clearly_not_atara
International Hazard
Posts: 2792
Registered: 3-11-2013
Member Is Offline
Mood: Big
|
|
Interaction between NaBH4 and CuCN in acetonitrile-water?
Copper cyanide is insoluble in water but appears to have significant solubility in mixtures of acetonitrile and water. See attached.
It is my impression that the interaction of dissolved CuCN with an equimolar amount of NaBH4 should be as follows:
2 CuCN + 2 NaBH4 >> 2 Cu (s) + H2 (g) + 2 NaBH3CN
If the solution containing CuCN is added slowly to the solution containing NaBH4 there should be little opportunity for over-oxidation of the
borohydride. The reaction is probably quite exothermic (∆V ≈ 0.4 V, 0.4 eV/molecule = 38 kJ/mol). It may also be possible to use CuCN in aqueous
NH3.
This would allow the preparation of cyanoborohydrides without the use of any volatile cyanides, but the use of cyanoborohydride is still dangerous.
Attachment: kurnia1996.pdf (550kB)
This file has been downloaded 60 times
|
|
|
walruslover69
Hazard to Others
Posts: 233
Registered: 21-12-2017
Member Is Offline
Mood: No Mood
|
|
This would be very interesting if feasible. The only reservation I might have is the copper nanoparticles that you generate during the initial
reduction are usually quite catalytic and might cause decomposition of the NaBH3CN. That's only a hunch. I think this idea is definitely worth
exploring as it would be a significant improvement over other ways of generating NaBH3CN.
How do you plan to isolate the formed cyanoborohydride?
|
|
|
Taba
Harmless
Posts: 5
Registered: 9-3-2014
Member Is Offline
Mood: No Mood
|
|
Depending on what you are trying to reduce you can also use acetylated versions of Borohydride instead of Cyanoborohydride.
Sodium triacetoxyborohydride for example is a bit weaker than Cyanoborohydride, but will still do reductive aminations.
The main advantage of using for example Sodium triacetoxyborohydride is that you are less likely to kill yourself and the synthesis is much easier.
|
|
|
Random
International Hazard
Posts: 1120
Registered: 7-5-2010
Location: In ur closet
Member Is Offline
Mood: Energetic
|
|
Quote: Originally posted by Taba  | Depending on what you are trying to reduce you can also use acetylated versions of Borohydride instead of Cyanoborohydride.
Sodium triacetoxyborohydride for example is a bit weaker than Cyanoborohydride, but will still do reductive aminations.
The main advantage of using for example Sodium triacetoxyborohydride is that you are less likely to kill yourself and the synthesis is much easier.
|
I was more scared of some toxic chemicals when I was 14 inside 2010.
|
|
|
clearly_not_atara
International Hazard
Posts: 2792
Registered: 3-11-2013
Member Is Offline
Mood: Big
|
|
| Quote: Originally posted by Taba | | Depending on what you are trying to reduce you can also use acetylated versions of Borohydride instead of Cyanoborohydride. |
I was originally interested in NaBH3CN for the conversion of aldehydes to primary amines in Dangerfield et al (attached), but then I realized that the
reason they used NaBH3CN was probably because the substrate has an alkene and they wanted to avoid reducing the alkene.
So I posted this thread and then decided it probably wasn't necessary 
Attachment: dangerfield2010.pdf (993kB)
This file has been downloaded 56 times
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
