23.1: Amines Compared with Alcohols

Last updated
Save as PDF

Page ID: 22336

\( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \) \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)\(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\) \(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\)\(\newcommand{\AA}{\unicode[.8,0]{x212B}}\)

As you read the chapter you will realize a similarity between the chemistry of amines and the chemistry of alcohols, which we discussed in Chapter 15. Primary amines \(\left( \ce{RNH_2} \right)\) and secondary amines \(\left( \ce{R_2NH} \right)\) are much weaker acids than alcohols \(\left( \ce{ROH} \right)\) and form strongly basic anions:

Acids

Roberts and Caserio Screenshot 23-1-1.jpg

Amines, like alcohols, have nonbonding electrons that impart basic and nucleophilic properties:

Bases

Roberts and Caserio Screenshot 23-1-2.png

Nucleophiles

Roberts and Caserio Screenshot 23-1-3.png

Also, amines and alcohols both can behave as carbon electrophiles under appropriate reaction conditions such that cleavage of \(\ce{C-N}\) and \(\ce{C-O}\) bonds occurs in the sense \(\overset{\delta \oplus}{\ce{C}} \vdots \overset{\delta \ominus}{\ce{N}}\) and \(\overset{\delta \oplus}{\ce{C}} \vdots \overset{\delta \ominus}{\ce{O}}\). However, because \(\ce{-NH_2}\) and \(\ce{-OH}\) both are poor leaving groups, each must be suitably activated to make this kind of reaction possible (see Section 8-7C). The \(\ce{OH}\) group can be activated by addition of a proton or conversion to a sulfonate ester, \(\ce{RO_3SR'}\), but these processes generally are ineffective for \(\ce{RNH_2}\). The most effective activation for \(\ce{RNH_2}\) is through conversion with nitrous acid, \(\ce{HONO}\), to \(\ce{R}- \overset{\oplus}{\ce{N}} \equiv \ce{N}\); then \(\ce{N_2}\) is the leaving group (this reaction is described in more detail in Section 23-10A):

\[\ce{R-OH} \overset{\ce{HBr}}{\longrightarrow} \ce{R-Br} + \ce{H_2O}\]

There is, though a major difference in the way that amines and alcohols behave toward oxidizing agents. Amines genearlly show more complex behavior on oxidation because, as we shall see, nitrogen has a larger number of stable oxidation states than oxygen.

Contributors and Attributions

John D. Robert and Marjorie C. Caserio (1977) Basic Principles of Organic Chemistry, second edition. W. A. Benjamin, Inc. , Menlo Park, CA. ISBN 0-8053-8329-8. This content is copyrighted under the following conditions, "You are granted permission for individual, educational, research and non-commercial reproduction, distribution, display and performance of this work in any format."