Alkene 1

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ALKENES

Alkenes
Hydrocarbons that contain a carbon-carbon double bond.
Important roles in biology, e.g ethene- plant hormone-effect seed
germination, flower germination/fruit ripening.
Systematic nomenclature of alkenes

The general formula of alkenes: CnH2n as a result of double bond,


alkene has 2 fewer H than alkane.
The general formula for cyclic alkene: CnH2n-2.
Double bond is the functional group of an alkene, its presence is
denoted by the suffix ene. Eg ethene, propene.
IUPAC rules for naming alkenes

1.Find parent (longest chain containing a double bond) - The double bond is
numbered in the direction that gives the suffix the lowest possible no.
2. For compound with 2 double bonds, the suffix is diene

3. Name of substituent is stated before the name of the longest


continuous chain that contains the functional group, together with
a no to designate the carbon to which the substituent is attached.

- Note: When there are both a functional group and a substituent,


the functional group gets the lowest number:
4. If a chain has more than 1 substituent, the substituents are
stated in alphabetical order. Appropriate no is assigned to each
substituent.

5. If counting in either direction results in the same no for the


alkene functional group, Name with the lowest functional group
number and then the lowest substituent numbers:
6. A no. is not needed to denote the position of the double bond in a cyclic
alkene- the ring is always numbered so that the double bond is between
C1 and C2.

- To assign no. to substituents, count around the ring in the direction that
put the lowest no. into the name.
Special nomenclatures
The sp2 carbons of alkene called vinylic carbons
sp3 carbon that is adjacent to vinylic carbon called an allylic
carbon.

Two groups containing a C-C double bond are used in common


names- the vinyl group and allyl group.
Vinyl group- smallest group containing vinylic carbon
Allyl group- smallest group containing allyllic C.
When vinyl or allyl is used, the substituent must be attached
to the vinylic or allylic C.
A hydrogen bonded to a vinylic C- vinylic H
A hydrogen bonded to a allylic C- allylic H
The structure of alkenes

Each double bond of an alkene has 3 sp2 orbitals overlaps an orbital of


another atom to form a bond. Thus one of the C-C bonds in a double bond is
a bond.
the 2nd C-C bond in the double bond (the bond) is formed from side-to-
side overlap of the remaining p orbital of 1 C with sp2 C with the remaining p
orbital of the other sp2 C.
Hybridisation Of Orbitals
Alternatively, only three orbitals (an s and two ps) combine or
HYBRIDISE to give three new orbitals. All three orbitals are
equivalent. The remaining 2p orbital is unchanged.

2s22p2 2s12p3 3 x sp2 2p

KNOCKHARDY PUBLISHING
THE STRUCTURE OF ALKENES

In ALKANES, the four sp3


orbitals repel each other into a
tetrahedral arrangement.

HOWEVER...

In ALKENES, the
three sp2 orbitals repel
each other into a
planar arrangement
and the 2p orbital lies
at right angles to them

KNOCKHARDY PUBLISHING
THE STRUCTURE OF ALKENES

Covalent bonds are formed An sp2 orbital from each carbon


by overlap of orbitals. overlaps to form a single C-C bond.

The resulting bond is called


a SIGMA () bond.

KNOCKHARDY PUBLISHING
THE STRUCTURE OF ALKENES

The two 2p orbitals also overlap to form a second bond. This is


known as a PI () bond.

For maximum overlap and hence the strongest bond, the 2p


orbitals are in line.

This gives rise to the planar arrangement around C=C bonds.

KNOCKHARDY PUBLISHING
ORBITAL OVERLAP IN ETHENE - REVIEW

two sp2 orbitals overlap to form a sigma two 2p orbitals overlap to form a pi
bond between the two carbon atoms bond between the two carbon atoms

s orbitals in hydrogen overlap with the sp2 the resulting shape is planar
orbitals in carbon to form C-H bonds with bond angles of 120

KNOCKHARDY PUBLISHING
Since 3 points determine a plane, each sp2 C and the two atoms
singly bonded to it lie in a plane.
(a plane-defined as sp2 hybridized carbon is bonded to 3 atoms)
In order to achieve max orbital-orbital overlap, the 2 p orbitals
must be parallel.
Therefore, all 6 atoms of the double bond system are in the
same plane.
Alkenes can have cis and trans isomers
(Geometrical isomerism)
To achieve max overlap- 2 p orbitals forming the bond must be
parallel.
Therefore rotation about double bond does not readily occur. If
rotation to occur, the 2 p orbitals would cease to overlap and the
bond would break. the energy barrier to rotation about a double
bond is high.
Geometrical Isomerism

RESTRICTED ROTATION OF C=C BONDS

Single covalent bonds can easily rotate. What appears to be a different structure is
not. It looks like it but, due to the way structures are written out, they are the same.

ALL THESE STRUCTURES ARE THE SAME BECAUSE C-C BONDS HAVE FREE ROTATION

Animation doesnt
work in old
versions of
Powerpoint
Geometrical Isomerism
RESTRICTED ROTATION OF C=C BONDS

C=C bonds have restricted rotation so the groups on either end of the bond are
frozen in one position; it isnt easy to flip between the two.

Animation doesnt
work in old
versions of
Powerpoint

This produces two possibilities. The two structures cannot interchange easily
so the atoms in the two molecules occupy different positions in space.
Because of the high energy barrier to rotation about C-C double
bond, an alkene such as 2-butene can exist in 2 distinct form. The
H bonded to the sp2 C can be on the same side of double bond or
on opposite side of double bond.

Compound with Hs on the same side of double bond- cis isomer


Hs on the opposite side of double bond- trans isomer
Cis isomer- substituents on the same side of the ring
Trans isomer- substituents on opposite sides of the ring.
If one of the sp2 Cs of the double bond is attached to 2 identical
substituents, there is only 1 possible structure for the alkenes.
Because of the energy barrier- cis and trans isomers of alkenes
cannot interconvert (except under extreme conditions that can
overcome the energy barrier)
They can be separated from each other
The 2 isomers are different compounds with different physical
properties ie. bp and different dipole moments
Naming alkenes using the e,z system

as long as each of the sp2 carbon of an alkene is bonded to only 1


substituent, we can use the term cis and trans to designate the
structure of alkenes
How to designate the isomers such as 1-bromo-2-chloropropene?
The E,Z system of nomenclature for alkenes with 2 substituents
on 1 or both of the sp2 carbons.
To name an isomer by E, Z system- determine the relative
priorities of the 2 groups bonded to 1 sp2 C
Then, the relative priorities of the 2 groups bonded to the
other sp2 carbon.

E,Z is from German:


Z, Zusammen (together) E, Entgegen (opposite)
The relative priorities of the 2 groups bonded to a sp2 carbon
are determined using the following rules:
1. Relative priorities of the 2 groups depend on the atomic no of
the atoms bonded directly to the sp2 C. the greater the no, the
higher priority.
2. If the 2 groups bonded to sp2 C start with the same atom, then
move outward from the point of attachment and consider the
atomic no of the atoms that are attached to the tied atoms.

- The C of the CH2Cl group is bonded to Cl, H, H and the C of the


CH2CH2Cl group is bonded to C, H, H.
- Cl has a greater atomic no. than C, so CH2Cl group has higher
priority.
- In CH2OH group and CH(CH3)2 group, both atoms are bonded C.
- The C of CH2OH group is bonded to O, H and H and the C for
CH(CH3)2 group is bonded to C, C and H.
- Of these 6 atoms, O has the greatest atomic no so CH2OH has a
higher priority.
3. Multiple bonds are treated as attachment of multiple single
bonds using divide-duplicate.
- If an atom is doubly bonded to another atom, the priority system
treats it as if it were singly bonded to two of those atoms. If an
atom is triply bonded to another atom, the priority system treats it
as if it were singly bonded to 3 of those atoms

- because the Cs immediately bonded to the sp2 carbon on the left


are both bonded to C, H and H- ignore them-look at the groups
that attached to them.
- 1 of the group is CH2OH and the other is C CH.
- 1 C is bonded to H, H and O; the triple bonded C is considered to
be bonded to C, C and C. of the 6 atoms, O has the greatest atomic
no, so CH2OH has higher priority.
At the other sp2 C- both atoms are Cs.

The 1st carbon of the CH2CH3 group is bonded to C, H and H.


1st C of the CH=CH2 is bonded to an H and doubly bonded to a C,
so it is considered to be bonded to H, C and C.
1 C cancels in each groups (cancel atoms that are identical in the 2
groups), leaving H and H in CH2CH3 group and H and C in the
CH=CH2. C has greater atomic no than H, so CH=CH2 has greater
priority.
4. If 2 isotopes (atoms with same atomic no but different mass
no) are compared, mass no is used to determine priorities.

- Deuterium (D) and H have same atomic no but different mass,


D has higher priority than H.
- the C that are bonded to the other sp2 C are both bonded to
C, C and H so the next atoms are looked to.
PHYSICAL PROPERTIES OF ALKENES

Boiling point trends are similar to those shown in alkanes


increases as they get more carbon atoms in their formula
more atoms = greater intermolecular Van der Waals forces
greater intermolecular force = more energy to separate molecules
greater energy required = higher boiling point
the lower members are gases at room temperature and pressure
cyclohexene C6H10 is a liquid
for isomers, greater branching = lower boiling point

C2H4 (- 104 C) C3H6 (- 48C) ....... C6H10 (83C)

Melting point general increase with molecular mass


the trend is not as regular as that for boiling point.

Solubility alkenes are non-polar so are immiscible (dont mix with) with water
miscible with most organic solvents.
Exercises
Provide the proper IUPAC name for the alkene shown below.

a)

b)

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