Sciencemadness Discussion Board

Alkyl nitrites reduction

morsagh - 23-3-2016 at 07:14

Hello,
Can be alkyl nitrites reduced to amines (what reagent)? Or what is product of reduction?

Metacelsus - 23-3-2016 at 07:40

Probably not, unless you could isomerize it to the nitro compound. My guess is that reducing conditions would just form the alcohol.

brubei - 23-3-2016 at 07:56

did you mean nitroalkyl to alkylamine ?

alkyl nitrite

morsagh - 23-3-2016 at 08:20

I mean nitrites, can be this isomerised to nitro compound?

brubei - 23-3-2016 at 08:56

alkyl nitrite react by losing NO gas, giving alkoxyradical RO, or used for oxime synthesis.
I don't think there is a way to induce simple isomerisation.


[Edited on 24-3-2016 by brubei]

PHILOU Zrealone - 24-3-2016 at 07:08

Quote: Originally posted by morsagh  
I mean nitrites, can be this isomerised to nitro compound?

Yes but it is risky because the isomerization temperature is very close to the explosion temperature of nitrite esters...
There are not alot of references about the isomerization.

morsagh - 24-3-2016 at 07:42

No catalyst can help? What´s mechanism?

PHILOU Zrealone - 24-3-2016 at 13:17

Quote: Originally posted by morsagh  
No catalyst can help? What´s mechanism?

As already written:
"There are not a lot of references about the isomerization. "
--> I have only seen a brief mention in one of my books.
--> This is open for your as a new research :D ;)

I invite you to try methyl nitrite at 100°C to 135°C (search the optimum) but don't go too fast because arround 130°C-135°C you get a risk of explosion/detonation. The methyl nitrite decompose generating heat --> exothermic.
--> Start small.
Don't forget to post you results.

A catalyst may be a good idea, but a catalyst may aswel increase sensitivity of the methyl nitrite ester or of the nitromethane to heat and lower the activation energy for an explosion/a detonation.
--> You'll have to test catalyst by trial and error BEHIND A SAFETY SHIELD SCREEN.

[Edited on 24-3-2016 by PHILOU Zrealone]

Σldritch - 6-5-2016 at 12:09

https://www.erowid.org/archive/rhodium/chemistry/nitrite2nit...

You might be able to make the copper catalyst in-situ by redeucing copper (II) oxide with hydrogen before distilling the nitrite.

Anyway seems very intresting considering how nitrites are so easy to prepare, now i wish i had some sodium nitrite...

aga - 6-5-2016 at 13:01

Quote: Originally posted by Σldritch  
now i wish i had some sodium nitrite...

Make some ! It's Easy (apparently)
Quote: Originally posted by Σldritch  
considering how nitrites are so easy to prepare

Start a new thread and show us a procedure and some photos of how it 'easy' it is.

Σldritch - 11-5-2016 at 08:13

I tought it was easy based on videos like this but maybe im wrong, atleast it would be easier for me considering i do not have acess to sulfuric acid and can not nitrate with nitrosyl sulfuric acid.

https://www.youtube.com/watch?v=bbmpmLjfkkM

EDIT: Im sorry i think you missunderstood me, i mean alipathic nitrites are easy to prepare not the nitrite ion. :)

[Edited on 11-5-2016 by Σldritch]

CuReUS - 11-5-2016 at 09:50

Quote: Originally posted by Σldritch  

You might be able to make the copper catalyst in-situ by redeucing copper (II) oxide with hydrogen before distilling the nitrite.

what copper catalyst are you talking about ? . Are you referring to the reduction process ?
wouldn't it be better to make the nitro compound first and do the reduction to amine using sodium dithionite rather trying to do a one pot conversion from the alkyl nitrite to amine ?

Σldritch - 11-5-2016 at 21:53

Quote: Originally posted by CuReUS  
Quote: Originally posted by Σldritch  

You might be able to make the copper catalyst in-situ by redeucing copper (II) oxide with hydrogen before distilling the nitrite.

what copper catalyst are you talking about ? . Are you referring to the reduction process ?
wouldn't it be better to make the nitro compound first and do the reduction to amine using sodium dithionite rather trying to do a one pot conversion from the alkyl nitrite to amine ?


Definetly but if you dont have sulfuric acid to make nitrosyl sulfuric acid and nitrate with that i do not know any other processes then using silver nitrite adn alkyl chloride and the one i posted a reference too.