Which amine is more nucleophilic

In the presence of excess ethylamine in the mixture, there is the possibility of a reversible reaction. The ethylamine removes a hydrogen from the diethylammonium ion to give free diethylamine - a secondary amine.

But it doesn't stop here! The diethylamine also reacts with bromoethane - in the same two stages as before. This is where the reaction would start if you reacted a secondary amine with a halogenoalkane.

There is again the possibility of a reversible reaction between this salt and excess ethylamine in the mixture. The ethylamine removes a hydrogen ion from the triethylammonium ion to leave a tertiary amine - triethylamine. The final stage! The triethylamine reacts with bromoethane to give tetraethylammonium bromide - a quaternary ammonium salt one in which all four hydrogens have been replaced by alkyl groups.

This time there isn't any hydrogen left on the nitrogen to be removed. The reaction stops here. Compare the nucleophilicity of piperidine The electron-withdrawing oxygen has the effect of reducing nucleophilicity by a factor of The Mayr parameters for t -butylamine, isopropylamine and n- propylamine show a clear trend, going from in water as solvent The measured set of nucleophilicity parameters give an estimate that hydroxylamine is about times more nucleophilic than ammonia in water , while hydrazine is about 10, times more nucleophilic.

Useful tidbit: never, ever use CH 2 Cl 2 or chloroform as solvent for any reaction involving the azide ion. The azide ion is so nucleophilic it will displace the chlorides, leading to the formation of a potentially explosive diazidomethane. Conspicuously absent from this whole discussion has been the question of tertiary amines. So are tertiary amines better or worse nucleophiles than secondary amines? In acetonitrile, it looks like tertiary amines are at least one, if not two orders of magnitude more nucleophilic than comparable secondary amines.

The nucleophilicity paramter of quninuclidine in acetonitrile is A caveat: Remember that the Mayr parameters work best with non sterically hindered electrophiles. So expect the reaction rate of a tertiary amine with a hindered electrophile to fall off a cliff, relative to a less hindered electrophile. Sometime in the future we can address hard soft acid base HSAB theory. On the other hand, at a lecture I saw Mayr give once on his reactivity tables, he was asked where hard and soft acid-base theory effects were in his data.

First, I think the blog is fantastic. Sometimes there is a turn of phrase or a description that helps when thinking about something differently, making it all the clearer. Second, here are a couple of papers from Mayr relating to, specifically, the alpha effect and HSAB for interest. In order for the lone pair to donate into the aromatic ring, it has to adopt a conformation where the substituents on nitrogen are in the same plane as the aromatic ring.

As steric bulk increases on the nitrogen, this conformation will become less favorable due to allylic strain. I have a question about the using N-methyl hydrazine as a nucleophile.

Both nitrogens experience the alpha effect from each other, right? Which of the two nitrogens is more nucleophilic then? Hello I have the task where tertiary anime reacts with 3-clorpentane. So if I am correct it is an SN2 reaction ant the product will be amonium salt.

But I am not sure why the reaction rate would increase if we replace solvents in this order: Tertiary-buthanol, ethanol, methanol and water? If you could help me I would be very grateful :. Think about the influence of solubility on reaction rate and how each of those solvents will affect the solubility of a tertiary amine. What can be done to increase the nucleophilicity of amines?

Very good explanation but could you clarify the influence of H2O in section about quantifying nucleophilicity? Water is polar protic solvent so why should the nucleophilicity of the amines NH3 vs secondary vs tertiary increase in water?

The nucleophilicity will certainly be solvent dependent. If you look at the tables from Mayr they all specify solvent and only should be compared directly when the numbers were obtained in the same solvent. Hydrogen bonding is one factor, but so is the increased electron density that comes with additional alkyl groups. Making a measurement is the best way to sort it all out. Hi James, I routinely conjugate proteins via their primary amines to substrates and tags containing NHS esters at pH 7.

It just occurred to me that at pH 7. How can the positively charged, protonated amine act as a nucleophile?? Thanks in advance, and I love reading your page! The pKa values you cite are for the conjugate acids of the amines, not the amines themselves. The neutral amines will not be protonated to any appreciable extent until pH4 or below, and even then they will be in equilibrium.

I am stuck with carrying out a nucleophilic substitution reaction of triethylamine with chloride atoms in Polyvinyl chloride. Could you gove some ideas please? Hi Guillaume — nitriles or cyanide ion? Nitriles themselves are really bad nucleophiles and will only work in Ritter-type reactions where they are reacting with an extremely good electrophile.

Tetrahedron , 75 33 , Site-selective phenol acylation mediated by thioacids via visible light photoredox catalysis. Organic Chemistry Frontiers , 5 8 , Charge transport and dipolar relaxations in phosphonium-based ionic liquids. The Journal of Chemical Physics , 23 , Green and highly efficient synthesis of perylene and naphthalene bisimides in nothing but water. Chemical Communications , 53 7 , Regioselective synthesis of cationic 6-deoxy N,N,N-trialkylammonio curdlan derivatives.

Carbohydrate Polymers , , The underlying mechanisms for self-healing of poly disulfide s. Physical Chemistry Chemical Physics , 18 39 , Lange , Stefan Verhoog , Hans J. Sanders , Arnold van Loevezijn , Chris G. A novel atom-efficient, one-pot synthesis of sulfonylguanidines and sulfamoylguanidines. Tetrahedron Letters , 52 25 , Menschutkin Reaction.

Fanwick , Hicham Fenniri. The Journal of Organic Chemistry , 73 3 , Suryanarayana , B. Saikia , I. Hydrogen bond formation between aliphatic alcohols and tertiary amines. Benzylamine and Dibenzylamine Revisited.

Synthetic Communications , 13 2 , Journal of Organometallic Chemistry , 1 , CC