Guru Nanak Institute of Pharmaceutical Science and

Technology
157/ F, Nilgunj Road, Panihati, Kolkata 700114

Title of Work: Postulates and Assumptions of Baeyer’s Strain Theory

Paper Code: R21_PT314

Paper Name: Pharmaceutical Organic Chemistry II

Report Submitted for the Evaluation of Continuous Assessment II

Submitted by

Name: Somali Sengupta

Roll No.: 186012101067

Program: B. Pharm

Semester: 3

1
ABSTRACT
In the following report a brief discussion on postulates and assumptions on Baeyer’s strain theory has been
undertaken. Strain can be defined as deformation of bond length and bond angle from their ideal values
under the influence of internal force. There are three types of Strain: (i) Torsional or Eclipsed Strain (ii)
Angle Strain, and (iii) Steric or Van-der Walls Strain. Torsional strain is the increase in potential energy of a
molecule due to repulsion between electrons in bonds not shared by an atom. Angle strain is defined as the
increase in potential energy of a molecule due to bond angles deviating from their ideal values. Steric strain
is related to Van Der Waals repulsion, or the strain that occurs as the distance between either two atoms or
substituents decreases. The various postulates, assumptions and limitations of the theory has been discussed.

1. Strain
Strain can be defined as deformation of bond length and bond angle from their ideal values under the
influence of internal force. This creates an instability within the structure with higher internal energy. Strain
refers to the energy associated with a system due to its geometry. Potential energy is stored in the molecule
when a bond length or bond angle is distorted. This energy is referred to as the strain or the strain energy.
There are three types of Strain: (i) Torsional or Eclipsed Strain (ii) Angle Strain (iii) Steric or Van-der Walls
Strain

1.1 Torsional Strain

Torsional strain, also known as eclipsing strain, is the increase in potential energy of a molecule due to
repulsion between electrons in bonds not shared by an atom. When a molecule is able to rotate around a
sigma bond, different levels of torsional strain exist that vary with the placements of the substituents relative
to one another. This leads to different conformations of molecules (such as staggered or eclipsed) with
different energy levels, leading to different levels of stability.

2
1.2 Angle Strain
Angle strain is defined as the increase in potential energy of a molecule due to bond angles deviating from
their ideal values. Cyclic molecules are an excellent example to demonstrate this type of strain.
Cyclopropane is a compound that has a very large amount of angle strain. The carbons in cyclopropane tend
to be in 109.5° angles with each other. However, owing to the geometry of the molecule, the carbons are
forced into 60° angles with each other. This creates severe strain in the molecule.

1.3 Steric Strain

Steric strain, also referred to as steric hindrance, is related to Van Der Waals repulsion, or the strain that
occurs as the distance between either two atoms or substituents decreases. Thus, it is also called Van-der

3
Walls Strain. Steric strain occurs when multiple substituents are so close together that they cannot be
separated by rotation. Van-der walls strain is the increase in potential energy of a molecule due to repulsion
between electrons in atoms that are not directly bonded to each other.

2. Relative Stability
The stability of any cycloalkane is indicated by its tendency of ring fission. Cyclopropane readily reacts with
bromine to form an open chain addition compound and its stability is least. Cyclobutane does not form any
addition compound with bromine at ordinary temperature but it reacts with hydrogen iodide with the opening
of the ring, thus showing that it is more stable than cyclopropane. Cyclopentane and cyclohexane, however,
react with bromine to form substitution products; the ring remains intact. This shows that these hydrocarbons
are very stable.
The relative stability of cycloalkanes is indicated clearly by the temperature of ring fission by catalytic
hydrogenation:
Cyclopropane Cyclobutane Cyclopentane
80° 120° 300°
Cyclopropane ring is least stable and is ruptured at the lowest temperature. Cyclobutane and cyclopentane
rings are comparably more stable as indicated by higher temperatures of reaction. Stability increases from
lower to higher carbon membered ring. The higher cycloalkanes are all very much stable as they do not
undergo catalytic hydrogenation. As is clear from above, the stability of cycloalkanes is directly proportional
to the size of the ring, that is, it increases with the size of the ring upto cyclopentane and from cyclohexane
and above, all hydrocarbons are quite stable. These stability relationships have been explained under
Baeyer's Strain Theory.

3. Baeyer’s Strain Theory

In 1885 Adolf von Baeyer, a German chemist, proposed a theory to account for certain aspects of the
chemistry of cyclic compounds. Although it is dressed in more modern language, the part of his theory
dealing with the ring-opening tendencies of cyclopropane and cyclobutene is generally accepted today.
Other parts of his theory have been proved to be based on false assumptions, and thus have been discarded.

4
3.1 Postulates
Baeyer's argument was essentially based on the following:
 In general, when carbon is bonded to four other atoms, the angle between any pair of bonds is 109.5°,
the tetrahedral angle. But the ring of cyclopropane is a triangle with three angles of 60° each, and the
ring of cyclobutane is a square with four angles of 90° each. Thus, in cyclopropane or cyclobutane,
one pair of bonds to each carbon cannot assume the tetrahedral angle, but must be compressed to
either 60° or 90° to fit the geometry of the ring.
 Such deviations of bond angles from the normal tetrahedral value cause the molecules to be strained
and unstable compared with molecules in which the bond angles are tetrahedral.
 Cyclopropane and cyclobutane undergo ring-opening reactions which relieve the strain and yield
more stable open chain compounds.
 Because the deviation of the bond angles in cyclopropane (109.5° - 60° = 49.5°) is greater than in
cyclobutane (109.5° - 90° = 19.5°), cyclopropane is highly strained, more unstable and more prone to
undergo ring-opening reactions than compared with cyclobutane.
 The angles of a regular pentagon (108°) are very close to the tetrahedral angle of 109.5°, and hence
cyclopentane should be virtually free of angle strain.
 Baeyer proposed that there should be a certain amount of strain in cyclohexane because the angles of
a regular hexagon (120°) are somewhat larger than the tetrahedral angle. This was later proved to be
incorrect.
 He also suggested that as one proceed to cycloheptane, cyclooctane, etc., the deviation of the bond
angles from 109.5° would become progressively larger and the molecules would become
progressively more strained. This was also proved to be incorrect later.
Thus, Baeyer considered that rings that were smaller or larger than cyclopentane or cyclohexane were
unstable; it was because of this instability that the three and four membered rings underwent ring-opening
reactions and great difficulty had been encountered in the synthesis of the larger rings.
Baeyer proposed “any deviation of bond angle from ideal bond angle value (109.5°) will produce a strain in
molecule. Higher the deviation lesser the instability”.

3.2 Assumptions
Baeyer’s strain theory is based upon some assumptions as follows:
 All existing ring systems are planar. Deviation from normal tetrahedral angles results in unstable
cycloalkanes.

 The larger ring systems involve negative strain hence do not exist.

5
  The bond angles in cyclohexane and other higher cycloalkanes like cycloheptane, cyclooctane,
cyclononane, etc. are not larger than 109.5° because the carbon rings of those compounds are not
planar but they are puckered.

According to Baeyer, the relative order of stability for some common cycloalkanes is as follows:
Cyclopentane > Cyclobutane > Cyclopropane
4. Limitations of Baeyer’s Strain Theory
4.1 Successfulness of the theory
 Baeyer had rightly proposed that cyclopropane and cyclobutane are flat molecules and have angle of
60° and 90° respectively, that are much deviated from the ideal tetrahedral value of 109.5° hence
these ring systems are unstable and easily undergo ring opening reactions. Much angle strain is
present in cyclopropane and cyclobutane.
 Baeyer also correctly proposed that cyclopentane does not need to be planar, although it is, and
hence, the angle is much nearer to the ideal tetrahedral angle.
4.2 Unsuccessfulness of the theory
 He was not able to explain the effect of angle strain in larger ring systems.
 According to the proposed theory, cyclopentane should be more stable than cyclohexane but
practically, it is reversed.
 Larger ring systems are not possible according to Baeyer as they have negative strain but they do
exist and are much stable.
 Larger ring systems are not planar but puckered (wrinkled) to eliminate the angle strain.

6
 Reference
1. Morrison R.T. and Boyd R.N. (2002) Organic Chemistry Sixth edition 9 281-317
2. Bahl Arun and Bahl B.S. (2000) A Textbook of Organic Chemistry Fifth edition 31 593-597
3. Wheiand G.W. Advanced Organic Chemistry Third edition Wiley, New York, 1960.
4. Mine J, Physical Organic Chemistry, 2nd ed., McGraw-Hill, New York, 1962.
5. Ingold C.K. Structure and Mechanism in Organic Chemistry, 2nd ed., Cornell University Press, 1969.
6. March J, Advanced Organic Chemistry, McGraw-Hill, New York, 1968.
7. Hammett L.P. Physical Organic Chemistry, 2nd ed., McGraw-Hill, New York, 1970.
8. Gould E.S. Mechanism and Structure in Organic Chemistry, Holt, New York, 1959.
9. Sykes P, A Guidebook to Mechanism in Organic Chemistry, 3rd ed., Wiley, New York, 1970.
10. Breslow R, Organic Reaction Mechanisms, W. A. Benjamin, New York, 1965.

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ABSTRACT

In the following report a brief discussion on postulates and assumptions on Baeyer’s strain
theory has been undertaken. Strain can be defined as deformation of bond length and bond
angle from their ideal values under the influence of internal force. There are three types of
Strain: (i) Torsional or Eclipsed Strain (ii) Angle Strain, and (iii) Steric or Van-der Walls
Strain. Torsional strain is the increase in potential energy of a molecule due to repulsion
between electrons in bonds not shared by an atom. Angle strain is defined as the increase in
potential energy of a molecule due to bond angles deviating from their ideal values. Steric
strain is related to Van Der Waals repulsion, or the strain that occurs as the distance between
either two atoms or substituents decreases. The various postulates, assumptions and
limitations of the theory has been discussed.
1. Strain

Strain can be defined as deformation of bond length and bond angle from their ideal

values under the influence of internal force. This creates an instability within the structure

with higher internal energy. Strain refers to the energy associated with a system due to its

geometry. Potential energy is stored in the molecule when a bond length or bond angle is

distorted. This energy is referred to as the strain or the strain energy.

8
There are three types of Strain: (i) Torsional or Eclipsed Strain (ii) Angle Strain (iii) Steric or

Van-der Walls Strain

1.1 Torsional Strain

Torsional strain, also known as eclipsing strain, is the increase in potential energy of a

molecule due to repulsion between electrons in bonds not shared by an atom. When a

molecule is able to rotate around a sigma bond, different levels of torsional strain exist

that vary with the placements of the substituents relative to one another. This leads to

different conformations of molecules (such as staggered or eclipsed) with different energy

levels, leading to different levels of stability.

1.2 Angle Strain

Angle strain is defined as the increase in potential energy of a molecule due to bond

angles deviating from their ideal values. Cyclic molecules are an excellent example to

demonstrate this type of strain. Cyclopropane is a compound that has a very large amount

of angle strain. The carbons in cyclopropane tend to be in 109.5° angles with each other.

However, owing to the geometry of the molecule, the carbons are forced into 60° angles

with each other. This creates severe strain in the molecule.

1.3 Steric Strain

Steric strain, also referred to as steric hindrance, is related to Van Der Waals repulsion, or

the strain that occurs as the distance between either two atoms or substituents decreases.

Thus, it is also called Van-der Walls Strain. Steric strain occurs when multiple substituents

are so close together that they cannot be separated by rotation. Van-der walls strain is the

increase in potential energy of a molecule due to repulsion between electrons in atoms that

are not directly bonded to each other.

2. Relative Stability

The stability of any cycloalkane is indicated by its tendency of ring fission. Cyclopropane

9
readily reacts with bromine to form an open chain addition compound and its stability is

least.

Cyclobutane does not form any addition compound with bromine at ordinary temperature

but it reacts with hydrogen iodide with the opening of the ring, thus showing that it is

more stable than cyclopropane. Cyclopentane and cyclohexane, however, react with

bromine to form substitution products; the ring remains intact. This shows that these

hydrocarbons are very stable. The relative stability of cycloalkanes is indicated clearly by

the temperature of ring fission by catalytic hydrogenation:

Cyclopropane Cyclobutane Cyclopentane

80° 120° 300°

Cyclopropane ring is least stable and is ruptured at the lowest temperature. Cyclobutane

and cyclopentane rings are comparably more stable as indicated by higher temperatures of

reaction. Stability increases from lower to higher carbon membered ring. The higher

cycloalkanes are all very much stable as they do not undergo catalytic hydrogenation. As

is clear from above, the stability of cycloalkanes is directly proportional to the size of the

ring, that is, it increases with the size of the ring upto cyclopentane and from cyclohexane

and above, all hydrocarbons are quite stable. These stability relationships have been

explained under Baeyer's Strain Theory.

3. Baeyer’s Strain Theory

In 1885 Adolf von Baeyer, a German chemist, proposed a theory to account for certain

aspects of the chemistry of cyclic compounds. Although it is dressed in more modern

language, the part of his theory dealing with the ring-opening tendencies of cyclopropane

and cyclobutene is generally accepted today.

Other parts of his theory have been proved to be based on false assumptions, and thus have

been discarded.
3.1 Postulates

Baeyer's argument was essentially based on the following:

10
 □ In general, when carbon is bonded to four other atoms, the angle between any pair of bonds is 109.5°, the

tetrahedral angle. But the ring of cyclopropane is a triangle with three angles of 60° each, and the ring of

cyclobutane is a square with four angles of 90° each. Thus, in cyclopropane or cyclobutane, one pair of

bonds to each carbon cannot assume the tetrahedral angle, but must be compressed to either 60° or 90° to

fit the geometry of the ring.

□ Such deviations of bond angles from the normal tetrahedral value cause the molecules to be strained

and unstable compared with molecules in which the bond angles are tetrahedral.

□ Cyclopropane and cyclobutane undergo ring-opening reactions which relieve the strain and yield more

stable open chain compounds.

□ Because the deviation of the bond angles in cyclopropane (109.5° - 60° = 49.5°) is greater than in

cyclobutane (109.5° - 90° = 19.5°), cyclopropane is highly strained, more unstable and more prone to

undergo ring-opening reactions than compared with cyclobutane.

□ The angles of a regular pentagon (108°) are very close to the tetrahedral angle of 109.5°, and hence

cyclopentane should be virtually free of angle strain.

□ Baeyer proposed that there should be a certain amount of strain in cyclohexane because the angles of a

regular hexagon (120°) are somewhat larger than the tetrahedral angle. This was later proved to be incorrect.

□ He also suggested that as one proceed to cycloheptane, cyclooctane, etc., the deviation of the bond

angles from 109.5° would become progressively larger and the molecules would become progressively

more strained. This was also proved to be incorrect later.

Thus, Baeyer considered that rings that were smaller or larger than cyclopentane or

cyclohexane were unstable; it was because of this instability that the three and four

membered rings underwent ring-opening reactions and great difficulty had been

encountered in the synthesis of the larger rings.

Baeyer proposed . undefined2 Assumptions

Baeyer’s strain theory is based upon some assumptions as follows:
□ All existing ring systems are planar. Deviation from normal tetrahedral angles results in unstable

cycloalkanes.

□ The larger ring systems involve negative strain hence do not exist.

□ The bond angles in cyclohexane and other higher cycloalkanes like cycloheptane, cyclooctane, cyclononane,

etc. are not larger than 109.5° because the carbon rings of those compounds are not planar but they are

11
 puckered.

According to Baeyer, the relative order of stability for some common cycloalkanes is as

follows: Cyclopentane > Cyclobutane > Cyclopropane

4. Limitations of Baeyer’s Strain Theory

4.1 Successfulness of the theory

□ Baeyer had rightly proposed that cyclopropane and cyclobutane are flat molecules and have angle of 60°

and 90° respectively, that are much deviated from the ideal tetrahedral value of 109. 5° hence these ring

systems are unstable and easily undergo ring opening reactions. Much angle strain is present in cyclopropane

and cyclobutane.

□ Baeyer also correctly proposed that cyclopentane does not need to be planar, although it is, and hence, the

angle is much nearer to the ideal tetrahedral angle.

4.2 Unsuccessfulness of the theory

□ He was not able to explain the effect of angle strain in larger ring systems.

□ According to the proposed theory, cyclopentane should be more stable than cyclohexane but

practically, it is reversed.

□ Larger ring systems are not possible according to Baeyer as they have negative strain but they do exist

and are much stable.

□ Larger ring systems are not planar but puckered (wrinkled) to eliminate the angle strain.

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