Organic Chemistry PDF

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Organic Chemistry
Engr. Peter Fowler, RCh
Organic Chemistry for ChE

• Introduction
• The Structural Theory and Bonding
• Properties, Nomenclature, Preparation, and Reactions of Organic
Compounds
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Introduction
Introduction
• Organic chemistry is the chemistry of the compounds of carbon
• Before, organic compounds were thought to come only from
vegetable or animal sources; inorganic compounds were those
obtained from minerals.
• In 1828, Friedrich Wöhler synthesized urea from ammonium
cyanate, an inorganic compound.
• This was counterevidence to the then-prevailing vitalist hypothesis that only
organisms can produce “organic” compounds.
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Introduction
• There are two large reservoirs of organic compounds:
• petroleum
• coal
• These are the “fossil fuels,” which are being consumed at an
alarmingly high rate.
• Alternative sources of organic raw materials must be utilized—especially
biomass, which is renewable.
Introduction
• The property that sets out carbon from all the rest of the elements
is its ability to attach to other carbon atoms and form chains,
known as catenation.
• Carbon atoms can form chains thousands of atoms long, or rings of all sizes;
these chains or rings can have branches and cross-links.
• Other atoms, chiefly H, O, N, and the halogens, can attach to the carbon atoms
as well.
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The Structural Theory and

Bonding
Structural Theory
• It is the framework of ideas about how atoms are put together
to make molecules.
• orders of attachments of atoms
• how electrons hold atoms together
• shapes and sizes of the molecules formed
• the way electrons are distributed over molecules
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Structural Theory
• In terms of the structural theory, we can know from a structural
formula:
• how to go about making a compound
• what physical properties to expect of a compound (melting point, boiling
point, specific gravity, solubility, color, etc.)
• the kind of reagents the compound will react with
• the kind of products its reactions will form
• whether the compound reacts rapidly or slowly
The Chemical Bond

• Before quantum mechanics was introduced in 1926, chemical
bonds were based on the following concept of the atom:
• A positively charged nucleus is surrounded by electrons arranged in
concentric shells or energy levels.
• There is a maximum number of electrons that can be accommodated in each
shell: 2 in the first, 8 in the second, 8 or 18 in the third, etc.
• The greatest stability is reached when the outer shell is full, as in the
noble gases.
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The Chemical Bond

IONIC BONDS
• result from transfer of electrons
• the electrostatic attraction between oppositely charged ions
• typical of salts formed by combinations of metals and nonmetals.
The Chemical Bond

COVALENT BONDS
• result from sharing of electrons
• the electrostatic attraction between shared
electrons and nuclei of participating atoms
• typical of the compounds of carbon; it is the
bond of chief importance in the study of
organic chemistry.
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Quantum Mechanics
• In 1926, Erwin Schrödinger worked out mathematical expressions
(wave equations) to describe the motion of an electron in terms of
its energy.
• The series of solutions, called wave functions, correspond to different
energy levels for the electron.
• A wave equation (i.e., the Schrödinger equation) cannot tell us
exactly where an electron is ay any particular moment, or how
fast it is moving.
• Instead, it tells us the probability of finding an electron at any particular
region in space.
Quantum Mechanics
• This region in space where an electron is likely to be found is called
an orbital.
• It is the shapes of these orbitals and their disposition with respect to each
other that help us determine the arrangement in space of the atoms of a
molecule, and even help determine its chemical behavior.
• The shape of the electron cloud is the shape of the orbital.
• This cloud is non-uniform, but is densest in regions where the
probability of finding the electron is highest—that is, where the
electron density is greatest.
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Quantum Mechanics
• The orbital at the lowest energy level is the 1s orbital.
Quantum Mechanics
• At the next higher energy level there is the 2s orbital, which is
naturally larger than the 1s orbital and is at a higher energy (lower
stability).
• Next, there are three orbitals of equal energy called 2p orbitals,
which are dumbbell-shaped.
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Quantum Mechanics
• Recall the Pauli exclusion principle in determining electronic
configuration: Only two electrons can occupy any atomic orbital,
and to do so these two must have opposite spins.
• Additionally, electrons of like spin tend to get as far from each
other as possible (Hund’s Rule of Maximum Multiplicity).
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Quantum Mechanics
• In molecules, as in isolated atoms, electron occupy orbitals—
molecular orbitals—which are considered to be centered about
many nuclei.
• The distribution of nuclei and electrons is simply the one that results in the
most stable molecule.
• In the MO approach, there are two simplifying assumptions:
• Each pair of electrons is essentially localized near just two nuclei.
• The shapes of these localized molecular orbitals and their disposition with
respect to each other are related in a simple way to the shapes and
disposition of atomic orbitals in the component atoms.
The Covalent Bond

• In the valence bond theory, for a covalent bond to form, two
atoms must be located so that an orbital of one overlaps an orbital
of another.
• Subsequently, the orbitals merge to form a single bond orbital, which is
occupied by electrons.
• This arrangement of electrons and nuclei contains less energy—it is more
stable.
• The formation of a bond is accompanied by evolution of energy.
• bond dissociation energy
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The Covalent Bond

• The greater the overlap of atomic orbitals, the stronger the bond.
• In the isolated atoms, each electron is attracted by—and attracts—one
positive nucleus; in the molecule, each electron is attracted by two
positive nuclei.
• The bond length is the internuclear distance leading to the lowest
energy (highest stability).
• Each kind of covalent bond has a characteristic length and
strength.
The Covalent Bond

• e.g., for each H atom, the
sole electron occupies the
1s orbital.
• If the bond orbital formed
is cylindrically
symmetrical about the
internuclear axis, it is
called a σ orbital and the
bond is called a σ bond.
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The Covalent Bond

• e.g., for each F atom, there
are two electrons in the 2s
orbital and two electrons
in each of the two 2p
orbitals.
• The formed bond has the
same general shape as that
in H2; it is also designated
as a σ bond.
Hybrid Orbitals
• Bond formation is an energy-releasing process, and the tendency is
to form bonds—and as many as possible—even if this results in
bond orbitals that bear little resemblance to the atomic orbitals.
• Consider BeCl2, which has no unpaired electrons:
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Hybrid Orbitals
• We “promote” one of the 2s electrons to an empty p orbital:
• Fact: the two bonds in BeCl2 are equivalent. So, we hybridize the
orbitals:
Hybrid Orbitals
• Various combinations of
one s orbital and one p
orbital are taken
mathematically, and the
mixed (hybrid) orbitals
with the greatest
degree of directional
character are found.
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Hybrid Orbitals
• Results:
• The “best” hybrid orbital
is much more strongly
directed than either the s
or the p orbital.
• The two best orbitals are
exactly equivalent to
each other.
• These orbitals point in
exactly opposite
directions.
Hybrid Orbitals
• bond angle – the angle between two specified bonds in a molecule
• For maximum overlap between the sp orbitals of beryllium and the
p orbitals of chlorine, the Cl atoms must be located on exactly
opposite sides of the beryllium atom.
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Hybrid Orbitals
• Next, consider BF3:
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Hybrid Orbitals
• Now, let’s turn to methane, CH4:
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Hybrid Orbitals
• with unshared electron pairs
Hybrid Orbitals
• with unshared electron pairs
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Bond and Molecular Polarity

• In most cases, the nuclei of covalently bonded atoms do not share
the electrons equally; the electron cloud is denser about one
atom than the other.
• Consequently, one end of the bond is relatively negative and the other end is
relatively positive. Such a bond is said to be a polar bond.
• We can expect polarity if a covalent bond joins two atoms that differ in
electronegativity.

• A general trend is as follows:
F > O > Cl, N > Br > C, H
• Bond polarities can lead to molecular polarities, which can
profoundly affect melting point, boiling point, and solubility.
• A molecule is polar IF the center of negative charge does not
coincide with the center of positive charge—in other words, they
are separated a certain distance.
• Such molecule constitutes a dipole: two opposite and equal charges
separated in space
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• Elements that exist as diatomic molecules have zero dipole
moments.
• Molecular polarity also depends on the shape of the molecule.
Structure and Physical Properties

MELTING POINT and BOILING POINT
• ionic compounds
• form crystals where structural units are ions
• units held together by strong electrostatic, interionic forces
• very high melting and boiling temperatures
• non-ionic compounds
• form crystals where structural units are molecules
• units held together by weak intermolecular forces
• low melting and boiling temperatures (except for associated liquids)
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intermolecular forces
• also electrostatic in nature, involving coulombic attraction
• two kinds: dipole-dipole interactions and van der Waals forces
• dipole-dipole interactions
• exist between polar molecules
• H-bonding: a hydrogen atom serves as a bridge between two electronegative
atoms; liquids whose molecules are held together by H-bonds are called
associated liquids
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intermolecular forces
• also electrostatic in nature, involving coulombic attraction
• two kinds: dipole-dipole interactions and van der Waals forces
• van der Waals forces
• exist between both polar and nonpolar molecules
• result from transient distortions of the electron cloud: induced dipoles

SOLUBILITY
• As in melting and boiling, energy must be supplied to overcome
interionic or intermolecular forces in solids.
• The energy required to break the bonds between solute particles is
supplied by the formation of bonds between the solute particles
and the solvent molecules: old attractive forces are replaced by
new ones.
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SOLUBILITY
• ionic solutes
• Only water or other highly polar solvents are able to dissolve ionic
compounds appreciably: ion-dipole interactions
• In solution, ions are surrounded by clusters of solvent molecules: solvation

SOLUBILITY
• non-ionic solutes
• “Like dissolves like.”
• Nonpolar organic compounds are not readily soluble in water (e.g., CCl4).
• Highly polar organic compounds are readily soluble in water (e.g., CH3OH).
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Acids and Bases

• Brønsted-Lowry definition
• Acids give up protons, bases accept protons.
• The strength of an acid depends upon its tendency to give up a proton, and
the strength of a base depends upon its tendency to accept a proton.
Acids and Bases

• Brønsted-Lowry definition
• Many organic compounds that contain oxygen can act as bases and accept
protons.
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Acids and Bases

• Lewis definition
• Acids accept electron pairs, bases donate electron pairs.
• This is the most fundamental of the acid-base concepts, and the most
general; it includes all other concepts.
• A proton is an acid because it is deficient in electrons, and needs an electron pair
to complete its valence shell.
• Hydroxide ion, ammonia, and water are bases because they contain electron pairs
available for sharing.
Acids and Bases

• Structure and Acidity
• To be acidic in the Brønsted-Lowry sense, a molecule must contain
hydrogen. The degree of acidity depends on the kind of atom that holds the
hydrogen, and by that atom’s ability to accommodate the electron pair left
behind by the departing hydrogen ion (electronegativity and size).
within a given row: H-CH3 < H-NH2 < H-OH < H-F
H-SH < H-Cl
within a given family: H-F < H-Cl < H-Br < H-I
H-OH < H-SH < H-SeH
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Acids and Bases

• Structure and Acidity
• To be acidic in the Lewis sense, a molecule must be electron-deficient; we
would look for an atom bearing only a sextet of electrons.
• Structure and Basicity
• To be basic in either theory, a molecule must have an electron pair available
for sharing.
• The availability of these unshared electrons is determined largely by the
atom that holds them: electronegativity, size, and charge.
• The better an atom accommodates the electron pair, the less available it is for
sharing.
Alkanes:
Structure, Preparation, and
Reactions
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Methane
• Methane, CH4, is the simplest member of the alkane family.
• We study methane since most of what we learn about it can be carried over
with minor modifications to any alkane.
Methane
• m.p. -183oC and b.p. -161.5oC; Methane is a gas at ordinary
temperatures.
• Methane is colorless and, when liquefied, is less dense than water.
Source
• natural gas (97%)
• “firedamp”
• “marsh gas”
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Reactions of Methane
• In its chemical properties, methane sets the pattern for the alkane
family.
• Typically, it reacts only with highly reactive substances—or under very
vigorous conditions, which amounts to the same thing.
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• OXIDATION
• Combustion to CO2 and H2O is characteristic of organic compounds; under
special conditions it is used to determine their C and H content.
• Burning of hydrocarbons takes place only
at high temperatures, as provided, for
example, by a flame or a spark.
• Through controlled partial oxidation,
methane is an increasingly important
source of H2, CO, and C2H4.
• HALOGENATION – with chlorine (Cl2)
• Under the influence of UV light or at a temperature of 250-400oC, a mixture
of methane and chlorine reacts vigorously to yield HCl and CH3Cl -
chlorination
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• HALOGENATION – with chlorine (Cl2)
• Since chlorination may yield any one of four organic products, there must be
control to limit the reaction to a certain stage.
• This is done by using a large excess of methane.
• The use of a large excess of one reactant is a common device in organic
chemistry to limit reactions to only one of a number of reactive sites in the
molecule of that reactant.
• HALOGENATION – with other halogens
• Methane reacts with bromine (bromination) at high temperatures or under
the influence of UV light to yield bromomethanes:
• Bromination takes place somewhat less readily than chlorination.

• Methane does not react with iodine at all. With fluorine, the reaction is so
vigorous even in the dark and at room temperature.
reactivity of halogens: F2 > Cl2 > Br2 (> I2)
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Ethane
• C2H6: each carbon atom is bonded to three H and the other C
• The C—H σ bonds result from overlap of the C-sp3 orbitals with H-s
orbitals.
• The C—C σ bond results from overlap of the two C-sp3 orbitals.
Ethane
• If various possible arrangements about the cylindrically
symmetrical σ bond do not differ in energy, then we say there is
free rotation around the carbon-carbon single bond.
• conformations – different arrangements of atoms that can be
converted into one another by rotation about single bonds
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Ethane
• Certain physical properties
show that rotation for the
ethane C—C bond is not
quite free: there is an energy
barrier of about 3 kcal/mol.
• This barrier is not a very high
one; even at room temperature,
there is rapid interconversion
between staggered
conformations.
Ethane
• torsional energy – energy required to rotate a molecule about the
C—C bond
• torsional strain – a consequence of torsional strain, resulting to
the relative instability of the eclipsed and skew conformations
• As the hydrogens of ethane are replaced by other atoms or groups
of atoms, other factors appear:
• van der Waals forces
• dipole-dipole interactions
• hydrogen-bonding
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Propane and the Butanes

• propane; C3H8; CH3CH2CH3 – rotation about the two C—C bonds is
essentially “free”
• The rotational barrier (3.3 kcal/mol) is due chiefly to torsional strain.
Propane and the Butanes

• butane; C4H10 – two possible structures corresponding to two
compounds with definite differences in their physical and chemical
properties - isomers
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van der Waals Repulsion

• Due to the presence of the methyl groups on both sides of the
middle C—C bond, there are two new points encountered:
• the presence of several different conformations
• a new factor besides torsional strain affecting conformational stability

• anti conformation – methyl groups are far apart as possible
(dihedral angle = 180oC)
• gauche conformation – methyl groups are 60oC
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• The anti conformation is more
stable by 0.8 kcal/mol than the
gauche.
• In the gauche conformation, the
methyl groups are thrown together
closer than the sum of their van
der Waals radii.
• We say that there is van der Waals
repulsion or steric repulsion.
Higher Alkanes
• There is a constant difference between successive members in the family
of alkanes: CH2
• Thus, the general formula for alkanes is: CnH2n+2.
• As we go up in the series, the number of isomers increases at a very high
rate.
• There are:
• 3 pentane isomers
• 5 hexane isomers
• 9 heptane isomers…
• 75 decane isomers…
• 366,319 icosane isomers
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Nomenclature
• For the isomers of butane and pentane:
• n-butane and n-pentane
• isobutene and isopentane
• neopentane
Nomenclature
alkyl groups: replace –ane with –yl
• propyl groups:
• butyl groups:
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Nomenclature
alkyl groups: replace –ane with –yl
• for larger alkyl groups, n- and iso- can still be used
Nomenclature: IUPAC System

Rules:
• Select as the parent structure the longest continuous chain. All other
branches are alkyl groups.
• Where necessary, indicate by a number the carbon to which the alkyl
group is attached.
• In number the parent chain, start at whichever end results in the use of
the lowest numbers.
• For repeating alkyl groups, use prefixes and indicate by various numbers
the positions of each group.
• If there are several different alkyl groups, name them in alphabetical
order. (excluding prefixes but including iso)
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3,3-diethyl-5-isopropyl-4-methyloctane
Classes of C and H Atoms

primary (10)
• attached to only one carbon
secondary (20)
• attached to two carbons
tertiary (30)
• attached to three carbons
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Physical Properties
• Alkanes are either non-polar or very weakly polar.
• Within a family, we would expect that the larger the molecule—
and hence the larger its surface area—the stronger the
intermolecular forces.
• The first four n-alkanes are gases.
• The next 13 n-alkanes are liquids.
• n-alkanes with more than 18 carbons are solids.
• Alkanes are soluble in nonpolar solvents and can themselves be
considered solvents for nonpolar solutes.
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Industrial Source
• The principal source of alkanes is petroleum and the
accompanying natural gas.
• Petroleum is separated by distillation into various fractions:
Fraction Distillation temp. (oC) Carbon number
Gas < 20 1-4
Petroleum ether 20-60 5-6
Ligroin (light naphtha) 60-100 6-7
Natural gasoline 40-205 5-10, cycloalkanes
Kerosene 175-325 12-18, aromatics
Gas oil >275 > 12
Lubricating oil non-volatile liquids long chains attached to cyclic structures
Asphaul or petroleum coke non-volatile solids polycyclic structures
Preparation of Alkanes
• HYDROGENATION OF ALKANES
𝐇𝟐 +𝐏𝐭, 𝐏𝐝, 𝐨𝐫 𝐍𝒊
𝑪𝒏 𝑯𝟐𝒏 𝑪𝒏 𝑯𝟐𝒏+𝟐
• When shaken under a slight pressure of hydrogen gas in the presence of a

small amount of catalyst, alkenes are converted smoothly and completely
into alkanes of the same carbon skeleton.
• The most important method of preparation of alkanes.
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• REDUCTION OF ALKYL HALIDES
• Hydrolysis of Grignard reagent
𝑯𝟐 𝑶
𝑹 − 𝑿 + 𝑴𝒈 → 𝑹 − 𝑴𝒈𝑿 𝑹−𝑯
• Grignard reagent – product of a vigorous reaction between an

alkyl halide and turnings of metallic magnesium in dry ether.
• Hydrolysis of Grignard reagent
𝑯𝟐 𝑶
𝑹 − 𝑿 + 𝑴𝒈 → 𝑹 − 𝑴𝒈𝑿 𝑹−𝑯
• The carbon-magnesium bond is highly polar with a partially

negative carbon. The magnesium-halide bond is essentially ionic.
• The organic group has considerable carbanion character!
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• The Grignard reagent can be considered to be the magnesium salt
of the extremely weak acid R—H. In other words, it is a strong
Lewis base.
• Reduction by metal and acid
𝑹 − 𝑿 + 𝒁𝒏 + 𝑯+ → 𝑹 − 𝑯 + 𝒁𝒏𝟐+ + 𝑿−
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• COUPLING OF ALKYL HALIDES WITH ORGANOMETALLIC
COMPOUNDS
Li CuX
𝑹−𝑿 𝑹 − 𝑳𝒊 𝑹𝟐𝑪𝒖𝑳𝒊 + 𝑹′ 𝑿 𝑹 − 𝑹′
• Two alkyl groups are coupled together via a lithium dialkylcopper, R2CuLi,
and an alkyl halide, R’X.
• For good yields, R’X should be a primary halide. The alkyl group in the
organometallic reagent may be 1o, 2o, or 3o.
• COUPLING OF ALKYL HALIDES WITH ORGANOMETALLIC
COMPOUNDS
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Reactions of Alkanes
• COMBUSTION
• PYROLYSIS/CRACKING
• HALOGENATION
• Much of the chemistry of alkanes, do to their low reactivity,
involves free-radical chain reactions which are initiated by high
temperature or ultraviolet radiation.
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• HALOGENATION
• Depending upon which hydrogen atom is replaced, any of a
number of isomeric products can be formed from a single alkane.
• With rare exceptions, halogenation of alkanes is not suitable for
the laboratory preparation of alkyl halides.
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Alkyl Halides
Alkyl Halides
• Alkyl halides have the general formula RX, in which R is an
alkyl or substituted alkyl group.
• Under the proper conditions, the alkyl portion of these molecules
undergo the reactions typical of alkanes.
• However, the reactions that are characteristic of the family are the
ones that occur on the halogen atom.
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Nomenclature
• IUPAC names – the compound is simply named as an
alkane with a halogen attached as a side chain
Physical Properties
• considerably higher boiling points than alkanes
• increasing boiling point with increasing atomic weight of
halogen
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Preparation
• from alcohols – nearly always
Preparation
• halogenation of certain hydrocarbons
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Preparation
• addition of hydrogen halides to alkenes
(hydrohalogenation)
Preparation
• addition of halogens to alkenes and alkynes
(halogenation)
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Reactions
• Halide ions are extremely weak bases; hydrogen halides are
highly acidic.
• When attached to carbon, halogens can easily be displaced by
other, stronger bases.
• These basic, electron-rich reagents are called nucleophilic
reagents.
• Thus, the typical reaction of alkyl halides is nucleophilic substitution.
• Characteristic of nucleophilic reagents are unshared electron pairs.
Reactions
• nucleophilic substitution
• SN2: second-order; loss of
leaving group and
nucleophilic attack occur
simultaneously
• SN1: first-order; loss of
leaving group occurs before
nucleophilic attack
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Reactions
• elimination: dehydrohalogenation
• preparation of Grignard reagents
Reactions
• nucleophilic substitutions: SN2 vs SN1
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Reactions
Reactions
• concentration of reagent: high concentration of the nucleophilic
reagent favors SN2, low concentration favors SN1
• nature of nucleophilic reagent: strong nucleophiles and bases
favor SN2, weak nucleophiles favor SN1
• solvent polarity: the more polar the solvent, the more likely it is
that an alkyl halide will react by the SN1 mechanism (solvation
effects)
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Alkenes
Alkenes
• Alkenes contain less hydrogen, carbon for carbon, than the
alkanes: CnH2n.
• They are thus unsaturated hydrocarbons.
• They can be converted back to alkanes by addition of hydrogen.
• The carbon-carbon double bond is the distinguishing
feature of alkenes—sp2!
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Nomenclature
• Common names are seldom used except for: ethylene,
propylene, and isobutylene.
• IUPAC rules:
• Select as the parent structure the longest continuous chain that
contains the carbon-carbon double bond. Each name is derived by
changing the ending –ane of the corresponding alkane to –ene.
• Indicate by a number the position of the double bond.
• Indicate by numbers the positions of the alkyl groups attached to
the parent chain.
Nomenclature
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Physical Properties
• As a class, the alkenes possess physical properties
essentially similar to those of alkanes.
• insoluble in water
• quite soluble in nonpolar solvents (benzene, ether, chloroform,
ligroin, etc.)
• less dense than water
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Industrial Source
• Alkenes are obtained in industrial quantities chiefly by the
cracking of petroleum.
• The smaller alkenes can be obtained in pure form by fractional
distillation and are thus available for conversion into a large
number of important aliphatic compounds.
• Higher alkenes remain as valuable components of gasoline.
Preparation
• dehydrohalogenation of alkyl halides - important
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Preparation
• dehydration of alcohols - important
Preparation
• dehalogenation of vicinal dihalides
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Preparation
• reduction of alkynes
Reactions
• In many of its reactions, the carbon-carbon double bond
serves as a source of electrons—it acts as a base.
• addition reaction – two molecules combine to yield a
single molecule of product
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Reactions: Additions
• addition of hydrogen (catalytic hydrogenation)
• addition of halogens
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• addition of hydrogen halides
• addition of water: hydration (prone to rearrangements)
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• oxymercuration-demercuration (not prone to
rearrangements)
• hydroboration-oxidation (not prone to rearrangements)
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• halohydrin formation
Reactions: Substitutions
• halogenation: allylic substitution
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Reactions: Cleavages
• ozonolysis
Alkynes
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Alkynes
• The carbon-carbon triple bond is the distinguishing
feature of alkynes, CnH2n-2.
• Like the double bond, it is unsaturated and highly reactive: toward
the reagents that double bonds react with, and toward some
others as well.
• sp-hybridized
Nomenclature
• IUPAC rules:
• exactly the same as for the naming of alkenes, except that the
ending –yne replaces –ene.
• The parent structure is the longest continuous chain that contains
the triple bond, and the positions both of substituents and of the
triple bond are indicated by numbers.
• Numbering starts from the end of the chain nearest the triple
bond.
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Physical Properties
• Being compounds of low polarity, the alkynes have physical
properties that are essentially the same as those of the
alkenes and alkanes.
• quite soluble in the usual organic solvents of low polarity: ligroin,
ether, benzene, carbon tetrachloride
• less dense than water
Industrial Source
• Acetylene, C2H2, can be prepared by the action of water on
calcium carbine, CaC2.
• Another is the controlled, high-temperature partial

oxidation of methane.
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Preparation
• dehydrohalogenation of alkyl dihalides
Preparation
• reaction of sodium acetylides with primary alkyl halides
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Preparation
• dehalogenation of tetrahalides
Reactions
• The carbon-carbon triple bond is less reactive than the
carbon-carbon double bond.
• Alkynes also undergo certain reactions that are due to the
acidity of a hydrogen atom held by triply-bonded carbon.
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• addition of hydrogen (hydrogenation)
• addition of halogens
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• addition of hydrogen halides
Benzene
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Benzene
• aromatic compounds – benzene and compounds that
resemble benzene in chemical behavior
• chemical formula C6H6
• undergoes substitution rather
than addition
• goes against the expectation that
cyclohexatriene should have the
same reactivity as alkenes
Aromatic Character: Huckel 4n+2 rule

• To be an aromatic compound, one must have a molecule
that contains
• cyclic clouds of delocalized pi electrons above and below the
plane of the molecule, and
• the pi clouds must contain a total of (4n + 2) pi electrons.
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Aromatic Character: Huckel 4n+2 rule
Nomenclature of Benzene Derivatives

• common names:
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• If several groups are attached to the benzene ring, we must
indicate their relative positions also
• ortho, meta, para prefixes
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• If more than two groups are attached to the benzene ring,
numbers are used to indicate their relative positions.

• If all the group are the same, each is given a number, the
sequence being the one that gives the lowest combination
of numbers.
• If the groups are different, then the last-named group is
understood to be in position 1 and the other numbers
conform to that.
• If one of the groups that gives a special name is present,
then the compound is named as having the special group in
position 1.
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Reactions
• Above and below the plane of the benzene ring there is a
cloud of pi electrons.
• These electrons are loosely held and are available to a reagent
that is seeking electrons.
Reactions
• In its typical reactions, the benzene ring serves as a source
of electrons; that is, as a base.
• Just as the typical reactions of the alkenes are electrophilic
addition reactions, so the typical reactions of the benzene
ring are electrophilic substitution reactions.
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Reactions
• nitration
• sulfonation
Reactions
• halogenation
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Reactions
• Friedel-Crafts alkylation
• Friedel-Crafts acylation
Effect of Substituent Groups

• activating group – makes the ring more reactive
• deactivating group – makes the ring less reactive
• ortho,para director – causes attack to occur chiefly at positions
ortho and para to it
• meta director – causes attack to occur chiefly at positions meta to
it
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• Strongly activating groups
generally win out over
deactivating or weakly
activating groups.
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• There is often little
substitution between two
groups that are meta to each
other.
Arenes
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Arenes
• Arenes are hydrocarbons that contain both aliphatic and
aromatic units.
• We might expect arenes to show two sets of chemical
properties.
• e.g., electrophilic substitution reactions for the benzene ring of
ethylbenzene, and radical halogenation for its alkyl group
Structure and Nomenclature
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Physical Properties
• As compounds of low polarity, the alkylbenzenes possess
physical properties that are essentially the same as those
of the hydrocarbons already studied.
• quite soluble in nonpolar solvents
• almost always less dense than water
• Among isomeric disubstituted benzenes, the para
isomer generally melts considerably higher than the
other two.
Preparation
• Friedel-Crafts alkylation
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Preparation
• conversion of side chain
Reactions
• hydrogenation (under extreme conditions)
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Reactions
• oxidation
Reactions
• substitutions in the ring
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Reactions
• substitutions in the side chain
Alcohols
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Alcohols
• Alcohols are compounds of the general formula ROH,
where R is any alkyl or substituted alkyl group.
• Compounds in which the hydroxyl group is attached
directly to an aromatic ring are not alcohols; they are
phenols.
Nomenclature
• IUPAC rules
• Select as the parent structure the longest continuous carbon chain
that contains the –OH group.
• Indicate by a number the position of the –OH group in the parent
chain, using the lowest possible number.
• Indicate by numbers the positions of other groups attached to the
parent chain.
• Alcohols containing two hydroxyl groups are called
glycols; they also follow the same IUPAC rules.
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Nomenclature
Physical Properties
• form associated liquids
• higher boiling points than alkane analogs
• increase in boiling points with increase in molecular
weight and decrease in branching
• only lower alcohols miscible with water; higher alcohols
less miscible due to larger alkyl groups
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Industrial Source
• hydration of alkenes obtained from the cracking of
petroleum
• fermentation of carbohydrates
Industrial Source
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Preparation
• oxymercuration-demercuration
Preparation
• hydroboration-oxidation
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Preparation
• Grignard synthesis – the most important method
Preparation
• hydrolysis of alkyl halides
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Preparation
• hydroxylation of alkenes
Reactions
• Reactions of an alcohol can involve the breaking of either
of two bonds:
• C—OH bond, with removal of the –OH group
• O—H bond, with removal of the –H group
• Either kind of reaction can involve substitution, in which a
group replaces the –OH or –H, or elimination, in which a
double bond is formed.
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Reactions: C—OH bond cleavage

• reactions with hydrogen halides

• reactions with phosphorus trihalides
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• dehydration
Reactions: O—H bond cleavage

• reactions as acids with active metals
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• ester formation

• oxidation
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• oxidation
Ethers
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• Ethers are compounds of the general formula R—O—R,
Ar—O—R, or Ar—O—Ar.
• Ethers may be named two ways:
• name the two groups that are attached to oxygen, followed by
ether
• name the –OR group as an alkoxy substituent
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Physical Properties
• Ethers possess a small net dipole moment because the two
C—O dipoles do not cancel each other.
• boiling point almost same as for alkane analogs
• solubility comparable to that of alcohols presumably due to
H-bonding with water molecules
Preparation
• Williamson synthesis
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Preparation
• alkoxymercuration-demercuration
Reactions
• Ethers are comparably unreactive substances.
• The ether linkage is quite stable toward bases, oxidizing agents,
and reducing agents.
• Ethers only undergo one kind of reaction: cleavage by
acids.
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Aldehydes and
Ketones
Structure
• Aldehydes are compounds of the general formula RCHO;
ketones are compounds of the general formula RR’CO.
• The groups R and R’ may be aliphatic or aromatic.
• carbonyl compounds – compounds that contain the
carbonyl group, C=O.
• It is the carbonyl group that largely determines the
chemistry of aldehydes and ketones.
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Structure
• Carbonyl carbon is sp2-hybridized, joining it to three other
atoms by sigma bonds.
• The remaining p orbital of the carbon overlaps a p orbital
of oxygen to form a pi bond.
• The electrons are not equally shared.
The mobile pi cloud is pulled strongly
toward the more electronegative
atom, oxygen.
Nomenclature
• Aldehydes
• The longest chain carrying the –CHO group is considered the
parent structure and is named by replacing the –e of the
corresponding alkane by –al.
• The position of a substituent is indicated by a number, the
carbonyl carbon always being considered as C-1.
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Nomenclature
Nomenclature
• Ketones
• The longest chain carrying the carbonyl group is considered the
parent structure and is named by replacing the –e of the
corresponding alkane by –one.
• The position of a substituent is indicated by a number, the
carbonyl carbon always being given the lowest number
possible.
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Nomenclature
Physical Properties
• Aldehydes and ketones have higher boiling points that
nonpolar compounds of comparable molecular weight.
• However, they have lower boiling points than comparable alcohols
or carboxylic acids.
• The lower aldehydes and ketones are appreciably soluble
in water; borderline solubility is reached at about C5.
• Aldehydes and ketones are soluble in the usual organic
solvents.
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Preparation: Aldehydes
• oxidation of primary alcohols (partial oxidation)
Preparation: Aldehydes
• reduction of acid chlorides (using a bulky hydride source)
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Preparation: Ketones
• oxidation of secondary alcohols
Preparation: Ketones
• Friedel-Crafts acylation
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Reactions
• oxidation
Reactions
• oxidation
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Reactions
• reduction
Reactions
• reduction
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Reactions
• addition of Grignard reagents
Reactions
• addition of derivatives of ammonia
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Reactions
• addition of alcohols – acetal formation
Carboxylic Acids
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Structure
• Of the organic compounds that show appreciable acidity,
by far the most important are the carboxylic acids.
• These compounds
contain the
carboxyl group,
RCOOH or
ArCOOH.
Nomenclature
• IUPAC rules:
• The longest chain carrying the carboxyl group is considered the
parent structure, and is named by replacing –e of the
corresponding alkane with –oic acid.
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Nomenclature
• IUPAC rules:
• The position of a substituent is indicated by a number. The
carboxyl carbon is always considered as C-1.
• The name of a salt of a carboxylic acid consists of the name of the
cation (sodium, potassium, etc.) followed by the name of the acid
with the ending –ic acid
changed to –ate.
Physical Properties
• The aliphatic acids show very much the same solubility
behavior as the alcohols: the first four are miscible with
water, C5 is partly soluble, and higher acids are virtually
insoluble.
• soluble in less polar solvents like ether, alcohol, benzene,
etc.
• A pair of carboxylic acid molecules are held together by
two hydrogen bonds.
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Preparation
• oxidation of primary alcohols
Preparation
• carbonation of Grignard reagents
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Preparation
• hydrolysis of nitriles
Reactions
• It is the –OH that actually undergoes nearly every
reaction—loss of H+, or replacement by another group.
• It does so in a way that is possible only because of the effect of the
C=O group.
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Reactions
• acidity: salt formation
Reactions
• conversion into functional derivatives: acid chlorides
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Reactions
• conversion into
functional derivatives:
esters
Reactions
• conversion into functional derivatives: amides
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Reactions
• reduction
Reactions
• substitution in alkyl group: alpha-halogenation
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Reactions
• substitution in aryl group: ring substitution
Carboxylic Acid
Derivatives
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Structure
• The functional derivatives of carboxylic acids are:
• acid chlorides
• anhydrides
• amides
• esters
• They all contain the acyl group, RCO—.
Nomenclature
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Physical Properties
• The presence of the C=O group makes the acid derivatives
polar compounds.
• Acid chlorides, anhydrides, and esters have boiling
points that are about the same as those of aldehydes and
ketones of comparable molecular weight.
• Amides have quite high boiling points due to strong
intermolecular hydrogen bonding.
Reactions: Acid Chlorides

• Chlorine is expelled either as chloride ion or hydrogen
chloride, and its place is taken by some other basic group.
• Acid chlorides are the most reactive of the derivatives of
carboxylic acids.
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• conversion into acids: hydrolysis

• conversion into amides: ammonolysis
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• conversion into esters: alcoholysis

• formation of ketones: Friedel-Crafts acylation
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• formation of aldehydes: reduction
Reactions: Acid Anhydrides

• Acid anhydrides undergo the same reactions as acid
chlorides, but a little more slowly.
• Where acid chlorides yield a molecule of HCl, anhydrides
yield a molecule of carboxylic acid.
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• conversion into acids – hydrolysis

• conversion into amides - ammonolysis
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• conversion into esters – alcoholysis

• formation of ketones:
Friedel-Crafts acylation
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Reactions: Amides
• Amides are hydrolyzed when heated with aqueous acids or
aqueous bases.
• The products are ammonia and the carboxylic acid.
Reactions: Amides
• hydrolysis
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Reactions: Esters
• Esters undergo the nucleophilic substitution that is typical
of carboxylic acid derivatives.
• Attack occurs at the electron-deficient carbonyl carbon,
and results in the replacement of the –OR’ group by –OH,
-OR’’, or –NH2.
• These reactions are sometimes carried out in the presence
of acid, rendering the carbonyl carbon more susceptible to
attack.
Reactions: Esters
• conversion into acids: hydrolysis
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Reactions: Esters
• conversion into amides: ammonolysis
Reactions: Esters
• conversion into esters: transesterification, alcoholysis
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Reactions: Esters
• reaction with Grignard reagents
Organic Chemistry
Engr. Peter Fowler, RCh
124

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1/23/2019

Organic Chemistry for ChE

The Structural Theory and

The Chemical Bond

The Chemical Bond

The Chemical Bond

The Covalent Bond

The Covalent Bond

The Covalent Bond

The Covalent Bond

Bond and Molecular Polarity

Bond and Molecular Polarity

Bond and Molecular Polarity

Structure and Physical Properties

Structure and Physical Properties

Structure and Physical Properties

Structure and Physical Properties

Structure and Physical Properties

Structure and Physical Properties

Acids and Bases

Acids and Bases

Acids and Bases

Acids and Bases

Acids and Bases

• Bromination takes place somewhat less readily than chlorination.

Propane and the Butanes

Propane and the Butanes

van der Waals Repulsion

van der Waals Repulsion

van der Waals Repulsion

• isobutene and isopentane

Nomenclature: IUPAC System

Classes of C and H Atoms

Asphaul or petroleum coke non-volatile solids polycyclic structures

• When shaken under a slight pressure of hydrogen gas in the presence of a

• Grignard reagent – product of a vigorous reaction between an

• The carbon-magnesium bond is highly polar with a partially

• preparation of Grignard reagents

• Another is the controlled, high-temperature partial

Aromatic Character: Huckel 4n+2 rule

Aromatic Character: Huckel 4n+2 rule

Nomenclature of Benzene Derivatives

Nomenclature of Benzene Derivatives

Nomenclature of Benzene Derivatives

Nomenclature of Benzene Derivatives

Nomenclature of Benzene Derivatives

Effect of Substituent Groups

Effect of Substituent Groups

Effect of Substituent Groups

Effect of Substituent Groups

Structure and Nomenclature

Reactions: C—OH bond cleavage

Reactions: C—OH bond cleavage

Reactions: C—OH bond cleavage

Reactions: O—H bond cleavage

Reactions: O—H bond cleavage

Reactions: O—H bond cleavage

Reactions: O—H bond cleavage

Structure and Nomenclature

Structure and Nomenclature

Reactions: Acid Chlorides

Reactions: Acid Chlorides

Reactions: Acid Chlorides