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Chemistry Forums for Students => Organic Chemistry Forum => Topic started by: GinaTageldin on October 22, 2017, 01:58:04 AM

Title: Addition rx by isocyanates on amino group
Post by: GinaTageldin on October 22, 2017, 01:58:04 AM
Is it easy to add isocyanates or isothiocyanate derivatives on the amino group of 2-amino-4,6-dichloropyrimdine or it is difficult since tautomerism can be occurred to imino form?? any conditions for this rx?
Title: Re: Addition rx by isocyanates on amino group
Post by: pgk on October 23, 2017, 11:37:15 AM
Aromatic conjugation decreases the nucleophilicity of amines and thus, the condensation with isocyanates will possibly be slower.  But for safety reasons, work in adequate dilution at room temperature and avoid heating.
Title: Re: Addition rx by isocyanates on amino group
Post by: GinaTageldin on October 26, 2017, 09:31:21 PM
Aromatic conjugation decreases the nucleophilicity of amines and thus, the condensation with isocyanates will possibly be slower.  But for safety reasons, work in adequate dilution at room temperature and avoid heating.
Sir, what did you mean by safety reasons? i didn't use isocyanates before and what about work in adequate dilution at room temperature and avoid heating? Thank you so much
Title: Re: Addition rx by isocyanates on amino group
Post by: wildfyr on October 27, 2017, 02:22:36 AM
Isocyanates react quite vigorously it is an exothermic reaction, which can cause thermal runaway leading to explosions, damaged materials, or a ruined reaction.

Dilutions and cooling can help avoid this issue.
Title: Re: Addition rx by isocyanates on amino group
Post by: GinaTageldin on October 27, 2017, 04:55:28 AM
Isocyanates react quite vigorously it is an exothermic reaction, which can cause thermal runaway leading to explosions, damaged materials, or a ruined reaction.

Dilutions and cooling can help avoid this issue.
Ahh, i got it now. Thank you Sir
Title: Re: Addition rx by isocyanates on amino group
Post by: rolnor on October 27, 2017, 05:28:42 AM
I dont understand, they are not more reactive than for example acid chlorides?
Title: Re: Addition rx by isocyanates on amino group
Post by: pgk on October 27, 2017, 09:04:19 AM
The reaction of aliphatic isocyanates with amines is instant; in contrast to aromatic isocyanates that delay their condensation with amines for a few minutes, due to the aromatic resonance, the electron attractor character of any o-,p-substituents and the steric hindrance of any o-substituents.
Title: Re: Addition rx by isocyanates on amino group
Post by: rolnor on October 27, 2017, 09:59:53 AM
The reaction between acid chlorides and amines are also instant? There is something wrong talking about these reactions as they are more dangerous than normal chemical reactions, there is nothing special about isocyanates or isothiocyanates, I have done dozens of this type of reactions, there is no problem at all.
Title: Re: Addition rx by isocyanates on amino group
Post by: pgk on October 27, 2017, 10:36:50 AM
Isothiocyanates are quite less reactive than isocyanates with amines.
Title: Re: Addition rx by isocyanates on amino group
Post by: rolnor on October 27, 2017, 11:02:00 AM
I have worked with both isocyanates and isothiocyanates and condensate them with both aliphatic and aromatic amines, there is nothing special at all.
Title: Re: Addition rx by isocyanates on amino group
Post by: pgk on October 27, 2017, 11:09:24 AM
Yes, if you work in adequate dilution and by gradual addition of the reagents.
Title: Re: Addition rx by isocyanates on amino group
Post by: rolnor on October 27, 2017, 12:41:09 PM
There seems to be a problem here, have you yourself worked with these type of reactions pgk? Do you yourself dilute this reactions more then you do otherwise?
Title: Re: Addition rx by isocyanates on amino group
Post by: pgk on October 27, 2017, 01:02:39 PM
Yes, because I have worked with these type of reactions in polymers and thus, in high "dilution" due to the high molecular weight. Nevertheless, I had got serious exothermic problems with short polymer chains and polyamines.
Title: Re: Addition rx by isocyanates on amino group
Post by: rolnor on October 27, 2017, 02:59:59 PM
Maybe you are working on a much larger scale then I have done, I do not have any problems of this sort.
Title: Re: Addition rx by isocyanates on amino group
Post by: hypervalent_iodine on October 27, 2017, 09:59:58 PM
Maybe you are working on a much larger scale then I have done, I do not have any problems of this sort.

Neither have I, though I work with amines similar to the OP and they tend not to be very reactive. That being said, others in my group working on separate projects have worked with aliphatic amines and isocyanates and the procedure they normally use is reflux in toluene. Probably a difference in scale, as you say.
Title: Re: Addition rx by isocyanates on amino group
Post by: pgk on October 28, 2017, 06:04:05 AM
Indeeed, I work in larger scales than usual. However, aliphatic isocyanates are less reactive than aromatic ones. But I cannot know whether the OP will use aliphatic or aromatic isocyanates. So, I have to warn the OP for the worst.