Inorganic and Organic Chemistry: Concepts and Applications (CYL120)

Semester-II (2014-2015), Department of Chemistry, IIT Delhi

Exam: I Minor
Day and Date: Sunday, February 15, 2015

Time: 5.30 p.m. to 6.30 p.m. (1 hour)

Max. Marks: Twenty five (25)

7.

Using the given molecular formula (C4H8O), write four different functional isomers
with their names. (2 Marks)

8.

What is optical activity? Calculate []D of compound X: 5.00 g of X is dissolved in 100 mL

ethanol. 20 mL of this solution is placed in a 25 cm polarimeter tube at 25 C.
The observed rotation is 17.29 clockwise. (2 Marks)

9.

10.

What is a carbocation? Discuss their structure, formation, and stability? (1.5 Marks)

The Fisher projection of 2,3 dihydroxy-butanal is given below:

a) How many chiral centers are present in the given compound? Assign them R or S.
b) Write Sawhorse projection and Newmann projection of this compound. (2 Marks)

11.

Write the name of the given compound using both cis/trans and E/Z notation. (2 Marks)

12.

Indicate the relationship between the molecules in each pair. (2 Marks)

a)

b)

OH

HO

13. What should be the observed specific rotation of a sample having 82% eeR?
(The pure S enantiomer in the sample has a specific rotation of 23.7)

(1 Marks)

###############*********************##################***********************

Cycloalkanes and their Stereochemistry

Saturated cyclic hydrocarbons are defined as a carbon ring which has
hydrogen in every position except the attachment point. These are also
called alicyclic compounds.

H
H

Cyclopropane

H H

H
H
H

H
H

Cyclo = the cyclic ring

propane = the number of carbons

Basic Examples of Cycloalkanes

Number of Carbons
3

Prop

But

Pent

Hex

Hept

Example: Cyclohexane = a ring of six carbons

10

Oct

Non

Dec

Naming Cycloalkanes
Rule 1 Find the parent: Count the number carbons in the chain and the substituents. If
the substituents is longer then the ring then the parent name is the substituent. If the ring
is longer then the ring is the parent.

CH3
1-Methylcyclopentane

CH2CH2CH2CH3
1-Cyclopropylbutane

If we look at the molecule on the left. A pentane ring has 5 carbons compared to its substituent (1 carbon)
a methyl. So the parent is the cyclopentane. However on the molecules on the right butane (4 carbons) is
larger than cyclopropane (3 carbons) so the butane is the parent name.

 Rule 2: Number the substituents, and write the name.

Make sure that you follow the ring so that the substituents have the lowest numbers.
Number the Substituents. C-1 always has a substituent attached. Number so that the second substituent
has the lowest number possible, etc,

CH 3
4

5
1

H 3C

CH 3

1,2,4-trimethylcyclopentane
Not 1,3,4-trimethylcyclopentane

 Rule 3: If two or more alkyl groups have potentially the same number, number
alphabetically.
CH3

1-ethyl-2-methylcyclohexane
CH2CH3

Not 1-methyl-2-ethylcyclohexane

Rule 4: Treat other substituents exactly like alkyl groups.

CH3
Br

1-Bromo-2-methylcyclohexane

Example for practice:

Stereoisomers
Unlike Constitutional Isomers which have the same molecular formula but a
different orientation.
Stereoisomers have the same order of connection but differ in spatial (or
three dimensional 3D) orientation.

Cis-Trans Isomerism in Cycloalkanes

Cycloalkanes are less flexible than open-chain alkanes
Much less conformational freedom in cycloalkanes
Because of their cyclic structure, cycloalkanes have 2 faces as viewed edge-on
top face bottom face
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

Cis Isomers

Trans Isomers

Ring Strain in Cycloalkanes

Types of Strain
Angle Strain also called Ring Strain is the strain due to
expansion or compression of bond angles.
Torsional Strain the strain due to eclipsing of bonds on
neighboring atoms.
Steric Strain the strain due to repulsive interactions when
atoms approach each other too closely.

Angle (Ring) Strain

Cyclopropane has angles of 60o when we know that SP3 carbons like to
bond at 109.5o. In cyclopropane there is angle strain.
expansion or compression of bond angles away from most stable
Example cyclopropane and cyclohexane:

60

~109.5o

Torsional Strain
Is the strain due to eclipsing of bonds on neighboring atoms.
When atoms are eclipsed then there is a natural tendency to
move away from each other this is called torsional strain.

H H
H
H
H
H

H
H
H
H

H
H
H

H
H

H
H
H

Steric Strain
Steric strain focuses on the strain of functional groups bound due to size onto
the cyclic ring. Because rings dont rotate freely in space like linear chains then
energy is higher when they are on the same side.
repulsive interactions between nonbonded atoms in close proximity
For example: cyclopropane

H
H

H
H

Higher Energy

Lower Energy

Stability of Cycloalkanes: Ring Strain

Rings larger than 3 atoms are not flat
Cyclic molecules can assume nonplanar conformations to minimize angle
strain and torsional strain by ring-puckering
Larger rings have many more possible conformations than smaller rings and
are more difficult to analyze
Larger rings have many more possible conformations than smaller rings and
are more difficult to analyze

Ring Strain in Cycloalkanes

Baeyer Strain Theory
Johann Friedrich Wilhelm
Adolf von Baeyer

First graduate student of Kekule

Developed theory that cycloalkanes possess different amounts
of strain or stability, depending on the size of the ring.
Awarded Nobel Prize in 1905 for work with organic dyes.
Total synthesis of indigo.

"I have never set up an experiment to see whether I was right,

but to see how the materials behave".

Ring Strain in Cycloalkanes

The relative stabilites of cycloalkanes are determined by measuring their heats of combustion.
The heat of combustion is the energy released as heat when a compound undergoes complete
combustion with oxygen under standard conditions.
The chemical reaction is typically a hydrocarbon reacting with oxygen to form carbon dioxide, water and heat.
[ -CH2- ]n +

1.5 nO2

nCO2 + nH2O + Heat

Ring Size

Heat per CH2

kcal/mol

Ring Strain per CH2,

kcal/mol

Total Ring Strain,

kcal/mol

Long-Chain Alkane

157.4

0.0

0.0

166.6

9.2

27.6

164.0

6.6

26.4

158.7

1.3

6.5

157.4

0.0

0.0

158.3

0.9

6.3

158,6

1.2

9.6

The more heat per CH2,

the less stable the alkane.

 Baeyer (1885): since carbon prefers to have bond angles of approximately 109, ring sizes other than
five and six may be too strained to exist
Rings from 3 to 30 Cs do exist but are strained due to bond bending distortions and steric interactions

Conformations of Cycloalkanes
Cyclopropane

3-membered ring must have planar structure, The most ring strained alkane ring
Symmetrical with CCC bond angles of 60 instead of 109.5o.
Requires that sp3 based bonds are bent (and weakened)
All C-H bonds are eclipsed
Bonds are weaker and more reactive than any other cycloalkanes.

Bent Bonds of Cyclopropane

In cyclopropane, the C-C bond is displaced outward from
internuclear axis

Cyclobutane
Cyclobutane has less angle strain than cyclopropane but more torsional strain
because of its larger number of ring hydrogens
Cyclobutane is slightly bent out of plane - one carbon atom is about 25 above
The bend increases angle strain but decreases torsional strain
Because of the increased torsional strain the total energy of cyclopropane
and cyclobutane are the same.

Cyclopentane
Planar cyclopentane would have no angle strain but very high torsional strain so
it twists to a puckered non-planar configuration.
Actual conformations of cyclopentane are nonplanar, reducing torsional strain
Four carbon atoms are in a plane
The fifth carbon atom is above or below the plane looks like an envelope

Conformations of Cyclohexane
Cyclohexane is strain free which means that it is stable.
Substituted cyclohexanes occur widely in nature
The cyclohexane ring is free of angle strain and torsional strain
The conformation is has alternating atoms in a common plane and
tetrahedral angles between all carbons
Adopt 2 three-dimensional structures or conformations (Chair and Boat).

Chair and Boat

There are two chair forms and one boat form. The boat form is a transition
between one chair form and the other. If you look closely then you will see
that if the red carbons bend up you will have the boat. If the blue carbons
bend down then you will have the second chair form.

Cyclohexane is free of ring strain? Why?

1. All Bonds are staggered and therefore no torsional strain.
2. All bond angles are near 109.50 so no angle strain.
3. It does possess steric strain (internal gauche interaction) but
no more than a noncyclic alkane.

Chair conformation showing

only carbon atoms

Cyclohexane the most stable conformation of cyclohexane is the chair.

Chair conformations showing
positions of hydrogens

Newman projection shows that

all bonds are staggered. Bond
angles are about 109.5o

How to Draw Cyclohexane

You need to be able to draw a both chairs of cyclohexane ring!

Axial and Equatorial Bonds in Cyclohexane

The chair conformation has two kinds of positions for substituents on the
ring: axial positions and equatorial positions
Chair cyclohexane has six axial hydrogens perpendicular to the ring (parallel
to the ring axis) and six equatorial hydrogens near the plane of the ring

Drawing the Axial and Equatorial Hydrogens

Conformational Mobility of Cyclohexane

Chair conformations readily interconvert, resulting in the exchange of
axial and equatorial positions by a ring-flip

Conformations of Monosubstituted Cyclohexanes

Cyclohexane ring rapidly flips between chair conformations at room temp.
Two conformations of monosubstituted cyclohexane arent equally stable.
The equatorial conformer of methyl cyclohexane is more stable than the axial by 1.8 kcal/mol

2 x 0.9 = 1.8 kcal/mol

5%

0.0 kcal/mol

95%

Other Substituents
X
X
X

Eaxial Eequatorial
kcal/mol

-H

0.0

-F

0.24

-CN

0.2

-Cl

0.50

-Br

0.50

-CH3

1.8

-CH2CH3

1.9

-CH(CH3)2

2.2

-C(CH3)3

5.4

1,3-Diaxial Interactions
Difference between axial and equatorial conformers is due to steric strain caused by
1,3-diaxial interactions
Hydrogen atoms of the axial methyl group on C1 are too close to the axial hydrogens
three carbons away on C3 and C5, resulting in 7.6 kJ/mol of steric strain

Conformational Analysis of Disubstituted Cyclohexanes

1,2 disubstituted cyclohexanes: axial-axial, equatorial-equatorial are trans
equatorial-axial, axial-equatorial are cis

H3C
CH3
equatorial axial
cis-1,2-dimethylcyclohexane

CH3
H3C

1,3 disubstituted cyclohexanes: axial-axial, equatorial-equatorial are cis

equatorial-axial, axial-equatorial are trans

equatorial - axial
trans-1,3-dimethylcyclhexane
CH3

CH3
axial-axial or diaxial

trans-1,4-dimethylcyclohexane

1,4 disubstituted cyclohexanes: axial-axial, equatorial-equatorial are trans

equatorial-axial, axial-equatorial are cis

Drawing Structures
CYCLIC ALKANES: Substituents on a cycloalkane can be cis or trans to
each other. You should draw the ring in the plane of the paper (solid lines)
and use dashes and wedges to show whether substitutents are above or
below the plane of the ring.

correct

cis

incorrect

trans

On occasion you may wish to distinguish the faces of a cycloalkane.

top face
a
a

a
a

b
b

bottom face

CYCLOHEXANE: For cyclohexanes you may be asked to draw a chair, in

which case all substituents must be either axial or equatorial. The following
is the correct way to draw chair cyclohexane. Note how the axial and
equatorial substituents are represented off each carbon.
a
a

Disubstituted chair cyclohexanes:

correct

trans

trans

trans

incorrect

trans

cis

cis

cis

trans

cis

The Conformations of Cyclohexane

and Their Energies

Cyclohexane Stereochemistry
Cis -Trans Isomers
a = axial; e = equatorial

Position
1,2

cis
e,a or a,e

trans
e,e or a,a

1,3
e,e or a,a

a,e or e,a

e,a or a,e

e,e or a,a

1,4

Conformational Analysis of Disubstituted Cyclohexanes

In disubstituted cyclohexanes the steric effects of both substituents must be taken into account
in both conformations
There are two isomers of 1,2-dimethylcyclohexane. cis and trans
In the cis isomer, both methyl groups are on the same face of the ring, and compound can exist
in two chair conformations
Consider the sum of all interactions
In cis-1,2, both conformations are equal in energy

Trans-1,2-Dimethylcyclohexane
Methyl groups are on opposite faces of the ring
One trans conformation has both methyl groups equatorial and only a gauche butane interaction between
methyls (3.8 kJ/mol) and no 1,3-diaxial interactions
The ring-flipped conformation has both methyl groups axial with four 1,3-diaxial interactions
Steric strain of 4 3.8 kJ/mol = 15.2 kJ/mol makes the diaxial conformation 11.4 kJ/mol less favorable than the
diequatorial conformation
trans-1,2-dimethylcyclohexane will exist almost exclusively (>99%) in the diequatorial conformation