Introduction to

Organic Chemistry
 Organic Chemistry
Why is it important?
>90% of compounds are organic

What is an organic compound

• is a compound made from carbon atoms.
• has one or more C atoms.
• has many H atoms.
• may also contain O, S, N, and halogens.
 Classes of Compounds

• Classifications are based on functional

group.
• Three broad classes:
– Hydrocarbons
– Compounds containing oxygen
– Compounds containing nitrogen
 Hydrocarbons
• Alkanes: Single bonds between the carbons;
all carbons are sp3.
• Cycloalkanes: sp3 carbons form a ring.
• Alkenes: Double bonds are present in the
molecule; sp2 carbons.
• Cycloalkenes: Double bond in a ring.
• Alkynes: Triple bonds are present; sp
carbons
• Aromatic: Contain a benzene ring.
 Alkanes

• General formula: CnH2n+2

• Found in everything from natural gas to
petroleum.
• The smaller alkanes have very low boiling
points (b.p.) therefore they are gases.

CH4 C 2H 6 C 3H 8
b.p. -160oC -89oC -42oC
 Butane: C4H10

CH3CH2CH2CH3 n-butane

CH3
CH3CHCH3 iso -butane

Constitutional isomers are compounds with the same

molecular formula but the carbons are connected differently.
 IUPAC
• International Union of Pure and Applied
Chemistry
• Common names kept: methane, ethane,
propane, butane.
• Alkanes: suffix “-ane” will be used after
the number of carbons.
– Example: An alkane with 5 carbons is “penta”
for five and the suffix “-ane”:
pentane
 IUPAC Rules
• Rule 1: Find the longest continuous chain of
carbon atoms, and use the name of this chain
as the base name of the compound.
• Rule 2: Number the longest chain, beginning
with the end of the chain nearest a
substituent.
• Rule 3: Name the groups attached to the
longest chain as alkyl groups. Give the
location of each alkyl group by the number of
the main chain carbon atom to which it is
attached.
• Write the alkyl groups in alphabetical order
regardless of their position on the chain.
Rule 1: Find the Longest Chain of
Consecutive Carbons.

The longest chain is

six carbons:

hexane
 Main Chain

When there are two longest chains of equal length, use the
chain with the greatest number of substituents.
Rule 2: Number the Longest Chain.
Methyl is closest to
this end of the main chain.

Number the longest chain, beginning with the end of the

chain nearest a substituent.

3-methylehexane
 Rule 3: Alkyl Substituents
2-methyl 4-ethyl

CH3 CH2CH3
CH3CHCH2CHCH2CH3
1 2 3 4 5 6

• Name the groups attached to the longest chain as

alkyl groups.
• Give the location of each alkyl group by the number
of the main chain carbon atom to which it is attached.
• Write the alkyl groups in alphabetical order regardless
of their position on the chain.
4-ethyl-2-methylhexane
 Organizing Multiple Groups
• When two or more of the same substituents are present,
use the prefixes di-, tri-, tetra-, etc. to avoid having to
name the alkyl group twice.

CH3 CH3
CH3CH2CH2CHCH2CHCH2CH2CHCH3
10 9 8 7 6 5 4 3 2 1
CH3

Three methyl groups at positions 2, 5, and 7

2,5,7-trimethyldecane
 Newman Projections

The Newman projection is the best way to judge the

stability of the different conformations of a molecule.
 H H
H
This represents a particular orientation
C C
H of the C-H bonds on adjacent Carbons
H H

Ethane H
H H
View along C-C bond:
H H
H
Newman projection

Can select one C-H bond on either

φ
H
carbon and define a dihedral angle H H
or torsional angle (φ)
H H
H
 H Staggered conformation
H H Minimum energy conformation
φ = 60o
H H (least crowded possible
H conformation)

C-C σ bonds: symmetrical about the bond axes.

In principle, no barrier to rotation about C-C bond
HH
H H
Could have φ = 0o = C C
H H H
H
H H H H
Eclipsed conformation
Maximum energy conformation
(most crowded possible conformation)
 Ethane Conformations

The torsional energy of ethane is lowest in the staggered

conformation. The eclipsed conformation is about 3.0 kcal/mol
(12.6 kJ/mol) higher in energy. At room temperature, this
barrier is easily overcome, and the molecules rotate constantly.
 Propane Conformations

Propane is shown here as a perspective drawing and as

a Newman projection looking down the C1—C2 bond.
 Propane Conformations

交錯 式

The staggered conformations of propane is lower in energy

than the eclipsed conformations. Since the methyl group
occupies more space than a hydrogen, the torsional strain
will be 0.3 kcal/mol higher for propane than for ethane.
間 扭 式 重疊 式
 Steric Strain 立體 應變

• The totally eclipsed conformation is higher in energy

because it forces the two end methyl groups so close
together that their electron clouds experience a strong
repulsion.
• This kind of interference between two bulky groups is
called steric strain or steric hindrance.
立 体 阻礙
 Physical Properties
• Non-polar
• Relatively inert
• Boiling point and melting point depends on
the molecular weight.
 Cycloalkane Nomenclature
命名 法 ,

• Cycloalkane is the
main chain: alkyl
CH2CH3
groups attached to the
cycloalkane will be
named as alkyl groups.
ethylcyclopentane
• If only one alkyl group
is present, then no
number is necessary.
 Cycloalkane Nomenclature
• If there are two or more substituents, number the
main chain to give all substituents the lowest
possible number.

H3C CH3
1 CH3
1

3 3 CH2CH3
CH3

1,3-dimethylcyclohexane 3-ethyl-1,1-dimethylcyclohexane
Geometric Isomers

1 CH3
Same side: cis-

cis-1,2-dimethylcyclohexane
2 CH3

2 CH3
Opposite side: trans-
1 CH2CH3 trans-1-ethyl-2-methylcyclohexane
 Stabilities of Cycloalkanes
• Five- and six-membered rings are the most common in
nature.
• Carbons of cycloalkanes are sp3 hybridized and thus
require an angle of 109.5º.
• When a cycloalkane has an angle other than 109.5º,
there will not be optimum overlap and the compound will
have angle strain.
• Angle strain is sometimes called Baeyer strain in honor
of Adolf von Baeyer who first explained this
phenomenon.
• Torsional strain arises when all the bonds are eclipsed.
 Cyclopropane: C3H6

• The bond angles are compressed to 60° from the usual

109.5° bond angle of sp3 hybridized carbon atoms.
• This severe angle strain leads to nonlinear overlap of the
sp3 orbitals and “bent bonds”.
 Torsional Strain

All the C—C bonds are eclipsed, generating torsional

strain that contributes to the total ring strain.
 Cyclobutane: C4H8

The ring strain of a planar cyclobutane results from two

factors: angle strain from the compressing of the bond
angles to 90° rather than the tetrahedral angle of 109.5°
and torsional strain from eclipsing of the bonds.
 Non-Planar Cyclobutane

• Cyclic compound with four carbons or more adopt non-

planar conformations to relieve ring strain. 信封 型 構形
• Cyclobutane adopts the folded conformation (“envelope”)
to decrease the torsional strain caused by eclipsing
hydrogens.
Conformational Energy Diagram of
Cyclohexane
 Covalent Bonding
• Electrons are shared between the atoms to
complete the octet.
• When the electrons are shared evenly the bond
is said to be nonpolar or pure covalent.
• When electrons are not shared evenly between
the atoms, the resulting bond will be polar.
The octet rule is a simple chemical
rule of thumb that states that atoms
tend to combine in such a way that
they each have eight electrons in
their valence shells, giving them the
same electronic configuration as a
noble gas.
 Resonance Forms
• In a resonance form, only the electrons are
moved. Connectivity between atoms stay the
same.
• The real structure is a hybrid of the different
resonance forms.
• Arrows connecting resonance forms are double
headed.
• Spreading the charges over two or more atoms
stabilize the ion.

O O
C C
H H H H
 Resonance Forms
Resonance Forms can be compared using
the following criteria, beginning with the
most important:
– Has as many octets as possible.
– Has as many bonds as possible.
– Has the negative charge on the most
electronegative atom.
– Has as little charge separation as possible.
 Major and Minor Contributors
• The major contributor is the one in which
all the atoms have a complete octet of
electrons.
O O
C C
H H H H
MAJOR MINOR

The carbon atom does

not have a complete
octet of electrons.
 Major and Minor Contributors
(Continued)
• When both resonance forms obey the octet
rule, the major contributor is the one with
the negative charge on the most
electronegative atom.

N C O N C O
MAJOR MINOR

The oxygen is more electronegative,

so it should have the negative
charge.
 Non-Equivalent Resonance
• Opposite charges should be on adjacent
atoms.
CH3 O N O CH3 O N O
- +
MAJOR MINOR

The most stable one is the one with the smallest

separation of oppositely charged atoms.
 Resonance Forms

• The structure of some compounds are not adequately represented

by a single Lewis structure.
• Resonance forms are Lewis structures that can be interconverted by
moving electrons only.
• The true structure will be a hybrid between the contributing
resonance forms.
 Arrhenius Acids
• Arrhenius acids are substances that
dissociate in water to give H3O+ ions.
 Arrhenius Bases
• Arrhenius bases are substances that
dissociate in water to give hydroxide ions.
Brønsted-Lowry Acids and Bases
Brønsted-Lowry acids are any species that donate a proton.
Brønsted-Lowry bases are any species that can accept a proton.
 Conjugate Acids and Bases 共 軛 酸鹼

• Conjugate acid: when a base accepts a proton,

it becomes an acid capable of returning that
proton.
• Conjugate base: when an acid donates its
proton, it becomes capable of accepting that
proton back.
 Effect of Electronegativity on pKa
• As the bond to H becomes more polarized, H becomes
more positive and the bond is easier to break.

morepolarized
⼆
 Effect of Size on pKa

• As size increases, the H is more loosely

held and the bond is easier to break.
• A larger size also stabilizes the anion.
 Nucleophiles and Electrophiles
• Nucleophile: Donates electrons to a
nucleus with an empty orbital.
• Electrophile: Accepts a pair of electrons.
• When forming a bond, the nucleophile
attacks the electrophile, so the arrow goes
from negative to positive.
• When breaking a bond, the more
electronegative atom receives the
electrons.
Nucleophiles and Electrophiles
 Sigma Bonding
• Electron density lies between the nuclei.
• A bond may be formed by s—s, p—p, s—
p, or hybridized orbital overlaps.
• The bonding molecular orbital (MO) is
lower in energy than the original atomic
orbitals.
• The antibonding MO is higher in energy
than the atomic orbitals.
Multiple Bonds
 Molecular Shapes

• Bond angles cannot be explained with simple s and p

orbitals.
• Valence-shell electron-pair repulsion theory (VSEPR)
is used to explain the molecular shape of molecules.
• Hybridized orbitals are lower in energy because
electron pairs are farther apart.
Valence shell electron pair repulsion
(VSEPR) rules are a model in
chemistry used to predict the shape of
individual molecules based upon the
extent of electron-pair electrostatic
repulsion.

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 Bonding in Ethane

• Ethane is composed of two methyl groups bonded by

the overlap of their sp3 hybrid orbitals.
• There is free rotation along single bonds.
Rotation Around Double Bonds

Be Carehl :

環狀 組織 的
• Single bonds can rotate freely. 不可 轉
singlebonds
• Double bonds cannot rotate. ( 但 可以 多 形狀 )

(Tple )
 Isomerism
• Molecules that have the same molecular
formula, but differ in the arrangement of their
atoms, are called isomers.
• Constitutional (or structural) isomers differ in
結構
their bonding sequence.
• Stereoisomers立differ
z .

体
only in the arrangement
of the atoms in space.
 Constitutional (structural) Isomers

• Constitutional isomers have the same chemical

formula, but the atoms are connected in a different
order. (i.e.,different atom-to-atom connectivity)
• Constitutional isomers have different properties.
• The number of isomers increases rapidly as the
number of carbon atoms increases.
•Structural isomers: different physical properties
CH3
CH3 CH2 CH2 CH3 CH3 CH CH3

n-butane isobutane
b.p. - 0.5oC b.p. - 12.0oC

•Are different chemical entities

 Geometric Isomers: Cis and Trans
序列
空間

• Stereoisomers are compounds with the atoms bonded in the

same order, but their atoms have different orientations in
space.
• Cis and trans are examples of geometric stereoisomers and
they occur when there is a double bond in the compound.
• Since there is no free rotation along the carbon–carbon double
bond, the groups on these carbons can point to different places
in space.
 Bond Dipole Moments

• Dipole moments are due to differences in

electronegativity.
• They depend on the amount of charge
and distance of separation.
• They are measured in debyes (D).
 Molecular Dipole Moments

• The molecular dipole moment is the vector sum

of the bond dipole moments.
• Depend on bond polarity and bond angles.
• Lone pairs of electrons contribute to the dipole
moment.
 Intermolecular Forces
• Strength of attractions between molecules
influences the melting point (m. p.), boiling
point (b. p.), and solubility of compounds.

• Classification depends on structure:

– Dipole–dipole interactions
– London dispersions
– Hydrogen bonding
) Van Derwaaliones
 Dipole–Dipole Interaction
• Dipole–dipole interactions result from the
approach of two polar molecules.
• If their positive and negative ends approach,
the interaction is an attractive one.
• If two negative ends or two positive ends
approach, the interaction is repulsive.
• In a liquid or a solid, the molecules are mostly
oriented with the positive and negative ends
together, and the net force is attractive.
attractioh

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 Hydrogen Bonding

• Strong dipole–dipole attraction. kot ihteraction )

• Organic molecules must have NH or OH to
be able to hydrogen bond.
• The hydrogen from one molecule is strongly
attracted to a lone pair of electrons on the
oxygen of another molecule.
• O—H more polar than N—H, so alcohols
have stronger hydrogen bonding.
 Boiling Points and
Intermolecular Forces
CH CH OH CH O CH
3 2 3 3

ethanol, b.p. = 78°C dimethyl ether, b.p. = -25°C

Hydrogen bonding increases the b. p. of the molecule.

CH CH OH CH CH NH
3 2 3 2 2
ethanol, b.p. = 78°C ethyl amine, b.p. 17°C

O—H is more polar than N—H, so alcohols have

stronger hydrogen bonding.
 Solubility

• Like dissolves like.

• Polar solutes dissolve in polar solvents.
• Nonpolar solutes dissolve in nonpolar
solvents.
• Molecules with similar intermolecular

矗
forces will mix freely.

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