ORGANIC CHEMISTRY 1000034-2

Cristian Ochoa Puentes

 History of the Development of the
Periodic Table of Elements

During the XIX century, chemists started to organize the

elements according with their physical and chemical properties.
In 1869 Dimitry Mendeleiev (1834 -
1907) published a table in which the
elements were organized according with
their atomic mass.
At the same time Lothar Meyer (1830 -
1895) published a table in which the
elements were organized according the
increase in their atomic mass.
 Known Elements in the XVII century
Mendeleiev and Meyer arrenged the elements according their
atomic mass. Both left empty places for unknown elements at
that time

? ? ?
Mendeleiev proposed that if the atomic weight placed an
element in a wrong group, the atomic weight should be wrong.
Having this statement in mind, he predicted the physical
properties of three unknown elements. Due to the accuracy on
his predictions, his periodic table of elements was accepted by
the scientific community.
In 1913 Henry Moseley (1887 - 1915) determined the
atomic number of the elements by means of X-ray. He sorted
the elements according their atomic number.
 Periodic Table of Elements

A period is formed by elements that have different chemical

properties but the same number of electron shells with
electrons on it. The number of the period is the total number of
electron shells
s1 p6
s2 p1 p2 p3 p4 p5

dddd ddd ddd

1 2 3 4 5 6 7 8 9 10

A group is formed by elements that have similar chemical and

physical properties

Elements located at the same group have the same electronic

configuration for the last electronic shell
1 Clasification of the Elements 18
IA
VIIIA
2 13 14 15 16 17
IIA IIIA IVA VA VIA VIIA

NOBLE
3 4 5 6 7 9 11 12
IIIB IVB VB VIB VIIB VIIIB IB IIB

GASES
M E T A L S

SEMIMETALS
 Electronic Structure and Bonding
Acids and Bases

The Structure of an Atom

• An atom consists of electrons, positively charged protons,
and neutral neutrons
• Electrons form chemical bonds
• Atomic number Z: numbers of protons in its nucleus
• Mass number: the sum of the protons and neutrons of an
atom
• Isotopes have the same atomic number but different mass
numbers
• The atomic weight: the average weighted mass of an
element´s isotopes
• Molecular weight: the sum of the atomic weights of all the
atoms in the molecule
 The Distribution of Electrons in an Atom
• Quantum mechanics uses the mathematical equation of wave
motions to characterize the motion of an electron around a
nucleus
• Wave functions or orbitals tell us the energy of the electron and
the volume of space around the nucleus where an electron is
most likely to be found
• The atomic orbital closer to the nucleus has the lowest energy
• Degenerate orbitals have the same energy

• The Aufbau principle: electrons occupy the orbitals with

the lowest energy first
• The Pauli exclusion principle: only two electrons can
occupy one atomic orbital and the two electrons have
opposite spin
• Hund’s rule: electrons will occupy empty degenerated
orbitals before pairing up in the same orbital
Table 1.1
Configuración electrónica para Cu, Al, K+, Ti, O-, S??
 Beginning of Organic Chemistry
Antoine Lauren Lavoisier
(determination of chemical composition by combustion)
XVIII century two branches of chemistry were stablished:
•Substances obtained from living sources
•Substances deived from minerals
Jöns Jacob Berzelius
(The term Organic Chemistry was proposed)
Vitalism theory: living systems have a vital force that is not
present in non living systems. Compounds derived from
natural sources can not be synthesized.

Friedrich Wöhler. 1823 Urea synthesis

Ammonium cyanate Urea

 Organic Chemistry in the ancient world
•Production of alcoholic beveraches.
•Transformation of wine into vinager.
•Ancient China, the use of ma huang as stimulant and to
increase the blood pressure (ephedrin)

•2500 B.C. Use of indigo in India

•Use of Tyrian purple by phenicians. (Dye extracted from a

mediterranean snail)
 Some organic chemicals

DNA

Medicines
•Active Pharmaceutical Ingredients
•Excipients

Ibuprofen
Metronidazole
Aspirin (antibiotic)
Materials

Capsaicin
Limonene
Fuels Essential oils

Methylene blue
Pigments
 Organic Chemistry
• Organic compounds are compounds containing carbon
• Carbon neither readily gives up nor readily accepts electrons

• Carbon shares electrons with other carbon atoms as well as

with several different kinds of atoms
• Ionic compounds are formed when an electropositive element
transfers electron(s) to an electronegative element
 Covalent Compounds
• Equal sharing of electrons: nonpolar covalent bond (e.g., H 2)
• Sharing of electrons between atoms of different electronegativities:
polar covalent bond (e.g., HF)
 Electrostatic Potential Maps

Red < Orange < yellow < Green < Blue

Most negative Most positive

Electrostatic potential Electrostatic potential
 A Dipole
A polar bond has a negative end and a positive end

dipole moment (D) = m = e x d

(e) : magnitude of the charge on the atom

(d) : distance between the two charges
 Lewis Structure

Lewis structures

Formal charge =
number of valence electrons –
(number of lone pair electrons +1/2 number of bonding electrons)

Formal charge =
Group in the periodic table – (number of not shared electrons
+1/2 number shared electrons)
 Important Bond Numbers

one bond H F Cl Br I

two bonds O

three bonds N

four bonds C
 Intramolecular Forces
Vanderwaal´s forces

London forces Hydrogen bonding

Multipolo-multipolo forces Ion-dipolo interaction
(dipolo-dipolo,
dipolo-induced dipolo)
 The shape of some simple molecules
Valence shell electron-pair repulsion (VSEPR) model.
The VSEPR model rests on the idea that an electron pair,
either a bonded pair or an unshared pair, associated with a
particular atom will be as far away from the atom’s other
electron pairs as possible.

Methane Ammonia Water

(tetrahedral) (trigonal pyramidal) (Bent)

Formaldehyde Carbon dioxide

(trigonal planar) (planar)
The s Orbitals
The p Orbitals
 Chemical bonds: H2 as example
The valence bond and molecular orbital theories differ in how
they use the orbitals of two hydrogen atoms to describe the
orbital that contains the electron pair in H2. Both theories
assume that electron waves behave much like more familiar
waves, such as sound and light waves.

The valence bond model: bonding in H2

The characteristic feature of valence bond theory is that it
describes a covalent bond between two atoms in terms of an in-
phase overlap of a half-filled orbital of one atom with a half-filled
orbital of the other

1S1 1S1
The molecular orbital model: bonding in H2

The molecular orbital approach to chemical bonding is based

on the notion that, as electrons in atoms occupy atomic
orbitals, electrons in molecules occupy molecular orbitals.

The model represents molecular orbitals as combinations of

atomic orbitals, the linear combination of atomic orbitals-
molecular orbital (LCAO-MO) method. In H2, two molecular
orbitals (MOs) are generated by combining the 1s atomic
orbitals (AOs) of two hydrogen atoms. In one combination, the
two wave functions are added; in the other they are
subtracted. The additive combination generates a bonding
orbital; the subtractive combination generates an
antibonding orbital
Molecular orbitales for H2 molecule
Sigma bond (s) is formed by end-on overlap of two p orbitals
Pi bond (p) is formed by sideways overlap of two parallel p orbitals
 Hybridization of orbitals:

Bonding in methane: single bonds

Since covalent bonding requires the overlap of half-filled
orbitals of the connected atoms (valence bond model),
carbon with an electron configuration of 1s22s22px12py1 has
only two half-filled orbitals, so how can it have bonds to four
hydrogens?

2p

px py pz px py pz 2sp3
Energy
sp3 hybrid state
2s of carbon
Ground electronic Higher energy
state of carbon electronic state
of carbon
The orbitals used in bond formation determine the bond angles

• Tetrahedral bond angle: 109.5°

• Electron pairs spread themselves into space as far from
each other as possible
Hybrid orbitals of ethane
 Bonding in ethene: a double bond

2p 2p

px py pz px py pz

Energy 2sp2

2s sp2 hybrid state

of carbon
Ground electronic Higher energy
state of carbon electronic state
of carbon
 An sp2-Hybridized Carbon

• The bond angle in the sp2 carbon is 120°

•The sp2 carbon is the trigonal planar carbon
• Carbon–carbon double bond both stronger and shorter than a
carbon–carbon single bond
 Bonding in Ethyne: A Triple Bond

2p 2p

px py pz px py pz

Energy 2sp

2s sp hybrid state
of carbon
Ground electronic Higher energy
state of carbon electronic state
of carbon
• A triple bond consists of one s bond and two p bonds
• Bond angle of the sp carbon: 180°
Bonding in the Methyl Cation
Bonding in the Methyl Radical
Bonding in the Methyl Anion
Bonding in Water
Bonding in Ammonia and in the Ammonium Ion
Bonding in Hydrogen Halides
 Summary

• The greater the electron density in the region of orbital overlap,

the stronger is the bond

• The more s character, the shorter and stronger is the

bond

• The more s character, the larger is the bond angle

 Molecular Dipole Moment

The vector sum of the magnitude and the direction of the individual
bond dipole determines the overall dipole moment of a molecule
 Brønsted–Lowry Acids and Bases

• Acid donates a proton

• Base accepts a proton

• Strong reacts to give weak

• The weaker the base, the stronger is its conjugate acid
• Stable bases are weak bases
 An Acid/Base Equilibrium

H2O + HA H3O+ + A-

[H3O+][A-]
Ka =
[H2O][HA]

pKa = -log Ka

Ka: The acid dissociation constant

 The Henderson–Hasselbalch Equation
The pH indicates the concentration of hydrogen ions (H +)

 pH  log
HA 
pK a
A 


• A compound will exist primarily in its acidic form at a pH < its pKa

•A compound will exist primarily in its basic form at a pH > its pKa

•A buffer solution maintains a nearly constant pH upon addition of

small amount of acid or base
• When atoms are very different in size, the stronger acid will have
its proton attached to the largest atom
• When atoms are similar in size, the stronger acid will have its
proton attached to the more electronegative atom

• Inductive electron withdrawal increases the acidity of a

conjugate acid
Acetic acid is more acidic than ethanol

O
CH3COH CH3CH2OH
pKa = 4.76 pKa = 15.9
acetic acid ethanol

The delocalized electrons in acetic acid are shared by more

than two atoms, thereby stabilizing the conjugated base

O O
CH3CO- CH3CO-
 Lewis Acids and Bases
• Lewis acid: non-proton-donating acid; will accept two electrons

• Lewis base: electron pair donors

Localized Electrons vs. Delocalized
Electrons
 Localized electrons:
Electrons that are restricted to a particular
region.

 Delocalized electrons:
Neither belong to a single atom nor are
confined to a bond between two atoms, but are
shared by three or more atoms.
6.1 Delocalized Electrons: Structure of
Benzene
The Lewis representation of benzene suggests that we
deal with a six-membered ring of carbon atoms that
are held together by alternating single and double
bonds.
H
H C: 6 • 4 = 24 valence electrons
H H: 6 • 1 = 6 valence electrons
----------------------------------------
Total = 30 electrons
H H = 15 bonds
H
 Benzene
This implies that we should observe alternating
short (1.33 Å) and long (1.54 Å) bond lengths.

Modern analytical techniques showed that all

bond lengths are the same (1.39 Å). Thus, they
must have the same number of electrons
between the carbon atoms, this can be so only if
the π electrons are delocalized around the ring.
 Benzene

Since both representations are equal, in average each

C-C bond has a bond character in between a single
and a double bond.

Measured bond length is: 1.39 Å

 Benzene
H
This also explains why H H 2x X

replacing two of the six

H H
hydrogens produces only H
three isomers. In case of X X X

alternating double and H X H H H H

single bonds, A and B H H H X H H

should be different and H
A H X
X
we should have four
isomers. X X X
H X H H H H

H H X H H H
H B H X
 6.2 The Bonding in Benzene

a. C-C and C-H sigma bonds in benzene

b. Benzene is planar and six p orbitals are parallel. P orbitals
are close enough for side-to-side overlap.
c. Overlapping p orbitals form a doughnut-shaped cloud of
electrons above and below the benzene ring.
d. All C-C bonds have the same electron density.
Resonance Contributors and Resonance Hybrid

When it is possible to draw more than one valid Lewis

diagram for a molecule or ion, that species is said to have
resonance (electrons are delocalized).

The molecule or ion is said to be a resonance hybrid of the

structures drawn.

For species with resonance, no single Lewis diagram will

suffice to describe them correctly.
• Dashed lines inside benzene do not show how many π
electrons are in the ring.
• Chemists prefer to use approximate structures.
• The approximate structure with localized electrons is called
a resonance contributor.
• The actual structure with delocalized electrons is called a
resonance hybrid.
• Electron delocalization occurs only if all the atoms sharing
the delocalized electrons lie in or close to the same plane,
so that their p orbitals can effectively overlap.
Constitutional
isomers
 The Effect of Delocalized Electrons on
Stablility
 Dienes are hydrocarbons with two double bonds.
 Conjugated dienes have conjugated double bonds, each
separated by one single bond.
 Isolated double bonds are separated by more than one
single bond.

 π Electrons in an isolated diene are localized, while π electrons in a

conjugated diene are delocalized.
 Conjugated dienes are more stable than isolated dienes.
 The Effect of Delocalized Electrons on
Stablility
 Because allylic cation and benzylic cation have
delocalized electrons, they are more stable than other
primary carbocations.
 The Effect of Delocalized Electrons on
Stablility
 Not all allylic and benzylic carbocations have the same
stability.
 The Effect of Delocalized Electrons on the
Nature of the Product Formed in a Reaction

 The reactions of isolated dienes are like the reactions of

alkenes.
 The Effect of Delocalized Electrons on the
Nature of the Product Formed in a Reaction
 When a conjugated diene reacts with a limited amount of
HX, only two addition products are formed:
One is a 1,2-addition product, the other is a 1,4-addition
product.
The Effect of Delocalized Electrons on pKa

 An increase in resonance stabilization means an

increase in stability.
 Loss of proton from a carboxylic acid is
accompanied by an increase in resonance
stabilization.
The Effect of Delocalized Electrons on pKa-
Phenol
The Effect of Delocalized Electrons on pKa-
Aniline
The Effect of Delocalized Electrons on pKa
 Drawing chemical structures
Name n-Pentane Ethylene glycol Benzoic acid
Molecular Formula C5H12 C2H6O2 C7H6O2
Empirical Formula C5H12 CH3O C7H6O2
Condensaded
Sructures CH3CH2CH2CH2CH3 HOCH2CH2OH

Kekulé Structure

Skeletal Structure

Three-dimensional
model
PROBLEM. Expand the following condensed formulas so as to show
all the bonds and unshared electron pairs.
(a) HOCH2CH2NH2 (d) CH3CHCl2
(b) (CH3)3CH (e) CH3NHCH2CH3
(c) ClCH2CH2Cl (f) (CH3)2CHCH=O

PROBLEM. Write the different representations for a molecule for the

following compounds.
 Functional group

The structural features that make it possible to classify

compounds by reactivity are called functional groups.

A functional group is a group of atoms within a molecule that

has a characteristic chemical behavior
Functional Groups in some important Classes of Organic Compounds
Class Generalized Representative example
abbreviation
Alkanes ---- ----
Alkenes R-CH=CH-R

Alkynes R-CΞC-R

Alcohols ROH

Alkyl halide RCl

Amine RNH2

Epoxide
Functional Groups in some important Classes of Organic Compounds
Class Generalized Representative example
abbreviation
Ether ROR

Nitrile R-CN

Nitrocompounds RNO2

Thiol RSH

Functional Groups that contain the carbonyl group (C=O)

Aldehyde RCHO

Ketone R-CO-R
Functional Groups that Contain the Carboxyl Group
Class Generalized Representative example
abbreviation
Carboxylic acid RCO2H

Ester RCO2R

Functional Groups derived from Carboxylic Acids

Acyl halide RCOCl

Acid anhydride

Amide RCONH2
 Nomenclature of organic compounds

In earlier times, when relatively few pure organic chemiclas were

known, new compounds were named at the whim of their
discoverer

Crystalline substance isolated from urine

Tranquilizing agent named by its discoverer in honor

of his friend Barbara

Analgesic named after Morpheus, the Greek god of dreams

 IUPAC Nomenclature
In the nineteenth century a systematic method of naming
organic compounds was stablished

IUPAC Interantional Union of Pure and Applied Chemistry

A chemical name has three parts in the IUPAC system

Prefix-Parent-Suffix

Where are the substituents? What family?

How many carbons?
 Alkyl groups
If a hydrogen is removed from an alkane, the partial structure that
remains is called alkyl group
Alkyl group are not satble compounds themselves; they are simply
parts of larger compounds

Alkyl groups are named by replacing the -ane ending of the parent
alkane with an –yl ending
The prefixes sec (for secondary) and tert (for tertiary) used
refer to the degree of alkyl substitution at the branching
carbon atom
Butyl group Butyl alcohol
Primary carbon
(Bonded to one carbon)

Isobutyl group Isobutyl alcohol

Secondary carbon
(Bonded to two carbons)

sec-Butyl group sec-Butyl alcohol

Tertiary carbon
(Bonded to three carbons)
tert-Butyl group tert-Butyl alcohol

Quaternary carbon 2,2-Dimethyl propane

(Bonded to four carbons)
• A compound can have more than one name, but a name must
specify only one compound

A C7H16 compound can be any one of the following:

 Naming Alkanes

Prefix-Parent-Suffix

Where are the substituents? What family?...ane

How many carbons?

The first four alkanes are named methane, ethane, propane,

and butane and contain one, two, three and four carbon atoms
respectively
Carbon Parent-suffix Carbon Parent-suffix Carbon Parent-suffix
atoms atoms atoms
1 Methane 16 Hexadecane 31 Hentriacontane
2 Ethane 17 Heptadecane 32 Dotriacontane
3 Propane 18 Octadecane 33 Tritriacontane
4 Butane 19 Nonadecane 34 Tetratriacontane
5 Pentane 20 Eicosane 35 Pentatriacontane
6 Hexane 21 Eneicosane 36 Hexatriacontane
7 Heptane 22 Docosane 37 Heptatriacontane
8 Octane 23 Tricosane 40 Tetracontane
9 Nonane 24 Tetracosane 50 Pentacontane
10 Decane 25 Pentacosane 60 Hexacontane
11 Undecane 26 Hexacosane 70 Heptacontane
12 Dodecane 27 Heptacosane 80 Octacontane
13 Tridecane 28 Octacosane 90 Nonacontane
14 Tetradecane 29 Nonacosane 100 Hectaane
15 Pentadecane 30 Triacontane 103 Dotriacontahectaane
Step 1. Determine the number of carbons in the parent
hydrocarbon
8 7 6 5 4 4 3 2 1
8 7 6 5 4 3 2 1
CH3CH2CH2CH2CHCH2CH3 CH3CH2CH2CHCH2CH2CH3
CH3CH2CH2CH2CHCH2CH2CH3
CH2CH2CH3 CH2CH2CH2CH3
CH3
3 2 1 5 6 7 8

Step 2. Number the chain so that the substituent gets the lowest
possible number

1 2 3 4 5 1 2 3 4 5 6 7 8
CH3
CH3CHCH2CH2CH3 CH3CH2CH2CHCH2CH2CH2CH3
CHCH3 CH3CHCH2CH2CH3
CH3
CH3
2-methylpentane common name: isohexane
4-isopropyloctane systematic name: 2-methylpentane
Step 3. Number the substituents to yield the lowest possible
number in the number of the compound

CH3CH2CHCH2CHCH2CH2CH3
CH3 CH2CH3 5-ehtyl-3-methyloctane
not
4-ethyl-6-methyloctane
because 3<4

(substituents are listed in alphabetical order)

Step 4. Assign the lowest possible numbers to all of the

substituents
CH3 CH3 CH2CH3 CH3

CH3CH2CHCH2CHCH3 CH3CH2CH2C CCH2CH3 CH3CH2CHCH2CH2CHCHCH2CH2CH3

CH3 CH3 CH3 CH3 CH2CH3 CH2CH3
2,4-dimethylhexane 3,3,4,4-tetramethylheptane 3,3,6-triethyl-7-methyldecane
Step 5. When both directions lead to the same lowest number for
one of the substituents, the direction is chosen that gives the
lowest possible number to one of the remaining substituents
CH3 CH3 CH2CH3
CH3CHCH2CHCH3 CH3CH2CHCHCH2CHCH2CH3
CH3 CH3 CH3
2,2,4-trimethylpentane
6-ethyl-3,4-dimethyloctane
not
not
2,4,4-trimethylpentane
3-ethyl-5,6-dimethyloctane
because 2<4
because 4<5

Step 6. If the same number is obtained in both directions, the first

group receives the lowest number
CH2CH3
Cl
CH3CH2CHCH2CHCH2CH3
CH3CH2CHCH3
CH3
Br
2-bromo-3-chlorobutane 3-ethyl-5-methylheptane
not not
3-bromo-2-chlorobutane
5-ethyl-3-methylheptane
Step 7. In the case of two hydrocarbon chains with the same
number of carbons, choose the one with the most substituents
3 4 5 6
1 2 3 4 5 6
CH3CH2CHCH2CH2CH3
CH3CH2CHCH2CH2CH3
2 CHCH3
CHCH3
1 CH3
CH3
3-ethyl-2-methylhexane 3-isopropylhexane
(two substituents) (one substituent)

Step 8. Certain common nomenclatures are used in the IUPAC

system
CH3CH2CH2CH2CHCH2CH2CH3 CH3CH2CH2CH2CHCH2CH2CH2CH2CH3

CHCH3 CH2CHCH3

CH3 CH3

4-isopropyloctane 5-isobutyldecane
or or
4-(1-methylethyl)octane 5-(2-methylpropyl)decane
Problem. Phytane is a naturally occurring alkane produced
by the alga Spirogyra and is a constituent of petroleum. The
IUPAC name for phytane is 2,6,10,14-
tetramethylhexadecane. Write a structural formula for
phytane.
Problem. Give an acceptable IUPAC name for each of the
following alkanes:

4-ethyl-2-methylhexane.

8-ethyl-4-isopropyl-2,6-dimethyldecane
When writing an alkane name, the prefix iso is considered part of
the alkyl-group name for alphabetizing purposes, but the prefixes
(sec- tert-) are not

Los prefijos escritos en itálica (sec- tert-) no se ignoran cuando

se organizan los sustituyentes en orden alfabético si se
comparan uno con otro
 Naming Cycloalkanes
Step 1. For unsubstituted cycloalkanes add the preffix cyclo
to the parent alkane

Cyclobutane Cycloheptane

Step 2. Find the parent. Count the number of carbon atoms in

the ring and the number in the largest substituent chain. If the
number of carbon atoms in the ring is equal or greater than
the number in the substituent, the compound is named as an
alkyl-substituted cycloalkane. If the number of carbon atoms in
the largest substituent is greater than the number in the ring,
the compound is named as a cycloalkyl-substituted alkane

Methylcyclopentane Cyclopropylbutane
Step 3. Number the substituents. For alkyl and halo-
substituted cycloalkanes, choose a point of attachment as C1
and number the substituents on the ring so that the second
substituent has a low number as possible. If ambiguity still
exists, number so that the third or four substituent has a low
number as possible, until a point of difference is found.

1,3-Dimethylcyclohexane

2-Ethyl-1,4-dimethylcycloheptane
When two or more different alkyl groups that could potentially
receive the same numbers are present, number them by
alphabetical priority

NOT

1-Ethyl-2-methylcyclopentane 2-ethyl-1-methylcyclopentane

When two or more different cyclic groups are present, the one
with more carbon atoms has the priority

(2-Cyclobutylethyl)cyclopentane
The hydroxyl group has priority over the alkyl group. The suffix
used in this case is ol

2-Methylcyclohexanol

3-Ethyl-4-methylcyclopentanol
PROBLEM. Write a structural formula for each of the following compounds:
(a) 6-Isopropyl-2,3-dimethylnonane (e) Cyclobutylcyclopentane
(b) 4-tert-Butyl-3-methylheptane (f ) (2,2-Dimethylpropyl)cyclohexane
(c) 4-Isobutyl-1,1-dimethylcyclohexane (g) Pentacosane
(d) sec-Butylcycloheptane (h) 10-(1-methylpentyl)pentacosane

(a) 6-Isopropyl-2,3-dimethylnonane

(b) 4-tert-Butyl-3-methylheptane
(c) 4-Isobutyl-1,1-dimethylcyclohexane

(d) sec-Butylcycloheptane (g) Pentacosane

CH3(CH2)23CH3.

(h) 10-(1-methylpentyl)pentacosane

(e) Cyclobutylcyclopentane

(f ) (2,2-Dimethylpropyl)cyclohexane
 Bicyclic alkanes
We name compounds containing 2 fused or bridged rings as
bicyclo alkanes and we use the name of the alkane
corresponding to the total number of carbon atoms as the
base name. The carbon atoms common to both the rings are
called bridgeheads, and each bond, or chain of atoms
connecting the bridgehead atoms, is called a bridge.
* Bridgehead
* One carbon bridge
Five carbon bridge
*
Bridge
One carbon bridge

*
Two carbon bridge Two carbon bridge
*
 In between the words bicyclo and alkane we interpose in the
name an expression in the square brackets that denotes the
number of carbon atoms in each bridge (in descending order).

Bicyclo[2.2.1]heptane Bicyclo[1.1.0]butane Bicyclo[1.1.1]pentane

Bicyclo[4.3.0]nonane Bicyclo[4.3.3]dodecane
If substitutions are present, we number the bridged ring
system beginning at one bridgehead, proceeding first along
the longest bridge to the other bridgehead, then along the
next longest bridge back to the first bridgehead. The shortest
bridge is numbered last. If ambiguity exists, number so that
the substituents have a low number as possible

2-Methylbicyclo[2.2.1]heptane

2,4,7,9 2,4,6,8 2,4,6,8

2-Ethyl-4,6,8-trimethylbicyclo[3.2.2]nonane
 Spirocyclic alkanes
We name compounds in which two rings share one common
atom (spirocenter) as spirocyclic alkanes
The root name is based on the number of C atoms in the ring
structure
The prefix spiro[x.y] is added. x and y indicate the size of the
rings excluding the spirocenter
The number of atoms indicated in square brackets is listed
smallest first

* Spirocenter

spiro[2.5]octane spiro[4.4]nonane spiro[3.6]decane

For substituted spiroalkanes, the rings are numbered starting
on the smallest ring adjacent to the spirocenter

1-Methylspiro[2.5]octane

6-Methylspiro[3.5]nonane
 Nomenclature of Alkyl Halides

CH3CHI CH3CH2CHBr
CH3Cl CH3CH2F
CH3 CH3
chloromethane fluoroethane
2-iodopropane 2-bromobutane

In the IUPAC system, alkyl halides are named as substituted

alkanes
CH3 CH3

CH3CH2CHCH2CH2CH2CH3 CH3CH2CHCH2CH2CH2Cl

Br CH3
2-bromo-5-methylheptane 1-chloro-5,5-dimethylhexane
Br

CH2CH3 Cl

CH3

1-ethyl-2-iodocyclopentane 4-bromo-2-chloro-1-methylcyclohexane
Different Kinds of Alkyl Halides
 Nomenclature of Ethers
CH3

CH3OCH2CH3 CH3CH2OCH2CH3 CH3CH2CHOCCH3

ethyl methyl ether diethyl ether CH3 CH3

tert-butyl isobutyl ether

CH3

CH3CHOCHCH2CH3

CH3

sec-butyl isopropyl ether

As substituents:
CH3

CH3CH2O CH3CH2CHO CH3CH2O

CH3O CH3CH2O
CH3 CH3 CH3
methoxy ethoxy
isopropoxy sec-butoxy tert-butoxy
 Nomenclature of Alcohols

• In an alcohol, the OH is a functional group

• A functional group is the center of reactivity in a molecule

1. Determine the parent hydrocarbon containing the functional

group

1 2 3 4 5 4 3 2 1 3 2 1
CH3CHCH2CH3 CH3CH2CH2CHCH2OH CH3CH2CH2CH2OCH2CH2CH2OH
OH 3-butoxy-1-propanol
CH2CH3
or
2-butanol 2-ethyl-1-pentanol
or 3-butoxypropan-1-ol
butan-2-ol or
2-ethylpentan-1-ol
2. The functional group suffix should get the lowest number
CH3
1 2 3 4 3 2 1 5 4 3 2 1
HOCH2CH2CH2Br ClCH2CH2CHCH3 CH3CCH2CHCH3

3-bromo-1-propanol OH CH3 OH
4-chloro-2-butanol 4,4-dimethyl-2-pentanol

3. When there is both a functional group suffix and a substituent,

the functional group suffix gets the lowest number
CH3

CH3CHCHCH2CH3 CH3CH2CH2CHCH2CHCH3

Cl OH OH CH3
2-chloro-3-pentanol 2-methyl-4-heptanol OH
not not
6-methyl-4-heptanol 3-methylcyclohexanol
4-chloro-3-pentanol not
5-methylcyclohexanol
4. If there is more than one substituent, the substituents are cited
in alphabetical order

CH2CH3 CH2CH3

CH3CHCH2CHCH2CHCH3

Br OH H 3C OH

6-bromo-4-ethyl-2-heptanol 2-ethyl-5-methylcyclohexanol

HO

CH3

CH3

3,4-dimethylcyclopentanol
 Nomenclature of Amines
1 2 3 4 5 6 3 2 1
4 3 2 1
CH3CH2CHCHCH2CH3 CH3CH2CH2NCH2CH3
CH3CH2CH2CH2NH2
NHCH2CH3 CH3
1-butanamine
or N-ethyl-N-methyl-1-propanamine
butan-1-amine N-ethyl-3-hexamine or
or N-ethyl-N-methylpropan-1-amine
N-ethylhexan-3-amine

• The substituents are listed in alphabetical order and a number or

an “N” is assigned to each one
CH3 Br
4 3 2 1 1 2 3 4 5 6 5 4 3 2 1
CH3CHCH2CH2NCH3 CH3CH2CHCHCHCH3 CH3CHCHCHCH3

Cl NHCH2CH3 N
H3C CH3
3-chloro-N-methyl-1-butanamine N-ethyl-5-methyl-3-hexanamine
4-bromo-N,N-dimethyl-2-pentanamine
CH2CH3

NHCH2CH2CH3

2-ethyl-N-propylcyclohexanamine
 Naming Quaternary Ammonium Salts

CH3

H3C N+ CH3
HO-
CH3

tetramethylammonium hydroxide