Isomers

Constitutional isomers Stereoisomers

consider the isomeric alkenes of
molecular formula C4H8
ALKENES
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R
R
R
R
ROTATION BREAKS THE BOND
Unlike bonds, bonds do not rotate.
It requires about 50-60 kcal/mole ( ~ 240 kJ/mole )
to break the bond - this does not happen at
reasonable temperatures.
NO!
2-Methylpropene 1-Butene
cis-2-Butene
trans-2-Butene
C C
H
H
H
CH2CH3
H3C
C C
CH3
H
H
H
CH3
C C
H3C
H
C C
H
H H3C
H3C
2-Methylpropene 1-Butene
cis-2-Butene
C C
H
H
H
CH2CH3
H
CH3
C C
H3C
H
C C
H
H H3C
H3C
Constitutional isomers
2-Methylpropene 1-Butene
trans-2-Butene
C C
H
H
H
CH2CH3
H3C
C C
CH3
H
H
C C
H
H H3C
H3C
Constitutional isomers
cis-2-Butene
trans-2-Butene
H3C
C C
CH3
H
H
H
CH3
C C
H3C
H
Stereoisomers
Naming of Alkenes
Number carbons in chain so that double bond carbons have
lowest possible numbers
Rings have cyclo prefixdouble bond always C#1, C#2
Multiple C=C are named as diene triene tetraene etc
Alkenes higher priority than alkanes: even shorter chain

8
Nomenclature/ Properties
Cis-Trans isomers (disubstituted)
Compounds that have one of their carbons bonded to two
identical groups cannot exist as cis-trans isomers.


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If an alkene has two identical substituents on one of
the double bond carbons, cis / trans isomers are
not possible.
all of these compounds are identical
Two identical substituents
no cis / trans isomers
C
H
H
C
CH
3
CH
2
-CH
3
C
H
3
C
CH
2
C
H
H CH
3
C
H
H
C
CH
2
-CH
3
CH
3
CH
3
CH
3
H
CH
3
CH
2
CH
3
H
C H
3
CH
3
CH
3
no cis / trans isomers
Some other compounds with no cis / trans isomers
cis-3-hexene trans-3-hexene
Naming cis / trans isomers of alkenes
notice that these
prefixes are in
italics
CH
2
CH
3
CH
3
CH
2
H H
H CH
3
CH
2
H CH
2
CH
3
main chain stays
on same side of
double bond = cis
main chain crosses
to other side of
double bond = trans
Stability of Alkenes
Cis alkenes are less stable than trans alkenes

Less stable isomer is higher in energy
tetrasubstituted > trisubstituted > disubstituted > monosusbtituted

13
if C<8 then the
chain is too short
to join together
Rings with double bonds
trans double bonds are not possible until the ring
has at least eight carbon atoms
CH
2
CH
2
CH
2
CH
2
cis
cis
cis
trans
smallest ring that
can have a trans
double bond
C = 5
C = 6
C = 8
Note that both cis and trans exist for C8.
trans
C C
R
H
R
H
C C
H
R
R
H
R R
R
R
Compare cis / trans isomers in ring compounds to alkenes
cis trans
cis / trans isomers are also called geometric isomers
Stereochemical Notation
cis and trans are useful when substituents
are identical or analogous (oleic acid has a cis
double bond)
cis and trans are ambiguous when
analogies are not obvious
C C
CH3(CH2)6CH2
CH2(CH2)6CO2H
H H
Oleic acid
CH
3
H CH
2
CH
3
CH
2
CH
3
CH
3
H CH
3
CH
3
cis-3-methyl-2-pentene trans-3-methyl-2-pentene
CIS OR TRANS !!!
This compound is cis
but the two methyl
groups are
.trans to each other.
This compound is trans
but the two methyl
groups are
.cis to each other.
The main chain determines cis / trans in the IUPAC name
but the terms cis and trans are also used to designate
the relative position of two groups: a new system is needed!
Sequence Rules: The E,Z Designation
Neither compound is clearly cis or trans

Substituents on C1 are different than those on C2

We need to define similarity in a precise way to
distinguish the two stereoisomers

Cis, trans nomenclature only works for disubstituted
double bonds

E/Z Nomenclature for 3 or 4 substituents


18
In this system the two groups attached to each carbon
are assigned a priority ( 1 or 2 ).

If priority 1 groups are both on same side of double bond:
E / Z Nomenclature
1 1
2 2
2 1
2 1
Z E
If priority 1 groups on opposite sides of double bond:
E isomer = entgegen = opposite (in German)
Z isomer = zusammen = together (in German)
same
side
opposite
sides
Assigning priorities
1. Look at the atoms attached to each carbon of
the double bond.
2. The atom of higher atomic number has higher (1)
priority.
example
I F
H Br
1
2
1
2
F > H
I > Br
Since the 1s are on the same side, this compound is Z
(Z)-1-bromo-2-fluoro-1-iodoethene
notice use of parentheses
Priorities in the E-Z
Nomenclature system
1
1
(Z)
(E)
C C
C C
1
1
3. If you cant decide using the first atoms attached,
go out to the next atoms attached. If there are
non-equivalent paths, always follow the path with
atoms of higher atomic number.
CH
2
F CH
3
H CH
2
CH
3
C
H
H
F
C C
H
H
Once you find a difference, you can stop.
1
2
1
2
This molecule has Z configuration.
comparison
stops here
path goes to
F not to H
path goes to
C not to H
C H
2
F C H
3
H C H
2
C H
3
Lets give this compound a cis/trans name
and an E/Z name
trans-3-fluoromethyl-2-pentene (longest chain)

(Z)-3-fluoromethyl-2-pentene (priorities)
C H C H
2
C O
H
4. C=C double bond: equivalent to having two carbons.
C=O double bond: equivalent to having two oxygens.
C H C H
2
C
C O
H
C O
1
2
C
C C
CH
2
CH
2
O
CH
3
H
2
N
Br
CH
2
CH
2
OH
1
2
1
2
(E)
C C
CH
2
CH
2
O
CH
3
H
2
N
Br
CH
2
OH
1
2
2
1
(Z)
trans, trans trans, cis
cis, cis
cis, trans
DIENES AND POLYENES
E,E E,Z
Z,Z Z,E
(2E,4E)-2,4-hexadiene
identical
(2E,4Z)-2,4-hexadiene
(2Z,4Z)-2,4-hexadiene (2Z,4E)-2,4-hexadiene
Hexadiene
28
Nomenclature
Question. Designate each double bond as E or Z, where applicable.
O H
H
H
B r
O H
geraniol