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Author: Subject: nitrile synthesis from aldehydes, amines, and alcohols
chemist1243
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[*] posted on 17-1-2020 at 05:51
nitrile synthesis from aldehydes, amines, and alcohols


i have a source stating that alcohols, aldehydes, and primary amines can be converted to Nitriles in 'excellent' yields. this is done by a 15M ammonia solution combined with an aldehyde, for example. the solution is heated at 60C for 2 hours, while a .75 equivalent TCCA is added in small portions.

if this holds true, then great. the only problem is the formation of toxic chloramines due to the TCCA ammonia reaction. is there a way to safely handle this? id assume you need very good ventilation along with a chem proof gas mask? how toxic are the chloramines? how would one dispose of the remaining reaction mixture safely once the nitrile has been isolated and collected?

https://www.organic-chemistry.org/synthesis/C3N/nitriles.sht...

[Edited on 17-1-2020 by chemist1243]

[Edited on 17-1-2020 by chemist1243]
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karlos³
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[*] posted on 17-1-2020 at 06:00


The real problem here is the formation of NCl3, which is, unlike NI3, explosive even in aqueous solution.
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[*] posted on 17-1-2020 at 06:44


Quote: Originally posted by karlos³  
The real problem here is the formation of NCl3, which is, unlike NI3, explosive even in aqueous solution.


ahh. good to know. ive also heard of a method using iodine in ammonia solution. said to work on aldehydes apparently. what do you think about this? the poster said it works in good yields, and the NI3 is, as you said, harmless in solution.
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[*] posted on 17-1-2020 at 07:28


I am the same poster on here who told you about this, I believe.
Important for the method using iodine in ammonia is the co-solvent, dioxane or THF, since the aldehyde you have in mind is not soluble otherwise.
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[*] posted on 17-1-2020 at 08:18


Quote: Originally posted by karlos³  
I am the same poster on here who told you about this, I believe.
Important for the method using iodine in ammonia is the co-solvent, dioxane or THF, since the aldehyde you have in mind is not soluble otherwise.


oh hey! could DMSO be used as a cosolvent? also, what are the products? i would assume its balanced like this:
2NH3+2I2+2RCOH ---------> 2RCN+2H2O+4HI

idk, let me know the ratios if im wrong.
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[*] posted on 17-1-2020 at 08:30


You need an ether as co-solvent.
Here is the paper: https://sci-hub.se/10.1016/S0040-4039(00)02195-X
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[*] posted on 17-1-2020 at 08:43


Quote: Originally posted by karlos³  
You need an ether as co-solvent.
Here is the paper: https://sci-hub.se/10.1016/S0040-4039(00)02195-X


thank you so much, this helps tremendously!
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[*] posted on 18-1-2020 at 03:42


You'd better use Hidroxylamine and DMSO to convert Aldehydes into nitriles. Ammonia and TCCA or Iodine generally works, but only for microscale amounts. It's very dangerous at high scale amounts cause the explosive NCl3 or NI3 also generated. See this procedure below, that is safer for what you're looking for:





Attachment: aldehydes to nitriles - NH2OH + DMSO.PDF (215kB)
This file has been downloaded 44 times

[Edited on 18-1-2020 by Chemi Pharma]
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[*] posted on 18-1-2020 at 04:23


It is not dangerous in case of NI3, because that is not a problem in aqueous solutions, unlike NCl3.
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[*] posted on 18-1-2020 at 07:25


Chemplayer made a video entitled "NITROGEN TRIIODIDE (ALDEHYDE TO NITRILE?)": https://www.bitchute.com/video/fg5qVRkJGbZn/

Here's their reference: https://sci-hub.tw/10.1016/S0040-4039(00)02195-X

(Sorry, just realised this same paper was linked above already)

[Edited on 18-1-2020 by DavidJR]
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[*] posted on 29-1-2020 at 08:59


Quote: Originally posted by Chemi Pharma  
You'd better use Hidroxylamine and DMSO to convert Aldehydes into nitriles. Ammonia and TCCA or Iodine generally works, but only for microscale amounts. It's very dangerous at high scale amounts cause the explosive NCl3 or NI3 also generated. See this procedure below, that is safer for what you're looking for:







[Edited on 18-1-2020 by Chemi Pharma]


eh, i dont wanna do any TCCA/ammonia anymore because thatll form NCl3. i've also heard about hydroxylamine exploding when heated? is that true? i havent heard of this actually happening but people claim that it can.
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[*] posted on 29-1-2020 at 13:34


Quote: Originally posted by chemist1243  
Quote: Originally posted by Chemi Pharma  
You'd better use Hidroxylamine and DMSO to convert Aldehydes into nitriles. Ammonia and TCCA or Iodine generally works, but only for microscale amounts. It's very dangerous at high scale amounts cause the explosive NCl3 or NI3 also generated. See this procedure below, that is safer for what you're looking for:







[Edited on 18-1-2020 by Chemi Pharma]


eh, i dont wanna do any TCCA/ammonia anymore because thatll form NCl3. i've also heard about hydroxylamine exploding when heated? is that true? i havent heard of this actually happening but people claim that it can.


Hydroxylamine only presents instability when heated at high temperatures in the pure form (the base) and even can decompose into a explosive way, but if you have read the paper I brought you can see that what's used is hydroxylamine hydrochloride, a stable salt form, even if heated, and look, 100ºC is not a so high temperature to get a runaway, isn't it?
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[*] posted on 29-1-2020 at 13:50


Quote: Originally posted by karlos³  
It is not dangerous in case of NI3, because that is not a problem in aqueous solutions, unlike NCl3.


But we must be careful with NI3 black powder Karlos. It's true that offers no danger while wet, but I never forget a long time ago I did NI3 to play around and have fun looking cars passing and exploding the powder I have spread on the street in front of my home when I was a teenager, and the nice purple clouds that have formed. The problem was I haven't cleaned well the round bottom glass I've used and some fine powder remained left. At night I woke up scared with the noise of it exploding alone at my home lab. I don't need to say I had to listen a lot from my father (heh, heh).
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