to prevent the degradation I alluded to. 

Slightly higher yields (3%ish) than the elemental bromine alone have to be balanced against the requirement for the additional regent. 95 vs 98 per cent yield. It looks like the work up will be more burdensome to neutralize the HBr

www.erowid.org/archive/rhodium/chemistry/mmda.mescaline.html

Alternative 3 under Osmiums narrative.

Refs in the first instance make this easier :)

Your imagination for this step seems to be in control.....so thats good.
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