Polycyclic Heterocycles -

As we saw in Section 15.6, quinoline, isoquinoline, indole, and purine are common polycyclic heterocycles. The first three contain both a benzene ring and a heterocyclic aromatic ring, while purine contains two heterocyclic rings joined together. All four ring systems occur commonly in nature, and many compounds with these rings have pronounced physiological activity. The quinoline alkaloid quinine, for instance, is widely used as an antimalarial drug; tryptophan is a common amino acid; and the purine adenine is a constituent of nucleic acids.
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Quinine (antimalarial)

Tryptophan
(amino acid)
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Polycyclic Heterocycles -

Adenine (DNA constituent)


Polycyclic Heterocycles -

The chemistry of these polycyclic heterocycles is just what you might expect from a knowledge of the simpler heterocycles pyridine and pyrrole. Quinoline and isoquinoline both have basic, pyridine-like nitrogen atoms, and both undergo electrophilic substitutions. As with pyridine, both quinoline and isoquinoline are less reactive toward electrophilic substitution than benzene because of the electronegative nitrogen atom that withdraws electrons from the ring. Reaction occurs on the benzene ring rather than on the nitrogen-containing pyridine ring, and a mixture of substitution products is obtained.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0879.jpg?height=839&width=1142&top_left_y=1185&top_left_x=489)


Polycyclic Heterocycles -

Indole has a nonbasic, pyrrole-like nitrogen and undergoes electrophilic substitution more easily than benzene. Substitution occurs at C3 of the electron-rich pyrrole ring rather than on the benzene ring.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0879.jpg?height=302&width=814&top_left_y=2120&top_left_x=653)


Polycyclic Heterocycles -

Purine has three basic, pyridine-like nitrogens with lone-pair electrons in $s p^{2}$ orbitals in the plane of the ring. The remaining purine nitrogen is nonbasic and pyrrole-like, with its lone-pair electrons as part of the aromatic
$\pi$ electron system.
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![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0880.jpg?height=365&width=445&top_left_y=262&top_left_x=970)


Polycyclic Heterocycles -

Purine
PROBLEM Which nitrogen atom in the hallucinogenic indole alkaloid $N, N$-dimethyltryptamine is more basic? 24-23 Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0880.jpg?height=313&width=525&top_left_y=819&top_left_x=426)


N,N-Dimethyltryptamine -

PROBLEM Indole reacts with electrophiles at C3 rather than at C2. Draw resonance forms of the intermediate 24-24 cations resulting from reaction at C2 and C3, and explain the observed results.


N,N-Dimethyltryptamine - 24.10 Spectroscopy of Amines


Infrared Spectroscopy -

Primary and secondary amines can be identified by a characteristic N-H stretching absorption in the 3300 to $3500 \mathrm{~cm}^{-1}$ range of the IR spectrum. Alcohols also absorb in this range (Section 17.11), but amine absorption bands are generally sharper and less intense than hydroxyl bands. Primary amines show a pair of bands at about 3350 and $3450 \mathrm{~cm}^{-1}$ from the symmetric and asymmetric stretching modes, and secondary amines show a single band at $3350 \mathrm{~cm}^{-1}$. Tertiary amines have no absorption in this region because they have no $\mathrm{N}-\mathrm{H}$ bonds. FIGURE 24.9 recalls the IR spectrum of cyclohexylamine from Section 12.8.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0880.jpg?height=478&width=1394&top_left_y=1713&top_left_x=368)


Infrared Spectroscopy -

FIGURE 24.9 IR spectrum of cyclohexylamine.


Nuclear Magnetic Resonance Spectroscopy -

Amines are difficult to identify solely by ${ }^{1} \mathrm{H}$ NMR spectroscopy because $\mathrm{N}-\mathrm{H}$ hydrogens tend to appear as broad signals without clear-cut coupling to neighboring $\mathrm{C}-\mathrm{H}$ hydrogens. As with $\mathrm{O}-\mathrm{H}$ absorptions (Section 17.11), amine $\mathrm{N}-\mathrm{H}$ absorptions can appear over a wide range and are best identified by adding a small amount of $\mathrm{D}_{2} \mathrm{O}$ to the sample. Exchange of $\mathrm{N}-\mathrm{D}$ for $\mathrm{N}-\mathrm{H}$ occurs, and the $\mathrm{N}-\mathrm{H}$ signal disappears from the NMR spectrum.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0881.jpg?height=120&width=524&top_left_y=189&top_left_x=795)


Hydrogens on the carbon next to nitrogen are deshielded because of the electron-withdrawing effect of the nitrogen, and they therefore absorb further downfield than alkane hydrogens. $N$-Methyl groups are particularly distinctive because they absorb as a sharp three-proton singlet at 2.2 to $2.6 \delta$. This $N$-methyl resonance at 2.42 $\delta$ is easily seen in the ${ }^{1} \mathrm{H}$ NMR spectrum of $N$-methylcyclohexylamine (FIGURE 24.10).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0881.jpg?height=514&width=1405&top_left_y=491&top_left_x=357)


FIGURE 24.10 Proton NMR spectrum of $\boldsymbol{N}$-methylcyclohexylamine.
Carbons next to amine nitrogens are slightly deshielded in the ${ }^{13} \mathrm{C}$ NMR spectrum and absorb about 20 ppm downfield from where they would absorb in an alkane of similar structure. In $N$-methylcyclohexylamine, for example, the ring carbon to which nitrogen is attached absorbs at a position 24 ppm downfield from any other ring carbon.
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PROBLEM Compound $\mathbf{A}, \mathrm{C}_{6} \mathrm{H}_{12} \mathrm{O}$, has an IR absorption at $1715 \mathrm{~cm}^{-1}$ and gives compound $\mathbf{B}, \mathrm{C}_{6} \mathrm{H}_{15} \mathrm{~N}$, when 24-25 treated with ammonia and $\mathrm{NaBH}_{4}$. The IR and ${ }^{1} \mathrm{H}$ NMR spectra of $\mathbf{B}$ are shown. What are the structures of $\mathbf{A}$ and $\mathbf{B}$ ?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0882.jpg?height=1042&width=1408&top_left_y=192&top_left_x=413)


Mass Spectrometry -

The nitrogen rule of mass spectrometry says that a compound with an odd number of nitrogen atoms has an odd-numbered molecular weight. Thus, the presence of nitrogen in a molecule is detected simply by observing its mass spectrum. An odd-numbered molecular ion usually means that the unknown compound has one or three nitrogen atoms, and an even-numbered molecular ion usually means that a compound has either zero or two nitrogen atoms. The logic behind the rule derives from the fact that nitrogen is trivalent, thus requiring an odd number of hydrogen atoms. For example, morphine has the formula $\mathrm{C}_{17} \mathrm{H}_{19} \mathrm{NO}_{3}$ and a molecular weight of 285 amu .


Mass Spectrometry -

Alkylamines undergo a characteristic $\alpha$ cleavage in the mass spectrometer, similar to the cleavage observed for alcohols (Section 17.11). $\mathrm{C}-\mathrm{C}$ bond nearest the nitrogen atom is broken, yielding an alkyl radical and a resonance-stabilized, nitrogen-containing cation.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0882.jpg?height=161&width=1060&top_left_y=1792&top_left_x=527)


Mass Spectrometry -

As an example, the mass spectrum of $N$-ethylpropylamine shown in FIGURE 24.11 has peaks at $m / z=58$ and $m / z=72$, corresponding to the two possible modes of $\alpha$ cleavage.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0883.jpg?height=478&width=1352&top_left_y=192&top_left_x=384)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0883.jpg?height=475&width=1308&top_left_y=695&top_left_x=387)

FIGURE 24.11 Mass spectrum of $N$-ethylpropylamine. The two possible modes of $\alpha$ cleavage lead to the observed fragment ions at $m / z=$ 58 and $m / z=72$.


(8) CHEMISTRY MATTERS -


Green Chemistry II: Ionic Liquids -

Liquids made of ions? Usually when we think of ionic compounds, we think of high-melting solids: sodium chloride, magnesium sulfate, lithium carbonate, and so forth. But yes, there are also ionic compounds that are liquid at room temperature, and they are gaining importance as reaction solvents, particularly for use in green chemistry processes (see the Chapter 11 Chemistry Matters). More than 1500 ionic liquids are known, and about 500 are available commercially.


Green Chemistry II: Ionic Liquids -

Ionic liquids have been studied for nearly a century; the first to be discovered was ethylammonium nitrate, $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{NH}_{3}{ }^{+} \mathrm{NO}_{3}{ }^{-}$, with a melting point of $12{ }^{\circ} \mathrm{C}$. More generally, however, the ionic liquids in use today are salts in which the cation is unsymmetrical and in which one or both of the ions are bulky so that the charges are dispersed over a large volume. Both factors minimize the crystal lattice energy and disfavor formation of the solid. Typical cations are quaternary ammonium ions from heterocyclic amines, either 1,3-dialkylimidazolium ions, $N$-alkylpyridinium ions, or ring-substituted $N$-alkylpyridinium ions.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0884.jpg?height=120&width=649&top_left_y=989&top_left_x=440)


Green Chemistry II: Ionic Liquids -

$$
\left[\begin{array}{rl}
\mathrm{R}= & -\mathrm{CH}_{3},-\mathrm{CH}_{2} \mathrm{CH}_{3},-\mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{3}, \\
& -\mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{3}
\end{array}\right]
$$


Green Chemistry II: Ionic Liquids -


Green Chemistry II: Ionic Liquids -

Anions are just as varied as the cations. Hexafluorophosphate, tetrafluoroborate, alkyl sulfates, trifluoromethanesulfonates (triflates), and halides are some anion possibilities.


Green Chemistry II: Ionic Liquids -

$$
\mathrm{Cl}^{-}, \mathrm{Br}^{-}, \mathrm{I}^{-}
$$


Green Chemistry II: Ionic Liquids -

Trifluoromethane- Halide sulfonate


Green Chemistry II: Ionic Liquids -

Ionic liquids have several important features that make them attractive for use, both as solvents in green chemistry and as specialty chemicals in such applications as paint additives and refrigerants:


Green Chemistry II: Ionic Liquids -

- They dissolve both polar and nonpolar organic compounds, giving high solute concentrations and thereby minimizing the amount of solvent needed.
- They can be optimized for specific reactions by varying cation and anion structures.
- They are nonflammable.
- They are thermally stable.
- They have negligible vapor pressures and do not evaporate.
- They are generally recoverable and can be reused many times.


Green Chemistry II: Ionic Liquids -

As an example of their use in organic chemistry, the analgesic drug pravadoline has been synthesized in two steps using 1-butyl-3-methylimidazolium hexafluorophosphate, abbreviated bmim, as the solvent for both steps. The first step is a base-induced $\mathrm{S}_{\mathrm{N}} 2$ reaction of 2-methylindole with a primary alkyl halide, and the second is a Friedel-Crafts acylation. Both steps take place with $95 \%$ yield, and the ionic solvent is recovered simply by washing the reaction mixture, first with toluene and then with water.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0885.jpg?height=676&width=1426&top_left_y=193&top_left_x=344)


Green Chemistry II: Ionic Liquids -

The first commercial process using an ionic liquid catalyst was introduced by PetroChina in 2008, when they opened a plant producing 65,000 tons per year of alkylate gasoline from isobutane. The aluminum-based ionic liquid catalyst replaced the sulfuric acid and hydrofluoric acid catalysts that had previously been used.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0885.jpg?height=289&width=1359&top_left_y=1013&top_left_x=378)


Key Terms -

- alkylamine
- amine
- arylamine
- azo compound ( $\mathrm{R}-\mathrm{N}=\mathrm{N}-\mathrm{R}^{\prime}$ )
- Curtius rearrangement
- Gabriel amine synthesis
- heterocyclic amine
- Hofmann elimination reaction
- Hofmann rearrangement
- imide $(\mathrm{O}=\mathrm{C}-\mathrm{N}-\mathrm{C}=\mathrm{O})$
- primary amine $\left(\mathrm{RNH}_{2}\right)$
- quaternary ammonium salt
- reductive amination
- Sandmeyer reaction
- secondary amine ( $\mathrm{R}_{2} \mathrm{NH}$ )
- tertiary amine ( $\mathrm{R}_{3} \mathrm{~N}$ )


Key Terms -


Summary -

We've now seen all the common functional groups that occur in organic and biological chemistry. Of those groups, amines are among the most abundant and have among the richest chemistry. In addition to proteins and nucleic acids, the majority of pharmaceutical agents contain amine functional groups and many of the common coenzymes necessary for biological reactions are amines.
Amines are organic derivatives of ammonia. They are named in the IUPAC system either by adding the suffix -amine to the name of the alkyl substituent or by considering the amino group as a substituent on a more complex parent molecule.
The chemistry of amines is dominated by the lone-pair electrons on nitrogen, which makes amines both basic and nucleophilic. The basicity of arylamines is generally lower than that of alkylamines because the nitrogen lone-pair electrons are delocalized by interaction with the aromatic $\pi$ system. Electron-withdrawing substituents on the aromatic ring further weaken the basicity of a substituted aniline, while electron-donating substituents increase basicity. Alkylamines are sufficiently basic that they exist almost entirely in their protonated form at the physiological pH of 7.3.


Summary -

Heterocyclic amines are compounds that contain one or more nitrogen atoms as part of a ring. Saturated
heterocyclic amines usually have the same chemistry as their open-chain analogs, but unsaturated heterocycles such as pyrrole, imidazole, pyridine, and pyrimidine are aromatic. All four are unusually stable, and all undergo aromatic substitution on reaction with electrophiles. Pyrrole is nonbasic because its nitrogen lone-pair electrons are part of the aromatic $\pi$ system. Fused-ring heterocycles such as quinoline, isoquinoline, indole, and purine are also commonly found in biological molecules.


Summary -

Arylamines are prepared by nitration of an aromatic ring followed by reduction. Alkylamines are prepared by $\mathrm{S}_{\mathrm{N}} 2$ reaction of ammonia or an amine with an alkyl halide or by the Gabriel amine synthesis. Amines can also be prepared by a number of reductive methods, including $\mathrm{LiAlH}_{4}$ reduction of amides, nitriles, and azides. Also important is the reductive amination reaction in which a ketone or an aldehyde is treated with an amine in the presence of a reducing agent such as $\mathrm{NaBH}_{4}$. In addition, amines result from Hofmann and Curtius rearrangements of carboxylic acid derivatives. Both methods involve migration of the -R group bonded to the carbonyl carbon and yield a product that has one less carbon atom than the starting material.


Summary -

Many of the reactions of amines are familiar from past chapters. Thus, amines react with alkyl halides in $\mathrm{S}_{\mathrm{N}} 2$ reactions and with acid chlorides in nucleophilic acyl substitution reactions. Amines also undergo E2 elimination to yield alkenes if they are first quaternized by treatment with iodomethane and then heated with silver oxide, a process called the Hofmann elimination.


Summary -

Arylamines are converted by diazotization with nitrous acid into arenediazonium salts, $\mathrm{ArN}_{2}{ }^{+} \mathrm{X}^{-}$. The diazonio group can then be replaced by many other substituents by the Sandmeyer reaction to give a wide variety of substituted aromatic compounds. Aryl chlorides, bromides, iodides, and nitriles can be prepared from arenediazonium salts, as can arenes and phenols. In addition to their reactivity toward substitution reactions, diazonium salts undergo coupling with phenols and arylamines to give brightly colored azo compounds.


Summary of Reactions -

1. Synthesis of amines (Section 24.6)
a. Reduction of nitriles


Summary of Reactions -

$$
\mathrm{RCH}_{2} \mathrm{X} \xrightarrow{\mathrm{NaCN}} \mathrm{RCH}_{2} \mathrm{C} \equiv \mathrm{~N} \xrightarrow[\text { 2. } \mathrm{H}_{2} \mathrm{O}]{\text { 1. } \mathrm{LiAlH}_{4} \text {, ether }} \underset{\mathrm{RCH}_{2}}{\text { - }}
$$


Summary of Reactions -

b. Reduction of amides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0886.jpg?height=134&width=605&top_left_y=1521&top_left_x=806)
c. Reduction of nitrobenzenes
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0886.jpg?height=150&width=684&top_left_y=1695&top_left_x=769)
d. $\mathrm{S}_{\mathrm{N}} 2$ Alkylation of alkyl halides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0886.jpg?height=351&width=1185&top_left_y=1890&top_left_x=519)
e. Gabriel amine synthesis
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0886.jpg?height=234&width=977&top_left_y=2282&top_left_x=623)
f. Reduction of azides


Summary of Reactions -

$$
\mathrm{RCH}_{2}-\mathrm{X} \xrightarrow[\text { ethanol }]{\mathrm{Na}^{+}{ }^{-} \mathrm{N}_{3}} \quad \mathrm{RCH}_{2}-\mathrm{N}=\stackrel{+}{\mathrm{N}}=\stackrel{-}{\mathrm{N}} \quad \xrightarrow[2 . \mathrm{H}_{2} \mathrm{O}]{\text { 1. } \mathrm{LiAlH}_{4} \text {, ether }} \quad \mathrm{R}-\mathrm{CH}_{2}-\mathrm{NH}_{2}
$$


Summary of Reactions -

g. Reductive amination of aldehydes/ketones
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0887.jpg?height=123&width=459&top_left_y=372&top_left_x=882)
h. Hofmann rearrangement of amides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0887.jpg?height=131&width=646&top_left_y=544&top_left_x=786)
i. Curtius rearrangement of acyl azides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0887.jpg?height=123&width=1104&top_left_y=725&top_left_x=559)
2. Reactions of amines
a. Alkylation with alkyl halides; see reaction 1(d)
b. Hofmann elimination (Section 24.7)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0887.jpg?height=153&width=567&top_left_y=997&top_left_x=833)
c. Diazotization (Section 24.8)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0887.jpg?height=164&width=1004&top_left_y=1200&top_left_x=607)
3. Reactions of arenediazonium salts (Section 24.8)
a. Nucleophilic substitutions
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0887.jpg?height=177&width=324&top_left_y=1467&top_left_x=1017)


Summary of Reactions -

| HCl
 CuCl | HBr
 CuBr | NaI | KCN
 CuCN | $\mathrm{Cu}_{2} \mathrm{O}, \mathrm{H}_{2} \mathrm{O}$
 $\mathrm{Cu}\left(\mathrm{NO}_{3}\right)_{2}$ |
| :--- | :--- | :--- | :--- | :--- | $\mathrm{H}_{3} \mathrm{PO}_{2}$


Summary of Reactions -


Additional Problems -


Visualizing Chemistry -

PROBLEM Name the following amines, and identify each as primary, secondary, or tertiary:


Visualizing Chemistry -


Visualizing Chemistry -

PROBLEM The following compound contains three nitrogen atoms. Rank them in order of increasing basicity.
24-27
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0888.jpg?height=453&width=584&top_left_y=1210&top_left_x=413)