Sciencemadness Discussion Board
Not logged in [Login - Register]
Go To Bottom

Printable Version  
Author: Subject: Oxidation of Nitriles to Nitro groups
LabRatNW
Harmless
*




Posts: 18
Registered: 9-8-2009
Member Is Offline

Mood: No Mood

[*] posted on 25-1-2019 at 08:27
Oxidation of Nitriles to Nitro groups


Has anyone played around with this idea before?

The idea is, generating an easy supply of Nitroalkanes or other nitro containing groups for fuel or synthetic material.

ACN + Oxidizer -> EtNO2 (Not necessarily functional, but the idea is there)

[Edited on 1-25-2019 by LabRatNW]
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 1480
Registered: 3-11-2013
Member Is Offline

Mood: No Mood

[*] posted on 25-1-2019 at 11:16


It doesn't really work. The nitrile oxide is produced and it dimerizes to a furoxan.

You can make nitro compounds from oximes by a complex method due to Corey, but it works by adding chlorines to the alpha carbon so that it won't get oxidized. Then the chlorines are reduced to leave the nitro compound.

And even if it did work acetonitrile isn't that easy to come by, or at least I don't see anyone using it, so I assume it must not be.




[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
LabRatNW
Harmless
*




Posts: 18
Registered: 9-8-2009
Member Is Offline

Mood: No Mood

[*] posted on 25-1-2019 at 15:51


Acetonitrile is easy as hell to get.

I don't know how it would dimerize to furoxan, That doesn't even make sense. How would you suddenly end up with another nitrogen on the methyl carbon?

[Edited on 1-25-2019 by LabRatNW]
View user's profile View All Posts By User
CuReUS
International Hazard
*****




Posts: 886
Registered: 9-9-2014
Member Is Offline

Mood: No Mood

[*] posted on 25-1-2019 at 21:14


http://www.publishchemidea.com/direct-conversion-of-nitriles...
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 1480
Registered: 3-11-2013
Member Is Offline

Mood: No Mood

[*] posted on 25-1-2019 at 21:25


Two equivalents of acetonitrile oxide dimerize to 4,5-dimethylfuroxan.



[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
LabRatNW
Harmless
*




Posts: 18
Registered: 9-8-2009
Member Is Offline

Mood: No Mood

[*] posted on 30-1-2019 at 14:16


Is there a published mechanism for that?
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 1480
Registered: 3-11-2013
Member Is Offline

Mood: No Mood

[*] posted on 30-1-2019 at 22:27


https://pubs.acs.org/doi/abs/10.1021/ja037325a



[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
zed
International Hazard
*****




Posts: 1736
Registered: 6-9-2008
Location: Great State of Jefferson, City of Portland
Member Is Offline

Mood: Semi-repentant Sith Lord

[*] posted on 2-2-2019 at 14:53


Oxidations are quirky. Hard to stop 'em on a dime.

Acetonitrile can be reduced to Ethylamine.

Which in turn, can be oxidized to Nitroethane, via Oxone-Acetone?

But, it is a fussy business involving lots of solvent.

Alas, the industrial techniques utilized by big chem, work very well at producing large quantities of inexpensive nitroalkanes.

Nitroalkanes, that most of us have difficulty accessing, and few good alternatives for synthesizing.

View user's profile View All Posts By User

  Go To Top