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Author: Subject: Sober Etaoin Shrdlu Challenge #1 - OTC TEMPO
Etaoin Shrdlu
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[*] posted on 14-11-2014 at 13:08
Sober Etaoin Shrdlu Challenge #1 - OTC TEMPO


Winner: First synthesis of TEMPO starting from OTC reagents.

Prize: Can only offer $300 at the moment. The girlfriend is already watching me side-eyed after my last chemical order.

Deadline: 5/1/2015

1. Definition of OTC is "something available to the general public for purposes other than synthesis." For example, sure, you could use a bar of silver or handfuls of lawn grass, even if you had to order them online/collect them yourself because no one around you actually sold them over a counter.

2. You can skip steps to non-OTC intermediates if you can link to a confirmed synthesis already performed and written up on ScienceMadness. Patent/research paper writeups must be confirmed by yourself or someone on ScienceMadness no matter how awesome they are.

3. All equipment reasonably well-available to the hobbyist is allowed.

4. Procedures must be clear, easy to follow, and accompanied by images where the synthesis was performed by yourself.

5. Teams are allowed. Name a head researcher, I'll send the prize to them, you split it up yourselves.

[Edited on 11-14-2014 by Etaoin Shrdlu]
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[*] posted on 14-11-2014 at 13:13


Wait - this would be better off with no expiration date...this seems kinda difficult.



At the end of the day, simulating atoms doesn't beat working with the real things...
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Etaoin Shrdlu
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[*] posted on 14-11-2014 at 13:19


There is an expiration date to make sure I don't wind up shutting the competition down when someone's halfway through working on it; they'd be rightfully angry there wasn't any notice. If nobody's managed this by the deadline I will extend it or put the funds towards an idea that has more interest.
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[*] posted on 14-11-2014 at 13:30


EditI don't care about winning, but I don't see why one couldn't try something such as:
1. acetone self condensation to phorone
2. phorone animation with ammonia (can be one pot with above under right conditions).
3. Wolff Kishner to TMP.
4. Oxidation to TEMPO.

Might give it a whirl this weekend if I can free up a little time. Don't have hydrazine on hand.
Edit: oh, this was actually discussed already in the other thread. I was hoping I was going to be the first to think of that.

There is even a very pertinent thread here with keto-TEMPO oxidation procedures and the like: https://www.sciencemadness.org/whisper/viewthread.php?tid=39...

[Edited on 14-11-2014 by Chemosynthesis]
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[*] posted on 14-11-2014 at 17:32


As I said in the other thread, I will attempt this.



As below, so above.
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[*] posted on 14-11-2014 at 20:00


Quote: Originally posted by Cheddite Cheese  
As I said in the other thread, I will attempt this.
I eagerly await your results. Seems like a ten day minimim experiment. If you want to PM about it at some point, let me know. You posted on it first, so I am not trying to scoop your ideas or work.
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[*] posted on 15-11-2014 at 05:35


Quote: Originally posted by Etaoin Shrdlu  
2. You can skip steps to non-OTC intermediates if you can link to a confirmed synthesis already performed and written up on ScienceMadness. Patent/research paper writeups must be confirmed by yourself or someone on ScienceMadness no matter how awesome they are.



To be clear, the SM post I linked to has at least three people synthing 2,2,6,6 tetramethylpiperidin-4-one. Does Rule 2. mean a challenger could use bought 2,2,6,6 tetramethylpiperidin-4-one? It would save time, of course.

Second question: would H3PO4 be considered OTC? In my country I can get it easily: eBay and also other sites.

Quote: Originally posted by Chemosynthesis  
EditI don't care about winning, but I don't see why one couldn't try something such as:
1. acetone self condensation to phorone
2. phorone animation with ammonia (can be one pot with above under right conditions).


No need for phorone: read the thread you linked too; acetone + NH3 works just fine (several variants) for 2,2,6,6 tetramethylpiperidin-4-one.


[Edited on 15-11-2014 by blogfast25]




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Etaoin Shrdlu
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[*] posted on 15-11-2014 at 05:48


Quote: Originally posted by blogfast25  
To be clear, the SM post I linked to has at least three people synthing 2,2,6,6 tetramethylpiperidin-4-one. Does Rule 2. mean a challenger could use bought 2,2,6,6 tetramethylpiperidin-4-one? It would save time, of course.

Yes, if they confirmed they really had usable 2,2,6,6 tetramethylpiperidin-4-one. (I think they did.) You'd still have to provide a clear writeup of how to get there, though.

Quote: Originally posted by blogfast25  
Second question: would H3PO4 be considered OTC? In my country I can get it easily: eBay and also other sites.

Yes. It is used as masonry cleaner and rust remover among other things in fairly high concentrations. I believe there is an OTC synth somewhere on this site as well.

[Edited on 11-15-2014 by Etaoin Shrdlu]
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[*] posted on 15-11-2014 at 06:03


Thanks, ES.



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[*] posted on 15-11-2014 at 06:12


Quote: Originally posted by blogfast25  


Second question: would H3PO4 be considered OTC? In my country I can get it easily: eBay and also other sites.

Quote: Originally posted by Chemosynthesis  
EditI don't care about winning, but I don't see why one couldn't try something such as:
1. acetone self condensation to phorone
2. phorone animation with ammonia (can be one pot with above under right conditions).


No need for phorone: read the thread you linked too; acetone + NH3 works just fine (several variants) for 2,2,6,6 tetramethylpiperidin-4-one.

1. While judging, remember it's in Coca Cola, though that hardly seems as viable volumetric/molarity-wise compared to hydroponics or the like.
2. Yeah, I hadn't tracked down J. Am. Chem. Soc., 79:5447 (1957) yet at that point or finished the thread to confirm 100% before editing. I guess that dramatically reduces time to completion.
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[*] posted on 15-11-2014 at 06:34


2,2,6,6 tetramethylpiperidin-4-one (aka triacetonamine) from Sigma:

http://www.sigmaaldrich.com/catalog/product/aldrich/459119?l...

As usual a bit pricy from the people with a 'licence to print money' but still.




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[*] posted on 15-11-2014 at 06:55


Phosphoric acid is definitely OTC; I can buy a gallon jug of 40% H3PO4 at Home Depot as Klean-Strip Prep & Etch.



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[*] posted on 15-11-2014 at 08:19


You can get 75% phosphoric acid sold as "anti-rust" solution.
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[*] posted on 15-11-2014 at 17:47


Quote: Originally posted by blogfast25  
2,2,6,6 tetramethylpiperidin-4-one (aka triacetonamine) from Sigma:

http://www.sigmaaldrich.com/catalog/product/aldrich/459119?l...

As usual a bit pricy from the people with a 'licence to print money' but still.


The prize is $300, and the 100 g bottle "only" costs $75 (even with shipping, still not as much as $300). Still, buying from Sigma is against the spirit of the challenge.

By the way, have a look at my start (gassing acetone/methanol/ammonium chloride with ammonia):
Photo on 11-15-14 at 3.10 PM.jpg - 187kB

After keeping the mixture at 50 C for 3 hours, it's turned a light orange. I'll let it react overnight.

[Edited on 16-11-2014 by Cheddite Cheese]




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[*] posted on 16-11-2014 at 05:00


Quote: Originally posted by Cheddite Cheese  

Still, buying from Sigma is against the spirit of the challenge.


The ‘spirit’, LOL? I’m a material boy. ;)

See his response to my question, here:

Quote: Originally posted by Etaoin Shrdlu  
Quote: Originally posted by blogfast25  
To be clear, the SM post I linked to has at least three people synthing 2,2,6,6 tetramethylpiperidin-4-one. Does Rule 2. mean a challenger could use bought 2,2,6,6 tetramethylpiperidin-4-one? It would save time, of course.


Yes, if they confirmed they really had usable 2,2,6,6 tetramethylpiperidin-4-one. (I think they did.) You'd still have to provide a clear writeup of how to get there, though.





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[*] posted on 17-11-2014 at 02:53


I am particularly curious to see if the expected TEMPO can be used for OTC acetonitrile:
DOI: 10.1055/s-0033-1338489
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[*] posted on 18-11-2014 at 05:42


i was completely disheartened after seeing that TEMPO could be made so easily from acetone and ammonia .
my method used malonyl choride (malonic acid can be made by oxidising malic acid ,which is OTC sold at home brew supplies ,with sodium hypochlorite)
see the 7th post by boffis in this thread for malonic acid-http://www.sciencemadness.org/talk/viewthread.php?tid=1600&a...

then malonic acid is converted to malonyl chloride using SOCl2 (thionyl choride can be extracted from batteries)
http://en.wikipedia.org/wiki/Thionyl_chloride#Batteries

then di-isopropylamine oxide is made (di isopropyl amine is made using isopropyl bromide and saccharin and then oxidized using hydrogen peroxide)

see this -use of saccharin as an alternative to pthalimide
http://pubs.acs.org/doi/abs/10.1021/ar00010a001?journalCode=...

and this thread ,8th post by chordate http://www.sciencemadness.org/talk/viewthread.php?tid=11081&...

finally malonyl choride and di-isopropylamine oxide is reacted in the presence of strong base (NaNH2 ) to form TEMPO 3,5 diketone

it is then reduced using hydrazine to get TEMPO

Quote:
I am particularly curious to see if the expected TEMPO can be used for OTC acetonitrile:
DOI: 10.1055/s-0033-1338489


chemosynthesis ,acetonitrile can be made easily from ethylamine using 30% hydrogen peroxide and conc sulphuric acid

ethylamine can be made using ethylbromide and hexamine (delepine reaction)
http://en.wikipedia.org/wiki/Del%C3%A9pine_reaction

take ethylamine and conc H2SO4 in a beaker
then slowly drip in 30% H2O2 into the beaker .
what happens is that the peroxide oxidises ethylamine to N-ethyl hydroxyl amine and the sulphuric acid immediately dehydrates the hydroxyl amine to give acetonitrile

since the hydroxyl amine is very prone to furthur oxidation by peroxide to form nitroethane ,the concentration of peroxide is kept at a minimum and any hydroxyl amine formed is immediately dehydrated as there is an excess of H2SO4 .
gentle heating of the beaker containing the (amine +acid) is required throughout the reaction

but obviously the one pot synthesis using TEMPO at room temp is much easier
and tert -butyl hypochlorite can be easily made
http://www.orgsyn.org/demo.aspx?prep=cv5p0184
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[*] posted on 18-11-2014 at 06:48


Quote: Originally posted by CuReUS  

chemosynthesis ,acetonitrile can be made easily from ethylamine using 30% hydrogen peroxide and conc sulphuric acid

ethylamine can be made using ethylbromide and hexamine (delepine reaction)
http://en.wikipedia.org/wiki/Del%C3%A9pine_reaction

Thanks. Delepine is a good fit for this small amine, though Gabriel synthesis is technically OTC as well, as is the modification using saccharine as a substitute, which you've obviously used to good effect with an additional alkylation during unmasking.

Quote:
take ethylamine and conc H2SO4 in a beaker
then slowly drip in 30% H2O2 into the beaker .
what happens is that the peroxide oxidises ethylamine to N-ethyl hydroxyl amine and the sulphuric acid immediately dehydrates the hydroxyl amine to give acetonitrile

since the hydroxyl amine is very prone to furthur oxidation by peroxide to form nitroethane ,the concentration of peroxide is kept at a minimum and any hydroxyl amine formed is immediately dehydrated as there is an excess of H2SO4 .
gentle heating of the beaker containing the (amine +acid) is required throughout the reaction

but obviously the one pot synthesis using TEMPO at room temp is much easier
Interesting. What are yields like? The only lit I saw on this used expensive ruthenium catalysis.
DOI: 10.1039/C3GC36513A
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[*] posted on 18-11-2014 at 09:00


chemosynthesis ,i am very sorry:(:(

you can dehydrate aldoximes to nitriles ,not hydroxyl amines
but nitriles can still be made from OTC chemicals

ethylamine could be oxidised to acetaldehyde(as acetaldehyde is not OTC),read the acetaldehyde synthesis in the organic chemistry section for more ways to make it
http://en.wikipedia.org/wiki/Ethylamine#Reactions_and_applic...

hydroxylamine could be prepared from nitromethane or just brought as HCl salt

http://www.sciencemadness.org/talk/viewthread.php?tid=15176

acetaldehyde oxime could be prepared and dehydrated to give nitriles

alternatively ,oximes could be prepared from reactions with nitrites(which can be found OTC in deodorants)
http://en.wikipedia.org/wiki/Oxime#Preparation

you could also make nitriles by oxidizing amines using TCCA
http://www.organic-chemistry.org/synthesis/C3N/nitriles.shtm


actually i am very depressed as i thought for two days to get a decent route for making TEMPO and then i see this method from acetone and ammonia

its like microwave cooking Vs bonfire

formaldehyde + ammmonia -hexamine
acetone +ammonia-TEMP
then acetaldehyde +ammonia=???

nicodem would to kill me if he/she saw my post:(:(:(:(
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[*] posted on 18-11-2014 at 10:26


Thanks. I would probably use nitrites from butcher's salts or pickling (preservative) due to relative purity rather than deodorants.

I am particularly interested in a TEMPO route, though, and it appears to be able to improve upon TCCA oxidation in many instances (Synthesis, 2003, 2629-2631).
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[*] posted on 18-11-2014 at 10:59


Quote: Originally posted by CuReUS  
actually i am very depressed as i thought for two days to get a decent route for making TEMPO and then i see this method from acetone and ammonia

Don't be depressed. I'm excited someone thought up a different path than acetone condensation.
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[*] posted on 19-11-2014 at 12:27


Depressed ?!?!

I would be ECSTATIC if i worked out a functioning route to TEMPO.

The fact that you worked it out is proof positive that you are at a level of understanding that many of us can only dream of.

The fact that Other routes exist would do absolutely nothing to dampen my happiness, and neither should it dampen yours.




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[*] posted on 19-11-2014 at 13:08


Quote: Originally posted by aga  
The fact that you worked it out is proof positive that you are at a level of understanding that many of us can only dream of.

I think he was referring to his pipe dream synthesis. Even though he calls it "my method" as if it was some proven synthesis, it is quite obviously a fabrication, as it makes no sense:
Quote: Originally posted by CuReUS  
then di-isopropylamine oxide is made (di isopropyl amine is made using isopropyl bromide and saccharin and then oxidized using hydrogen peroxide)

...

finally malonyl choride and di-isopropylamine oxide is reacted in the presence of strong base (NaNH2 ) to form TEMPO 3,5 diketone

it is then reduced using hydrazine to get TEMPO

I would feel equally depressed, if I came up with such ideas.




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[*] posted on 19-11-2014 at 13:10


Doh.



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[*] posted on 19-11-2014 at 17:11


Quote: Originally posted by Nicodem  
Quote: Originally posted by CuReUS  
finally malonyl choride and di-isopropylamine oxide is reacted in the presence of strong base (NaNH2 ) to form TEMPO 3,5 diketone

I would feel equally depressed, if I came up with such ideas.

I thought I saw where he was going with this when I glanced over it earlier but looking at it again I'd expect just a bunch of malonamide. Still, would appreciate to know what makes it particularly depressing, and would be interested what the actual thought process behind it was.
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