Organic Chemistry I Phan Minh Giang

Chapter 2
SATURATED HYDROCARBONS
ALKANES AND CYCLOALKANES
Organic Chemistry

Alkanes

IUPAC nomenclature of alkanes and alkyl groups

Molecular structure and Reactivity
Geometry of alkanes: sp3 tetrahedral shape
Newman projection formulas
Perspective (3D) formulas
Conformation and Conformational analysis
Organic Chemistry

Important Terms and Concepts

Saturated hydrocarbon
Unsaturated hydrocarbon
Straight chain (linear) alkane
Branched alkane
IUPAC (Systematic, Substitutive) name
Common name
Primary, Secondary, Tertiary, Quaternary carbon (hydrogen)
Newman projection
Perspective 3D formula
Organic Chemistry

Alkanes Are Saturated Hydrocarbons

Alkanes are saturated hydrocarbons.

Hydrocarbons: compounds having C and H.
Saturated hydrocarbons: compound has the maximum possible
number of C-H bonds.

Hydrogenation
Organic Chemistry

Alkanes and Cycloalkanes

Alkanes are saturated hydrocarbons, that is, molecules containing
carbon and hydrogen connected by single bond only.
Linear or Acyclic saturated
hydrocarbons (Alkanes): Saturated
hydrocarbons can be in continuous chains.
Cyclic saturated hydrocarbons
(Cycloalkanes): Saturated hydrocarbons
can be in rings.
Organic Chemistry

Linear (Straight-chain) and Branched-chain Alkanes

• Linear (Normal, Straight-chain)

Alkanes (n-Alkanes): compounds
like n-butane, whose carbons are
connected in a row.
• Branched (branched-chain)
Alkanes: compounds with
branched chains, such as
isobutane (2-methylpropane).
Organic Chemistry

The Occurrence of Branched-chain Alkanes

Organic Chemistry

NOMENCLATURE OF ORGANIC COMPOUNDS

Organic Chemistry

IUPAC NOMENCLATURE OF ORGANIC COMPOUNDS

International Union of Pure and Applied Chemistry = IUPAC

Organic Chemistry

IUPAC Nomenclature of Alkanes and Cycloalkanes

The names of alkanes and cycloalkanes are the root names of
organic compounds. Beginning with the five-carbon alkane, the number
of carbons in the chain is indicated by the Greek or Latin prefix. Rings are
designated by the prefix “cyclo”.

Linear alkanes are named according to the number of carbon atoms they
contain. The suffix –ane is added to the end of each name to identify the
molecule as an alkane.
Branched alkanes are named as the linear alkanes showing the
substituents and their position on the longest continuous carbon chain
(that chain gives the parent name)

Alkyl group
If a hydrogen atom is removed from an alkane, the partial structure that
remains is an alkyl group. Alkyl group are named by replacing the –ane
ending with an –yl ending.
Organic Chemistry

IUPAC Nomenclature of Alkanes and Cycloalkanes

Organic Chemistry

IUPAC Nomenclature of Alkanes

Organic Chemistry

IUPAC Nomenclature of Functionalized Alkanes

Organic Chemistry

IUPAC Names of Branched-chain Alkyl Groups

Alkyl groups: common name (IUPAC name – substitutive name)
Organic Chemistry

IUPAC Nomenclature of Alkanes

correct the name of this alkane

Organic Chemistry

IUPAC Nomenclature of Alkanes and Cycloalkanes

Organic Chemistry

Classification of sp3 Carbon Atoms

Organic Chemistry

Classification of sp3 Carbon Atoms

Organic Chemistry

Classification of sp3 Carbon Atoms

Organic Chemistry

Alkanes: Molecular Structures

C-C bonds in alkanes result from sigma overlap of two tetrahedrally

oriented sp3 orbitals and give alkanes three-dimensional structures.
Organic Chemistry

Hybridization
Organic Chemistry

Alkanes: Molecular Structures

• Free bond rotation: Rotation is possible around C-C single bonds

(sigma bonds) because this motion does not change the amount of
orbital overlap.
• What are the spatial relationship between the hydrogens on one
carbon and the hydrogens on the other?
The different arrangements (3D shapes) of atoms that result from rotation
about a single bond are called conformations, and they interconverted too
rapidly for them to be isolated.
Organic Chemistry

Conformation and Configuration

Organic Chemistry

Bond Rotation and Newman Projection

symmetry different potential energy

free bond rotation

Organic Chemistry

Newman Projection and Sawhorse Projection

d
View C-C bond from View C-C bond end-on.
an oblique angle. b c
The C in front is
represented by a dot
f e from which three bonds
a
radiate. The C in back is
represented by a circle.

ad

b
f e
c

II
Organic Chemistry

Newman Projection: How to Draw?

Newman
projections show
relative positions
of substituents
Organic Chemistry

Conformational Analysis

Conformational analysis: energy analysis of conformations

Organic Chemistry

Conformational Analysis

Limiting conformations: conformations which have the maximum

(eclipsed) and minimum (staggered) energies.
Organic Chemistry

Conformational Analysis

How to calculate the relative energies of conformations?

Electron-electron repulsion between bonds (C-H, C-C, C-X).

Organic Chemistry

Energy diagram

Conformational analysis
1. Presentation of Newman projection: relative positions of bonds
2. Calculate relative energies for limiting conformations
3. Plot the potential energy diagram.
Organic Chemistry

Rotation about Single Bond in Ethane

Organic Chemistry

Rotation about Single Bond in Ethane

Organic Chemistry

Rotation about Single Bond in Butane

Organic Chemistry

Rotation about Single Bond in Butane

Organic Chemistry

Rotation about Single Bond in Butane

Organic Chemistry

Energy diagram
Organic Chemistry

Rotation about Single bond in Butane

Organic Chemistry

Rotation about Single Bond in Butane

Interactions
H-H eclipsing (torsional strain) 1.0 kcal/mol
H-Me eclipsing (mostly torsional strain) 1.3 kcal/mol
Me-Me eclipsing (steric and torsional strain) 4.0 kcal/mol
Me-Me gauche interaction (steric strain) 0.9 kcal/mol
Organic Chemistry

Cycloalkanes

IUPAC nomenclature of monocyclic cycloalkanes

Molecular structures of cycloalkanes
Ring strain of cycloalkanes
Conformation of cycloalkanes
Organic Chemistry

IUPAC Nomenclature of Cycloalkanes

Alkanes: Open-chain compounds

Cycloalkanes: Cyclic compounds (compounds with rings of carbons).
They are alicyclic (aliphatic - “fat” - cyclic) compounds.
Organic Chemistry

IUPAC Nomenclature of Cycloalkanes

Organic Chemistry

Cycloalkanes: Ring Strain

Organic Chemistry

Cycloalkanes: Are They Flat Molecules?

Organic Chemistry

Ring Strain (?) And the Heats of Combustion

Organic Chemistry

Ring Strain And the Shapes (!) of Cycloalkanes

Cycloalkanes tend to have conformations (shapes) to minimize the strains.

Organic Chemistry

Cyclopropane
Organic Chemistry

Cyclobutane: Folded Conformation

Organic Chemistry

Cyclopentane: Envelope Conformation

Organic Chemistry

Cyclohexane: Chair Conformation

Organic Chemistry

Cyclohexane: Chair Conformation

Organic Chemistry

Axial and Equatorial Hydrogens (Bonds)

Organic Chemistry

Conformational Mobility of Cyclohexanes

The equatorial conformation is more

stable than the axial conformation
due to unfavorable steric interaction.
Organic Chemistry

Stability of Cyclohexane Conformations

1,3-Diaxial interaction

axial
Organic Chemistry

Newman Projection for Methylcyclohexanes

Organic Chemistry

Newman Projection for Methylcyclohexanes

Organic Chemistry

Ring Flip of (Mono)Substituted Cyclohexanes

Organic Chemistry

Ring Flip of (Mono)Substituted Cyclohexanes

Ring flip: The interconversion of chair conformations.

Organic Chemistry

cis-Disubstituted Cyclohexanes
Organic Chemistry

trans-Disubstituted Cyclohexanes

Problem:
Organic Chemistry

Alkanes

Molecular structure and Reactivity

Chemical properties
1) Halogenation of alkenes
Mechanism of radical substitution reactions and regioselectivity
of the reactions
Selectivity of halogens
Stereochemistry of radical reactions of alkanes
2) (Cracking and oxidative reactions)
Organic Chemistry

Halogenation Reactions

Free-radical chain reactions

Radical mechanism (SR: S – substitution, R - radical)
Using arrow-pushing in describing reaction mechanism
Reactants (Starting materials)
Reagents and Reaction conditions (why light or heat necessary?)
Intermediates of the reaction: the influence of their stability on the rates of
the reactions
Selectivity of halogens
Can the product ration can be controlled?
Stereochemistry of the reactions: generation of stereocenters
Organic Chemistry

Halogenation of Alkanes

A multiple reaction

Radical Substitution
Organic Chemistry

Halogenation of Alkanes
Organic Chemistry

Free-radical halogenation mechanism

Organic Chemistry

Energy Diagram for the Chlorination of Methane

Multi-step reaction has more than one
transition state (TS). The rate-determining
step is the step with the highest energy TS.
Organic Chemistry

Selectivity in Radical Halogenation

Organic Chemistry

Free Radical Stability

Organic Chemistry

Regioselectivity in Radical Halogenation

Organic Chemistry

Energy Diagram for the Chlorination of Methane

Organic Chemistry

Regioselectivity in Radical Halogenation

Reactivity: F > Cl > Br >> (I)

Organic Chemistry

Selectivity in Radical Halogenation

Reactivity: F >> Cl > Br > I Halogen CH3 CH2 CH

Calculate selectivity of halogens F2 (25oC, gas) 1 1.2 1.4

Cl2 (25oC, gas) 1 3.8 5.0
Relative reactivity = Selectivity
Br2 (98oC, gas) 1 250 6300

Calculate selectivity for bromine

of primary/secondary hydrogens.
Organic Chemistry

Selectivity of Bromination

Selectivity: Br > Cl
Organic Chemistry

Selectivity in Radical Halogenation

Organic Chemistry

Selectivity in Radical Halogenation

Tỷ lệ các sản phẩm (từ trái sang phải) theo tốc độ phản ứng x số nguyên tử hydro bị thay thế:
bậc 1 (6H) : bậc 3 (1H) : bậc 2 (2H) : bậc 2 (2H) : bậc 1 (9H) = 6x1 : 5x1 : 3,8x2 : 3,8x2 : 9x1
% các sản phẩm: bậc 1 (6H) = 6/35,2 = 17%; bậc 3 (1H) = 5/35,2 = 14,2%; bậc 2 (2H) =
7,6/35,2 = 21,6%; bậc 2 (2H) = 7,6/35,2 = 21,6%; bậc 1 (9H) = 9/35,2 = 25,6%.
Organic Chemistry

Stereochemistry of Halogenation
Organic Chemistry

Generation of Stereocenters