Functional Group Names, Properties, and Reactions

Functional Groups
Functional groups refer to specific atoms bonded in a certain arrangement that give a compound certain
physical and chemical properties.
LEARNING OBJECTIVES
Define the term “functional group” as it applies to organic molecules
KEY TAKEAWAYS

Key Points
 Functional groups are often used to “functionalize” a compound, affording it different physical
and chemical properties than it would have in its original form.
 Functional groups will undergo the same type of reactions regardless of the compound of which
they are a part; however, the presence of certain functional groups within close proximity can limit
reactivity.
 Functional groups can be used to distinguish similar compounds from each other.

Key Terms
 functional group: A specific grouping of elements that is characteristic of a class of compounds,
and determines some properties and reactions of that class.
 functionalization: Addition of specific functional groups to afford the compound new, desirable
properties.

The Role of Functional Groups

In organic chemistry, a functional group is a specific group of atoms or bonds within a compound that is
responsible for the characteristic chemical reactions of that compound. The same functional group will
behave in a similar fashion, by undergoing similar reactions, regardless of the compound of which it is a
part. Functional groups also play an important part in organic compound nomenclature; combining the
names of the functional groups with the names of the parent alkanes provides a way to distinguish
compounds.
The atoms of a functional group are linked together and to the rest of the compound by covalent bonds. The
first carbon atom that attaches to the functional group is referred to as the alpha carbon; the second, the beta
carbon; the third, the gamma carbon, etc. Similarly, a functional group can be referred to as primary,
secondary, or tertiary, depending on if it is attached to one, two, or three carbon atoms.

Classification of alcohols: Alcohols are a common functional group (-OH). They can be classified as
primary, secondary, or tertiary, depending on how many carbon atoms the central carbon is attached to.
Functional Groups and Reactivity
Functional groups play a significant role in directing and controlling organic reactions. Alkyl chains are
often nonreactive, and the direction of site-specific reactions is difficult; unsaturated alkyl chains with the
presence of functional groups allow for higher reactivity and specificity. Often, compounds are
functionalized with specific groups for a specific chemical reaction. Functionalization refers to the addition
of functional groups to a compound by chemical synthesis. Through routine synthesis methods, any kind of
organic compound can be attached to the surface. In materials science, functionalization is employed to
achieve desired surface properties; functional groups can also be used to covalently link functional
molecules to the surfaces of chemical devices.
In organic chemistry, the most common functional groups are carbonyls (C=O), alcohols (-OH), carboxylic
acids (CO2H), esters (CO2R), and amines (NH2). It is important to be able to recognize the functional groups
and the physical and chemical properties that they afford compounds.

Organic chemistry functional groups lesson: This video provides a great overview of the various
functional groups in organic chemistry.

Alcohols
Alcohols are functional groups characterized by the presence of an -OH group.
LEARNING OBJECTIVES
Identify the general properties of the alcohol functional group
KEY TAKEAWAYS

Key Points
 Due to the presence of an -OH group, alcohols can hydrogen bond. This leads to higher boiling
points compared to their parent alkanes.
 Alcohols are polar in nature. This is attributed to the difference in electronegativity between the
carbon and the oxygen atoms.
 In chemical reactions, alcohols often cannot leave the molecule on their own; to leave, they often
become protonated to water, which is a better leaving group. Alcohols also can become
deprotonated in the presence of a strong base.

Key Terms
 alkane: Any of the saturated hydrocarbons—including methane, ethane, and compounds with long
carbon chain known as paraffins, etc.— that have a chemical formula of the form CnH2n+2.
 aldehyde: Any of a large class of reactive organic compounds (R·CHO) having a carbonyl
functional group attached to one hydrocarbon radical and a hydrogen atom.
 carboxylic acid: Any of a class of organic compounds containing a carboxyl functional group—a
carbon with a double bond to an oxygen and a single bond to another oxygen, which is in turn
bonded to a hydrogen.
 leaving group: In organic chemistry, the species that leaves the parent molecule following a
substitution reaction.
Alcohols are organic compounds in which the hydroxyl functional group (-OH) is bound to a carbon atom.
Alcohols are an important class of molecules with many scientific, medical, and industrial uses.

Nomenclature of Alcohols

According to the IUPAC nomenclature system, an alcohol is named by dropping the terminal “-e” of the
parent carbon chain (alkane, alkene, or alkyne in most cases) and the addition of “-ol” as the ending. If the
location of the hydroxyl group must be specified, a number is inserted between the parent alkane name and
the “-ol” (propan-1-ol) or before the IUPAC name (1-propanol). If a higher priority group is present, such as
an aldehyde, ketone or carboxylic acid, then it is necessary to use the prefix “hydroxy-” instead of the
ending “-ol.”
Alcohols are classified as primary, secondary, or tertiary, based upon the number of carbon atoms connected
to the carbon atom that bears the hydroxyl group.

The alcohol functional group: Alcohols are characterized by the presence of an -OH group, which is
generally in a bent shape, like that of water.

Structure and Physical Properties of Alcohols

The structure of an alcohol is similar to that of water, as it has a bent shape. This geometrical arrangement
reflects the effect of electron repulsion and the increasing steric bulk of the substituents on the central
oxygen atom. Like water, alcohols are polar, containing an unsymmetrical distribution of charge between
the oxygen and hydrogen atoms. The high electronegativity of the oxygen compared to carbon leads to the
shortening and strengthening of the -OH bond. The presence of the -OH groups allows for hydrogen
bonding with other -OH groups, hydrogen atoms, and other molecules. Since alcohols are able to hydrogen
bond, their boiling points are higher than those of their parent molecules.

Alcohols are able to participate in many chemical reactions. They often undergo deprotonation in the
presence of a strong base. This weak acid behavior results in the formation in an alkoxide salt and a water
molecule. Hydroxyl groups alone are not considered good leaving groups. Often, their participation in
nucleophilic substitution reactions is instigated by the protonation of the oxygen atom, leading to the
formation a water moiety—a better leaving group. Alcohols can react with carboxylic acids to form an ester,
and they can be oxidized to aldehydes or carboxylic acids.

Alcohols have many uses in our everyday world. They are found in beverages, antifreeze, antiseptics, and
fuels. They can be used as preservatives for specimens in science, and they can be used in industry as
reagents and solvents because they display an ability to dissolve both polar and non-polar substances.

Ethers

Ethers are a class of organic compounds characterized by an oxygen atom connected to two alkyl or aryl
groups.

Learning Objectives

Define the term “ether” as it relates to organic compounds

Key Takeaways

Key Points

 Ethers have relatively low boiling points due to their inability to form hydrogen bonds with each
other.
 Due to the electronegativity difference between the oxygen and carbon atoms of an ether, the
molecule is slightly polar.
 Although they have low reactivity overall, the two lone pairs of electrons on the oxygen atom do
afford the ether molecule some reactivity; the ether molecule is subject to reacting with strong acids
and serves as a Lewis base.
Key Terms

 alkene: An unsaturated, aliphatic hydrocarbon with one or more carbon–carbon double bond.
 ester: A compound most often formed by the condensation of an alcohol and an acid, with elimination
of water. It contains the functional group C=O joined via carbon to another oxygen atom.
 ether: Compound containing an oxygen atom bonded to two hydrocarbon groups.
 amide: Any derivative of an oxoacid in which the hydroxyl group has been replaced with an amino or
substituted amino group; especially such derivatives of a carboxylic acid, the carboxamides.

Structure of Ethers

Ethers are a class of organic compounds that contain an ether group. An ether group is an oxygen atom
connected to two alkyl or aryl groups. They follow the general formula R-O-R’. The C-O-C linkage is
characterized by bond angles of 104.5 degrees, with the C-O distances being about 140 pm. The oxygen of
the ether is more electronegative than the carbons. Thus, the alpha hydrogens are more acidic than in regular
hydrocarbon chains.

Ethers: The general structure of an ether. An ether is characterized by an oxygen bonded to two alkyl or aryl
groups, represented here by R and R’. The substituents can be, but do not need to be, the same.

Nomenclature of Ethers

There are two ways to name ethers. The most common way is to identify the alkyl groups on either side of
the oxygen atom in alphabetical order, then write “ether.” For example, ethyl methyl ether is the ether that
has an ethyl group and a methyl group on either side of the oxygen atom. If the two alkyl groups are
identical, the ether is called di[alkyl] ether. For example, diethyl ether is the ether with an ethyl group on
each side of the oxygen atom.

The other way of naming ethers is the formal, IUPAC method. This way, the form is: [short alkyl chain]
[oxy][long alkyl chain]. For example, the IUPAC name for ethyl methyl ether would be methoxyethane.

In cyclic ethers, the stem of the compound is known as a oxacycloalkane. The “oxa” is an indicator of the
replacement of the carbon by an oxygen in the ring. An example is oxacyclopentane, a five-membered ring
in which there are four carbon atoms and one oxygen atom.
Tetrahydrofuran (THF): The common name of the cyclic ether “oxacyclopentane” is tetrahydrofuran, or
THF. It is a common organic solvent that is miscible with water.

Properties of Ethers

Ethers are rather nonpolar due to the presence of an alkyl group on either side of the central oxygen. The
presence of the bulky alkyl groups that are adjacent to it means that the oxygen atom is largely unable to
participate in hydrogen bonding. Ethers, therefore, have lower boiling points compared to alcohols of similar
molecular weight. However, as the alkyl chain of the ethers becomes longer, the difference in boiling points
becomes smaller. This is due to the effect of increased Van der Waals interactions as the number of carbons
increases, and therefore the number of electrons increases as well. The two lone pairs of electrons present on
the oxygen atoms make it possible for ethers to form hydrogen bonds with water. Ethers are more polar than
alkenes, but not as polar as esters, alcohols or amides of comparable structures.

Reactions

Ethers have relatively low chemical reactivity, but they are still more reactive than alkanes. Although they
resist undergoing hydrolysis, they are often cleaved by acids, which results in the formation of an alkyl
halide and an alcohol. Ethers tend to form peroxides in the presence of oxygen or air. The general formula is
R-O-O-R’. Ethers can serve as Lewis and Bronsted bases, serving to donate electrons in reactions, or accept
protons. Ethers can be formed in the laboratory through the dehydration of alcohols (2R-OH → R-O-R +
H2O at high temperature), nucleophilic displacement of alkyl halides by alkoxides (R-ONa + R’-X → R-O-
R’ + NaX), or electrophilic addition of alcohols to alkenes (R2C=CR2 + R-OH → R2CH-C(-O-R)-R2).

Aldehydes and Ketones

Aldehydes and ketones are classes of organic compounds that contain a carbonyl (C=O) group.

Learning Objectives

Identify the general properties of ketones and aldehydes

Key Takeaways

Key Points

 The carbonyl functional group is a carbon double bonded to an oxygen. Depending on the location of
the carbonyl group, it is termed differently; ketones contain the carbonyl inside the compound and
aldehydes contain the carbonyl at the end of the organic compound.
 Ketones and aldehydes can undergo keto- enol tautomerism. This refers to the equilibrium between
the two possible tautomers. The interconversion of the two forms involves the movement of a proton
and the shifting of bonding electrons. This equilibrium affords the compounds more reactivity.
 Ketones and aldehydes participate in a variety of reactions. They can undergo oxidation reactions, in
which they become oxidized to the corresponding carboxylic acids.

Key Terms

 tautomerism: A form of isomerism in which a dynamic equilibrium between multiple isomers exists,
such as that between an enol and a ketone.
 oxidize: To increase the valence (the positive charge) of an element by removing electrons.
 aldehyde: An organic compound containing a formyl group, which is a functional group with the
structure R-CHO.
 sp2: Hybrid orbital that forms when one pi bond is required for the double bond, and only three σ
bonds are formed per carbon atom. The 2s orbital is mixed with only two of the three 2p orbitals.
  ketone: A compound containing an oxygen atom joined to a carbon atom by a double bond.

In organic chemistry, a carbonyl group is a functional group which has a carbon double bonded to an oxygen
atom: C=O.

Keto-enol tautomers: There exists an equilibrium between the ketone and the enol forms, which involves a
shifting of the double bond and the movement of a proton.

Ketones

When a carbonyl functional group is placed within a molecule, it is known as a ketone. Ketones are organic
compounds with the structure RC(=O)R’, where R and R’ can be a variety of carbon-containing substituents.
IUPAC nomenclature rules dictate that ketone molecules are named by changing the suffix of the parent
carbon molecule to “-one.” If the position of the ketone must be specified, then a number is placed between
the parent chain name and the “-one” prefix (e.g., propan-2-one), or at the beginning of the IUPAC name.
The prefixes “oxo-” and “keto-” are used to describe the ketone functional group.

Ketone: A ketone is a type of organic compound where a carbonyl group bonds to two other carbon atoms
of the carbon backbone.

The ketone carbon is sp2 hybridized, and it adopts a trigonal planar geometry around the ketonic carbon. As
such, the C–C–O and C–C–C bond angles are approximately 120 degrees. Due to the carbonyl group,
ketones are polar and are able to interact with other compounds through hydrogen bonding; this hydrogen
bond capability makes ketones more soluble in water than related methylene compounds. Ketones are not
usually hydrogen bond donors, and they tend not to exhibit intermolecular attractions with other ketones. As
a result, ketones are often more volatile than alcohols and carboxylic acids of comparable molecular
weights. Ketones have alpha -hydrogens which participate in keto-enol tautomerism. In the presence of a
strong base, enolate formation and subsequent deprotonation of the enolate will occur.

Aldehydes

Aldehyde: An aldehyde is characterized by the presence of a carbonyl functional group at the end of a
compound’s carbon skeleton.
An aldehyde is an organic compound that contains a carbonyl group with the central carbon bonded to a
hydrogen and R group (R-CHO). Aldehydes differ from ketones in that the carbonyl is placed at the end of
the carbon skeleton rather than between two carbon atoms of the backbone. Like ketones, aldehydes are sp2
hybridized and can exist in the keto or enol tautomer. Aldehydes are named by dropping the suffix of the
parent molecule, and adding the suffix “-al.” For instance, a three-carbon chain with an aldehyde group on a
terminal carbon would be propanal. If there are higher order functional groups on the compound, the prefix
“oxo-” can be used to indicate which carbon atom is part of the aldehyde group. If the location of the
aldehyde must be specified, a number can be used in between the parent chain and suffix, or at the beginning
of the compound name.

Similarities of Aldehydes and Ketones

Both aldehydes and ketones exist in an equilibrium with their enol forms; the enol form is defined as an
alkene with a hydroxyl group affixed to one of the carbon atoms composing the double bond. The keto form
predominates at equilibrium for most ketones. However, the enol form is important for some reactions
because the deprotonated enolate form is a strong nucleophile. The equilibrium is strongly
thermodynamically driven, and at room temperature the keto form is favored. The interconversion can be
catalyzed by the presence of either an acid or a base.

Keto-enol tautomerism: The interconversion between the two forms can be catalyzed by an acid or a base.

Ketone and Aldehyde Spectroscopy

Both ketones and aldehydes can be identified by spectroscopic methods. They display strong CO absorption
bands near 1700 cm-1. In NMR spectroscopy, the carbonyl hydrogen shows a strong absorption peak, and
any coupling to protons on the alpha carbon will also show strong signals.

Ketones and aldehydes can both be readily reduced to alcohols, usually in the presence of a strong reducing
agent such as sodium borohydride. In the presence of strong oxidizing agents, they can be oxidized to
carboxylic acids. As electrophiles, they are subject to attack by nucleophiles, meaning they participate in
many nucleophilic addition reactions.

Carboxylic Acids

Carboxylic acids are organic acids that contain a carbon atom that participates in both a hydroxyl and a
carbonyl functional group.

Learning Objectives

Recognize the general properties of carboxylic acids

Key Takeaways

Key Points

 Carboxylic acids are used as precursors to form other compounds such as esters, aldehydes, and
ketones.
 Carboxylic acids can exhibit hydrogen bonding with themselves, especially in non- polar solvents; this
leads to increased stabilization of the compounds and elevates their boiling points.
 Since they contain both hydroxyl and carbonyl functional groups, carboxylic acids participate in
hydrogen bonding as both hydrogen acceptors and hydrogen donors.

Key Terms
  nitrile: Any of a class of organic compounds containing a cyano functional group (-C≡N).
 olefin: Any of a class of unsaturated, open-chain hydrocarbons such as ethylene; an alkene with only
one carbon-carbon double bond.
 ester: A compound most often formed by the condensation of an alcohol and an acid, with elimination
of water. It contains the functional group C=O joined via carbon to another oxygen atom.

A carboxyl group (COOH) is a functional group consisting of a carbonyl group (C=O) with a hydroxyl
group (O-H) attached to the same carbon atom. Carboxyl groups have the formula -C(=O)OH, usually
written as -COOH or CO2H. Carboxylic acids are a class of molecules which are characterized by the
presence of one carboxyl group. As proton donors, carboxylic acids are characterized as Brønsted-Lowry
acids. Acids with two or more carboxylic groups are called dicarboxylic, tricarboxylic, etc. Salts and esters
of carboxylic acids are called carboxylates. Carboxylate ions are resonance-stabilized. This increased
stability leads to increased acidity compared to that of alcohols. Generally, in IUPAC nomenclature,
carboxylic acids have an “-oic acid ” suffix, although “-ic acid” is the suffix most commonly used.

A carboxylic acid: Carboxylic acids are organic oxoacids characterized by the presence of at least one
carboxyl group, which has the formula -C(=O)OH, usually written as -COOH or -CO2H.

Physical Properties of Carboxylic Acids

Carboxylic acids act as both hydrogen bond acceptors, due to the carbonyl group, and hydrogen bond
donors, due to the hydroxyl group. As a result, they often participate in hydrogen bonding. Carboxylic acids
usually exist as dimeric pairs in nonpolar media because of their tendency to “self-associate.” This tendency
to hydrogen bond gives them increased stability as well as higher boiling points relative to the acid in
aqueous solution. Carboxylic acids are polar molecules; they tend to be soluble in water, but as the alkyl
chain gets longer, their solubility decreases due to the increasing hydrophobic nature of the carbon chain.
Carboxylic acids are characterized as weak acids, meaning that they do not fully dissociate to produce H+
cations in a neutral aqueous solution.

Hydrogen bonding between carboxylic acids: Carboxylic acids hydrogen bond with themselves, giving
them an increased level of stability.

Spectroscopy of Carboxylic Acids

Carboxylic acids can be characterized by IR spectroscopy; they exhibit a sharp band associated with
vibration of the C-O bond between 1680 and 1725 cm-1. Additionally, a broad peak appears in the 2500 to
3000 cm-1 region. By 1H NMR spectroscopy, the hydroxyl hydrogen appears in the 10–13 ppm region,
although it is often either broadened or not observed owing to exchange with traces of water.

Applications and Reactivity of Carboxylic Acids

Carboxylic acids are used in the production of polymers, pharmaceuticals, solvents, and food additives. As
such, they are often produced industrially on a large scale. Carboxylic acids are generally produced from
oxidation of aldehydes and hydrocarbons, and base catalyzed dehydrogenation of alcohols. They can be
produced in the laboratory for small scale reactions via the oxidation of primary alcohols or aldehydes,
oxidative cleavage of olefins, and through the hydrolysis of nitriles, esters, or amides.
arboxylic acids are widely used as precursors to produce other compounds. Upon exposure to a base, the
carboxylic acid is deprotonated and forms a carboxylate salt. They also react with alcohols to produce esters
and can undergo reduction reactions by hydrogenation or the use of reducing agents. There are also various
specialized reactions that carboxylic acids participate in that lead to the formation of amines, aldehydes, and
ketones.

Esters

Esters are functional groups produced from the condensation of an alcohol with a carboxylic acid, and are
named based on these components.

Learning Objectives

Identify the general properties of the ester functional group

Key Takeaways

Key Points

 Esters are a functional group commonly encountered in organic chemistry. They are characterized by
a carbon bound to three other atoms: a single bond to a carbon, a double bond to an oxygen, and a
single bond to an oxygen. The singly bound oxygen is bound to another carbon.
 Ester names are derived from the parent alcohol and the parent acid. While simple esters are often
called by their common names, all esters can be named using the systematic IUPAC name, based on
the name for the acid followed by the suffix “-oate.”
 Esters react with nucleophiles at the carbonyl carbon. The carbonyl is weakly electrophilic, but is
attacked by strong nucleophiles. The C-H bonds adjacent to the carbonyl are weakly acidic, but
undergo deprotonation with strong bases.

Key Terms

 carboxylic acid: Any of a class of organic compounds containing a carboxyl functional group—a
carbon with one double bond to an oxygen and a single bond to another oxygen, which is in turn
bonded to a hydrogen.
 alcohol: Class of organic compounds containing a hydroxyl functional group.
 nucleophile: A compound or functional group that is attractive to centers of positive charge and
donates electrons; donates an electron pair to an electrophile to form a bond.

Esters are an important functional group in organic chemistry, and they are generally written RCOOR’ or
RCO2R’.

Esters: An ester is characterized by the orientation and bonding of the atoms shown, where R and R’ are
both carbon-initiated chains of varying length, also known as alkyl groups.

As usual, R and R’ are both alkyl groups or groups initiating with carbon. Esters are derivative of carboxylic
acids where the hydroxyl (OH) group has been replaced by an alkoxy (O-R) group. They are commonly
synthesized from the condensation of a carboxylic acid with an alcohol:
RCO2H+R′OH→RCO2R′+H2ORCO2H+R′OH→RCO2R′+H2O

Esters are ubiquitous. Most naturally occurring fats and oils are the fatty acid esters of glycerol. Esters are
typically fragrant, and those with low enough molecular weights to be volatile are commonly used as
perfumes and are found in essential oils and pheromones. Polymerized esters, or polyesters, are important
plastics, with monomers linked by esteric units like this:
CO2RCO2RCO2R… etc.

Nomenclature

The word “ester” was coined in 1848 by German chemist Leopold Gmelin, probably as a contraction of the
German Essigäther, meaning acetic ether.

Ester names are derived from the parent alcohol and acid. For example, the ester formed by ethanol and
ethanoic acid is known as ethyl ethanoate; “ethanol” is reduced to “ethyl,” while “ethanoic acid” is reduced
to “ethanoate.” Other examples of ester names include methyl propanoate, from methanol and propanoic
acid, and butyl octanoate, from butane and octanoic acid.
In the case of esters formed from common carboxylic acids, more colloquial terms are sometimes used. For
example, ethanoic acid is more commonly known as acetic acid, and thus its esters contain “acetate” instead
of “ethanoate” in their names. Other such substitutions include “formate” instead of “methanoate,”
“propionate” instead of “propanoate,” and “butyrate” instead of “butanoate.”
The chemical formulas of organic esters are typically written in the format of RCO2R’, where R and R’ are
the hydrocarbon parts of the carboxylic acid and alcohol, respectively. For example, butyl acetate,
systematically known as ethanoic acid, is derived from butanol and acetic acid and would be written
CH3CO2C4H9. Alternative presentations are common, including BuOAc and CH3COOC4H9. Cyclic esters are
known as lactones.

Structure and Bonding

Esters contain a carbonyl center, which gives rise to 120 degree C-C-O and O-C-O bond angles due to sp2
hybridization. Unlike amides, esters are structurally flexible functional groups because rotation about the C-
O-C bonds has a lower energy barrier. Their flexibility and low polarity affects their physical properties on a
macroscopic scale; they tend to be less rigid, leading to a lower melting point, and more volatile, leading to a
lower boiling point, than the corresponding amides. The pKa of the alpha-hydrogens, or the hydrogens
attached to the carbon adjacent to the carbonyl, on esters is around 25, making them essentially non-acidic
except in the presence of very strong bases.

Physical Properties and Characterization

Esters are more polar than ethers, but less so than alcohols. They participate in hydrogen bonds as hydrogen
bond acceptors, but cannot act as hydrogen bond donors, unlike their parent alcohols and carboxylic acids.
This ability to participate in hydrogen bonding confers some water-solubility, depending on the length of the
alkyl chains attached. Since they have no hydrogens bonded to oxygens, as alcohols and carboxylic acids do,
esters do not self-associate. Consequently, esters are more volatile than carboxylic acids of similar molecular
weight.

Characterization and Analysis

Esters are usually identified by gas chromatography, taking advantage of their volatility. IR (infrared)
spectra for esters feature an intense, sharp band in the range 1730–1750 cm−1 assigned to νC=O, or vibration
of the C=O bond. This peak changes depending on the functional groups attached to the carbonyl. For
example, a benzene ring or double bond in conjugation with the carbonyl will bring the wavenumber down
to around 30 cm−1.

Reactivity
Esters react with nucleophiles at the carbonyl carbon. The carbonyl is weakly electrophilic, but is attacked
by strong nucleophiles such as amines, alkoxides, hydride sources, and organolithium compounds. The
carbonyl’s electrophilicity can increase if it is protonated; in acidic media, an ester can be hydrolyzed by
water to form a carboxylic acid and an alcohol.
The C-H bonds adjacent to the carbonyl are weakly acidic, but undergo deprotonation with strong bases.
This process is the one that usually initiates condensation reactions. The carbonyl oxygen is weakly basic
(less so than in amides), but can form adducts with Lewis acids.
Amines
Amines are compounds characterized by the presence of a nitrogen atom, a lone pair of electrons, and three
substituents.
LEARNING OBJECTIVES
Identify the general properties of amines
KEY TAKEAWAYS

Key Points
 Due to the lone pair of electrons, amines are basic compounds. The basicity of the compound can
be influenced by neighboring atoms, steric bulk, and the solubility of the corresponding cation to
be formed.
 Amine compounds can hydrogen bond, which affords them solubility in water and elevated
boiling points.
 The general structure of an amine is a nitrogen atom with a lone pair of electrons and three
substituents. However, the nitrogen may bind to four substituents, leaving a positive charge on the
nitrogen atom. These charged species can serve as intermediates for important reactions.

Key Terms
 aliphatic: Of a class of organic compounds in which the carbon atoms are arranged in an open
chain.
 chiral: Literally, “handedness;” refers to a compound in which central atoms are bonded to
multiple different substituents, such that the mirror image of the compound is not identical to the
original.
 amine: Organic compounds or the functional group that contains a basic nitrogen atom with a lone
pair.
 inversion: For a secondary or tertiary amine bonded to three different substitutents, the flipping of
the three bonds about the central N atom, resulting in the opposite stereoisomer.
The amine functional group contains a basic nitrogen atom with a lone pair of electrons. As such, the group
is derivative of ammonia, in which one or more hydrogen atoms have been replaced by a carbon-containing
substituent. Compounds with the nitrogen group attached to a carbonyl within the structure are referred to as
amides, and they have the structure R-CO-NR’R”. Amine groups bonded to an aromatic (conjugated cyclic)
structure are known as aromatic amines. The aromatic structure effectively decreases the alkalinity of the
amine, while the presence of the amine group significantly decreases the reactivity of the ring due to an
electron donating effect. The prefix “amino-” or the suffix “-amine” is used when naming an amine
compound. An organic compound with multiple amino groups is called a diamine, triamine, tetramine, etc.

Amine Structure
Amines are generally organized into categories based on their bonding environments. Amines that have one
of their three hydrogen atoms replaced by an alkyl or aromatic substituent are referred to as primary amines.
Secondary amines are those that have two substituents and one hydrogen bonded to a nitrogen. Tertiary
amines are amines whose hydrogens have been completely replaced by organic substituents. Finally, cyclic
amines are those in which the nitrogen has been incorporated into a ring structure, effectively making it
either a secondary or tertiary amine. The general structure of an amine contains a nitrogen atom, a lone pair
of electrons, and three substituents. However, it is possible to have four organic substituents on the nitrogen,
making it an ammonium cation with a charged nitrogen center.

Tertiary amine: The central carbon is attached to an amine group and three other carbon atoms.

Physical Properties of Amines

Amines are able to hydrogen bond. As a result, the boiling points of these compounds are higher than those
of the corresponding phosphines, but lower than those of the corresponding alcohols, which hydrogen bond
to a stronger extent. Amines also display some solubility in water. However, the solubility decreases with an
increase in carbon atoms, due to the increased hydrophobicity of the compound as the chain length
increases. Aliphatic amines, which are amines connected to an alkyl chain, display solubility in organic
polar solvents. Aromatic amines, which are amines that participate in a conjugated ring, donate their lone
pair of electrons into the benzene ring, and thus their ability to engage in hydrogen bonding decreases. This
results in a decrease in their solubility in water and high boiling points.

Acidity and Alkalinity of Amines

Amines of the type NHRR’ and NR’R”R”’ are chiral molecules and can undergo inversion. Since the barrier
for inversion is quite low (~7 kcal/mol), these compounds cannot be resolved optically. Amines are bases,
and their basicity depends on the electronic properties of the substituents (alkyl groups enhance the basicity;
aryl groups diminish it), steric hindrance, and the degree of solvation of the protonated amine. In general,
the effect of alkyl groups raises the energy of the lone pair of electrons, thus elevating the basicity. Thus, the
basicity of an amine can be expected to increase with the number of alkyl groups on the amine. Additionally,
the effect of the aromatic ring delocalizes the lone pair of electrons on nitrogen into the ring, resulting in
decreased basicity. The solvation of protonated amines changes upon their conversion to ammonium
compounds. Typically, salts of ammonium compounds exhibit the following order of solubility in water:
primary ammonium (RNH3+) > secondary ammonium (R2NH2+) > tertiary ammonium (R3NH+). Quaternary
ammonium salts usually exhibit the lowest solubility of the series.

Amine Preparation and Reactivity

Imine formation: A primary amine is reacted with an aldehyde to produce an imine.

Industrially, amines are prepared from ammonia by alkylation with alcohols. They can also be prepared via
reduction of nitriles to amines using hydrogen in the presence of a nickel catalyst. Amines are quite reactive
due to their basicity as well as their nucleophilicity. Most primary amines are good ligands and react with
metal ions to yield coordination complexes. One of the most important reactions for amines is their
formation of imines, or organic compounds where nitrogen participates in a double bond, upon reacting with
ketones or aldehydes.

Applications of Amines
Amines are ubiquitous in biology. Many important molecules are amine-based, such as neurotransmitters
and amino acids. Their applications in the world include being starting material for dyes and models for drug
design. They are also used for gas treatment, such as removing CO2 from combustion gases.