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PREPARED BY:
MR. NADIM MR CHHIPA
ASSOCIATE PROFESSOR,
ASP & BRI, ADALAJ
DEFINITION
• The isomerism which occurs due to difference of the positions of the
substituents about a double bond or a ring due to restricted rotation is called
geometric isomerism.
• They do not rotate the plane of polarised light (unless they also happen to be
chiral), and do not have identical properties.
• Conditions for geometric isomerism
There must be a carbon-carbon double bond in the compounds.
Each of the carbon of the double bond must be attached to two different
substituents
CIS-TRANS ISOMERSIM
Configuration of the isomeric but-2-ene shown in figure. They differ in their names
by the prefixes cis- (Latin: on same side) and trans- (Latin across), which indicate
that methyl group are in same side or on opposite side of the molecule.
These forms are not interconvertible due to restricted rotation of double bond.
First we will determine which of the two chair conforms of cis- 1,4-dimethyl-
cyclohexane is more stable. One chair conformer has one methyl group in an
equatorial position and one methyl group in an axial position. The other chair
conformer also has one Therefore, both chair conformers are equally stable.
This method of denoting geometric isomerism works best when the alkene is di-
substituted. In fact, it will always work when the alkene is di-substituted (and other
conditions are fulfilled). But this method can fail with tri-substituted or tetra-
substituted
alkenes.
For this cis/trans method of denoting to work, there must be at least one
identical group on each carbon of the double ,bond. For example:
Cis isomer is less stable than trans isomer
• In cis isomer, two large groups on the separate carbons are always on the same side.
Thus, these two groups are closer to each other and repel each other. This is called
steric strain.
• On the other hand, in trans isomer the two large groups are on the opposite sides. So
they are far apart. Hence they don’t repel each other. So, the steric strain is far less.
E AND Z NOMENCLATURE
• For denoting Geometrical isomers by cis/trans, is not sufficient when there are
more than two different substituents on a double bond. So denote them E/Z
nomenclature is adopted.
• If the group of highest priority on both carbon are on the same side, then it is
Z (Z = Zusammen = Together) isomer, if they are on opposite sides, then it is E
(E = Entgegen =Opposite) isomer.
• Theletters E and Z are represented within parantheses and are separated
from rest of the name with a hyphen.
• thegroups attached to each carbon of the double bond are analyzed and
then given priorities according to Cahn-Ingold-Prelog (CIP) rules.
CIP RULES FOR E/Z NAMING CONVENTION
• Substituents on any one of the two double-bonded carbon atom is looked at.
• First, the atom which is directly attached to the double bond carbon is looked
at. This is the first atom. The group where first atom has higher atomic number
has higher priority.
• If, both groups are attached by the same first atom, then the atomic number of
the second atom (atom attached to first atom) is looked at.
• Similarly, if the second atoms are also same, third atoms are looked at.
If the first atoms of two groups have the same higher atomic number
substituents, one with more such substituent is given higher priority.
If there is any double bond or triple bond within the group, it is considered at two
or three single bonds respectively. So:
If there is a phenyl group attached to first atom, then it is thought that First atom is
attached to three carbons.
If isotopes of same element are present, the higher priority is given to the isotope
with higher atomic mass. E.g. the Deuterium isotope (H2 or D) has more priority
than protium (H1 or H). The C13 isotope has more priority than C12.
SYN-ANTI SYSTEM
• This is used for compounds which are oximes of aldehyde, hydrazones and
Semicarbazide, in which carbon is joined to nitrogen by double bond also exhibit
geometrical isomerism.
• Since H and OH group can arrange on same side or opposite sides of the double
bond.
• when hydrogen and hydroxyl group are on the same side, the isomer is known as syn
(analogous to cis) and when these groups are on the opposite sides, the isomer is
known as anti (analogous to trans).
In Aldoxime the syn isomer- in which –OH group of the oxime is on the
side of the hydrogen of the aldehyde carbon
In Ketoxime - specify the group with respect to which the oxime -OH
group is syn
DETERMINATION OF CONFIGURATION OF
GEOMETRICAL ISOMERISM
1. Dipole Moment
Cis isomer have higher dipole moment than trans-isomer. As in trans-isomer two
bond moments are opposed because of the symmetry of molecule, where sys
isomer being non-symmetrical has a finite dipole moment as bond moments are
not opposed.
2. Melting/ Boiling Point
trans isomer have higher Melting and Boiling than cis-isomer. As in trans-isomer
molecules are more symmetrical and hence fit more closely in the crystal lattice
as compared to the molecules of cis isomer.
Intermolecular forces work well in trans isomer and U shape of cis isomer can
not fir perfectly in crystal lattice. Poor packing is leads to poor intermolecular
forces. So they required less energy to break.
3. Solubility.
• In general, solubility of a cis isomer is higher than that of the corresponding
trans isomer. This is due to the reason that the molecules of a cis isomer are less
tightly held in the crystal lattice.
4. Stability
• The trans isomer is more stable than cis isomer due to steric hindrance.
Intermolecular reactions occur easily when reacting groups are close together.
Hence, the cis isomer will form cyclic derivatives more readily as against
trans derivatives. But this reaction will take place in only those cis isomers in
which the substituent’s on two double bonded carbons are capable of
intramolecular reaction with each other.
CONFORMATIONAL ISOMERISM
• Different spatial arrangement of atoms that can be generated or converted
into one another by free rotation about single bond is known as confirmations.
• Differentconfirmation of same molecule also called confirmers, rotamers or
conformational isomers.
• It
can be determined by use of x-ray and electron differenction, IR, Raman,
UV and NMR, etc.
• Confirmations can be calculated by method called molecular mechanics.
REPRESENTATION OF CONFORMATIONAL ISOMERS
Br2 CH3
H
H Br
H3C C
C CH3 H Br
H CH3
C C C C anti-addition
C C C C syn-addition