Reductions...

[spectralmagic]

I haven't strayed too far from the Couch for several months so I'm a little out of practice...  SWISM has a question I can't answer.

If a synthesis calls for NaBH4, could another reduction scheme, such as Al/Hg, be used instead?  In SWISM's dreams lower yields are not a nightmare...  but if it isn't possible at all, he might bite the bullet and dream of obtaining NaBH4...  in this particular case he's dreaming of reducing a ketone to an alcohol, in an OTC manner.

TFSE suggests that it might be possible...  lots of examples of NaBH4 being used instead of Al/Hg, but nothing that I could find going the other way.
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[foxy2]

You better bee specific.

I think LiAlH4 will usually work in place of NaBH4  
Read and Listen!!! 

http://www.zmag.org/chomsky/index.cfm

[spectralmagic]

LAH, eh?  Right, I'm sure SWISM will jump all over that one  

To bee specific, he's wondering about reducing cathinone to PPA.
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[Kinetic]

So is this PPA going to then be reduced to amphetamine? SWIK is also interested in a very similar idea if so (see

Post 355271

(Kinetic: "How does this sound?", Novel Discourse)), and was hoping the usual iodine/red phosphorus reduction would do the trick from cathinone straight to amphetamine. I can't see any reason why not, since a ketone is much easier to reduce than an alcohol, and iodine/RP (or is it HI/RP?) is a powerful reducing agent.

Sorry if this is not the intention you had in mind for your PPA, but I can't think of much else that can be done with it, unless you have a blocked nose maybe...

[spectralmagic]

PPA is a direct precursor to 4-methylaminorex (U4Euh), but I'm sure that's not what SWISM has in mind...

So, reducing PPA further yields amphetamine... that would not make SWISM happy...  I wonder how easily that happens... now, if ketones reduce easily, and alcohols do not, I suppose a decent yield can be achieved through timing and/or choice of reducing agent.  Hence the original question...  my gut tells me SWISM is going to think about Al/Hg anyway in his dreams.
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[hest]

Kinetic, dont think so. In the red off eph. with I2 you make an substitution(sn1/sn2) of the alcohol to the iodide and then reduce the iodide(werry easye). You can't sub. the ketone with iodine.

[Kinetic]

hest, you saved me a lot of time and money trying! I posted this as a suggestion because I wanted to try it and hoped it would work, but wanted input from other bees more knowledgeable than I (most of you then ) as to whether it would work before I did so. Thankyou!

[spectralmagic]

reducing PPA further yields amphetamine

Hold on a minute, that can't be right.

Amphetamine is based around phenyl-2-propanone, PPA is based around phenyl-1-propanone (well, propanol perhaps), or am I missing something?  Grrr... maybe SWISM should just dream about it and see where it goes...

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[PrimoPyro]

Neither are based around either except in your mind. We make the associations, the chemistry couldn't care less what X is related to what Y or Z, etc.

Reducing PPA's hydroxyl does indeed yield amphetamine. You can make amphetamine from P2P as well, but the processes are completely different. I think you should look at the structures of these three chemicals and you will understand.

PrimoPyro
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[spectralmagic]

[Homer]Doh![/Homer]

Yes, I see it now.  Scratch the previous post.  But still no definitive answer on the substitution...  I guess he'll find out himself.
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[spectralmagic]

OK, after some research, how about this:

Reduce phenyl-2-nitropropanol to phenylpropanolamine using Urushibara (sp?) nickel?

And does anyone know how much nickel is actually in nickels (the currency), particularly in Canada?  I'm currently dissolving some nickels in HCl, the solution seems to be turning the right colour... 
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[Organikum]

Nickel catalyst needs some pressure...

Starts at +60bar and up to +250bar and more. I read that it might be possible to do these reactions on a very small scale at atmospheric pressure by using a very huge amount of catalyst, but if somebody did do it is unknown to me.

Sorry for the bad news.
There have been rumors about urushibara Ni working in CTH/microwave setups. But nothing I would bet on.

ORGY
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[spectralmagic]

Well, I got the idea from

https://www.thevespiary.org/rhodium/Rhodium/chemistry/amph.urushibara.html

, seemed like a nice OTC way of going about what I want (the goal is a theoretical path from toluene to 4-MAR completely OTC, lots of labour involved though).

An observation on the nickels: Canadian nickels from 1994 and prior are reacting with the HCl nicely, the 2001 I threw in there is barely even touched - either they changed the type of metal in use, or there's some sort of coating that hasn't rubbed off yet.  I didn't have any nickels from 1995-2000, or 2002, so can't comment on them.

Edit: Further examination reveals that the 2001 nickel responds strongly to a magnet, whereas the others respond very weakly if at all (placed the beaker on a magnetic stirrer, the only nickel to jump around was the 2001).  Clipping a piece off of the 2001 reveals what looks like a copper core, the a 1994 is uniform throughout.
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[cilliersb]

Swim ran NaBH4/AL/Hg on the weekend on 2,5-DMP2NP.

The reaction (unlike some warnings on Rhod's page) with NaBH4 ran fine in MeOH (anhydrous!!) (I also thought this was odd as MeOH is meant to be to reactive toward NaBH4.) 5g 2,5-DMP2NP was added to Methanol 250ml (the reaction mixture became very light yellow color within 15 mins of adding 2g NaBH4 (mag stirring on fast!). Some HCl 30ml and HgCl2 200mg was added after around 40 mins followed by shredded Al 10.5g. The temp rose for a while to around 50C and slowly returned to around 35C where it sat for hours. I put the hotplate on very low (40C)

Stirred at 40C over night (16H). Not all the Al reacted!! Solution was basified, vac filtered and extracted with Toluene 150ml, 100ml, 80ml. The toluene was vac distilled off at 37-40C. After this the dist setup was allowed to reach 60C before distillation was discontinued which left swim with around 2.5ml of a light yellow oil. To this was added 5ml AcOH followed by 2.5g Br2 in 5ml AcOH. My 2C-B.HBr is busy cryst. and so far looks around 1.5g.

This synth is easy and cheap as hell. I will post my final yeild ASAP. At least we know this works bees!! The original writeup can be found at Rhod's page.

Personally I feel that this synth can be done a hell of a lot better than swim did it as my lab technique sucks to say the least.

The only thing that went down strange here is that the 2C-B took 24 hours to start cryst. out of the AcOH/Br2 sol. Every mornings there are more and larger crystals. This doesn't seem to always happen as quickly as it has before. Maybe my 2C-H base was still quite dirty, who knows.

[Barium]

You said that you started with 2,5-DMP2NP (I assume you mean 1-[2,5-dimethoxyphenyl]-2-nitropropene). Then you said you in the end made 2C-B. This means you started with 1-(2,5-dimethoxyphenyl)-2-nitroethene. There is a huge diffrence in how the nitropropene and the nitroethene behave when reduced by NaBH4 in MeOH. Beaker and myself have never said it is impossible to reduce the nitroethene in MeOH with NaBH4, just that the yields really sucks. Therefore we gave you the methods to get the good yields.

[cilliersb]

You're right Barium.

I reduced the Nitrostyrene not the Nitropropene. It is 2C-B and not DOB I'm talking about. Yeilds are not great as you stated as well. I merely posted this to confirm the functionality of that synth as stated on Rhodium's page.

I tried an LAH reduction once before and screwed it up properly with my super wet THF. Swim will post yields for this in a week or so and also of my current project which reduces the nitrostyrene with Red-AL.

Just trying to be of help to bees wondering about the validity of things they read. Sorry, I did not mean to mislead anyone.

[Barium]

I saw that you didn´t perform an acid wash of the amine after you was done with the Al/Hg reduction. This means that god-knows-what might be in there, especially since you added the bromine directly to the isolated unwashed product. If I were you I would definetly distill the 2C-B freebase. I can guarantee you that the reason for the slow crystallisation is because the product is immensly dirty. I wouldn´t taste it for my life!

[Rhodium]

Good 2C-H bromination writeup:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/2cb.bromination.html

Only apply to vacuum distilled 2C-H freebase!

[cilliersb]

Yip, sooo Right dude!

Swim was thinking of washing 2C-B freebase while converting to 2C-B.HCl

Basify, solvent extract, wash, wash, wash, crystallize. Hope this will clean up enough.

[Antoncho]

Dear Rhodi!

Pray, tell!

Why it is always distilled 2C-H freebase that is used in bromination?

What will happen with the non-distilled base?

Is there any other suitable substitute (e.g., steam-distillation) for it?





Antoncho