Name: Deane Marc A.

Torio Subject: Organic Chemistry

Classification of Matter
Chemists study the structures, physical properties, and chemical properties of material substances. These consist of matter, which is anything that occupies space and has
mass. Gold and iridium are matter, as are peanuts, people, and postage stamps. Smoke, smog, and laughing gas are matter. Energy, light, and sound, however, are not matter;
ideas and emotions are also not matter.

The mass of an object is the quantity of matter it contains. Do not confuse an object’s mass with its weight, which is a force caused by the gravitational attraction that operates
on the object. Mass is a fundamental property of an object that does not depend on its location.In physical terms, the mass of an object is directly proportional to the force
required to change its speed or direction. A more detailed discussion of the differences between weight and mass and the units used to measure them is included in Essential
Skills 1 (Section 1.9). Weight, on the other hand, depends on the location of an object. An astronaut whose mass is 95 kg weighs about 210 lb on Earth but only about 35 lb on
the moon because the gravitational force he or she experiences on the moon is approximately one-sixth the force experienced on Earth. For practical purposes, weight and
mass are often used interchangeably in laboratories. Because the force of gravity is considered to be the same everywhere on Earth’s surface, 2.2 lb (a weight) equals 1.0 kg (a
mass), regardless of the location of the laboratory on Earth.

Under normal conditions, there are three distinct states of matter: solids, liquids, and gases. Solids are relatively rigid and have fixed shapes and volumes. A rock, for example,
is a solid. In contrast, liquids have fixed volumes but flow to assume the shape of their containers, such as a beverage in a can. Gases, such as air in an automobile tire, have
neither fixed shapes nor fixed volumes and expand to completely fill their containers. Whereas the volume

 of gases strongly depends on their temperature and pressure (the amount of force exerted on a given area), the volumes of liquids and solids are virtually independent of
temperature and pressure. 
Matter can often change from one physical state to another in a process called a physical change. For example, liquid water can be heated to form a gas called steam, or steam
can be cooled to form liquid water. However, such changes of state do not affect the chemical composition of the substance.
Figure 1.2.11.2.1: The Three States of Matter. Solids have a defined shape and volume.
Liquids have a fixed volume but flow to assume the shape of their containers. Gases
completely fill their containers, regardless of volume. Figure used with permission
from Wikipedia
 Name: Deane Marc A. Torio Subject: Organic Chemistry

Pure Substances and Mixtures

A pure chemical substance is any matter that has a fixed chemical composition and characteristic properties. Oxygen, for example, is a pure chemical substance that is a
colorless, odorless gas at 25°C. Very few samples of matter consist of pure substances; instead, most are mixtures, which are combinations of two or more pure substances in
variable proportions in which the individual substances retain their identity. Air, tap water, milk, blue cheese, bread, and dirt are all mixtures. If all portions of a material are in
the same state, have no visible boundaries, and are uniform throughout, then the material is homogeneous. Examples of homogeneous mixtures are the air we breathe and
the tap water we drink. Homogeneous mixtures are also called solutions. Thus air is a solution of nitrogen, oxygen, water vapor, carbon dioxide, and several other gases; tap
water is a solution of small amounts of several substances in water. The specific compositions of both of these solutions are not fixed, however, but depend on both source and
location; for example, the composition of tap water in Boise, Idaho, is not the same as the composition of tap water in Buffalo, New York. Although most solutions we encounter
are liquid, solutions can also be solid. The gray substance still used by some dentists to fill tooth cavities is a complex solid solution that contains 50% mercury and 50% of a
powder that contains mostly silver, tin, and copper, with small amounts of zinc and mercury. Solid solutions of two or more metals are commonly called alloys.If the
composition of a material is not completely uniform, then it is heterogeneous (e.g., chocolate chip cookie dough, blue cheese, and dirt). Mixtures that appear to
be homogeneous are often found to be heterogeneous after microscopic examination. Milk, for example, appears to be homogeneous, but when examined under a microscope,
it clearly consists of tiny globules of fat and protein dispersed in water. The components of heterogeneous mixtures can usually be separated by simple means. Solid-liquid
mixtures such as sand in water or tea leaves in tea are readily separated by filtration, which consists of passing the mixture through a barrier, such as a strainer, with holes or
pores that are smaller than the solid particles. In principle, mixtures of two or more solids, such as sugar and salt, can be separated by microscopic inspection and sorting.
More complex operations are usually necessary, though, such as when separating gold nuggets from river gravel by panning. First solid material is filtered from river water;
then the solids are separated by inspection. If gold is embedded in rock, it may have to be isolated using chemical methods.

Figure 1.2.21.2.2: A 
Heterogeneous Mixture. Under a microscope, whole milk is actually a heterogeneous
mixture composed of globules of fat and protein dispersed in water. Figure used with permission from
WikipediaHomogeneous mixtures (solutions) can be separated into their component substances by physical processes
that rely on differences in some physical property, such as differences in their boiling points. Two of these separation
methods are distillation and crystallization. 

Distillation
 Name: Deane Marc A. Torio Subject: Organic Chemistry
 makes use of differences in volatility, a measure of how easily a substance is converted to a gas at a given temperature. A simple distillation apparatus for separating a mixture
of substances, at least one of which is a liquid. The most volatile component boils first and is condensed back to a liquid in the water-cooled condenser, from which it flows into
the receiving flask. If a solution of salt and water is distilled, for example, the more volatile component, pure water, collects in the receiving flask, while the salt remains in
the distillation flask.

Figure 1.2.31.2.3: The Distillation of a Solution of Table Salt in Water. The solution

of salt in water is heated in the distilling flask until it boils. The resulting vapor is
enriched in the more volatile component (water), which condenses to a liquid in the
cold condenser and is then collected in the receiving flask.Mixtures of two or more
liquids with different boiling points can be separated with a more
complex distillation apparatus. One example is the refining of crude petroleum into a
range of useful products: aviation fuel, gasoline, kerosene, diesel fuel, and lubricating oil
(in the approximate order of decreasing volatility). Another example is the distillation of
alcoholic spirits such as brandy or whiskey. (This relatively simple procedure caused
more than a few headaches for federal authorities in the 1920s during the era of
Prohibition, when illegal stills proliferated in remote regions of the United States!)

Crystallization
 separates mixtures based on differences in solubility, a measure of how much solid substance remains dissolved in a given amount of a specified liquid. Most substances are
more soluble at higher temperatures, so a mixture of two or more substances can be dissolved at an elevated temperature and then allowed to cool slowly. Alternatively, the
liquid, called the solvent, may be allowed to evaporate. In either case, the least soluble of the dissolved substances, the one that is least likely to remain in solution, usually
forms crystals first, and these crystals can be removed from the remaining solution by filtration.
 Name: Deane Marc A. Torio Subject: Organic Chemistry

Figure 1.2.41.2.4: The 
Crystallization
 of Sodium Acetate from a Concentrated Solution of Sodium Acetate in Water.
The addition of a small “seed” crystal (a) causes the compound to form white
crystals, which grow and eventually occupy most of the flask. Video can be found
here: www.youtube.com/watch?v=BLq5NibwV5gcloseup of bulb flask
containing liquid with many thin spike crystals radially emerging from the
center.

Most mixtures can be separated into pure substances, which may be either
elements or compounds. An element, such as gray, metallic sodium, is a
substance that cannot be broken down into simpler ones by chemical changes;
a compound, such as white, crystalline sodium chloride, contains two or more
elements and has chemical and physical properties that are usually different
from those of the elements of which it is composed. With only a few exceptions, a
particular compound has the same elemental composition (the same elements in
the same proportions) regardless of its source or history. The chemical
composition of a substance is altered in a process called a 

chemical change
. The conversion of two or more elements, such as sodium and chlorine, to a chemical compound, sodium chloride, is an example of a chemical change, often called a chemical
reaction. Currently, about 118 elements are known, but millions of chemical compounds have been prepared from these 118 elements. The known elements are listed
in the periodic table.
 Name: Deane Marc A. Torio Subject: Organic Chemistry

Figure 1.2.51.2.5: The Decomposition of Water to Hydrogen and Oxygen by Electrolysis. Water is a chemical compound; hydrogen and oxygen are elements.a battery wired to
an anode and cathode placed in a beaker filled with water. Two inverted test tubes are submerged in the water and placed over each of the electrodes to collect the gaseous
products. Magnifying pointers show the molecular structure of water in the beaker as well as the hydrogen gas collected on the anode side and oxygen gas on the cathode side.

In general, a reverse chemical process breaks down compounds into their elements. For example, water (a compound) can be decomposed into hydrogen and oxygen (both
elements) by a process called electrolysis. In electrolysis, electricity provides the energy needed to separate a compound into its constituent elements (Figure 1.2.51.2.5). A
similar technique is used on a vast scale to obtain pure aluminum, an element, from its ores, which are mixtures of compounds. Because a great deal of energy is required for
electrolysis, the cost of electricity is by far the greatest expense incurred in manufacturing pure aluminum. Thus recycling aluminum is both cost-effective and ecologically
sound.

The overall organization of 

matter
 and the methods used to separate mixtures are summarized in Figure 1.2.61.2.6.
 Name: Deane Marc A. Torio Subject: Organic Chemistry
Figure 1.2.61.2.6: Relationships between the Types of 
Matter and the Methods Used to Separate Mixtures
Contributors and Attributions

 Modified by Joshua Halpern (Howard University)

Major Classes of Organic Compounds

Organic Compounds
The chemical compounds of living things are known as organic compounds because of their association with organisms and because they are carbon-containing compounds.
Organic compounds, which are the compounds associated with life processes, are the subject matter of organic chemistry. Among the numerous types of organic compounds,
four major categories are found in all living things: carbohydrates, lipids, proteins, and nucleic acids.

Almost all organisms use carbohydrates as sources of energy. In addition, some carbohydrates serve as structural materials. Carbohydrates are molecules composed of
carbon, hydrogen, and oxygen; the ratio of hydrogen atoms to oxygen and carbon atoms is 2:1.

Simple carbohydrates, commonly referred to as sugars, can be monosaccharides if they are composed of single molecules, or disaccharides if they are composed of two
molecules. The most important monosaccharide is glucose, a carbohydrate with the molecular formula C6H12O6. Glucose is the basic form of fuel in living things. In
multicellular organisms, it is soluble and is transported by body fluids to all cells, where it is metabolized to release its energy. Glucose is the starting material for cellular
respiration, and it is the main product of photosynthesis (see Chapters 5 and 6).
 Name: Deane Marc A. Torio Subject: Organic Chemistry
Three important disaccharides are also found in living things: maltose, sucrose, and lactose. Maltose is a combination of two glucose units covalently linked. The table sugar
sucrose is formed by linking glucose to another monosaccharide called fructose. (Figure 2-2 shows that in the synthesis of sucrose, a water molecule is produced. The process
is therefore called a dehydration reaction. The reversal of the process is hydrolysis, a process in which the molecule is split and water is added.) Lactose is composed of glucose
and galactose units.

Figure 2-2     Glucose and fructose molecules combine to form the disaccharide sucrose.

Complex carbohydrates are known as polysaccharides. Polysaccharides are formed by linking innumerable monosaccharides. Among the most important polysaccharides is
starch, which is composed of hundreds or thousands of glucose units linked to one another. Starch serves as a storage form for carbohydrates. Much of the world’s human
population satisfies its energy needs with starch in the form of rice, wheat, corn, and potatoes.

Two other important polysaccharides are glycogen and cellulose. Glycogen is also composed of thousands of glucose units, but the units are bonded in a different pattern than
in starch. Glycogen is the form in which glucose is stored in the human liver. Cellulose is used primarily as a structural carbohydrate. It is also composed of glucose units, but
the units cannot be released from one another except by a few species of organisms. Wood is composed chiefly of cellulose, as are plant cell walls. Cotton fabric and paper are
commercial cellulose products.
 Name: Deane Marc A. Torio Subject: Organic Chemistry

Lipids are organic molecules composed of carbon, hydrogen, and oxygen atoms. The ratio of hydrogen atoms to oxygen atoms is much higher in lipids than in carbohydrates.
Lipids include steroids (the material of which many hormones are composed), waxes, and fats.

Fat molecules are composed of a glycerol molecule and one, two, or three molecules of fatty acids (see Figure 2-3). A glycerol molecule contains three hydroxyl (–OH) groups.
A fatty acid is a long chain of carbon atoms (from 4 to 24) with a carboxyl (–COOH) group at one end. The fatty acids in a fat may all be alike or they may all be different. They
are bound to the glycerol molecule by a process that involves the removal of water.

Certain fatty acids have one or more double bonds in their molecules. Fats that include these molecules are unsaturated fats. Other fatty acids have no double bonds. Fats that
include these fatty acids are saturated fats. In most human health situations, the consumption of unsaturated fats is preferred to the consumption of saturated fats.

Fats stored in cells usually form clear oil droplets called globules because fats do not dissolve in water. Plants often store fats in their seeds, and animals store fats in large,
clear globules in the cells of adipose tissue. The fats in adipose tissue contain much concentrated energy. Hence, they serve as a reserve energy supply to the organism. The
enzyme lipase breaks down fats into fatty acids and glycerol in the human digestive system

Figure 2-3     A fat molecule is constructed by combining a glycerol molecule with three fatty acid molecules. (Two saturated fatty acids
and one unsaturated fatty acid are shown for comparison.) The constructed molecule is at the bottom.

Proteins, among the most complex of all organic compounds, are composed of amino acids (see Figure 2-4), which contain carbon,
hydrogen, oxygen, and nitrogen atoms. Certain amino acids also have sulfur atoms, phosphorus, or other trace elements such as iron or
copper.
 Name: Deane Marc A. Torio Subject: Organic Chemistry
Figure 2-4     The structure and chemistry of amino acids. When two amino acids are joined in a dipeptide, the –OH of
one amino acid is removed, and the –H of the second is removed. So, water is removed. A dipeptide bond (right)
forms to join the amino acids together.

Many proteins are immense and extremely complex. However, all proteins are composed of long chains of relatively
simple amino acids. There are 20 kinds of amino acids. Each amino acid (see the left illustration in Figure 2-4) has an
amino (–NH2) group, a carboxyl (–COOH) group, and a group of atoms called an –R group (where R stands
for radical). The amino acids differ depending on the nature of the –R group, as shown in the middle illustration of
Figure 2-4. Examples of amino acids are alanine, valine, glutamic acid, tryptophan, tyrosine, and histidine.

The removal of water molecules links amino acids to form a protein. The process is called dehydration synthesis, and a by-product of the synthesis is water. The links forged
between the amino acids are peptide bonds, and small proteins are often called peptides.

All living things depend on proteins for their existence. Proteins are the major molecules from which living things are constructed. Certain proteins are dissolved or suspended
in the watery substance of the cells, while others are incorporated into various structures of the cells. Proteins are also found as supporting and strengthening materials in
tissues outside of cells. Bone, cartilage, tendons, and ligaments are all composed of proteins.

One essential function of proteins is as an enzyme. Enzymes catalyze the chemical reactions that take place within cells. They are not used up in a reaction; rather, they remain
available to catalyze succeeding reactions.

Every species manufactures proteins unique to that species. The information for synthesizing the unique proteins is located in the nucleus of the cell. The so-called genetic
code specifies the amino acid sequence in proteins. Hence, the genetic code regulates the chemistry taking place within a cell. Proteins also can serve as a reserve source of
energy for the cell. When the amino group is removed from an amino acid, the resulting compound is energy-rich.

Nucleic acids

Like proteins, nucleic acids are very large molecules. The nucleic acids are composed of smaller units called nucleotides. Each nucleotide contains a carbohydrate molecule
(sugar), a phosphate group, and a nitrogen-containing molecule that, because of its properties, is a nitrogenous base.

Alkanes, Alkenes, and Alkynes

The boiling points of alkanes increase smoothly with increasing molecular mass. They are similar to those of the corresponding alkenes and alkynes because of
similarities in molecular mass between analogous structures (Table 23.6.123.6.1). In contrast, the melting points of alkanes, alkenes, and alkynes with similar
molecular masses show a much wider variation because the melting point strongly depends on how the molecules stack in the solid state. It is therefore sensitive to
relatively small differences in structure, such as the location of a double bond and whether the molecule is cis or trans.
 Name: Deane Marc A. Torio Subject: Organic Chemistry
Table 23.6.123.6.1: Boiling Points (in °C) of Alkanes, Alkenes, and Alkynes of Comparable Molecular Mass

Length of Carbon Chain

Class Two C Atoms Three C Atoms Four C Atoms

alkane −88.6 −42.1 −0.5

alkene −103.8 −47.7 −6.3

alkyne −84.7 −23.2 8.1

Because alkanes contain only C–C and C–H bonds, which are strong and not very polar (the electronegativities of C and H are similar), they are not easily attacked by
nucleophiles or electrophiles. Consequently, their reactivity is limited, and often their reactions occur only under extreme conditions. For example, catalytic cracking can
be used to convert straight-chain alkanes to highly branched alkanes, which are better fuels for internal combustion engines. Catalytic cracking is one example of a
pyrolysis reaction (from the Greek pyros, meaning “fire,” and lysis, meaning “loosening”), in which alkanes are heated to a sufficiently high temperature to induce
cleavage of the weakest bonds: the C–C single bonds. The result is a mixture of radicals derived from essentially random cleavage of the various C–C bonds in the
chain. Pyrolysis of n-pentane, for example, is nonspecific and can produce these four radicals:

2CH3CH2CH2CH2CH3−→ΔCH3⋅+CH2CH2CH2⋅+CH3CH2⋅+CH3CH2CH2⋅(24.5.1)(24.5.1)2CH3CH2CH2CH2CH3→ΔCH3⋅+CH2CH2CH2⋅+CH3CH2⋅+CH3CH2CH2⋅

Recombination of these radicals (a termination step) can produce ethane, propane, butane, n-pentane, n-hexane, n-heptane, and n-octane. Radicals that are formed in
the middle of a chain by cleaving a C–H bond tend to produce branched hydrocarbons. In catalytic cracking, lighter alkanes are removed from the mixture by distillation.

Radicals are also produced during the combustion of alkanes, with CO 2 and H2O as the final products. Radicals are stabilized by the presence of multiple carbon
substituents that can donate electron density to the electron-deficient carbon. The chemical explanation of octane ratings rests partly on the stability of radicals
produced from the different hydrocarbon fuels. Recall that n-heptane, which does not burn smoothly, has an octane rating of 0, and 2,2,4-trimethylpentane
 Name: Deane Marc A. Torio Subject: Organic Chemistry
(“isooctane”), which burns quite smoothly, has a rating of 100. Isooctane has a branched structure and is capable of forming tertiary radicals that are comparatively
stable.

In contrast, the radicals formed during the combustion of n-heptane, whether primary or secondary, are less
stable and hence more reactive, which partly explains why burning n-heptane causes premature ignition and
engine knocking.

In Section 24.2, we explained that rotation about the carbon–carbon multiple bonds of alkenes and alkynes
cannot occur without breaking a π bond, which therefore constitutes a large energy barrier to rotation
(Figure 23.6.123.6.1). Consequently, the cis and trans isomers of alkenes generally behave as distinct
compounds with different chemical and physical properties. A four-carbon alkene has four possible isomeric
forms: three structural isomers, which differ in their connectivity, plus a pair of geometric isomers from one
structural isomer (2-butene). These two geometric isomers are cis-2-butene and trans-2-butene. The four
isomers have significantly different physical properties.

Figure 23.6.123.6.1: Carbon–Carbon Bonding in Alkenes and Interconversion of Cis and Trans Isomers
 Name: Deane Marc A. Torio Subject: Organic Chemistry
In butane, there is only a small energy barrier to rotation about the C2–C3 σ bond. In the formation of cis- or trans-2-butene from butane, the p orbitals on C2 and C3
overlap to form a π bond. To convert cis-2-butene to trans-2-butene or vice versa through rotation about the double bond, the π bond must be broken. Because this
interconversion is energetically unfavorable, cis and trans isomers are distinct compounds that generally have different physical and chemical properties.

Alkynes in which the triple bond is located at one end of a carbon chain are called terminal alkynes and contain a hydrogen atom attached directly to a triply bonded
carbon: R–C≡C–H. Terminal alkynes are unusual in that the hydrogen atom can be removed relatively easily as H +, forming an acetylide ion (R–C≡C−). Acetylide ions
are potent nucleophiles that are especially useful reactants for making longer carbon chains by a nucleophilic substitution reaction. As in earlier examples of such
reactions, the nucleophile attacks the partially positively charged atom in a polar bond, which in the following reaction is the carbon of the Br–C bond:
 Name: Deane Marc A. Torio Subject: Organic Chemistry

Alkenes and alkynes are most often prepared by elimination reactions. A typical example is the preparation of 2-methyl-1-propene, whose derivative, 3-chloro-2-methyl-
1-propene, is used as a fumigant and insecticide. The parent compound can be prepared from either 2-hydroxy-2-methylpropane or 2-bromo-2-methylpropane:

The reaction on the left proceeds by eliminating the elements of water (H + plus OH−), so it is a dehydration reaction. If an alkane contains two properly located
functional groups, such as –OH or –X, both of them may be removed as H 2O or HX with the formation of a carbon–carbon triple bond:
 Name: Deane Marc A. Torio Subject: Organic Chemistry

Alkenes and alkynes are most often prepared by elimination reactions.

Arenes

Most arenes that contain a single six-membered ring are volatile liquids, such as benzene and the xylenes, although some arenes with substituents on the ring are solids
at room temperature. In the gas phase, the dipole moment of benzene is zero, but the presence of electronegative or electropositive substituents can result in a net
dipole moment that increases intermolecular attractive forces and raises the melting and boiling points. For example, 1,4-dichlorobenzene, a compound used as an
alternative to naphthalene in the production of mothballs, has a melting point of 52.7°C, which is considerably greater than the melting point of benzene (5.5°C).

Certain aromatic hydrocarbons, such as benzene and benz[a]pyrene, are potent liver toxins and carcinogens. In 1775, a British physician, Percival Pott, described the
high incidence of cancer of the scrotum among small boys used as chimney sweeps and attributed it to their exposure to soot. His conclusions were correct:
benz[a]pyrene, a component of chimney soot, charcoal-grilled meats, and cigarette smoke, was the first chemical carcinogen to be identified.

Although arenes are usually drawn with three C=C bonds, benzene is about 150 kJ/mol more stable than would be expected if it
contained three double bonds. This increased stability is due to the delocalization of the π electron density over all the atoms of the
ring. Compared with alkenes, arenes are poor nucleophiles. Consequently, they do not undergo addition reactions like alkenes;
instead, they undergo a variety of electrophilic aromatic substitution reactions that involve the replacement of –H on the arene by a
group –E, such as –NO2, –SO3H, a halogen, or an alkyl group, in a two-step process. The first step involves addition of the
electrophile (E) to the π system of benzene, forming a carbocation. In the second step, a proton is lost from the adjacent carbon on
the ring:
 Name: Deane Marc A. Torio Subject: Organic Chemistry

The carbocation formed in the first step is stabilized by resonance.

Arenes undergo substitution reactions rather than elimination because of increased stability arising from delocalization of their π electron density.

Many substituted arenes have potent biological activity. Some examples include common drugs and antibiotics such as aspirin and ibuprofen, illicit drugs such as
amphetamines and peyote, the amino acid phenylalanine, and hormones such as adrenaline (Figure 23.6.223.6.2).
 Name: Deane Marc A. Torio Subject: Organic Chemistry

Figure 23.6.223.6.2: Biologically Active Substituted Arenes

Aspirin (antifever activity), ibuprofen (antifever and anti-inflammatory activity), and amphetamine (stimulant) have pharmacological effects. Phenylalanine is an amino
acid. Adrenaline is a hormone that elicits the “fight or flight” response to stress. Chiral centers are indicated with an asterisk.
 Name: Deane Marc A. Torio Subject: Organic Chemistry
Alcohols and Ethers

Both alcohols and ethers can be thought of as derivatives of water in which at least one hydrogen atom has been replaced by an organic group, as shown here.
Because of the electronegative oxygen atom, the individual O–H bond dipoles in alcohols cannot cancel one another, resulting in a substantial dipole moment that allows
alcohols to form hydrogen bonds.

Alcohols therefore have significantly higher boiling points than alkanes or alkenes of comparable molecular mass, whereas ethers, without a polar O–H bond, have
intermediate boiling points due to the presence of a small dipole moment (Table 23.6.223.6.2). The larger the alkyl group in the molecule, however, the more “alkane-
like” the alcohol is in its properties. Because of their polar nature, alcohols and ethers tend to be good solvents for a wide range of organic compounds.
Table 23.6.223.6.2: Boiling Points of Alkanes, Ethers, and Alcohols of Comparable Molecular Mass

Name Formula Molecular Mass (amu) Boiling Point (°C)

propane C3H8 44 −42.1

alkane n-pentane C5H12 72 36.1

n-heptane C7H16 100 98.4

 Name: Deane Marc A. Torio Subject: Organic Chemistry
Table 23.6.223.6.2: Boiling Points of Alkanes, Ethers, and Alcohols of Comparable Molecular Mass

Name Formula Molecular Mass (amu) Boiling Point (°C)

dimethylether (CH3)2O 46 −24.5.1

ether diethylether (CH3CH2)2O 74 34.5

di-n-propylether (CH3CH2CH2)2O 102 90.1

ethanol CH3CH2OH 46 78.3

alcohol n-butanol CH3(CH2)3OH 74 117.7

n-hexanol CH3(CH2)5OH 102 157.6

Alcohols are usually prepared by adding water across a carbon–carbon double bond or by a nucleophilic
substitution reaction of an alkyl halide using hydroxide, a potent nucleophile (Figure 23.6.123.6.1). Alcohols
can also be prepared by reducing compounds that contain the carbonyl functional group (C=O; part (a) in
Figure 24.5.7). Alcohols are classified as primary, secondary, or tertiary, depending on whether the –OH
group is bonded to a primary, secondary, or tertiary carbon. For example, the compound 5-methyl-3-hexanol
is a secondary alcohol.
 Name: Deane Marc A. Torio Subject: Organic Chemistry
Ethers, especially those with two different alkyl groups (ROR′), can be prepared by a substitution reaction in which a nucleophilic alkoxide ion (RO −) attacks the partially
positively charged carbon atom of the polar C–X bond of an alkyl halide (R′X):

Although both alcohols and phenols have an –OH functional group, phenols are 10 6–108 more acidic than alcohols. This is largely because simple alcohols have the –OH
unit attached to an sp3 hybridized carbon, whereas phenols have an sp2 hybridized carbon atom bonded to the oxygen atom. The negative charge of the phenoxide ion
can therefore interact with the π electrons in the ring, thereby delocalizing and stabilizing the negative charge through resonance. In contrast, the negative charge on
an alkoxide ion cannot be stabilized by these types of interactions.

Alcohols undergo two major types of reactions: those involving cleavage of the O–H bond and those involving cleavage of the C–O bond. Cleavage of an O–H bond is a
reaction characteristic of an acid, but alcohols are even weaker acids than water. The acidic strength of phenols, however, is about a million times greater than that of
ethanol, making the pKa of phenol comparable to that of the NH4+ ion (9.89 versus 9.25, respectively):

C6H5OH+H2O⇌H3O++C6H5O−(24.5.1)(24.5.1)�6�5��+�2�⇌�3�++�6�5�−

Alcohols undergo two major types of reactions: cleavage of the O–H bond and cleavage of the C–O bond.

Cleavage of the C–O bond in alcohols occurs under acidic conditions. The –OH is first protonated, and nucleophilic substitution follows:

In the absence of a nucleophile, however, elimination can occur, producing an alkene (Figure 24.5.6). Ethers lack the –OH unit that is central to the reactivity of
alcohols, so they are comparatively unreactive. Their low reactivity makes them highly suitable as solvents for carrying out organic reactions.
 Name: Deane Marc A. Torio Subject: Organic Chemistry
Aldehydes and Ketones

Aromatic aldehydes, which have intense and characteristic flavors and aromas, are the major components of such well-known flavorings as vanilla and cinnamon (Figure
24.5.3). Many ketones, such as camphor and jasmine, also have intense aromas. Ketones are found in many of the hormones responsible for sex differentiation in
humans, such as progesterone and testosterone.

Figure 23.6.323.6.3: Some Familiar Aldehydes and Their Uses

In compounds containing a carbonyl group, nucleophilic attack can occur at the carbon atom of the
carbonyl, whereas electrophilic attack occurs at oxygen.

Aldehydes and ketones contain the carbonyl functional group, which has an appreciable
dipole moment because of the polar C=O bond. The presence of the carbonyl group
results in strong intermolecular interactions that cause aldehydes and ketones to have
higher boiling points than alkanes or alkenes of comparable molecular mass (Table
 Name: Deane Marc A. Torio Subject: Organic Chemistry
24.5.3). As the mass of the molecule increases, the carbonyl group becomes less important to the overall properties of the compound, and the boiling points approach
those of the corresponding alkanes.

Table 23.6.223.6.2: Boiling Points of Alkanes, Aldehydes, and Ketones of Comparable Molecular Mass

Name Formula Molecular Mass (amu) Boiling Point (°C)

n-butane C4H10 58 −0.5

alkane

n-pentane C5H12 72 36.1

propionaldehyde (propanal) C3H6O 58 48.0

aldehyde

butyraldehyde (butanal) C4H8O 72 74.8

acetone (2-propanone) C3H6O 58 56.1

ketone

methyl ethyl ketone (2-butanone) C4H8O 72 79.6

Aldehydes and ketones are typically prepared by oxidizing alcohols (part (a) in Figure 24.5.7). In their reactions, the partially positively charged carbon atom of the
carbonyl group is an electrophile that is subject to nucleophilic attack. Conversely, the lone pairs of electrons on the oxygen atom of the carbonyl group allow
electrophilic attack to occur. Aldehydes and ketones can therefore undergo both nucleophilic attack (at the carbon atom) and electrophilic attack (at the oxygen atom).

Nucleophilic attack occurs at the partially positively charged carbon of a carbonyl functional group. Electrophilic attack occurs at the lone pairs of electrons on the
oxygen atom.
 Name: Deane Marc A. Torio Subject: Organic Chemistry
Aldehydes and ketones react with many organometallic compounds that contain stabilized carbanions. One of the most important classes of such compounds are the
Grignard reagents, organomagnesium compounds with the formula RMgX (X is Cl, Br, or I) that are so strongly polarized that they can be viewed as containing R − and
MgX+. These reagents are named for the French chemist Victor Grignard (1871–1935), who won a Nobel Prize in Chemistry in 1912 for their development. In a Grignard
reaction, the carbonyl functional group is converted to an alcohol, and the carbon chain of the carbonyl compound is lengthened by the addition of the R group from the
Grignard reagent. One example is reacting cyclohexylmagnesium chloride, a Grignard reagent, with formaldehyde:

The nucleophilic carbanion of the cyclohexyl ring attacks the

electrophilic carbon atom of the carbonyl group. Acidifying the
solution results in protonation of the intermediate to give the
alcohol. Aldehydes can also be prepared by reducing a
carboxylic acid group (–CO2H) (part (a) in Figure 24.5.7), and ketones can be prepared by reacting a carboxylic acid derivative with a Grignard reagent. The former
reaction requires a powerful reducing agent, such as a metal hydride.