UNIT 1 THEME 1: ALKANES AND

CYCLOALKANES

Organic Chemistry (ORH115B)

CLASS 2023 B
Prescribed book: Fundamentals of Organic Chemistry by
John McMurry, 7th edition
Mr THUKWANE
([email protected])
 UNIT 1 THEME 1: ALKANES AND
CYCLOALKANES
❖ STUDY UNIT 1.1: STRUCTURE AND REACTIONS

❖ STUDY UNIT THEME 1.1.1: HYBRIBIZATION AND

COVALENT BONDS OF CARBON

❖ SPECIFIC OUTCOMES:
❑ Explain the concept of hybridization in covalent bond
formation

❑ Discuss the differences in reactivity of C-C bonds

 ORBITALS
▪ An orbital is defined as the region of space found
around the nucleus.

▪ There are four different types of orbitals, namely: s, p,

d and f.

▪ Each have different shapes.

▪ s and p orbitals are the most common in organic and

biological chemistry
 ORBITALS
▪ An s orbital is spherical, with the nucleus in its centre.

▪ p orbital: dumbshell-shaped.

▪ The p orbital can be orientated in space along any of

the three mutually perpendicular direction
 ELECTRON SHELL
▪ Orbitals are arranged into different layers/shells.

▪ 1st shell which is 1s- holds 2 electrons.

▪ 2nd shell which is 2s and 2p- holds 8 electrons.

▪ 3rd shell containing 3s, 3p and 3d orbital- holds 18

electrons.
 ELECTRON CONFIGURATIONS
▪ Ground-state electron configuration of an atom is a list of
orbitals in an atom that have electrons occupying them.

▪ The arrangement can be predicted by following 3 rules:

❑ Rule 1: orbitals of the lowest energy are filled first,

according to the order : 1s → 2s → 2p → 3s → 3p → 4s→ 3d.

❑ Rule 2: two electrons can occupy an orbital, and they can

be of opposite spins.
 ELECTRON CONFIGURATIONS

▪ Rule 3: If two or more empty orbitals of equal energy

are available, one electron occupies each with the
spins parallel until all orbitals are half full.
 DEVELOPMENT OF CHEMICAL
BONDING THEORY
▪Jacobus van’t Hoff and Joseph Le Bel proposed that four bonds
of carbon sit at the corners of a regular tetrahedron, with Carbon
at the center.

❑ Solid line- bonds in the plane of the page

❑ Wedge line- bond coming out of the page toward the viewer

❑ Dash line- bond receding back behind the page from the viewer
THE NATURE OF CHEMICAL BONDS

▪ Atoms form bonds because the compound that results

is more stable than the separate atoms

▪ Ionic bonds in salts form as a result of electron

transfer

▪ Organic compounds have covalent bonds from sharing

electrons
THE NATURE OF CHEMICAL BONDS

▪ Lewis structures (electron dot) show valence electrons

of an atom as dots.

▪ Hydrogen has one dot, representing its 1s electron

▪ Carbon has four dots (2s2 2p2)

https://www.chemistrylearner.com/wp-
content/uploads/2021/10/Lewis-Structure.jpg
 THE NATURE OF CHEMICAL BONDS

▪ Stable molecule results whenever a noble gas configuration

is achieved for all atoms - octet (eight dots) for main-group
atoms.

▪ Kekule’s structures have a line drawn between two atoms

indicating a covalent bond of two electrons.
 FORMING COVALENT BONDS:
VALENCE BOND THEORY
• A covalent bond forms when two atoms approach
each other closely, a singly occupied orbital on one
atom overlaps singly occupied orbital on the other
atom Valence bond theory

• H–H bond results from the overlap of two singly

occupied hydrogen 1s orbitals
 sp3 HYBRID ORBITALS AND THE
STRUCTURE OF METHANE

▪ Methane (CH4) carbon has four valence electrons (2s2 2p2) --

> forms 4 bonds

▪ In 1931, Linus Pauling proposed that an s and three p orbital

can combine or hybridize to form four equivalent atomic
orbitals with tetrahedral orientation called sp3 hybridized.
 sp3 HYBRID ORBITALS AND THE
STRUCTURE OF METHANE
• The name sp3 tells how many of each of atomic orbital
combine to form the hybrid, not how many electrons occupy
it.

• The concept of hybridization- how carbon forms four

equivalent tetrahedron bonds.
 THE STRUCTURE OF METHANE
• sp3 orbitals on C overlap with 1s orbitals on 4 H atoms to
form four identical C-H bonds.

• Each C–H bond has a strength of 436 kJ/mol (104 kcal/mol)

and length of 109 pm (1.09Å).

• Bond angle: each H–C–H is 109.5°, the tetrahedral angle.

 sp3 HYBRID ORBITALS AND THE
STRUCTURE OF ETHANE

▪ Orbitals hybridization that accounts for C-H bonding in CH4

also applies to the bonding of carbon chains and ring.

▪ In ethane - two carbon atom bond to each other by overlap

of an sp3 hybrid from each.
 sp3 HYBRID ORBITALS AND THE
STRUCTURE OF ETHANE
▪ Two carbons will bond to each other by overlapping of
sp3 orbitals.

▪ The remaining three sp3 orbitals on each C will overlap

with the 1s orbitals of three hydrogens atoms to form
six C–H bonds.
 sp3 HYBRID ORBITALS AND THE
STRUCTURE OF ETHANE
▪ The C-H bond in CH3-CH3 are similar to those found in
methane, but just slightly weaker.

▪ CH3-CH3 has a Bond strength of 421KJ/mol (101kcal/mol).

▪ The C-C Bond length is 154pm with the bond strength of 377
KJ/mol (90 kcal/mol).

▪ The bond angle is tetrahedral angle (109.5o or near)

 OTHER KINDS OF HYBRID ORBITALS
SP2 AND SP
▪ Bonds in methane and ethane are all single bonds due to the
sharing of one electron pair between bonded atoms.

▪ Carbon atoms can form double bonds by sharing two

electron pairs. e.g Ethylene H2C=CH2.

▪ They also form triple bonds by sharing three electron pairs.

e.g Ethyne
 OTHER KINDS OF HYBRID ORBITALS
SP2 AND SP

▪ The sp2-Hybrid orbitals are formed When 2s orbital

combines with only two 2p orbitals of the three 2p orbitals
(only one unhybridized 2p orbital remain unchanged).

▪ The sp-Hybrid orbitals are formed When 2s orbital

combines with only one 2p orbitals of the three 2p orbitals
(only two unhybridized 2p orbital remain unchanged).

• Like sp3 hybrids, also sp2 and sp hybrid orbitals are

unsymmetrical about the nucleus.
 sp2 HYBRID ORBITALS AND THE
STRUCTURE OF ETHYLENE
▪ sp2 hybrid orbitals: 2s orbital combines with two 2p orbitals,
giving 3 orbitals (spp = sp2) (Green).

▪ sp2 orbitals are in a plane with 120° angles.

▪ Remaining p orbital (red/blues) is perpendicular to the plane.

 sp2 HYBRID ORBITALS AND THE
STRUCTURE OF ETHYLENE
▪ When two sp2-hybrized carbon atoms approach each other,
they form strong bond by sp2-sp2 head on overlaps.

▪ At the same time, unhybridized p orbitals interact by sideways

to form a second bond.

▪ Head-on over-lap (green) gives a sigma bond, while the

sideways over-lap (red/blue) gives pi bond.
 sp2 HYBRID ORBITALS AND THE
STRUCTURE OF ETHYLENE
▪ H-C-H and H-C=C bond angles are about 120°, and the
geometry is a trigonal planar.

▪ C=C double bond in ethylene is shorter and stronger than

single bond in ethane (C-C).

▪ Ethylene has a C=C bond strength of 728 KJ/mol

(174kcal/mol) and a length of 134 pm (the C–C single bond
is 154 pm).
 sp HYBRID ORBITALS AND THE
STRUCTURE OF ACETYLENE
▪ The 2s orbitals of C (green) hybridizes with a single p orbital
giving two sp hybrids.

▪ Two p (blue/red) orbitals remain unchanged.

▪ sp orbitals are linear, 180° apart on x-axis.

▪ Two p orbitals are perpendicular on the y-axis and the z-axis.

 sp HYBRID ORBITALS AND THE
STRUCTURE OF ACETYLENE
▪ When two sp-hybridized carbon atoms approach each
other, sp hybrid orbitals from each overlap head-on to
form strong sp-sp sigma bond.

▪ At the same time, the pz orbitals from each carbon

form a pz-pz pi bond by side way overlap.

▪ The py orbitals over-laps similarly to form a py-py pi

bond.
 sp HYBRID ORBITALS AND THE
STRUCTURE OF ACETYLENE
▪ The net effect is the formation of one sigma bond and
two pi bonds, forming a carbon-carbon triple bond.

▪ Each of the remaining sp hybrid orbitals forms a sigma

bond to a H atom to complete the acetylene molecule.

▪ The Bond angle is 180⁰ and the C-C bond length is 120
pm with a strength of 965KJ/mol (231Kcal/molTriple
bond has a shortest and strongest C-C bond.
 Exercise
Determine the hybridization state of each carbon and heteroatom (any

atom except C and H) in the following compounds. Hint: Remember to

add any missing lone pairs of electrons where necessary.

1. H2C = C = CH – CH3

Ans: C1-sp2, C2-sp, C3-sp2 and C4-sp3

2. (a)

Ans: C1-sp3, C2-sp3, C3-sp2, O4-sp3

(b) State the geometry at each of these atoms

Ans: C1-tetrahedral, C2-tetrahedral, C3-trigonal planar and O4

tetrahedral
 Exercise
For the molecule below give the information corresponding to each
letter as indicated below.

(a) Give the hybridization of these atoms.

(b) give these bond angles.

 STUDY UNIT THEME 1.1.2:
ISOMERISM AND NOMENCLATURE

❖ SPECIFIC OUTCOMES:

o Classify carbons according to their substitution

patterns: primary, secondary, tertiary or quaternary.

o Define and give examples that illustrate the terms

homologous series, isomers, constitutional isomers,
rotational isomers, cis and trans isomers.

o Give the IUPAC names for alkanes and cycloalkanes.

ALKANES ALKYL GROUPS: ISOMERS
▪ When two, three or more carbons are joined by C-C
single bonds then an alkanes family is generated.

▪ Alkanes are often described as saturated

hydrocarbons, because they contain only carbon and
hydrogen atoms.

▪ They are made of C-C and C-H single bonds only.

▪ They have the general formula CnH2n+2 where the

number of C’s is n.
ALKANES ALKYL GROUPS: ISOMERS

▪ They are also called aliphatic compounds.

▪ CH4 = methane, C2H6 = ethane, C3H8= propane.

ALKANES ALKYL GROUPS: ISOMERS

▪ The molecular formula of an alkane with more than three

carbons can give more than one structure:

– C4 (butane) = butane and isobutane

– C5 (pentane) = pentane, 2-methylbutane (isopentane), and

2,2-dimethylpropane (neopentane)
ALKANES ALKYL GROUPS: ISOMERS
ALKANES ALKYL GROUPS: ISOMERS
ALKANES ALKYL GROUPS: ISOMERS
 ALKANES ALKYL GROUPS: ISOMERS
▪ Alkanes with Carbons connected to not more than 2 other
Carbons are called straight-chain or normal alkanes.

▪ Alkanes with one or more Carbons connected to 3 or 4 Carbons

are branched-chain alkanes

▪ The names of alkanes straight chains.

 ISOMERS: CONSTITUTIONAL ISOMERS
▪ Isomers are molecules with the same chemical formula but
different structures. (that is, same numbers and kinds of
atoms but different ways in which atoms are arranged)

▪ Isomers originated from a Greek word isos + meros “ made

of same parts”.

▪ Constitutional isomers – compounds of butane and isobutane

have atoms connected differently but have the same
chemical formula.
ALKANES ALKYL GROUPS: ISOMERS

▪ We can represent an alkane in a brief form or in many other

types of extended form

▪ A condensed structure does not show bonds but lists atoms

in order, such as;

– CH3CH2CH3 (propane)

- CH3(CH2)2CH3 (2,2-dimethylpropane)
 ALKYL GROUPS

▪ If a hydrogen is removed from an alkane, a partial structure

remains is called an alkyl group.

▪ Alkyl group are named by replacing –ane ending of the

parent with –yl ending.
 ALKYL GROUPS
▪ Branched alkyl group are generated by removing a
hydrogen atom from an internal carbon
 ALKYL GROUPS
▪ A carbon at the beginning or end of a chain (primary alkyl group)

▪ A carbon in the middle of a chain (secondary alkyl group)

▪ A carbon with three carbons attached to it (tertiary alkyl group)

 ALKYL GROUPS
▪ Symbol R – represent generalized alkyl group

▪ The R can be methyl, ethyl etc.,

▪ R can represent rest of the molecule.

 Exercise
• Classify the carbons atoms in the following
organic molecules in primary (1◦), secondary
(2◦), tertiary (3◦) and quaternary (4◦).
 Exercise
Classify the carbons atoms in the following organic molecules in primary,
secondary, tertiary and quaternary.
 Exercise
Answers
30 20
40
30

10
20 30

10
30
40

10

20 40
 NOMENCLATURE OF BRANCHED-
CHAIN ALKANES
▪ Chemical name has four parts in IUPAC system of
nomenclature:

▪ Prefix→ specifies the location and identity of various substituent

groups in the molecule
 NOMENCLATURE OF BRANCHED-
CHAIN ALKANES
▪ Parent→ selects the main part of the molecule and shows how
many carbon atoms are in that part.

▪ Locant → gives the location of the primary functional group

▪ Suffix→ identifies the primary functional group

 NOMENCLATURE OF BRANCHED-
CHAIN ALKANES

▪ Nomenclature of branched-chain alkanes follows specific

rules:

– Named as longest continuous chain of Carbons

– Carbons in that chain are numbered in a sequence

– Substituents are numbered at their point of attachment in

the chain

– Compound name is one word (German style)

– Complex substituents are named similarly

NOMENCLATURE OF BRANCHED-
CHAIN ALKANES
▪ Find the Parent: longest continuous carbon chain
 NOMENCLATURE OF BRANCHED-
CHAIN ALKANES
▪ Start numbering the carbon atoms in the chain from the end
of the chain that is nearer to the first substituent.

▪ Substituents must have lowest carbon number as possible.

 NOMENCLATURE OF BRANCHED-
CHAIN ALKANES
▪ Identify & number the substituents. When two substituents are
present at an equal distance from either end of the longest
chain, then start numbering the chain from the side that has the
first letter alphabets.

▪ In deciding on alphabetical order, disregard multiplying prefixes

such as “di” and “tri” etc. and the prefixes like sec- or tert.
 NOMENCLATURE OF BRANCHED-
CHAIN ALKANES
▪ When three or more substituents are present, start numbering
the carbons/substituent in an order that leads to the lowest
set of locants.
 NOMENCLATURE OF BRANCHED-
CHAIN ALKANES
▪ Write the name as single word and use hyphens to separate
various prefixes.

▪ Use commas to separate numbers and if there’s two or more

different side chains – then cite them in alphabetical order.

▪ If there’s two or more identical side chains – use multiplier

prefixes such, di-, tri-, tetra- etc.
 CYCLOALKANES

▪ Cycloalkanes are alkanes that have carbon atoms bonded in

a form of a ring (called alicyclic compounds)

▪ Simple cycloalkanes are rings of ⎯CH2⎯ units,

(CH2)n or CnH2n
 CYCLOALKANES
▪ Cycloalkanes structures are shown as regular polygons with
the number of vertices equaling the number of C’s (a
projection of the actual structure)
 STEPS IN NAMING CYCLOALKANES
▪ Step 1: find the parent of the molecule

▪ Count the number of C atoms in the ring and then count the
number of C atoms in the largest substituent chain.

▪ If the number of C atoms in the ring is equal to or greater

than the number of C atoms in the substituent chain, then
the compound is named as a cycloalkane with an alkyl-
substituent. If the ring has fewer C atoms then its named as
a substituent
 STEPS IN NAMING CYCLOALKANES
▪ Step 2: Number the substituents and write the name.

▪ For substituted cycloalkanes, start numbering at the point of

attachment and go around the ring.

▪ If two or more substituent are present, start by numbering

around the ring in the direction that gives the second group
the lowest number possible.
STEPS IN NAMING CYCLOALKANES
 CIS-TRANS ISOMERISM IN
CYCLOALKANES
▪ Cycloalkanes behave similarly to open chain acyclic alkanes.

Similarities

▪ Both are non-polar and chemically inert to most reagents.

Differences

▪ Open chain alkanes are more flexible than cycloalkanes.

▪ Open chain alkanes have free rotation and cycloalkanes

have much less freedom of motion.
 CIS-TRANS ISOMERISM IN
CYCLOALKANES
▪ Rotation takes place around C-C bond in ethane, no rotation
is possible around cyclopropane without breaking open the
ring.
 CIS-TRANS ISOMERISM IN
CYCLOALKANES
▪ cycloalkanes have 2 faces as viewed edge-on

“top” face and “bottom” face

▪ isomerism is possible in substituted cycloalkanes
▪ There are two different 1,2-dimethyl-cyclopropane isomers

▪ Both of these isomers are stable.

▪ They cannot be converted without breaking the bonds
▪ Compounds with atoms connected in the same order but differ
in three–dimensional orientation are called Stereochemical
isomers or stereoisomers.

▪ Stereochemistry - is referred to three-dimensional aspects of

chemical structures.

▪ 1,2 –dimethyl cyclopropane are members of subclass

stereoisomers called - cis-trans isomers.
 STUDY UNIT 1.2.3: CONFORMATION AND
STEREOISOMERS
• SPECIFIC OUTCOMES:

• Draw conformational and rotational isomers.

• Draw Newman projections for the conformation of alkanes and

cycloalkanes.

• Explain the stabilities of the conformations of substituted

cyclohexane molecules.

• Distinguish between axial and equatorial substituents in

cyclohexanes
 CONFORMATION OF ETHANE

• Previously studied C-C single bonds results from head-on-

overlap of two atomic orbitals.

• The extend of this orbital overlap is the same regardless of

the geometric arrangements of other atoms attached to the

Carbons.

• Therefore - rotation is possible around C-C single bonds.

 CONFORMATION OF ETHANE
• Conformation - is the arrangements of atoms that results from
bond rotation.

• Conformational isomers – are molecules that have different

arrangement and usually interconvert.

• Below are two conformations of the ethane.

 SAWHORSE REPRESENTATION OF ETHANE

• Chemist represent different conformations in two ways:

1. A Sawhorse representation -

➢ views C-C bond from oblique angle and indicates spatial relationship
by showing all C-H bonds.
 NEWMAN PROJECTION
2. A Newman projection -

➢ Views the C-C bond directly end-on and represent the two carbon
atoms by a circle.

➢ Bonds attached to the front carbon are represents by lines to a dot

in the center of circle.

➢ Bonds attached to the rear carbon are represented by lines to the

edge of the lines.
 STAGGERED AND ECLIPSED CONFORMATION OF
ETHANE
❑Experiments shows that there is a slight energy barrier to rotation (12
KJ/mol; 2.9kcal/mol). Therefore, some conformation are stable than
others.

❑Most stable conformation, lowest energy, has bonds that are far away
from one another. (staggered when viewed from end-on in a Newman
projection).

❑Least stable conformation, highest energy, has six C-H bonds that are as
close as possible (eclipsed in a Newman projection).
 MOST FAVOURABLE CONFORMATION IN ALKANE

• The most stable conformation in any alkane - is when bonds on

adjacent carbons are staggered.
 CONFORMATION OF SOME
CYCLOALKANES:CYCLOPROPANE, CYCLOBUTANE AND
CYCLOPENTANE.
❑Cyclopropane – is flat, triangular molecule with C-C-C bond angles of
60⁰.

The deviation of bond angle from 109.5◦ tetrahedral causes an angle strain
in the molecule that raises its energy and makes it more reactive than
unstrained molecules.

• All six C-H bonds are in an eclipse arrangement, rather than a staggered
arrangement with their neighbours.
 ANGLE STRAIN

• The deviation of bond angles from the normal 109.5⁰

tetrahedral values.

8/23/2023 These are not for sale or distribution. Only for learning purposes
 CONFORMATION OF SOME CYCLOALKANES

• Cyclobutane and cyclopentane are puckered rather than

flat and that makes C-C-C- bond angles a bit smaller.

• They are roughly squared shaped bond angle 90⁰

 TORSINAL STRAIN

• Torsional strain is an increase in potential energy of a

molecule caused by eclipsing interaction.

• Torsional strain: When rotating a molecule around a bond,

the torsional strain is the repulsion caused by the electrons
in between different groups when they pass by each other.
 CYCLOHEXANE
• Substituted cyclohexane are very common cycloalkanes in
nature.
• The cycloalkane structures are observed in steroids and
many pharmaceutical agents and most contains
cyclohexane rings.
 CYCLOHEXANE
❑Cyclohexane
• is not flat, but puckered in strain free.
• In a three-dimensional shape it sits in a chair conformation
• All C-C-C bond are near 109⁰.
• All C-H bonds are staggered.
 CHAIR CONFORMATION OF CYCLOHEXANE
• Step 1: draw two parallel lines, slanted downward
and slightly offset from each other. This means that
four of the cyclohexane carbons lie in plane.

• Step 2: Place the topmost carbon atom above and

to the right of the plane of the other four, and
connect the bonds.

• Step 3: Place the bottommost carbon atom below

and to the left of the plane of the middle four, and
connect the bonds. Note that the bonds to the
bottommost carbon atom are parallel to the bonds
to the topmost carbon.
 AXIAL AND EQUATORIAL BONDS IN
CYCLOHEXANE
• Chair conformation has two kinds of position for substituent's on
the hexane ring: axial and equatorial positions.

• Axial position – six axial position are perpendicular to the ring and
parallel to the ring axis.

• equatorial positions – are in rough plane of the ring, around ring

equator.

• Each C atom has one axial and one equatorial position in alternating
arrangements.
 AXIAL AND EQUATORIAL BONDS IN
CYCLOHEXANE
• Each C atom one axial and one equatorial position in alternating
arrangements.
• Below is the strain free chair conformation of cyclohexane
• Red - represents axial
• Blue - represents equatorial
• The six axial are all parallel to the ring axis
• The six equatorial hydrogens are in a band around the ring equator
 AXIAL AND EQUATORIAL BONDS IN
CYCLOHEXANE

❑Axial bonds: Each carbon has one axial position and they are parallel
and alternating up and down.

❑Equatorial bonds: Each carbon has one equatorial bond;

o Comes in three sets of two parallel lines
o Each set is parallel to two ring bonds.
o Equatorial bonds alternate between sides around the ring

❑Completed cyclohexane
 CONFORMATIONAL MOBILITY OF
CYCLOHEXANE - RING FLIP

• There are two kinds of chair conformations.

• Because cyclohexane rings are conformationally mobile at room

temperature.

• Therefore, chair conformation readily interconvert by a process called

ring-flip
CONFORMATIONAL MOBILITY OF
CYCLOHEXANE - RING FLIP
 CHAIR CONFORMATION OF
METHYLCYCLOHEXANES
• Axial and equatorial methylcyclohexanes interconvert rapidly and are
not equally stable.

• Equatorial conformation is more stable than axial conformation by

7.6 KJ/mol.