 Hydrocarbon that contains a C=C double bond

 Sometimes called an olefin but alkene is better

 Includes many naturally occurring materials
 Flavors, fragrances, vitamins
 Hydrocarbon that contains a C≡C triple bond

 Less common than alkenes

 Simplest member acetylene

 Alkenes & alkynes are said to be unsaturated

 Name the parent hydrocarbon using suffix –ene in place of -ane
 Number the carbons in chain so that double bonded carbons have
lowest possible numbers

Note – the branch point gets the lowest number above right
Write the full name- Number substituents according to:
1) Position in chain, 2) Alphabetically

Rings have “cyclo” prefix

 Give IUPAC names for the following compounds
 a)

 b)
 Solution:

 a)

 The longest chain is a pentene

 Consists of three methyl groups
 The methyl groups are attached to C3 and C4
 Using tri- before methyl and using numbers to signify the location of the double
bond
 The compound is 3,4,4-Trimethyl-1-pentene
 b)

 The longest chain is a hexane

 The methyl group is attached to C3
 Using numbers to signify the location of the double bond
 The compound is 3-Methyl-3-hexene
 General hydrocarbon rules apply with “ -yne” as a suffix indicating an
alkyne
 Numbering of chain with triple bond is set so that the smallest number
possible is assigned to the first carbon of the triple bond
 Name the following alkynes:

 A)

 B)
 Solution:

 A) 2,5-Dimethyl-3-hexyne

 B) 3,3-Dimethyl-1-butyne
 Rotation of  bond is prohibitive
  bond must break for rotation to occur (unlike a carbon-carbon
single bond).
 Creates possible alternative structures
 Carbon atoms in a double bond are sp2-hybridized
 Three equivalent orbitals at 120º separation in plane
 Fourth orbital is atomic p orbital
 Combination of electrons in two sp2 orbitals of two atoms
forms  bond between them
 Additive interaction of p orbitals creates a  bonding orbital
 Occupied  orbital prevents rotation about -bond
 Rotation prevented by  bond - high barrier, about 268
kJ/mole in ethylene
 the presence of a carbon-carbon double bond can create two possible
structures
 cis isomer - two similar groups on same side of the double bond
 trans isomer - similar groups on opposite sides

cis alkenes are less

stable than trans alkenes
 Which compound in each pair is more stable

 a)

 b)
 Solution:
 a)

 b)
 Cis-Trans Isomerization requires that end groups differ
in pairs
 Bottom pair cannot be superposed without breaking
C=C
 Cis-Trans naming system discussed thus far only works
with disubstituted alkenes

 Tri- and Tetra substituted double bonds require more

general method

 Method referred to as the E,Z system

 Priority rules of Cahn,
Ingold, and Prelog
 Compare where higher
priority groups are with
respect to bond and
designate as prefix
 E -entgegen, opposite
sides
 Z - zusammen, together
on the same side Z zame zide
RULE 1
 Rank substituent atoms according to atomic number of first
atom
 Higher atomic number gets higher priority
 Br > Cl > S > P > O > N > C > H
RULE 2
 If atomic numbers are the same, compare at next connection point at
same distance
 Compare until something has higher atomic number
 Do not combine – always compare
RULE 3
 Multiple-bonded atoms are equivalent to the same number of single-
bonded atoms
 Substituent is drawn with connections shown and no double or triple
bonds
 Assign stereochemistry (E or Z) to the double bond in the following
compound
 Convert the drawing into a skeletal structure (red = O)
 Solution:
 Common patterns describe the changes in organic reactions
 Addition reactions – two molecules combine

 Elimination reactions – one molecule splits into two

 Substitution – parts from two molecules exchange
 Rearrangement reactions – a molecule undergoes
changes in the way its atoms are connected
 In a clock the hands move but the mechanism behind the face is
what causes the movement
 In an organic reaction, we see the transformation that has
occurred. The mechanism describes the steps behind the changes
that we observe
 Reactions occur in defined steps that lead from reactant to
product – invariably this involves the flow of electrons from one
atom to another
 We classify the types of steps in a sequence
 A step involves either the formation or breaking of a covalent
bond
 Steps can occur individually or in combination with other steps
 When several steps occur at the same time, they are said to be
concerted
 Bond formation or breakage can be symmetrical or
unsymmetrical
 Symmetrical- homolytic
 Unsymmetrical- heterolytic
 Curved arrows indicate breaking and forming of bonds
 Arrowheads with a “ half” head (“ fish-hook” ) indicate homolytic and
homogenic steps (called ‘radical processes’) – one electron processes
 Arrowheads with a complete head indicate heterolytic and heterogenic steps
(called ‘polar processes’) – two electron processes
 Not as common as polar reactions
 Radicals react to complete electron octet of valence shell
 A radical can break a bond in another molecule and abstract
a partner with an electron, giving substitution in the original
molecule
 A radical can add to an alkene to give a new radical, causing
an addition reaction
 Molecules can contain local unsymmetrical electron
distributions due to differences in electronegativities

 This causes a partial negative charge on an atom and a

compensating partial positive charge on an adjacent atom

 The more electronegative atom has the greater electron density

 Elements such as O, F, N, Cl are more electronegative than

carbon
 An electrophile, an electron-poor species, combines with a nucleophile, an
electron-rich species
 An electrophile is a Lewis acid (+ or +)
 A nucleophile is a Lewis base (electron pair)
 The combination is indicated with a curved arrow from nucleophile to
electrophile
 HBr (Note: The text uses HCl.) adds to the  part of a C-C
double bond
 The  bond is electron-rich, allowing it to function as a
nucleophile
 H-Br is electron deficient at the H since Br is much more
electronegative, making HBr an electrophile
 HBr electrophile is attacked by 
electrons of ethylene (nucleophile)
to form a carbocation intermediate
and bromide ion
 Bromide adds to the positive
center of the carbocation, which
is an electrophile, forming a C-Br
 bond
 The result is that ethylene and HBr
combine to form bromoethane
 All polar reactions occur by
combination of an electron-rich
site of a nucleophile and an
electron-deficient site of an
electrophile
 The highest energy point in
a reaction step is called the
transition state
 The energy needed to go
from reactant to transition
state is the activation
energy (Eact)
 If a reaction occurs in more
than one step, it must
involve species that are
neither the reactant nor the
final product
 These are called reaction
intermediates or simply
“ intermediates”
 Each step has its own free
energy of activation
 The complete diagram for
the reaction shows the free
energy changes associated
with an intermediate
 A catalyst is a substance that increases the rate of a reaction by
providing an alternative mechanism.
 The catalyst participates in the reaction.
 It is regenerated during the reaction.
 The catalyst provided a mechanism with a lower activation energy.

Example:
Hydrogenation
of double bond
with Pd