Alcohol

CHEMICAL COMPOUND

WRITTEN BY:

 Leroy G. Wade
LAST UPDATED: Feb 28, 2019 See Article History

Alcohol, any of a class of organic compounds characterized by one or more

hydroxyl (―OH) groups attached to a carbon atom of an alkyl group
(hydrocarbon chain). Alcohols may be considered as organic derivatives
of water (H2O) in which one of the hydrogen atoms has been replaced by an
alkyl group, typically represented by R in organic structures. For example, in
ethanol (or ethyl alcohol) the alkyl group is the ethyl group, ―CH2CH3.

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chemical compound: Alcohols and phenols

An oxygen atom normally forms two σ bonds with other atoms; the water

molecule, H2O, is the simplest and most common example.…

Alcohols are among the most common organic compounds. They are used as
sweeteners and in making perfumes, are valuable intermediates in the
synthesis of other compounds, and are among the most abundantly produced
organic chemicals in industry. Perhaps the two best-known alcohols are
ethanol and methanol (or methyl alcohol). Ethanol is used in toiletries,
pharmaceuticals, and fuels, and it is used to sterilize hospital instruments. It
is, moreover, the alcohol in alcoholic beverages. The anesthetic ether is also
made from ethanol. Methanol is used as a solvent, as a raw material for the
manufacture of formaldehydeand special resins, in special fuels, in antifreeze,
and for cleaning metals.
Alcohols may be classified as primary, secondary, or tertiary, according to
which carbon of the alkyl group is bonded to the hydroxyl group. Most
alcohols are colourless liquids or solids at room temperature. Alcohols of
low molecular weight are highly soluble in water; with increasing molecular
weight, they become less soluble in water, and their boiling points, vapour
pressures, densities, and viscosities increase.
This article covers the structure and classification, physical properties,
commercial importance, sources, and reactions of alcohols. For more
information about closely related compounds, see chemical
compound, phenol, and ether.

Structure And Classification Of Alcohols

Similar to water, an alcohol can be pictured as having an sp3 hybridized
tetrahedral oxygen atom with nonbonding pairs of electrons occupying two of
the four sp3 hybrid orbitals. (See chemical bonding for a discussion of hybrid
orbitals.) Alkyl groups are generally bulkier than hydrogen atoms, however, so
the R―O―H bond angle in alcohols is generally larger than the 104.5°
H―O―H bond angle in water. For example, the 108.9° bond angle
in methanol shows the effect of the methyl group, which is larger than the
hydrogen atom of water.

One way of classifying alcohols is based on which carbon atom is bonded to

the hydroxyl group. If this carbon is primary (1°, bonded to only one other
carbon atom), the compound is a primary alcohol. A secondary alcohol has
the hydroxyl group on a secondary (2°) carbon atom, which is bonded to two
other carbon atoms. Similarly, a tertiary alcohol has the hydroxyl group on a
tertiary (3°) carbon atom, which is bonded to three other carbons. Alcohols are
referred to as allylic or benzylic if the hydroxyl group is bonded to an allylic
carbon atom (adjacent to a C=C double bond) or a benzylic carbon atom (next
to a benzene ring), respectively.
Nomenclature
As with other types of organic compounds, alcohols are named by both formal and
common systems. The most generally applicable system is that adopted at a meeting
of the International Union of Pure and Applied Chemistry (IUPAC) in Paris in 1957.
Using the IUPAC system, the name for an alcohol uses the -ol suffix with the name of
the parent alkane, together with a number to give the location of the hydroxyl group.
The rules are summarized in a three-step procedure:
1. Name the longest carbon chain that contains the carbon atom bearing the ―OH group.
Drop the final -e from the alkane name, and add the suffix -ol.
2. Number the longest carbon chain starting at the end nearest the ―OH group, and use the
appropriate number, if necessary, to indicate the position of the ―OH group.
3. Name the substituents, and give their numbers as for an alkane or alkene.
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The first example below has a longest chain of six carbon atoms, so the root name is
hexanol. The ―OH group is on the third carbon atom, which is indicated by the name
3-hexanol. There is a methyl group on carbon 3 and a chlorine atom on carbon 2. The
complete IUPAC name is 2-chloro-3-methyl-3-hexanol. The prefix cyclo- is used for
alcohols with cyclic alkyl groups. The hydroxyl group is assumed to be on carbon 1,
and the ring is numbered in the direction to give the lowest possible numbers to the
other substituents, as in, for example, 2,2-dimethylcyclopentanol.

Common names

The common name of an alcohol combines the name of the alkyl group with the
word alcohol. If the alkyl group is complex, the common name becomes awkward and
the IUPAC name should be used. Common names often incorporate obsolete terms in
the naming of the alkyl group; for example, amyl is frequently used instead of pentyl
for a five-carbon chain.
Physical Properties Of Alcohols
Most of the common alcohols are colourless liquids at room temperature.
Methyl alcohol, ethyl alcohol, and isopropyl alcohol are free-flowing liquids
with fruity odours. The higher alcohols—those containing 4 to
10 carbon atoms—are somewhat viscous, or oily, and they have heavier fruity
odours. Some of the highly branched alcohols and many alcohols containing
more than 12 carbon atoms are solids at room temperature.
common
IUPAC name formula mp (°C)
name

*Ph represents the phenyl group, C6H5—.

methanol methyl alcohol CH3OH −97

ethanol ethyl alcohol CH3CH2OH −114

1-propanol n-propyl alcohol CH3CH2CH2OH −126

2-propanol isopropyl alcohol (CH3)2CHOH −89

1-butanol n-butyl alcohol CH3(CH2)3OH −90

 common
IUPAC name formula mp (°C)
name
2-butanol sec-butyl alcohol (CH3)CH(OH)CH2CH3 −114

2-methyl-1-propanol isobutyl alcohol (CH3)2CHCH2OH −108

2-methyl-2-propanol t-butyl alcohol (CH3)3COH 25

1-pentanol n-pentyl alcohol CH3(CH2)4OH −79

3-methyl-1-butanol isopentyl alcohol (CH3)2CHCH2CH2OH −117

2,2-dimethyl-1-
neopentyl alcohol (CH3)3CCH2OH 52
propanol

cyclopentyl
cyclopentanol cyclo-C5H9OH −19
alcohol

1-hexanol n-hexanol CH3(CH2)5OH −52

cyclohexyl
cyclohexanol cyclo-C6H11OH 25
alcohol

1-heptanol n-heptyl alcohol CH3(CH2)6OH −34

1-octanol n-octyl alcohol CH3(CH2)7OH −16

1-nonanol n-nonyl alcohol CH3(CH2)8OH −6

1-decanol n-decyl alcohol CH3(CH2)9OH 6

2-propen-1-ol allyl alcohol H2C=CH−CH2OH −129

phenylmethanol benzyl alcohol Ph−CH2OH* −15

diphenylmethanol diphenylcarbinol Ph2CHOH* 69

triphenylmethanol triphenylcarbinol Ph3COH* 162

density (grams per solubility in

IUPAC name bp (°C)
millilitre) water
methanol 65 0.79 miscible

ethanol 78 0.79 miscible

1-propanol 97 0.80 miscible

2-propanol 82 0.79 miscible

 common
IUPAC name formula mp (°C)
name
1-butanol 118 0.81 9.1%

2-butanol 100 0.81 7.7%

2-methyl-1-propanol 108 0.80 10.0%

2-methyl-2-propanol 83 0.79 miscible

1-pentanol 138 0.82 2.7%

3-methyl-1-butanol 132 0.81 2.0%

2,2-dimethyl-1-
113 0.81 3.5%
propanol

cyclopentanol 141 0.95

1-hexanol 156 0.82 0.6%

cyclohexanol 162 0.96 3.6%

1-heptanol 176 0.82 0.1%

1-octanol 194 0.83

1-nonanol 214 0.83

1-decanol 233 0.83

2-propen-1-ol 97 0.86

phenylmethanol 205 1.05

diphenylmethanol 298

triphenylmethanol 380 1.20

Physical properties of selected alcohols

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The boiling points of alcohols are much higher than those of alkanes with
similar molecular weights. For example, ethanol, with a molecular
weight (MW) of 46, has a boiling point of 78 °C (173 °F),
whereas propane(MW 44) has a boiling point of −42 °C (−44 °F). Such a large
difference in boiling points indicates that molecules of ethanol are attracted to
one another much more strongly than are propane molecules. Most of this
difference results from the ability of ethanol and other alcohols to form
intermolecular hydrogen bonds. (See chemical bonding: Intermolecular
forces for a discussion of hydrogen bonding.)

The oxygen atom of the strongly polarized O―H bond of an alcohol pulls
electron density away from the hydrogen atom. This polarized hydrogen,
which bears a partial positive charge, can form a hydrogen bond with a pair of
nonbonding electrons on another oxygen atom. Hydrogen bonds, with a
strength of about 5 kilocalories (21 kilojoules) per mole, are much weaker than
normal covalent bonds, with bond energies of about 70 to 110 kilocalories per
mole. (The amount of energy per mole that is required to break a given bond
is called its bond energy.)
Water and alcohols have similar properties because water molecules
contain hydroxyl groups that can form hydrogen bonds with other water
molecules and with alcohol molecules, and likewise alcohol molecules can
form hydrogen bonds with other alcohol molecules as well as with water.
Because alcohols form hydrogen bonds with water, they tend to be relatively
soluble in water. The hydroxyl group is referred to as a hydrophilic (“water-
loving”) group, because it forms hydrogen bonds with water and enhances the
solubility of an alcohol in water. Methanol, ethanol, n-propyl alcohol, isopropyl
alcohol, and t-butyl alcohol are all miscible with water. Alcohols with higher
molecular weights tend to be less water-soluble, because
the hydrocarbon part of the molecule, which is hydrophobic (“water-hating”), is
larger with increased molecular weight. Because they are strongly polar,
alcohols are better solvents than hydrocarbons for ionic compounds and other
polar substances.

Commercially Important Alcohols

Methanol
Methanol (methyl alcohol) was originally produced by heating wood chips in the
absence of air. Some of the carbohydrates in the wood are broken down to form
methanol, and the methanol vapour is then condensed. This process led to the
name wood alcohol as another common name for methanol. Methanol is synthesized
commercially by a catalytic reaction of carbon monoxide (CO) with hydrogen gas
(H2) under high temperature and pressure.

The mixture of carbon monoxide and hydrogen needed to make methanol can be
generated by the partial burning of coal in the presence of water. By carefully
regulating the amount of water added, the correct ratio of carbon monoxide to
hydrogen can be obtained.

Methanol has excellent properties as a polar organic solvent and is widely used as an
industrial solvent. It is more toxic than ethanol, however, and may cause blindness or
death if large amounts are inhaled or ingested.
Methanol has a high octane rating and a low emission of pollutants—characteristics
that make it a valuable fuel for automobile engines. From the late 1960s until 2006,
the cars at the Indianapolis 500, the automobile race held annually at the Indianapolis
Motor Speedway, were powered by methanol-burning engines. Methanol was once
under consideration as a commercial motor fuel because it is cheaper than ethanol and
can be made from natural gas and coal resources. However, increasing interest in
ethanol-based fuels and difficulties involving the solvent properties of methanol,
which cause problems with fuel systems—especially in fuel-injected cars—have
resulted in diminished commercial interest in methanol fuels. Methanol tends to
dissolve the plastic and rubber components employed in modern fuel systems, and
different materials must be used that can survive exposure to methanol over long
periods of time without dissolving or cracking.
Ethanol
Ethanol (ethyl alcohol) has been produced since prehistoric times, mostly through
the fermentation of fruit juices. The fermented juice could be stored in a sealed
container, and this primitive wine remained safe to drink throughout the winter. Many
different sources can provide the sugars and starches that are broken down to
simpler compoundsduring fermentation. Ethanol is called grain alcohol because it is
often made from grains, such as corn (maize), wheat, rye, and barley. The grain is first
boiled in water to produce the mash, which is incubated with malt(sprouted barley) to
yield the wort. Malt provides an enzyme (diastase) that converts starches in the grain
to the sugar maltose. The wort is incubated with brewer’s yeast, which secretes the
enzyme maltase to convert maltose to glucose and the enzyme zymase to convert
glucose to ethanol. Two of the six carbon atoms in glucose are oxidized to carbon
dioxide (CO2); this oxidation provides energy to the yeast cells.

Fermentation yields a solution that is only about 12–15 percent alcohol because higher
concentrations are toxic to the yeast cells. This solution can be distilled, however, to
raise the ethanol content to as high as 95 percent.

Fermentation is a relatively expensive method of making ethanol. Industrial ethanol is

more commonly synthesized by the high-temperature catalytic addition of water
to ethylene (C2H4).

Ethanol is an excellent motor fuel with a high octane rating and low emissions;
however, it should be used in a fuel system designed to withstand the alcohol’s
tendency to dissolve plastic parts. Solutions of 10 percent ethanol
in gasoline (gasohol) can be used in most cars without any adjustments. Today,
ethanol fuels are typically made from natural products, such as corn or sugar.
Isopropyl alcohol
Isopropyl alcohol (2-propanol) is made by indirect hydration
of propylene(CH2CHCH3). Isopropyl alcohol is commonly used as an industrial
solvent and as a rubbing alcohol applied to the skin. Although isopropyl alcohol is
more toxic than ethanol, it has less of a drying effect on the skin, and it is not
regulated and taxed by the U.S. government as is ethanol.
Ethylene glycol
The name ethylene glycol refers literally to “the glycol made from ethylene.” Its
systematic name is ethane-1,2-diol. Ethylene glycol is commonly used as
automotive antifreeze and as an ingredient in hydraulic fluids, printing inks, and paint
solvents. It is also used as a reagent in making polyesters, explosives, alkyd resins,
and syntheticwaxes.

Glycerol
Glycerol (also called glycerine) is a sweet syrupy substance with three alcohol
hydroxyl groups. Its systematic name is propane-1,2,3-triol. Glycerol was first
obtained as a by-product of soap manufacture, through the saponification
(hydrolysis in base) of fats. About 25 kg (60 pounds) of glycerol is obtained with each
ton of soap. It can also be obtained by fermentation from molasses and sugar.
During World War II, large quantities of glycerol were needed for the production of
glyceryl trinitrate (nitroglycerin); this need was met by synthetic glycerol made
from propylene, CH2=CH―CH3.
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A large amount of glycerol is still used for making nitroglycerin, which is the primary
explosive in dynamite and blasting gelatin. Nitroglycerin is also used as a coronary
vasodilator (a drug that relaxes and expands blood vessels) for symptomatic relief of
chest pain caused by poor circulation to the heart. Glycerol is also used as a solvent,
moisturizing agent, plasticizer, antifreeze, and water-soluble lubricant. It is found in a
wide variety of products, including foods, soaps, cosmetics, printing inks, hydraulic
fluids, and pharmaceuticals.

Sources Of Alcohols

Natural products

The common sources of methanol, ethanol, and isopropyl alcohol have been discussed
above. Larger, more complicated alcohols are often isolated from volatile oils of
plants by the process of steam distillation. The plant material is boiled in water, and
the volatile oils are carried over by the steam, condensed, and separated from the
water. Substances such as cholesterol, found in most animal tissues (and abundant in
egg yolks), and retinol (vitamin A alcohol), extracted from fish liver oils, are
examples of naturally occurring sources of alcohols.


 
Cholesterol, found in most animal tissues and in egg yolks, contains a hydroxyl group (―OH), making it a naturally
occurring source of alcohol.Encyclopædia Britannica, Inc.
Peppermint (Mentha piperita) is a natural source of menthol.Shunji Watari/Encyclopædia Britannica, Inc.
Long-chain alcohols can be obtained from fats and waxes by hydrolysisin base, called
saponification, followed by reduction.
Reduction of carbonyl compounds

The addition of two hydrogen atoms to a carbonyl group produces an alcohol. This is
an example of a reduction. Ketones, aldehydes, and carboxylic acids are reduced by
the catalytic addition of gaseous hydrogen (H2) or by a wide variety of specific
reducing agents, such as lithium aluminum hydride (LiAlH 4) and sodium borohydride
(NaBH4).
Hydration of alkenes
The addition of water (hydration) across the double bond of an alkeneyields an
alcohol. Alkenes are available as products of coal tar and petroleum refining, and a
variety of catalytic conditions can support the addition of water across the double
bond. In most cases, water adds in the direction that places the new hydroxyl group on
the more highly substituted end of the double bond according to the Markovnikov
rule, as in acid-catalyzed hydrations. (The more highly substituted end of the double
bond is the one that is bonded to more carbon atoms.)
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Hydroboration-oxidation is also useful for adding water across the double bond of an
alkene; however, hydroboration-oxidation gives an anti-Markovnikov orientation of
the addition product, with the hydroxyl group adding to the less-substituted end of the
double bond.

Alkenes may be converted to diols (dialcohols) by oxidizing agents such as potassium

permanganate (KMnO4).

These oxidations must be carried out carefully to avoid overoxidation and breaking of
the double bond.

Displacement of halides
A hydroxide ion can displace a halide ion from a primary alkyl halide (RCH2X, where
X is a halogen) to give an alcohol. This displacement reaction is not frequently used to
synthesize alcohols, however, because alkyl halides are more commonly synthesized
from alcohols rather than vice versa.

Using Grignard and organolithium reagents

Grignard and organolithium reagents are powerful tools for organic synthesis, and the
most common products of their reactions are alcohols. A Grignard reagent is formed
by reaction of an alkyl halide (RX, where X is a halogen) with magnesium metal (Mg)
in an ether solution. The product is written as R―Mg―X, although Grignard reagents
are known to be more complicated than this simple structure suggests. Organolithium
reagents (RLi) are formed in much the same way as Grignard reagents, except that
an ether solvent is not required. Most reactions of organolithium reagents are similar
to those of Grignard reagents; however, there are some important differences.

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Grignard reagents add to carbonyl compounds (i.e., compounds containing the
C=O functional group) to produce magnesium alkoxides (ROMgX) that are
hydrolyzed to alcohols. A wide variety of alcohols can be synthesized by Grignard
additions. A Grignard reagent adds to formaldehyde to give a primary alcohol with
one additional carbon atom, to an aldehyde to give a secondary alcohol, and to
a ketone to yield a tertiary alcohol.
Grignard reagents add twice to esters to give alcohols (upon hydrolysis). This
technique is valuable for making secondary and tertiary alcohols with two identical
alkyl groups. They also add to epoxides, yielding primary alcohols in which two
additional carbon atoms have been added to the chain of the Grignard reagent.
Reactions Of Alcohols
Because alcohols are easily synthesized and easily transformed into other compounds,
they serve as important intermediates in organic synthesis. A multistep synthesis may
use Grignard-like reactions to form an alcohol with the desired carbon structure,
followed by reactions to convert the hydroxyl group of the alcohol to the desired
functionality. The most common reactions of alcohols can be classified as oxidation,
dehydration, substitution, esterification, and reactions of alkoxides.
Oxidation
Alcohols may be oxidized to give ketones, aldehydes, and carboxylic acids. These
functional groups are useful for further reactions; for example, ketones and aldehydes
can be used in subsequent Grignard reactions, and carboxylic acids can be used for
esterification. Oxidation of organic compounds generally increases the number of
bonds from carbon to oxygen (or another electronegative element, such as a halogen),
and it may decrease the number of bonds to hydrogen.

Alcohols may be oxidized to give aldehydes, ketones, and carboxylic acids. The oxidation of organic compounds
generally increases the number of bonds from carbon to oxygen, and it may decrease the number of bonds to
hydrogen.Encyclopædia Britannica, Inc.

Secondary alcohols are easily oxidized without breaking carbon-carbon bonds only as
far as the ketone stage. No further oxidation is seen except under very stringent
conditions. Tertiary alcohols cannot be oxidized at all without breaking carbon-carbon
bonds, whereas primary alcohols can be oxidized to aldehydes or further oxidized to
carboxylic acids.
Chromic acid (H2CrO4, generated by mixing sodium dichromate, Na2Cr2O7,
with sulfuric acid, H2SO4) is an effective oxidizing agent for most alcohols. It is a
strong oxidant, and it oxidizes the alcohol as far as possible without breaking carbon-
carbon bonds. Chromic acid oxidizes primary alcohols to carboxylic acids, and it
oxidizes secondary alcohols to ketones. Tertiary alcohols do not react with chromic
acid under mild conditions. With a higher temperature or a more concentrated acid,
carbon-carbon bonds may be oxidized; however, yields from such strong oxidations
are usually poor.
Oxidizing a primary alcohol only as far as the aldehyde stage is more difficult because
of the ease with which aldehydes are oxidized to acids. Special reagents have been
developed to convert primary alcohols to aldehydes. Pyridinium chlorochromate,
often abbreviated PCC, is a milder oxidant than chromic acid and oxidizes most
primary alcohols to aldehydes. PCC is a complex of chromium trioxide (CrO 3)
with pyridine(C5H5N) and hydrogen chloride (HCl), written as pyridine ∙ CrO3 ∙ HCl.

Biological oxidation
All substances are toxic if taken in large enough quantities, and alcohols are no
exception. Although ethanol is less toxic than methanol, it is nonetheless a poisonous
substance, and many people die each year from ethanol poisoning. When someone is
suffering from mild ethanol poisoning, the person is said to be intoxicated. Because
animals often consume food that has fermented and contains ethanol, their bodies
have developed methods to remove or detoxify ethanol before it can accumulate and
poison the brain. One way the body detoxifies ethanol is to oxidize it, using
an enzyme produced by the liver, alcohol dehydrogenase, or ADH. Alcohol
dehydrogenase catalyzes the oxidation of ethanol to acetaldehyde, which is further
oxidized to acetic acid (as the acetate ion), a normal metabolite. The actual oxidizing
agent is the oxidized form of nicotinamide adenine dinucleotide, NAD+.
The body’s response to simple alcohols is to oxidize them. This strategy works well
with ethanol, because the product is acetate, a normal metabolite. When other alcohols
are ingested, however, oxidation may lead to other toxic products. For example,
oxidation of methanol produces formaldehyde and subsequently formic acid (as the
formate ion); both of these products are more toxic than methanol itself. Ethylene
glycol (automotive antifreeze) is oxidized to oxalic acid (as the oxalate ion), the
toxic compound found in rhubarb leaves and many other plants. Ethylene glycol has a
sweet taste, and many dogs and cats are poisoned each year by drinking
automotive antifreeze that has been carelessly discarded.
One common treatment for methanol or ethylene glycol poisoning is to give the
patient intravenous infusions of diluted ethanol. The ADH enzyme is kept occupied
by oxidizing ethanol to acetic acid, giving the kidneys time to excrete most of the
methanol or ethylene glycol before it is oxidized to more toxic compounds. This is an
example of competitive inhibition of an enzyme (see poison: Nature of a toxic
substance).
Dehydration to alkenes
Converting an alcohol to an alkene requires removal of the hydroxyl group and a
hydrogen atom on the neighbouring carbon atom. Because the elements of water are
removed, this reaction is called a dehydration. Dehydrations are most commonly
carried out by warming the alcohol in the presence of a strong dehydrating acid, such
as concentrated sulfuric acid.

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Most alcohol dehydrations take place by the mechanism shown below. Protonation of
the hydroxyl group allows it to leave as a water molecule. The species that remains
has a carbon atom with only three bonds and a positive charge and is called a
carbocation. This intermediate species can be stabilized by loss of a proton from a
carbon atom adjacent to the positively charged carbon ion, giving the alkene.
Because they involve carbocation intermediates, alcohol dehydrations go more
quickly and easily if they form relatively stable carbocations. More highly substituted
carbocations are more stable (3° > 2° > 1°); therefore, more highly substituted
alcohols undergo dehydration more readily than less highly substituted alcohols (3° >
2° > 1°). Carbocations can undergo rearrangements in which an alkyl group, aryl
group, or hydrogen atom, along with its bonding electrons, shifts to the positively
charged carbon atom to form a more stable species. Rearrangements are thus a
common nuisance in alcohol dehydrations. If more than one alkene can be formed in a
dehydration, the major product is usually the product with the most highly substituted
double bond (Saytzeff’s rule).

Dehydration to ethers
Under carefully controlled conditions, simple alcohols can undergo intermolecular
dehydration to give ethers. This reaction is effective only with methanol, ethanol, and
other simple primary alcohols, but it is the most economical method for making ethyl
ether (also known as diethyl ether), an important industrial solvent.

Substitution to form alkyl halides

Alkyl halides are often synthesized from alcohols, in effect substituting
a halogen atom for the hydroxyl group. Hydrochloric (HCl), hydrobromic (HBr), and
hydroiodic (HI) acids are useful reagents for this substitution, giving their best yields
with tertiary alcohols. Thionyl chloride (SOCl2), phosphorus tribromide (PBr3), and
phosphorus triiodide (generated from phosphorus, P, and molecular iodine, I2) are also
useful for making alkyl chlorides, bromides, and iodides, respectively.

Esterification
Alcohols can combine with many kinds of acids to form esters. When no type of acid
is specified, the word ester is assumed to mean a carboxylic ester, the ester of an
alcohol and a carboxylic acid. The reaction, called Fischer esterification, is
characterized by the combining of an alcohol and an acid (with acid catalysis) to yield
an ester plus water.

Under appropriate conditions, inorganic acids also react with alcohols to form esters.
To form these esters, a wide variety of specialized reagents and conditions can be
used.
Acidity of alcohols: formation of alkoxides
Alcohols are weak acids. The most acidic simple alcohols (methanol and ethanol) are
about as acidic as water, and most other alcohols are somewhat less acidic.
A strong base can deprotonate an alcohol to yield an alkoxide ion(R―O−). For
example, sodamide (NaNH2), a very strong base, abstracts the hydrogen atom of an
alcohol. Metallic sodium (Na) or potassium (K) is often used to form an alkoxide by
reducing the proton to hydrogen gas.

Alkoxides can be useful reagents. For example, the most common synthesis
of ethers involves the attack of an alkoxide ion on an alkyl halide. This method is
called Williamson ether synthesis (see ether).
Leroy G. Wade
 Aldehyde
CHEMICAL COMPOUND

WRITTEN BY:

 Jerry March
 William H. Brown
See Article History

Aldehyde, any of a class of organic compounds, in which a carbon atom

shares a double bond with an oxygen atom, a single bond with
a hydrogen atom, and a single bond with another atom or group of atoms
(designated R in general chemical formulas and structure diagrams). The
double bond between carbon and oxygen is characteristic of all aldehydes
and is known as the carbonyl group. Many aldehydes have pleasant odours,
and in principle, they are derived from alcohols by dehydrogenation (removal
of hydrogen), from which process came the name aldehyde.

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chemical compound: Aldehydes and ketones

 When an oxygen atom forms a double bond to a carbon atom, a carbonyl

functional group is obtained. The carbon atom of a carbonyl group is…

Aldehydes undergo a wide variety of chemical reactions,

including polymerization. Their combination with other types of molecules
produces the so-called aldehyde condensation polymers, which have been
used in plastics such as Bakelite and in the laminate tabletop
material Formica. Aldehydes are also useful as solvents
and perfumeingredients and as intermediates in the production
of dyes and pharmaceuticals. Certain aldehydes are involved in physiological
processes. Examples are retinal (vitamin A aldehyde), important in human
vision, and pyridoxal phosphate, one of the forms of vitamin B6. Glucose and
other so-called reducing sugars are aldehydes, as are several natural
and synthetic hormones.

Structure Of Aldehydes
In formaldehyde, the simplest aldehyde, the carbonyl group is bonded to two
hydrogen atoms. In all other aldehydes, the carbonyl group is bonded to one
hydrogen and one carbon group. In condensed structural formulas, the
carbonyl group of an aldehyde is commonly represented as ―CHO. Using
this convention, the formula of formaldehyde is HCHO and that

of acetaldehyde is CH3CHO.
 The carbon atoms
bonded to the carbonyl group of an aldehyde may be part of saturated or
unsaturated alkyl groups, or they may be alicyclic, aromatic, or heterocyclic
rings.
Nomenclature Of Aldehydes
There are two general ways of naming aldehydes. The first method is based
on the system used by the International Union of Pure and Applied Chemistry
(IUPAC) and is often referred to as systematic nomenclature. This method
assumes the longest chain of carbon atoms that contains the carbonyl group
as the parent alkane. The aldehyde is shown by changing the suffix -e to -al.
Because the carbonyl group of an aldehyde can only be on the end of the
parent chain and, therefore, must be carbon 1, there is no need to use a
number to locate it.
In the compound named 4-methylpentanal, the longest carbon chain contains
five carbon atoms, and so the parent name is pentane; the suffix -al is added
to indicate the presence of the aldehyde group, and the chain is numbered
beginning at the carbonyl group. The methyl group is given the number 4,
because it is bonded to the fourth carbon of the chain.
The other method of nomenclature for aldehydes, referred to as common
nomenclature, is to name them after the common name of the
corresponding carboxylic acid; i.e., the carboxylic acid with the same structure
as the aldehyde except that ―COOH appears instead of ―CHO. The acids
are usually given a name ending in -ic acid. Aldehydes are given the same
name but with the suffix -ic acid replaced by -aldehyde. Two examples are
formaldehyde and benzaldehyde.

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As another example, the common name of CH2=CHCHO, for which the IUPAC
name is 2-propenal, is acrolein, a name derived from that of acrylic acid, the
parent carboxylic acid.

Properties Of Aldehydes
The only structural difference between hydrocarbons and aldehydes is the
presence in the latter of the carbonyl group, and it is this group that is
responsible for the differences in properties, both physical and chemical. The
differences arise because the carbonyl group is inherently polar—that is,
the electrons that make up the C=O bond are drawn closer to the oxygen than
to the carbon. This gives the oxygen a partial negative charge and the carbon
a partial positive charge. The polarity of a carbonyl group is often represented
using the Greek letter delta (δ) to indicate a partial charge (that is, a charge
less than one).
The negative end of one polar molecule is attracted to the positive end of
another polar molecule, which may be a molecule either of the same
substance or of a different substance.
Physical properties

The polarity of the carbonyl group notably affects the physical properties of melting
point and boiling point, solubility, and dipole moment.
Hydrocarbons, compounds consisting of only the elements hydrogenand carbon, are
essentially nonpolar and thus have low melting and boiling points. The melting and
boiling points of carbonyl-containing compounds are considerably higher. For
example, butane(CH3CH2CH2CH3), propanal (CH3CH2CHO),
and acetone (CH3COCH3) all have the same molecular weight (58), but the boiling
point of the hydrocarbon butane is 0 °C (32 °F), while those of propanal and acetone
are 49 °C (120 °F) and 56 °C (133 °F), respectively. The reason for the large
difference is that polar molecules have a greater attraction for each other than do
nonpolar molecules, requiring more energy—and thus a higher temperature—to
separate them, which must occur if compounds are to melt or boil. Formaldehyde
(HCHO) is a gas under standard conditions, and acetaldehyde (CH3CHO) boils at
about room temperature. Other aldehydes, except those of high molecular weight,
are liquids under ordinary conditions.
Polar molecules do not mix easily with nonpolar ones, because polar molecules attract
one another and nonpolar ones are unable to squeeze between them. Thus,
hydrocarbons are insoluble in water, because water molecules are polar. Aldehydes
with fewer than about five carbon atoms are soluble in water; however, above this
number, the hydrocarbon portion of their molecules makes them insoluble. The
solubility of low-molecular-weight carbonyl compounds in water is caused by
hydrogen bonds that form between the oxygen atom of the carbonyl group and

hydrogen atoms of water molecules.

The polarity of molecules can be quantified by a number called a dipole moment. This
value is obtained by putting the compound into an electric field and measuring the
facility with which its molecules line up with the field, the negative ends pointing to
the positive side of the field and the positive ends pointing to the negative side. Most
hydrocarbons have no or only exceedingly small dipole moments, but those of
aldehydes are much higher.

Tautomerism
If an aldehyde possesses at least one hydrogen atom on the carbon atom adjacent to
the carbonyl group, called the alpha (α) carbon, this hydrogen can migrate to the
oxygen atom of the carbonyl group. The double bond then migrates to the α-carbon.
As a result, a carbonyl compound with an α-hydrogen can exist in two isomeric forms,
called tautomers. In the keto form, the hydrogen is bonded to the α-carbon, while in
the enol form it is bonded to the carbonyl oxygen with the migration of the double

bond.
The name enol is derived from the IUPAC designation of it as both an alkene (-ene)
and an alcohol (-ol). Keto and enol isomers exist in equilibrium in which both
tautomers are present but, in simple cases, the keto form is much more stable than the
enol form. In acetaldehyde, for example, only about 6 of every 10 million molecules
are in the enol form at any given time. Nevertheless, the equilibrium always exists,
and every molecule of acetaldehyde (as well as any other aldehyde or ketonewith an
α-hydrogen) is converted to the enol form (and back again) several times per second.
This is an important characteristic because a number of reactions of
carbonyl compounds take place only through the enol forms. Certain carbonyl
compounds have a much higher percentage of its molecules in the enol form,
however.
Synthesis Of Aldehydes
Because aldehydes are important building blocks in organic chemistry, they are used
to synthesize many other compounds, and there are also many ways to prepare them.
Oxidation is among the principal methods. Primary alcohols can be oxidized to
aldehydes (RCH2OH → RCHO, where R is an alkyl or aryl group). This is generally
not easy to do, because most reagents that oxidize primary alcohols to aldehydes will
oxidize the aldehyde further to a carboxylic acid. To produce aldehydes on an
industrial scale, the primary alcohol can be passed over hot copper (Cu) or copper
chromite (Cu[CrO2]2) catalyst, but this method is less useful on a smaller scale such as
in chemistry laboratories. On a laboratory scale, a number of reagents have been used,
most notably pyridinium chlorochromate, PCC.
A method for reducing carboxylic acids to aldehydes (RCOOH → RCHO) in one step
would be useful, but no general technique has been devised for accomplishing this.
However, acyl chlorides, RCOCl can be reduced to aldehydes by several reagents,
including lithium tri-tert-butoxyaluminum hydride, Li+H―Al−(OC[CH3]3)3.
A formyl group (―CHO) can be put onto an aromatic ring by several methods (ArH
→ ArCHO). In one of the most common of these, called the Reimer-Tiemann
reaction, phenols (ArOH) are converted to phenolic aldehydes by treatment
with chloroform in basic solution. The ―CHO group usually goes into the position
adjacent to the ―OH group.
Acetylene, which is an alkyne (a compound containing a carbon-carbon triple bond),
reacts with water, in the presence of mercuric salts to yield acetaldehyde (CH3CHO).
In a process called hydroformylation, alkenes can be treated with carbon monoxide,
(CO), hydrogen (H2), and a transition metal catalyst, most
commonly cobalt (Co), rhodium (Rh), or ruthenium (Ru), to give aldehydes.
Hydroformylation of propylene, for example, gives a mixture of butanal and 2-
methylpropanal.
Hydroformylation is more important in commercial applications (where it is known as
the oxo process) than in laboratory syntheses. Oxo aldehydes are of little importance
themselves as final products. Rather, they are reduced to alcohols or oxidized to
carboxylic acids. Oxo alcohols are used as raw materials for the synthesis
of detergents and textilefibres. Oxo carboxylic acids are converted to esters and used
as industrial and laboratory solvents.

Principal Reactions Of Aldehydes

Aldehydes are important starting materials and intermediates in organic synthesis,
because they undergo a wide variety of reactions and are readily available by
many synthetic methods. The reactivity of these compounds arises largely through
two features of their structures: the polarity of the carbonyl group and the acidity of
any α-hydrogens that are present.
Aldehydes are polar molecules, and many reagents seek atoms with a deficiency of
electrons. Such reagents are called nucleophiles, meaning nucleus-loving.
A nucleophile has electrons that it can share with a positively-charged centre to form a
new covalent bond. Many reactions of carbonyl compounds begin with an attack of a
nucleophile (abbreviated as Nu−) at the carbon atom of a carbonyl group, followed by
combination of the now-negatively charged oxygen with a positive hydrogen ion.
Under acidic conditions this sequence can be reversed, with the positive hydrogen
ion adding to the carbonyl oxygen first and then the nucleophile attacking the
carbonyl carbon. In some cases the reaction ends with this step, but in many other
cases there are one or more subsequent steps, the most common being the loss of
water. The newly formed ―OH group leaves together with a hydrogen from an
adjoining atom. The result is formation of a double bond between the carbon and the
nucleophile. If the nucleophile added to the carbonyl group is a sulfur atom, for
example, then loss of water gives a C=S bond.

Because of tautomerism, the carbon atom adjacent to the carbonyl group is also
susceptible to attack if that carbon atom possesses a hydrogen atom (an α-hydrogen);
many reactions of such carbonyl compounds involve replacement of the α-hydrogen.

Uses Of Aldehydes
Hundreds of individual aldehydes are used by chemists daily to synthesize
other compounds, but they are less important in industrial synthesis (that is,
the production of compounds on a scale of tons). Only one
aldehyde, formaldehyde, is used to a significant degree in industry worldwide,
as determined by the number of tons of the chemical utilized per year.
Formaldehyde
Formaldehyde (made predominantly by the oxidation of methanol) is a gas but is
generally handled as a 37 percent solution in water, called formalin. It is used in
tanning, preserving, and embalming and as a germicide, fungicide, and insecticide for
plants and vegetables, but its largest application is in the production of certain
polymeric materials. The plastic Bakelite is made by a reaction between formaldehyde
and phenol. It is not a linear chain but has a three dimensional structure. Similar three-
dimensional polymers are made from formaldehyde and the
compounds urea and melamine. These polymers are used not only as plastics but even
more importantly as adhesives and coatings. Plywood consists of thin sheets of wood
glued together by one of these polymers. In addition to Bakelite, the trade
names Formica and Melmac are used for some of the polymers made from
formaldehyde.
 Phenol-formaldehyde resins are heat-resistant and waterproof, though somewhat brittle. They are formed
through the reaction of phenol with formaldehyde, followed by cross-linking of the polymeric chains.Encyclopædia
Britannica, Inc.

Other carbonyl compounds of industrial use

Other aldehydes of industrial significance are mainly used as

solvents, perfumes, and flavouring agents or as intermediates in the
manufacture of plastics, dyes, and pharmaceuticals. Certain aldehydes occur
naturally in flavouring agents. Among these are benzaldehyde, which provides
the odour and flavour of fresh almonds; cinnamaldehyde, or oil of cinnamon;
and vanillin, the main flavouring agent of vanilla beans.

In addition, certain aldehydes perform essential functions in humans and other

living organisms. Examples are the carbohydrates (including sugars, starch,
and cellulose), which are based on compounds that possess an aldehyde
or ketone group along with hydroxyl groups; the steroid hormones, many of
which, including progesterone, testosterone, cortisone, and aldosterone, are
ketones; and retinal, an aldehyde, which, upon combining with
a protein (opsin) in the retina of the eye to form rhodopsin, is the
main compound involved in the process of vision. Exposure of rhodopsin to
light initiates a cis-trans isomerization in the retinal portion. The resulting
change in molecular geometry is responsible for generating a nerve impulse
that is sent to the brain and perceived as a visual signal (see
also photoreception).
Jerry MarchWilliam H. Brown
Formaldehyde has an irritating odor. Because of its reactivity, it is difficult to handle in the
gaseous state. For many uses, it is therefore dissolved in water and sold as a 37% to
40% aqueous solution called formalin. Formaldehyde denatures proteins, rendering them
insoluble in water and resistant to bacterial decay. For this reason, formalin is used in
embalming solutions and in preserving biological specimens.
Aldehydes are the active components in many other familiar substances. Large quantities
of formaldehyde are used to make phenol-formaldehyde resins for gluing the wood sheets
in plywood and as adhesives in other building materials. Sometimes the formaldehyde
escapes from the materials and causes health problems in some people. While some
people seem unaffected, others experience coughing, wheezing, eye irritation, and other
symptoms.
The odor of green leaves is due in part to a carbonyl compound, cis-3-
hexenal, which with related compounds is used to impart a “green”
herbal odor to shampoos and other products.
Acetaldehyde is an extremely volatile, colorless liquid. It is a starting material for the
preparation of many other organic compounds. Acetaldehyde is formed as a metabolite
in the fermentation of sugars and in the detoxification of alcohol in the liver. Aldehydes
are the active components of many other familiar materials (Figure 10.2.210.2.2).

Figure 10.2.210.2.2 Some Interesting Aldehydes. (a) Benzaldehyde is an oil found in

almonds; (b) cinnamaldehyde is oil of cinnamon; (c) vanillin gives vanilla its flavor;
(d) cis-3-hexenal provides an herbal odor; and (e) trans-2-cis-6-nonadienal gives a
cucumber odor.
Acetone is the simplest and most important ketone. Because it is miscible with water as
well as with most organic solvents, its chief use is as an industrial solvent (for example,
for paints and lacquers). It is also the chief ingredient in some brands of nail polish
remover.
Acetone is formed in the human body as a by-product of lipid metabolism. Normally,
acetone does not accumulate to an appreciable extent because it is oxidized to carbon
dioxide and water. The normal concentration of acetone in the human body is less than
1 mg/100 mL of blood. In certain disease states, such as uncontrolled diabetes mellitus,
the acetone concentration rises to higher levels. It is then excreted in the urine, where it
is easily detected. In severe cases, its odor can be noted on the breath.
Ketones are also the active components of other familiar substances, some of which are
noted in the accompanying figure.

Some ketones have interesting properties: (a) Butter flavoring comes from 2,3-
butanedione; (b) β-ionone is responsible for the odor of violets; (c) muscone is musk oil,
an ingredient in perfumes; and (d) camphor is used in some insect repellents.
Certain steroid hormones have the ketone functional group as a part of their structure.
Two examples are progesterone, a hormone secreted by the ovaries that stimulates the
growth of cells in the uterine wall and prepares it for attachment of a fertilized egg, and
testosterone, the main male sex hormone. These and other sex hormones affect our
development and our lives in fundamental ways.
Summary
The polar carbon-to-oxygen double bond causes aldehydes and ketones to have higher
boiling points than those of ethers and alkanes of similar molar masses but lower than
those of comparable alcohols that engage in intermolecular hydrogen bonding. Aldehydes
are readily oxidized to carboxylic acids, whereas ketones resist oxidation.
A Carboxylic Acid is an organic compound containing a carboxyl functional group. They occur widely
in nature and are also synthetically manufactured by humans. Upon deprotonation, carboxylic acids
yield a carboxylate anion with the general formula R-COO–, which can form a variety of useful salts
such as soaps.

General Formula and Structure

The general formula of a carboxylic acid is R-COOH, were COOH refers to the carboxyl group, and R
refers to the rest of the molecule to which this group is attached. In this carboxyl group, there exists a
carbon which shares a double bond with an oxygen atom and a single bond with a hydroxyl group.
The general structure of a carboxylic acid is illustrated below.

From the illustration provided above, it can be observed that a carboxylic acid contains a hydroxyl
group attached to a carbonyl carbon. Due to the electronegativity of the oxygen atom, this functional
group can undergo ionization and discharge a proton.
The carboxylate ion, produced from the removal of a proton from the carboxyl group, is stabilized by
the presence of two oxygen atoms (through which the negative charge can move). Some common
examples of carboxylic acids include acetic acid (a component of vinegar) and Formic acid.

Nomenclature of Carboxylic Acids

Generally, these organic compounds are referred to by their trivial names, which contain the suffix “-
ic acid”. An example of a trivial name for a carboxylic acid is acetic acid (CH 3COOH). In the IUPAC
nomenclature of these compounds, the suffix “-oic acid” is assigned.
The guidelines that must be followed in the IUPAC nomenclature of carboxylic acids are listed below.

 the suffix “e” in the name of the corresponding alkane is replaced with “oic acid”.
 When the aliphatic chain contains only one carboxyl group, the carboxylic carbon is always
numbered one. For example, CH3COOH is named as ethanoic acid.
 When the aliphatic chain contains more than one carboxyl group, the total number of carbon
atoms is counted and the number of carboxyl groups is represented by Greek numeral prefixes
such as “di-”, “tri-“, etc.
 A carboxylic acid is named by adding these prefixes and suffixes to the parent alkyl chain.
Arabic numerals are used for indicating the positions of the carboxyl group.
 The name “carboxylic acid” or “carboxy” can also be assigned for a carboxyl substituent on a
carbon chain. An example of such nomenclature is the name 2-carboxyfuran for the compound
2-Furoic acid.
Examples
Some examples describing the nomenclature of carboxylic acids as per IUPAC guidelines are provided
below.

Trivial Name and Formula IUPAC Name of the Carboxylic Acid

Formic acid, H-COOH Methanoic acid

Crotonic acid, CH3CH=CH-COOH But-2-enoic acid

Carbonic acid, OH-COOH Carbonic acid

Butyric acid, CH3(CH2)2COOH Butanoic acid

Properties of Carboxylic Acids

Most of the properties of carboxylic acids are a result of the presence of the carboxyl group. Some of
the physical and chemical properties of these compounds are discussed in this subsection.

Physical Properties
 Carboxylic acid molecules are polar due to the presence of two electronegative oxygen atoms.
 They also participate in hydrogen bonding due to the presence of the carbonyl group (C=O)
and the hydroxyl group.
 When placed in nonpolar solvents, these compounds form dimers via hydrogen bonding
between the hydroxyl group of one carboxylic acid and the carbonyl group of the other.

 The solubility of compounds containing the carboxyl functional group in water depends on the
size of the compound. The smaller the compound (the shorter the R group), the higher the
solubility.
 The boiling point of a carboxylic acid is generally higher than that of water.
 These compounds have the ability to donate protons and are therefore Bronsted-Lowry acids.
  They generally have a strong sour smell. However, their esters have pleasant odors and are
therefore used in perfumes.

Chemical Properties
 The α-carbon belonging to a carboxylic acid can easily be halogenated via the Hell-Volhard-
Zelinsky reaction.
 These compounds can be converted into amines using the Schmidt reaction.
 A carboxylic acid can be reduced to an alcohol by treating it with hydrogen to cause a
hydrogenation reaction.
 Upon reaction with alcohols, these compounds yield esters.

Uses of Carboxylic Acids

 Fatty acids that are essential to human beings are made up of carboxylic acids. Examples
include omega-6 and omega-3 fatty acids.
 Higher fatty acids are also used in the manufacture of soaps.
 The production of soft drinks and many other food products involve the use of many carboxylic
acids.
 The manufacture of rubber involves the use of acetic acid as a coagulant.
 Hexanedioic acid is used in the manufacture of nylon-6,6.
 Carboxylic acids have numerous applications in the rubber, textile, and leather industries.
 Ethylenediaminetetraacetic acid is a widely used chelating agent.
 The synthesis of many drugs involves the use of these compounds. Therefore, carboxylic acids
are very important in pharmaceuticals.
 The production of many polymers involves the use of compounds containing the carboxyl
functional group.

We may not know it, but we encounter compounds called carboxylic acids regularly. These
substances are in our kitchens and medicine cabinets and are used in various industrial applications.
In this lesson, we will learn all about carboxylic acids.

Structural Formula and Properties

Carboxylic acids are among us - they are used in manufacturing common items we have at home,
like soap, vinegar, and aspirin. There are so many commercial products that we use that are
manufactured using carboxylic acids. So, what exactly are carboxylic acids? Carboxylic acids are a
classification of organic compounds. They are organic because they contain carbon (C) in their
chemical structure.
 These Substances are Manufactured Using Carboxylic Acids

What makes an organic compound a carboxylic acid? An organic compound that is a carboxylic
acid includes the carboxyl group, -COOH, in its chemical structure. In this case, we need to take a
closer look at the structural formula of a carboxylic acid. The structural formula of a carboxylic acid is
RCOOH, as shown in the following illustration. Here, the R group is a side group that can contain
hydrogen and/or carbon and other atoms. The R group is bonded to the carboxyl group (boxed in
blue). In the carboxyl group, the carbon (C) atom is bonded to -OH and has a double bond with
oxygen (O).

Structural Formula of a Carboxylic Acid

We can see that the structural formula of a carboxylic acid can be written in two ways. On the left
(1), it shows all the carbon, hydrogen, and oxygen bonds, while on the right (2), the carbon atom is
represented by a bend in the structural formula.
For instance, in benzoic acid, the R group (boxed in red) is a ring of carbon and hydrogen atoms
with alternating double bonds. In salicylic acid, shown below, the R group (boxed in red) is a ring of
carbon and hydrogen atoms bonded together with an -OH group attached to the ring.

Examples of Carboxylic Acids

Carboxylic acids are polar substances. When we say polar, this means that the electrical charge
within the compound is not balanced; there is a part of the compound that has a partial positive
charge and another part with a partial negative charge. Because carboxylic acids are polar
substances, they can dissolve in other polar substances like water.

Carboxylic Acids Are Polar Substances

Another property of carboxylic acids is their boiling points tend to be higher than water. For instance,
the boiling point of water is 100 degrees Celsius. Salicylic acid, a carboxylic acid, has a boiling point
of 211 degrees Celsius - much higher than water.
Carboxylic acids are also classified as weak acids, and they tend to have strong odors. For
instance, acetic acid, a carboxylic acid, is a component of vinegar, and this acid accounts for the
strong pungent smell of vinegar. Let's also think about the strong smell of vomit - its strong smell can
also be attributed to the carboxylic acid, butyric acid, present in the vomit.
There are so many carboxylic acids with various uses. We have a lot of household products that
have carboxylic acids as components. Carboxylic acids are not only in commercial products - they
are also an important part of nutrition. Let's take a look at some common carboxylic acids and how
they are used.

In Fatty Acids
Did you know that fatty acids fall under the classification of carboxylic acids? These fatty acids have
the carboxyl group (-COOH), and attached to the carboxyl group is a long chain of carbon and
hydrogen atoms.
Peanut butter, cheese, chicken, and eggs - all of these contain fatty acids. Fatty acids, which make
up fat, are an important part of our nutrition. Having the right amount and the healthy type of fat daily
is great for our health because it can help our bodies function efficiently each day. This way, our
blood cholesterol would be at a healthy level, it would lower the risk of heart disease, and it could
even reduce the risk of cancer. Here is an image showing a few examples of carboxylic acids (fatty
acids) and their sources.
 Some Fatty Acids and Their Sources

Carboxylic acid
CHEMICAL COMPOUND

WRITTEN BY:

 William H. Brown
 Jerry March
See Article History

Carboxylic acid, any of a class of organic compounds in which a carbon(C) atom is

bonded to an oxygen (O) atom by a double bond and to a hydroxyl group (―OH) by a
single bond. A fourth bond links the carbon atom to a hydrogen (H) atom or to some
other univalent combining group. The carboxyl (COOH) group is so-named because
of the carbonyl group (C=O) and hydroxyl group.

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chemical compound: Carboxylic acids

The conjunction of a carbonyl and a hydroxyl group forms a functional group known as a

carboxyl group.
The chief chemical characteristic of the carboxylic acids is their acidity. They are
generally more acidic than other organic compoundscontaining hydroxyl groups but
are generally weaker than the familiar mineral acids (e.g., hydrochloric acid,
HCl, sulfuric acid, H2SO4, etc.).
Carboxylic acids occur widely in nature. The fatty acids are components of glycerides,
which in turn are components of fat. Hydroxyl acids, such as lactic acid (found in
sour-milk products) and citric acid (found in citrus fruits), and many keto acids are
important metabolic products that exist in most living cells. Proteins are made up
of amino acids, which also contain carboxyl groups.
Compounds in which the ―OH of the carboxyl group is replaced by certain other
groups are called carboxylic acid derivatives, the most important of which are acyl
halides, acid anhydrides, esters, and amides.

Carboxylic acid derivatives have varied applications. For example, in addition to its
use as a disinfectant, formic acid, the simplest carboxylic acid, is employed
in textile treatment and as an acid reducing agent. Acetic acid is extensively used in
the production of cellulose plastics and esters. Aspirin, the ester of salicylic acid, is
prepared from acetic acid. Palmitic acid and stearic acid are important in the
manufacture of soaps, cosmetics, pharmaceuticals, candles, and protective coatings.
Stearic acid also is used in rubber manufacture. Acrylic acid is employed as an ester in
the production of polymers (long-chain molecules) known as acrylates. Methacrylic
acid serves as an ester and is polymerized to form Lucite. Oleic acid is used in the
manufacture of soaps and detergents and of textiles.
Nomenclature Of Carboxylic Acids And Their
Salts
The IUPAC name of a carboxylic acid is derived from that of the longest carbon chain
that contains the carboxyl group by dropping the final -e from the name of the parent
alkane and adding the suffix -oic followed by the word “acid.” The chain is numbered
beginning with the carbon of the carboxyl group. Because the carboxyl carbon is
understood to be carbon 1, there is no need to give it a number. For example,
the compound CH3CH2COOH has three carbon atoms and is called propanoic acid,
from propane, the name for a three-carbon chain, with -oic acid, the suffix for this
class of compounds, appended. If the carboxylic acid contains a carbon-carbon double
bond, the ending is changed from -anoic acid to -enoic acid to indicate the presence of
the double bond, and a number is used to show the location of the double bond.
Most simple carboxylic acids, rather than being called by their IUPAC names, are
more often referred to by common names that are older than their systematic names.
Most simple carboxylic acids were originally isolated from biological sources;
because their structural formulas were often unknown at the time of isolation they
were given names that were generally derived from the names of the sources. For
example, CH3CH2CH2COOH, butyric acid, first obtained from butter, was named after
the Latin butyrum, meaning “butter.” The acids containing an odd number of carbon
atoms greater than nine generally do not have common names. The reason is that
long-chain carboxylic acids were originally isolated from fats (which are carboxylic
esters), and generally these fats contain carboxylic acids with only an even number of
carbon atoms (because the process by which living organisms synthesize such fatty
acids puts the molecules together in two-carbon pieces).
When common names are used, substituents on the hydrocarbon chain are designated
by Greek letters rather than by numbers, and counting begins not with the carboxyl
carbon but with the adjacent carbon. For example, the common name of the following
compound γ-aminobutyric acid, abbreviated GABA. Its IUPAC name is 4-
aminobutanoic acid. GABA is an inhibitory neurotransmitter in the central nervous
system of humans.
Salts of carboxylic acids are named in the same manner as are the salts of inorganic
compounds; the cation is named first and then the anion, as in sodium chloride. For
carboxylic acids, the name of the anion is derived by changing the ending -oic acid of
the IUPAC name or -ic acid of the common name to -ate. Some examples are sodium
acetate, CH3COONa; ammonium formate, HCOONH4; and potassium butanoate
(potassium butyrate), CH3CH2CH2COOK.

Properties Of Carboxylic Acids

Acidity
The most important property of carboxylic acids, and the one that is responsible for
naming them such, is their acidity. An acid is any compound that donates a
hydrogen ion, H+ (also called a proton), to another compound, termed a base.
Carboxylic acids do this much more readily than most other classes of organic
compounds, so they are said to be stronger acids, even though they are much weaker
than the most important mineral acids—sulfuric (H2SO4), nitric (HNO3),
and hydrochloric (HCl). The reason for the enhanced acidity of this group of
compounds can best be demonstrated by a comparison of their acidity with that
of alcohols, both of which contain an ―OH group. Alcohols are neutral compounds in
aqueous solution. When an alcohol donates its proton, it becomes a negative ion
called an alkoxide ion, RO−. When a carboxylic acid donates its proton, it becomes a
negatively charged ion, RCOO−, called a carboxylate ion.
A carboxylate ion is much more stable than the corresponding alkoxide ion because of
the existence of resonance structures for the carboxylate ion which disperse its
negative charge. Only one structure can be drawn for an alkoxide ion, but two
structures can be drawn for a carboxylate ion. When two or more structures that differ
only in the positions of valence electrons can be drawn for a molecule or ion, it means
that its valence electrons are delocalized, or spread over more than two atoms. This
phenomenon is called resonance, and the structures are called resonance forms. A
double-headed arrow is used to show that the two or more structures are related by
resonance. Because there are two resonance forms but only one real ion, it follows
that neither of these forms is an accurate representation of the actual ion. The real
structure incorporates aspects of both resonance structures but duplicates neither.
Resonance always stabilizes a molecule or ion, even if charge is not involved. The
stability of an anion determines the strength of its parent acid. A carboxylic acid is,
therefore, a much stronger acid than the corresponding alcohol, because, when it loses
its proton, a more stable ion results.
Some atoms or groups, when attached to a carbon, are electron-withdrawing, as
compared with a hydrogen atom in the same position. For example, consider
chloroacetic acid (Cl―CH2COOH) compared with acetic acid (H―CH2COOH).
Because chlorine has a higher electronegativity than hydrogen, the electrons in the
Cl―C bond are drawn farther from the carbon than the electrons in the corresponding
H―C bond. Thus, chlorine is considered to be an electron-withdrawing group. This is
one example of the so-called inductive effect, in which a substituent affects a
compound’s distribution of electrons. There are a number of such effects, and atoms
or groups may be electron-withdrawing or electron-donating as compared with
hydrogen. The presence of such groups near the COOH group of a carboxylic acid
often has an effect on the acidity. In general, electron-withdrawing groups increase
acidity by increasing the stability of the carboxylate ion. In contrast, electron-donating
groups decrease acidity by destabilizing the carboxylate ion. For example, the methyl
group, ―CH3, is generally regarded as electron-donating, and acetic acid,
CH3 COOH, is about 10 times weaker as an acid than formic acid, HCOOH.
Similarly, chloroacetic acid, ClCH2 COOH, in which the strongly electron-
withdrawing chlorine replaces a hydrogen atom, is about 100 times stronger as an acid
than acetic acid, and nitroacetic acid, NO2CH2 COOH, is even stronger. (The
NO2 group is a very strong electron-withdrawing group.) An even greater effect is
found in trichloroacetic acid, Cl3CCOOH, whose acid strength is about the same as
that of hydrochloric acid.
Solubility
The solubility of carboxylic acids in water is similar to that of alcohols, aldehydes,
and ketones. Acids with fewer than about five carbons dissolve in water; those with a
higher molecular weight are insoluble owing to the larger hydrocarbon portion, which
is hydrophobic. The sodium, ammonium, and potassium salts of carboxylic acids,
however, are generally quite soluble in water. Thus, almost any carboxylic acid can be
made to dissolve in water by converting it to such a salt, which is easily done by
adding a strong base—most commonly sodium hydroxide (NaOH) or potassium
hydroxide, (KOH). The calcium and sodium salts of propanoic (propionic) acid are
used as preservatives, chiefly in cheese, bread, and other baked goods.
Boiling point
Carboxylic acids have much higher boiling points than hydrocarbons, alcohols, ethers,
aldehydes, or ketones of similar molecular weight. Even the simplest carboxylic
acid, formic acid, boils at 101 °C (214 °F), which is considerably higher than the
boiling point of ethanol (ethyl alcohol), C2H5OH, which boils at 78.5 °C (173 °F),
although the two have nearly identical molecular weights. The difference is that two
molecules of a carboxylic acid form two hydrogen bonds with each other (two alcohol
molecules can only form one). Thus, carboxylic acids exist as dimers(pairs of
molecules), not only in the liquid state but even to some extent in the gaseous state.

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Therefore, boiling a carboxylic acid requires the addition of more heat than boiling the
corresponding alcohol, because (1) if the dimer persists in the gaseous state, the
molecular weight is in effect doubled; and, (2) if the dimer is broken upon boiling,
extra energy is required to break the two hydrogen bonds. Carboxylic acids with
higher molecular weights are solids at room temperature (e.g., benzoic and palmitic
acids). Virtually all salts of carboxylic acids are solids at room temperature, as can be
expected for ionic compounds.
Odour

Unbranched-chain carboxylic acids (fatty acids) that are liquids at room temperature,
especially those from propanoic (C3) to decanoic (C10) acid, have very foul,
disagreeable odours. An example is butanoic (butyric) acid (C4), which is the main
ingredient in stale perspiration and thus the chief cause of “locker-room” odour.

Classes Of Carboxylic Acids

Saturated aliphatic acids

Formic acid, HCOOH, is found not only in ants but also in the droplets on the tiny
hairs of the stinging nettle plant (in the family Urticaceae), and the acidity of this
compound causes the stinging sensation felt when these hairs are touched.
 The New Zealand tree nettle (Urtica ferox), showing secretory (glandular), or stinging, hairs (trichomes). Most
herbivores are discouraged from grazing on this plant because of irritating toxins secreted by the trichomes.G.R.
Roberts, Nelson, New Zealand

Acetic acid, CH3COOH, has been known to humankind for thousands of years (at
least in water solution). It is the compound that gives the sourness to vinegar and is
produced by the bacterial oxidation of ethanol in wine. Household vinegar contains
about five percent acetic acid. Acetic acid is important in the metabolic processes of
humans and, indeed, of all animals and plants. In these processes, the CH 3CO (acetyl)
group of the acetic acid molecule is attached to a large biochemical molecule
called coenzyme A; the entire compound is known as acetyl coenzyme A. In the
metabolism of food materials (the body’s conversion of food to energy), the carbon
atoms of carbohydrates, fats, and, to some degree, proteins are converted to acetyl
groups that are bonded to coenzyme A to form acetyl coenzyme A. The acetyl groups
of acetyl coenzyme A are then converted, by means of the tricarboxylic acid cycleand
oxidative phosphorylation (see metabolism), to energy (in the form of adenosine
triphosphate, or ATP) and carbon dioxide (CO2), which is exhaled. Not all the acetyl
groups of acetyl coenzyme A of an organism is converted to energy. Some is used to
synthesize fatty acids, terpenes, steroids, and other needed molecules. The carboxylic
acids that occur in fats have an even number of carbon atoms because they are
synthesized entirely from the two-carbon acetyl units of acetyl coenzyme A.



In animals, molecules of acetic acid (acetate) serve as precursors in the biosynthesis of steroid
hormones.Encyclopædia Britannica, Inc.
The eight-step tricarboxylic acid cycle.Encyclopædia Britannica, Inc.

The even-numbered fatty acids from 4 to 10 carbon atoms are mostly found
in milk fats. Butanoic (butyric) acid, CH3CH2CH2COOH, is an important component
of cow’s milk. Goat’s milk is rich in fats containing the 6-, 8-, and 10-carbon
acids: hexanoic (caproic), octanoic (caprylic), and decanoic (capric) acids,
respectively. Common names for these three acids are derived from the Latin caper,
meaning “goat.” Some hard cheeses (e.g., Swiss cheese) contain natural propanoic
acid. The higher even-numbered saturated acids, from C12 to
C18 (lauric, myristic, palmitic, and stearic), are present in the fats and oils of many
animals and plants, with palmitic and stearic acids being the most prevalent. Lauric
acid (C12) is the main acid in coconut oil (45–50 percent) and palm kernel oil (45–55
percent). Nutmeg butter is rich in myristic acid (C14), which constitutes60–75 percent
of the fatty-acid content. Palmitic acid (C16) constitutes between 20 and 30 percent of
most animal fats and is also an important constituent of most vegetable fats (35–45
percent of palm oil). Stearic acid (C18) is also present in most fats but usually in
smaller amounts than palmitic. Cocoa butter is unusually rich in stearic acid (35
percent).
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Even-numbered saturated fatty acids higher than C18 are much less common in fats but
do occur in some waxes. Waxes obtained from animal and plant sources typically
consist of carboxylic esters derived from long-chain acids and long-chain alcohols.
For example, beeswaxcontains, among other components, the ester made from cerotic
acid (C26) and the unbranched-chain alcohol containing 30 carbons, triacontanol. Odd-
numbered fatty acids have been found only in trace amounts in natural compounds,
but many have been produced synthetically in the laboratory.
Unsaturated aliphatic acids

A number of acids important in organic chemistry contain carbon-carbon double

bonds.
There exist α,β-unsaturated acids, in which the double bond is between the second and
third carbons of the chain, as well as unsaturated acids, in which the double bond
occurs in other positions. Although many of these latter acids occur in nature, they are
less easy to synthesize than α,β-unsaturated acids. Esters of acrylic acid (ethyl and
butyl acrylate) and methacrylic acid (methyl methacrylate) are
important monomers for the synthesis of polymers. Methyl methacrylate polymerizes
to yield a strong transparent solid that is used as a plastic under
such proprietary names as Plexiglas and Lucite. The trans isomer of crotonic acid is
found in croton oil. The cis isomer does not occur in nature but has been synthesized
in the laboratory. Angelic and tiglic acids are a pair of cis-trans isomers. Angelic acid
is found as an ester in angelica root, whereas tiglic acid occurs in croton oil and in
several other natural products.
Ricinoleic acid, an unsaturated hydroxy acid (i.e., one containing an ―OH group),
occurs in castor oil. When this acid is pyrolyzed (heated in the absence of air), it
breaks down to give undecylenic acid and n-heptaldehyde.
The zinc salt of undecylenic acid is used to treat fungal infections of the skin,
especially tinea pedis (athlete’s foot). Esters of this acid are used in perfumery. Sorbic
acid, CH3CH=CHCH=CHCOOH, which has two double bonds in conjugation (that is,
two double bonds separated only by one single bond), and its potassium salt
(potassium sorbate) are used as preservatives in many food products as well as in their
packaging materials, since they inhibit the growth of molds and other fungi.
Many unsaturated acids occur in fats.

These naturally occurring unsaturated fatty acids have certain characteristics. (1) If
there are two or more carbon-carbon double bonds, each double bond is separated
from the next by a CH2 (called methylene) group. (2) Virtually all double bonds in
these and other naturally occurring unsaturated fatty acids have the cis configuration.
(3) Linoleic and linolenic acids are needed by the human body, but the body cannot
synthesize them. They must be obtained in the diet and, therefore, are called essential
fatty acids. (4) Many unsaturated fatty acids are liquids at room temperature, in
contrast to the saturated stearic (C18) and arachidic (C20) acids, which are solids. The
reason is that the regular nature of the saturated hydrocarbon chains allows the
molecules in the solid to stack in a close parallel arrangement, while the presence
of cis double bonds in the unsaturated hydrocarbon chains breaks up this arrangement
and forces the molecules to remain farther apart. Since the molecules in the
unsaturated fatty acids are not as close to each other, less energy is needed to separate
them, and a lower melting-point results. This situation is paralleled in the fats
themselves, which are esters of these long-chain carboxylic acids where the alcohol
component is glycerol, (HOCH2)2CHOH. Solid fats, obtained mostly from animal
sources, have a high percentage of saturated fatty acids. Liquid fats (often called oils),
obtained mainly from plant or fish sources, have a high percentage of unsaturated
fatty acids. An exception is coconut oil, which, though obtained from a plant, has only
a low percentage of unsaturated acids. The liquidity in this case is because of the high
percentage of lauric acid (C12), which has a low molecular weight. Polyunsaturated
fats may be defined as those containing an average of more than one double bond
per fatty acid molecule.
Arachidonic acid is important because the human body uses it as a starting material in
the synthesis of two kinds of essential substances, the prostaglandins and
the leukotrienes, both of which are also unsaturated carboxylic acids. Examples are
PGE2 (a prostaglandin) and LTB4 (a leukotriene). The symbol PG
represents prostaglandin, E indicates the presence of a keto group on the five-
membered ring, and the subscript 2 indicates two double bonds. Similarly, LT
represents leukotriene, B is one form, and the subscript 4 indicates four double bonds.

Prostaglandins and leukotrienes are made in small amounts, but they are significant
because they act as hormone mediators. Some prostaglandins raise blood pressure,
whereas others lower it. PGE2induces labour in pregnant women and is used
medicinally for this purpose, as well as for therapeutic abortions. The PGEs, along
with several other PGs, suppress gastric ulceration and appear to heal peptic ulcers.
The PGE1 analog, misoprostol, is currently used to prevent ulceration associated with
the use of nonsteroidal anti-inflammatory drugs (NSAIDs).
Unsaturated acids exhibit chemical properties expected of compounds that contain
both a COOH group and one or more carbon-carbon double bonds. Like all carboxylic
acids, they are acidic; can be reduced to alcohols; can be converted to acid
derivatives; and, like other compounds containing double bonds, can undergo the
normal double-bond addition reactions and oxidation-reduction reactions.
Aromatic acids
Aromatic acids include compounds that contain a COOH group bonded to an aromatic
ring. The simplest aromatic acid is benzoic acid.

Aromatic carboxylic acids show not only the acidity and other reactions expected of
carboxylic acids (as an acid, benzoic acid is slightly stronger than acetic acid) but,
similar to other aromatic compounds, also undergo electrophilic substitution reactions.
The COOH group is deactivating, meaning electrophilic substitutions take place less
readily than with benzene itself (Friedel-Crafts reactions do not occur), and meta-
directing, meaning that the incoming entity will enter at a position meta to the COOH
group, rather than at an ortho or paraposition, as in, for example, the nitration of
benzoic acid.
Benzoic acid, a solid at room temperature (melting point 122 °C [252 °F]), was first
described in 1560, having been prepared by distilling gum benzoin, a resin obtained
from certain Asian trees. It occurs in various plants, both in free acid form and in ester
form. It is also a constituent of the urine of certain animals, especially horses, as
an amide of glycinecalled hippuric acid, C6H5CONHCH2COOH. The sodium
salt, sodium benzoate, is used as a preservative in many foods.
Some other important aromatic acids include the following:

Salicylic acid is both a carboxylic acid and a phenol, so it can be esterified in two
ways, with both giving rise to familiar products. In methyl salicylate (oil
of wintergreen), the COOH group of salicylic acid is esterified
with methanol (CH3OH), whereas in acetylsalicylic acid (aspirin) the acid component
of the ester is acetic acid, and salicylic acid contributes the phenolic ―OH group.

Gallic acid is found in tea, as well as in other plants, and it also occurs as part of a
larger molecule, called tannin, which is present in galls (such as the swellings of the
tissue of oak trees caused by the attack of wasps). Tannins are used in making leather,
and gallic acid is employed in the production of inks. Three of the most important
aromatic dicarboxylic acids are called phthalic, isophthalic, and terephthalic acid, for
the ortho, meta, and para isomers, respectively. Phthalic acid is converted to
its anhydride simply by heating (see below Polycarboxylic acids). Phthalic
anhydride is used to make polymeric resins called alkyd resins, which are used as
coatings, especially for appliances and automobiles. The paraisomer, terephthalic
acid, is also used to make polymers—namely, polyesters (see below Derivatives of
carboxylic acids: Carboxylic esters).
Several important acids contain an aromatic ring but, because the carboxyl group is
not bonded directly to it, they are not considered to be aromatic acids.

Phenylacetic acid is used to synthesize many other organic compounds. Mandelic acid
is toxic to bacteria in acidic solution and is used to treat urinary infections. Cinnamic
acid, an unsaturated carboxylic acid, is the chief constituent of the fragrant balsamic
resin storax. Ibuprofen and naproxen are important painkilling and anti-inflammatory
drugs. Ibuprofen is sold over-the-counter under proprietary names such as Advil and
Nuprin. Naproxen is sold under names such as Aleve. Both ibuprofen and naproxen
have a stereocentre and are chiral. The physiologically active stereoisomer of each is
the S enantiomer.
Polycarboxylic acids
Unbranched-chain dicarboxylic acids contain two COOH groups. As a result they can
yield two kinds of salts. For example, if oxalic acid, HOOCCOOH, is half-neutralized
with sodium hydroxide, NaOH (i.e., the acid and base are in a 1:1 molar ratio),
HOOCCOONa, called sodium acid oxalate or monosodium oxalate, is obtained.
Because one COOH group is still present in the compound, it has the properties of
both a salt and an acid. Full neutralization (treatment of oxalic acid with NaOH in a
1:2 acid-to-base molar ratio) yields NaOOCCOONa, sodium oxalate. If desired, the
half-neutralization can be done with one base and the rest with another, to produce a
mixed salt, as, for example, KOOCCOONa—sodium potassium oxalate. All
dicarboxylic acids can be neutralized or half-neutralized in a similar manner.
The first three simple unbranched-chain dicarboxylic acids give very different results
upon heating.
Oxalic acid decomposes by losing carbon dioxide (CO2) to give formic
acid (HCOOH), which itself decomposes to yield carbon monoxide (CO)
and water (H2O). Malonic acid loses carbon dioxide by a mechanism in which three
electron pairs (covalent bonds) move around a ring.

A hydrogen atom of the unstable initial enol product moves from an oxygen atom to a
carbon atom (a property known as tautomerism) to give the stable acetic acid. Not
only malonic acid but all carboxylic acids with two COOH groups on the same carbon
atom react in the same manner. With succinic acid, the two COOH groups combine
with the loss of a water molecule to produce succinic anhydride. Glutaric acid, with
five carbon atoms, behaves similarly to yield glutaric anhydride. These reactions
produce five- and six-membered rings, respectively, which are in general the easiest
ring sizes to produce. Because adipic (six carbons) and longer-chain dicarboxylic
acids would give rings of seven or more members, heating of these acids does not
generally lead to cyclic anhydrides, though this conversion sometimes can be
accomplished by using special techniques. Upon heating, phthalic acid readily
yields phthalic anhydride (with a five-membered ring), but isophthalic and
terephthalic acids do not undergo this reaction.
Oxalic acid, in the form of its monopotassium salt, is found in
many vegetables and fruits—in considerable amounts in spinach and rhubarb but also
to a lesser degree in cabbages, tomatoes, and grapes, among others.
Of much greater importance than malonic acid is its diethyl ester,
CH2(COOCH2CH3)2, called diethyl malonate. This compound is used in
a synthetic process to produce a variety of monosubstituted and disubstituted
derivatives of acetic acid.
The series of reactions in the formation of acetic acid derivatives (called the malonic
ester synthesis) is feasible because a methylene groupconnected to two carbonyl
groups (as in diethyl malonate) is somewhat more acidic than similar groups
connected to only one carbonyl groupand can lose a hydrogen ion to a strong base
such as sodium ethoxide (C2H5ONa). When heated with urea and sodium ethoxide,
diethyl malonate yields barbituric acid.
A number of derivatives of barbituric acid have powerful sedative and hypnotic
effects. One such derivative is pentobarbital. As with other derivatives of barbituric
acid, pentobarbital is quite insoluble in water and body fluids. To increase its
solubility in these fluids, pentobarbital is converted to its sodium salt, which is given
the name Nembutal.

Other examples of barbiturates are secobarbital and thiopental, each of which is most
commonly administered as its sodium salt. Thiopental is similar in structure to
pentobarbital, except that an atom of sulfur is substituted for an oxygen in one of the
C=O groups of the six-membered ring.

Barbiturates have two principal effects. In small doses, they are sedatives
(tranquilizers); in larger doses they induce sleep. Pentothal is used as a
general anesthetic. Pentobarbital and secobarbital are often used as a preanesthetic to
prepare patients for surgery. Barbituric acid has none of these effects.
Succinic acid occurs in many plants; its name comes from the Latin succinum,
meaning “amber,” from which it was first isolated. It is an important component of
the tricarboxylic acid cycle (or Krebs cycle), a part of the process by which animals
convert food to energy. Adipic acid, HOOC(CH2)4COOH, is used in the manufacture
of nylon-6,6, the most common form of nylon (see below Derivatives of carboxylic
acids: Amides).
Several important di- and polycarboxylic acids contain one or more hydroxyl groups.

Malic acid is found in many fruits, including apples; tartaric acid occurs in grapes;
and citric acid is present in lemons, oranges, and other citrus fruits. The
monopotassium salt of tartaric acid, commonly called cream of tartar, is obtained from
wine casks, where it crystallizes as a hard crust. In the past, it was used in baking
powders as a leavening agent, but this application has largely (though not entirely)
been superseded by cheaper substances such as monocalcium phosphate. Similar to
succinic acid, malic and citric acids are components of the tricarboxylic acid cycle.
The two most important unsaturated dicarboxylic acids are fumaric and maleic acids,
a pair of cis-trans isomers.

Although these two acids have the same structural formula and differ only in the
three-dimensional geometry of their molecules, their properties are very
different. Maleic acid melts at 130 °C (266 °F) and fumaric acid at 286 °C (547 °F); at
room temperature, maleic acid is about 100 times more soluble in water and about 15
times as strong an acid (although fumaric acid gives up its second proton more readily
than maleic acid does). Only maleic acid forms an anhydride; fumaric acid does not.
Fumaric acid occurs in nature and is a component of the tricarboxylic acid cycle,
whereas maleic acid is not a natural product. Maleic anhydride, which is made
industrially by oxidation of benzene(C6H6), is often used as a dienophile
(isolated alkene component) in Diels-Alder reactions.
Hydroxy and keto acids
The 2-, 3-, 4-, and 5-hydroxycarboxylic acids all lose water upon heating, although
the products are not the same. The 2-hydroxy acids form cyclic dimeric esters (formed
by the esterification of two molecules of the acid) called lactides, whereas the 3- and
4-hydroxy acids undergo intramolecular esterification to give cyclic esters
called lactones. These reactions take place so readily, even without heating, that in
most cases the only way to keep these kinds of hydroxy acids from forming cyclic
esters is to convert them to their sodium or potassium salts. 2-Hydroxy acids lose
water upon heating to yield α,β-unsaturated acids.

The simplest hydroxy acids, glycolic and lactic, occur in nature.

Lactic acid is formed when milk turns sour (hence the name, from Latin lactis,
“milk”) and was first isolated from sour milk by the Swedish chemist Carl Wilhelm
Scheele in 1780. It occurs in plants as well. Lactic acid in the form of its salt (lactate)
is produced in muscle tissue as a result of the anaerobic breakdown of glucose. Excess
lactate is the cause of muscle soreness produced after strenuous exercise when the
body’s supply of oxygen is reduced. Lactic and glycolic acids can be copolymerized
to give a type of polyester that can be made into absorbable surgical sutures.
Traditional suture materials such as catgut must be removed by a health care specialist
after they have served their purpose. These polyester sutures, however, are hydrolyzed
slowly over a period of approximately two weeks. By the time the torn tissues have
healed, the sutures have hydrolyzed, and no surgical removal is necessary. Glycolic
and lactic acids formed during this hydrolysis are metabolized and excreted by the
body.
Pyruvic acid and acetoacetic acid are the simplest and most important of the α-keto
and β-keto acids, respectively.

Pyruvic acid (in the form of its salt pyruvate) is involved in the normal metabolism
of carbohydrates as the final product of a series of some 11 or 12 steps starting from
glucose or fructose. It is then converted (by loss of carbon dioxide) to acetyl
coenzyme A, which enters the tricarboxylic acid cycle. Pyruvate is also used by the
body to synthesize alanine, an amino acid required for the synthesis of proteins.
Acetoacetic acid (in the form of its ethyl ester, called ethyl acetoacetate) is the starting
compound in a series of reactions (the acetoacetic ester synthesis) that is parallel to
the malonic ester synthesis.
The product in this case is an α-substituted acetone (acetone is (CH3)2C=O), and many
mono- and disubstituted acetones have been made by this procedure. Like 2,4-
pentanedione, ethyl acetoacetate exists predominantly in the enol form owing to
stabilization by internal hydrogen bonding. Acetoacetic acid itself is unstable and
loses carbon dioxide to give acetone: CH3COCH2COOH → CH3COCH3+ CO2. In
severe diabetes the body converts acetyl coenzyme A to acetoacetic acid and its
decarboxylation product, acetone—excess quantities of which are secreted in the
urine. These two compounds, along with β-hydroxybutyric acid (in which the acids
are in the form of their salts), are collectively called ketone bodies, although the third
of these is not a ketone; they are used to diagnose diabetes.
Amino acids
Compounds containing both a carboxyl group and an amino group are called amino
acids. Twenty of these are found in proteins, all of which are α-amino acids with the
following formula:

Glutamic acid is one of the amino acids found in proteins, and its sodium
salt, monosodium glutamate (MSG), is often used as a food additive. Although it
imparts no flavour of its own, it enhances the flavours of meats, fish, and vegetables.
Some people experience an allergic reaction to MSG; the allergy is commonly known
as “Chinese restaurant syndrome,” because MSG has been a widely used ingredient in
the cuisine of many Chinese restaurants.

MSGLearn about the myths and safety of monosodium glutamate (MSG).© American Chemical Society

Because carboxyl groups are acidic and amino groups are basic, amino acids undergo
internal acid-base reactions and exist in the form of internal salts known
as zwitterions (from German zwitter, “hybrid”). Because they are internal salts, amino
acids are all solids at room temperature, and most of them are soluble in water.

Para-aminobenzoic acid (p-aminobenzoic acid, PABA) is an aromatic amino acid that

is a part of the folic acid molecule.

Folic acid is required by many organisms. Humans cannot synthesize it and must
obtain it from their diet (it is a B vitamin). Bacteria produce folic acid, using PABA in
this synthesis. In the 1930s it was discovered that when certain disease-causing
bacteria are fed sulfanilamide, a compound with a structure similar to that of PABA,
the bacterial enzymes involved in the incorporation of PABA into folic acid combine
with sulfanilamide instead of PABA. Thus, the enzymes are inhibitedfrom catalyzing
the synthesis of folic acid and, deprived of folic acid, the bacteria die. Sulfanilamide
proved unsuitable for use as a drug, but some of its derivatives (the sulfa drugs) are
used to cure many bacterial diseases.