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Topic: Basicity of Cyclic Amines  (Read 4848 times)

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Offline AlbertoA

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Basicity of Cyclic Amines
« on: October 15, 2011, 06:18:46 PM »
let's consider the (Me)2NH3+ pKa=10.7
piperidineH+ pKa =11.2
pyrrolidineH+ pKa= 11.3

although the 3 amines are secondary, the pyrrolidine is more basic, it is a five member ring, so, I think that the angle strain is a factor but I'm not shure how that applies to the acyclic amine

Offline fledarmus

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Re: Basicity of Cyclic Amines
« Reply #1 on: October 15, 2011, 06:43:30 PM »
Diethylamine is actually a better comparator than dimethylamine - most of the difference between dimethyl amine and either of the other two can be accounted for by the difference in electronics between a methyl group and a higher chain alkane. My table shows 11.02 for diethylamine, 11.13 for piperidine, and 11.27 for pyrrolidine. (10.68 for dimethylamine). I believe the remaining differences can be accounted for by the difference in axial interactions in the two rings for lone pairs and protons.

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