SKO 3013 BASIC ORGANIC CHEMISTRY

NAME

NO. MATRIC

NG SENG WEI
TAY SIEW BEE

D20091035105
D20081032270

Geometric al isomer
Introduction/ eliciting ideas
Overview previous lesson Learning outcomes

Structuring/ restructuring ideas

Cis-trans isomer Structures Activity

Applications of ideas
Problem solving 1

Reflection/ closure

The E, Z rules

Short quiz Learning outcomes homework

Physical properties Games

WHAT HAVE YOU LEARNED FROM THE PREVIOUS LESSON?

Constitutional Isomers ~Chain ~Position ~Functional group Conformation Isomers
Stereoisomers Configurational Isomers

Isomerism

Geometrical Isomers
Optical Isomers

Geometrical Isomers

LEARNING OUTCOMES
At the end of this subtopic, student should be able to
Distinguish

geometrical isomers (C4).

Identify

cis-trans isomerism of a given structural formula. Use sequence rules: The E, Z designation.

How geometric arise ??

What happen in molecules where is involving unrestricted rotation about carbon bonds - in other words where the carbon-carbon bonds are all single?

Two possible of configuration 1,2 dichoroethane

Two models exactly same molecules and not isomer

Organic compounds which have same molecular formula but different non-interchangable geometry due to different orientation of atoms in space.

Restricted rotation (often involving carboncarbon double bonds) Maximum overlap between the p orbital of a pi bond.

CIS-TRANS ISOMERISM
PROBLEM 1
There are two steps to determine the cis or trans structure below:

First step

Draw an imaginary line collinear with that carbon-carbon double bond

--------------------

Second steps

The structure that has the equivalent substituent on the same side of the imaginary is the cis stereoisomer and the opposite side is trans stereoisomer.

--------------------

--------------------

Cis-1-chloro-1-propene

Trans-1-chloro-1-propene

Apply in daily item to remember!!

Cis isomer

The two wheels on a motorcycle show the equivalent substituent on the same side of the imaginary. The body of the motorcycle shows the C=C double bond.

Trans isomer

Unbalanced seesaw

Results from rigidity in molecules and occurs in only two classes of compound:

i.

Alkenes

ii.

Cyclic compounds

i. Alkenes
1,2 -dichloroethene

These two molecules aren't the same. The carboncarbon double bond wont rotate and would have to take the models to pieces in order to convert one

structure into other one. That is simple test for isomer.

Two chlorine atoms are locked on opposite side of double bond. Known as trans isomer.

Two chlorine atoms are locked on same side of double bond. Known as cis isomer.

EXAMPLE:

ii. Cyclic compound

Because ring dont rotate freely in space like linear chains two different possibilities exist. Cis Isomers are when two atoms are on the same side of a ring. Trans Isomers are when two atoms are on different side of a ring.

H H H H
H

H H

Cis Isomers

Trans Isomers

EXAMPLE:

CH3 H H

CH3 CH3
cis-1,2-dimethylcyclohexane

CH3

trans-1,2-dimethylcyclohexane

Both are same molecule

YOU WONT HAVE GEOMETRIC ISOMERS IF THERE

ARE TWO GROUPS THE SAME ON ONE END OF THE BOND. THE TWO PINK GROUPS ON THE LEFT HAND END.

There must be two different groups on left and right carbon to get geometric isomer.

i)

CH3CH2 C=C

ii) H C=C

CH3

H3C
iii) H3C C=C H3C H

Cl

CH3

CH3

For these molecules above , give IUPAC name for the compounds and indicate if they are geometric isomers or neither.

i) CH3CH2 C=C H3C

ii) H C=C

CH3

Cl

CH3

2-methyl-1-butene

1-chloro-2-methylpropene

No cis trans isomer

iii) H3C C=C CH3

No cis trans isomer

2-methyl-2-butene

H3C

No cis trans isomer

Planner Geometry (real or virtual)

Geometrical Isomerism is found in compound which have Different substituent on either side of imaginary or real planner geometry. No interconvertibility (presence of pi bond ,continuous pi bond)

!!DONT FORGET TO TAKE NOTE

THE EFFECT OF GEOMETRIC ISOMERISM ON PHYSICAL PROPERTIES

ISOMER CIS TRANS

MELTING POINT (C) -80 -50

BOILING POINT(C) 60 48

Table shown the melting and boiling point of cis and trans isomer of 1,2-dichloroethene

YOU WILL NOTICE THAT

The trans isomer has the higher melting point.

The cis isomer has the lower boiling point.

Alkyl groups attached to carbon-carbon double bond tend to push electrons away from themselves and get polar molecules. Why is the boiling point of the cis isomer higher?

Cis isomer is polar whereas trans is not polar.

Higher dipoledipole interaction as well as dispersion forces.

Stronger intermolecular forces.

The U shape of cis isomer does not pack as well as the straighter shape of the trans isomer.

The poor packing in the cis isomer means that the intermolecular forces weak and less energy is needed to melt the molecule.

Why is the melting point of the cis isomer lower??

Crossword Puzzle Games

DOWN: When two identical substituent groups are oriented in the same site, it is called the ___(1)___ isomer. Geometry isomerism is a form of ___(2)___. The boiling point of the cis isomer is higher because it is a ___(3)___molecule. CROSS: The trans isomer has the ___(4)___ melting point than cis isomer because the ___(5)___ forces are stronger. ___(6)___ isomer is the planar geometry when the two substituent groups are oriented in opposing site. (2)

S
(1) (5) I

(3)

P R
(4) H

(6)

ANSWER

(2)

(3) S (1) T P C E O (5) I N T E R M O L E C U L A R S E A O R (4) H I G H E R S O M E (6) T R A N S I S M

But even different things still have geometric isomers.

Here the blue and green groups are either on the same side of the bond or the apposite side.

Sequence rules: The E, Z designation

Priority Rules for designating the precise isomer configuration in stereoisomerism. E and Z notations are introduced to designate geometrical isomers of any type.

Geometrical isomer
Cahn-IngoldPrelog priority sequence rules

Optical isomer

When dealing with a C-X bond grouping, the priority of X is given by ....
Sequence priority Rule 1:
The higher the atomic number of an atom the higher the priority it is assigned.
e.g. for typical non-metals ZX (Z = proton/atomic number) encountered in organic compounds ...

X=

53I

> 35Br > 17Cl > 16S > 15P > 8O > 7N > 6C > 1H

Sequence priority Rule 2:

If the relative priority of two groups cannot be decided by Rule 1, it shall be determined by applying Rule 1 to the next atom or sequence of atoms in the group 'X'.
e.g. for typing groupings in organic molecules where X is more than one atom ....

X = -CH2CH2CH3 > -CH2CH3 > -CH3 > -H

(the longer the hydrocarbon carbon chain the higher its priority)

Sequence priority Rule 3:

In groups containing multiple bonds, then for the purposes of determining priority the atom at the end of the bond is duplicated or triplicated as required.

PROBLEM 1
Determine the stereochemistry (E or Z ) below

First step

We assure ourselves that the carbon-carbon double bond is indeed stereogenic. We draw an imaginary line perpendicular to the carboncarbon double bond

Second steps

Now rank the atoms directly bonded to the alkene carbons on each side of the imaginary line by atomic number high to-low.

The two groups of higher priority are label as 1 whereas the other two groups with lower priority are label as 2.

Third steps

Finally we connect the winning group

Fourth steps

In this case, we cross the double bond to connect the higher ranking groups. Thus alkene has the E stereochemistry and the systematic name of the molecule is (1E)-1bromo-2-fluoro-1propene where 1 in 1 E refer to the location of the carbon-carbon double bond.

All the four steps were same in order to determine stereochemistry (E or Z ) for the structure below.

The structure above is (1Z)-1-bromo-2-fluoro-propene

The Z isomer
(Zusammen)
Both highest priority groups are on the same side of the double bond (includes all cis configurations of the old convention). Example:

The E isomer
(Entgegen)
Two highest priority atoms/groups are diagonally opposite each other on differentsides of the plane of the double bond system (includes all trans isomers of the old convention). Example:

Z-hep-2-ene

cis/trans 2-heptene

E-hep-2-ene

Rank the set of substituents below in order of priority according to the Cahn-Ingold-Prelog sequence rules. 1 = highest priority.

a) -COOH b) -CN c) -C=O d) -CH2Br

Explain why certain ones were ranked higher than others?

a) -COOH-----2 b) -CN----4 c) -C=O-----3 d) -CH2Br ----1

To establish priority, you look at the atoms' atomic numbers and whichever one is greater takes priority. If they are equal, then you look at the next atom that it is bonded to and compare their atomic numbers. Now, if you encounter a double bond, you count that atom twice (so C=O is counted as C,O,O).

summary
Students divide into two groups Each group choose one item below for your quizzes.

1. What is the difference between structural isomer and geometric isomer? Answers:

Structural isomerism is the same emperical formula but constructed differently and different structural formula. Geometric isomerisim is where you have different isomers due to differences arrising from cis and trans arrangements of atoms.

2. Can the compound below exhibit geometrical isomerism? Why?

1,1-dibromocyclobutane

Answers:
1,1-dibromocyclobutane, is a positional isomer of C4H6Br2 and cannot exhibit geometrical isomerism because the two bromine atoms are attached to the same carbon.

3. Determine the stereochemistry (E or Z) of the double bonds in this molecule:

Answers:

E-3-methylhex-3-ene

4. Give two examples of cis-trans isomerism in cyclic compounds.

Answers:

Z-1,2-dichlorocyclopropane (cis)

E-1,2-dichlorocyclopropane (trans)

Z/cis

E/trans

LEARNING OUTCOMES
At the end of this subtopic, students are able to
Distinguish

geometrical isomers (C4).

Identify

cis-trans isomerism of a given structural formula. Use sequence rules: The E, Z designation.

HOMEWORK

Text book

Study problems page 59 No 4.3 i, ii, iii and iv. No 4.4

Worksheets

(2 members per group).

THE END

REFERENCES
1.

Saripah Salbiah Syed Abdul Azziz, Azmi Mohamed, Mohamad Saufi Rosmi, Nurul Aini Binti Bakar dan Mimi Marzziana Hamzah. Basic Organic Chemistry. Sultan Idris Education University. Stereoisomerism Geometric Isomerism. Retrieved on 15 March 2011 at http://www.chemguide.co.uk/basicorg/isomerism/geometric.html Organic Chemistry. Retrieved on 15 March 2011 at people.bu.edu/birubio/ch203ampmpdfs/l13.pdf Cahn-Ingold-Prelog Priority Rule. Retrieved on 16 March 2011 at http://askville.amazon.com/Cahn-Ingold-Prelog-PriorityRule/AnswerViewer.do?requestId=4776615 Organic Stereoisomerism-E/Z isomerism. Retrieved on 16 March 2011 at http://www.docbrown.info/page07/isomerism2.htm

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