Sciencemadness Discussion Board

Nitroethane from ethylamine and ozone

madcedar - 6-10-2009 at 09:18

I'm putting this post up because I would like someone with access to the Journal of Organic Chemistry to get the following articles for the Sciencemadness community and post them here for all to see. The journal articles I'd like to read are:

Bailey, P. S., and J. E. Keller. J. Org. Chemistry. 33, 2680 (1968)
Keinan, E., and Y. Mazur. J. Org. Chemistry. 42, 844 (1977)
Zajac, W. W., Jr., T. R. Walters, and J. M. Woods. J. Org. Chemistry. 54, 2468 (1989)

I have attached a patent that claims that organic amines can be oxidized into nitro compounds.

I got the three references above from The Nitro Group in Organic Synthesis by Noboru Ono, page 20.
Quote:

2.2 SYNTHESIS OF NITRO COMPOUNDS BY OXIDATION
2.2.1 Oxidation of Amines

The direct oxidation of primary amines into the corresponding nitro derivatives is very useful for fundamental and industrial applications because it provides nitro compounds, which may otherwise be difficult to synthesise by direct nitration methods. Efficient synthetic methods for the conversion of primary amines into the nitro compounds are described in this section. Saturated primary amines undergo oxidation reactions by ozone to give the corresponding nitroalkanes accompanied by several other compounds depending on the reaction conditions. (ref. 107). This drawback is overcome by ozonation on silica gel. Amines are absorbed on the silica gel by mixing with dry silica gel (dried for 24 h at 450 C). The silica gel (ca 30 g) containing the amine (0.1-0.2 wt/wt%) was cooled to -78 C and a stream of 3 % of ozone in oxygen passed through it. By this procedure, nitro compounds are obtained in 60 - 70 % yield. (ref. 108). 1-Nitroadamantane is prepared by oxidation of 1-aminoadamantane with peracetic acid and ozone in 95 % yield. (ref 109).

(107) Bailey, P. S., and J. E. Keller. J. Org. Chemistry. 33, 2680 (1968)
(108) Keinan, E., and Y. Mazur. J. Org. Chemistry. 42, 844 (1977)
(109) Zajac, W. W., Jr., T. R. Walters, and J. M. Woods. J. Org. Chemistry. 54, 2468 (1989)

I'm not claiming any of these methods to be efficient or practical.

Attachment: Process of Preparing Nitro Compunds by Reacting Organic Amines with Ozone pat3377387.pdf (426kB)
This file has been downloaded 780 times

DDTea - 17-10-2009 at 11:04

I only have access to Journal of Organic Chemistry from 1996-present. Are there any more recent articles on this topic, maybe?

DJF90 - 17-10-2009 at 12:18

This isnt the place to request references. Try the references section ;)

madcedar - 3-11-2009 at 00:35

I'd love to but I'm locked out of the references section and I don't know who to ask for access.

DJF90 - 3-11-2009 at 03:55

"Articles or books may be requested or shared in this forum. Access must be requested of a moderator. Contact an admin if you formerly had access and are now shut out."

hissingnoise - 3-11-2009 at 06:04

Somehow, I don't think many members could splash-out on an ozone generator capable of oxidising amines with any efficiency.

DJF90 - 3-11-2009 at 08:35

There are instructions for such a contraption in Brauer, if you care to look. It shouldnt be too hard to construct supposing you have a mains=>8000V transformer, some copper sulfate solution and some glass (and the necessary glassworking skills).

hissingnoise - 3-11-2009 at 14:40

With 8000V you'd probably be looking at a few gms of product per day at best. . .

DJF90 - 3-11-2009 at 14:58

I doubt it, the ozone concentration using air in that kinda setup is said to be about 3%, using oxygen gas IIRC it rises to between 8-12%? Now that means for every 24 litres passed, 0.1mols of ozone is generated (using the latter percentages) so long as I havent messed up my brief mental calculations. And it wont take long to pass 24litres of oxygen gas - factor in that the yield is supposedly very high (remember that the ethylamine needs to be adsorped onto silica gel); about 95%+ IIRC. So I think you can swap out "gms" for "moles" in your above statement.

Also, anyone with a remote interest in electronics would be able to make a transformer that'd provide higher voltages. Considering its likely you'd have to make one yourself anyway, it'd make sense to.

hissingnoise - 3-11-2009 at 15:30

You're probably right---I just make a quick guesstimate. . .
A full calculation would be time-consuming!

Sedit - 3-11-2009 at 15:35

An air cored Hf resonace transformer AKA tesla coil can be made with a little determination and ease on a small scale and produce a large amount of ozone with ease. I have a little 1 1/2"d coil made from hair thin wire for the secondary years ago and it produces a 4" streamer with ease even when it was out of tune. Simply hooking this up to a terminal of an ozone tube should generate more then enough for efficent use.

entropy51 - 3-11-2009 at 17:31

Quote:
It shouldnt be too hard to construct supposing you have a mains=>8000V
8 Kv is only a modest neon sign transformer and high voltage diodes to handle those voltages are relatively cheap. I guess my hesitation would be that some ozonides are said to be explosive.

kclo4 - 3-11-2009 at 18:14

Electrolysis of sulfuric acid anyone?

This creates ozone...

Sedit - 3-11-2009 at 18:38

Heres one way I can think of that generated alot of Ozone for me on accident one time.
Quote: Originally posted by Sedit  
Has anyone else ever experianced this while cleaning there H2SO4 with H2O2, I did as I always do and added a few caps to a flask of dark H2SO4 to make it clear. Problem was I had the heat to high and walked away from it and when I came back to it there was the normal thick 'smoke' comming off when its concentrated all the way. The H2O2 boiled out of the solution before it had time to work and I was left with a concentrated H2SO4. Yes I screwed it up by walking away but no matter I just thought I would add a little more H2O2 and put it on the correct setting this time. The second that the H2O2 hit the now cooled down acid it started fizzing greatly and what struck me by suprize was the very strong smell of Ozone comming off the mixture. Has anyone else experianced this? I have never heard of O3 being generated by these means and it struck me as odd. I am very formilar with the smell of ozone from working with High voltage since I was very young and there is no mistaking that this was O3 bubbling out of the concentrated H2SO4/H2O2 solution.
Is this normal or what?

Quote: Originally posted by Formatik  
It's normal alright. The source is the decomposing H2SO5. Bach in Ber. 33 [1900] 3117 had already noted the evolution of O3 by decomposition of H2SO5 in conc. H2SO4. And then Arnold in Ber. 35 [1902] 2903, 2906 describes evolution of rich amounts of O3 through H2O2 and H2SO4.

Source:http://www.sciencemadness.org/talk/viewthread.php?tid=10639&...

I managed to smell it another time as well when attempting Mn(IV)sulfate synthesis. The cell temperature would rise to about 120 degrees F and I would allow it to run until it turned dark brown. After this I would allow it to cool down and as soon as I started to run current thru the now cold solution the smell of Ozone would present itself strongly and the solution would turn to a black mush which would clear itself up again as the temperature increased from the current.



Quote: Originally posted by entropy51  
Quote:
It shouldnt be too hard to construct supposing you have a mains=>8000V
8 Kv is only a modest neon sign transformer and high voltage diodes to handle those voltages are relatively cheap. I guess my hesitation would be that some ozonides are said to be explosive.


There is also the option of using an OBIT(oil burner ignition transformer) I have a ton of these things floating around and they run at 10kv 23/24ma rectified already comming out of the terminals. The newer smaller more stable ones are less prone to burn outs since the old ones where grounded to the outer casing and if the tar insulation got to hot it would arc internaly. They currently run at about 15kv 35-45ma anymore and are contained in a plastic casing. Whatever the choice Im quite sure one of these could be had rather cheep with a quick call to your local oil heater man since he more then likely has A ton of these laying around.;)

[Edited on 4-11-2009 by Sedit]

madcedar - 4-11-2009 at 00:40

Big Clive has built some ozone generators here:

http://www.bigclive.com/ozone.htm

Old neon light sign transformers deliver several kilovolts. They seem perfect for the job of generating ozone.

hissingnoise - 4-11-2009 at 04:07

Quote: Originally posted by DJF90  
Also, anyone with a remote interest in electronics would be able to make a transformer that'd provide higher voltages. Considering its likely you'd have to make one yourself anyway, it'd make sense to.

Winding a HV secondary would be quite a challenge, even for 12AX7!
Older NSTs used to be centre-tapped in compliance with a regulation limiting them to 5 kV so that the discharge could run @ 10 kV.
Good for running B.E.s (Jacob's Ladder) NO2 generators but efficiency was still very low.
Electrolytic ozone is produced in high conc. but with lower efficiency than corona-discharge.
OBITs are not intended for continuous running, though a large heatsink with forced-air cooling might work but a thermal cut-out would still be needed.
Has anyone considered H2O2?





[Edited on 4-11-2009 by hissingnoise]

DJF90 - 4-11-2009 at 05:07

How do you intend to use H2O2 to generate ozone?

I did not imply that the construction of a suitable transformer would be easy. However, with alot of patience (and copper wire!), it is not an impossible feat.

hissingnoise - 4-11-2009 at 06:04

DJF90, consider the H2O2 ref. a momentary amnesia. . .
Quote: Originally posted by DJF90  
However, with alot of patience (and copper wire!), it is not an impossible feat.

The wire you'd be using for the rough equivalent of an NST would be little thicker than a strand of hair and each layer (and there are very many) needs its own waxed or lacquered insulating sleeve, correctly positioned.
Even with a motorised spindle it'd still be pretty daunting. . .and frustrating!

Sedit - 4-11-2009 at 06:27

DJF90 ny post above stated how I achieved a large quantiaty of Ozone using H2O2 and H2SO4 that had been concentrated to the point of thick white vapors comming off of it. The large concentration of the H2SO4 was an accident but Im sure it could be done with ease by anyone determined enough. Placing H2O2 in a dropper funnel at that point would give someone Ozone on demand slowly generating it as one pleased.

Formatik stated that this has to do with the decomposition of the peroxyacid H2SO5 so I can't help but wonder if a salt of this could possibly be used as well with much greater ease then dealing with the H2SO4.


On the topic of winding a transformer there is no better way to go if your looking to make your own then to use an air core. It only needs one layer and can reach 100kv with ease using high frequency resonance. There is also a solid state version of the tesla coil that would be much better for this IMO which is the kind they use in the plasma globes you see a novelty stores. These are very compact and more stable then an air core and can reach very large Kv levels with ease as well. Plus they don't have the down side of the noisy spark gap so all you get out of them is a loud hum as the are in operation. If some one is not up to the task themselfs then dismantaling an old plasma globe to recover the circuit would bet the best way to an ozone generator.

spong - 15-10-2010 at 22:46

:)

Attachment: Bailey, P. S., and J. E. Keller. J. Org. Chemistry. 33, 2680 (1968).pdf (666kB)
This file has been downloaded 857 times

Attachment: Keinan, E., and Y. Mazur. J. Org. Chemistry. 42, 844 (1977).pdf (454kB)
This file has been downloaded 666 times

Attachment: Zajac, W. W., Jr., T. R. Walters, and J. M. Woods. J. Org. Chemistry. 54, 2468 (1989).pdf (665kB)
This file has been downloaded 1401 times