Submitted By:

Mr. Prayatna Kunj.

PharmD 1st Year​.

Under The Supervision Of:​

​Dr. Rahul Kumar Maurya.

Faculty of Pharmacy​.

Amity Institute of Pharmacy​.

Amity University , Lucknow​.

prayatna.kunj@gamil.com
 Cycloalkane

Content

• 1. Introduction
• 2. Physical properties
• 3. Prepration
• 4. Baeyer’s strain theory
• 5. Orbital picture of angle strain
Cyclooctane
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 1. Introduction:- prayatna.kunj@gamil.com

Example:-
• They are saturated hydrocarbon in
which the carbon atom joined by single
covalent bond to form a ring
• They are also called cycloparaffins and
salicylic compound
• Hybridization - sp³ hybridization
• IUPAC(Nomenclature) - Same as
alkanes, but use cycle as prefix

3
 2. Physical property of Cycloalkane

• Cyclopropane and Cyclobutane are gases at room temperature , remaining are liquids.
• Cycloalkane are insoluble in water but dissolve in ethanol and ether.
• Melting and boiling points of cycloalkane shows a gradual increase with the increase
in molecular weight.
• Example:- Boiling point(⁰C) Melting point(⁰C)

1.Cyclopropane. -32.8 -127.4

2.Cyclobutane. 12.5 -90.7
3.Cyclopentane. 49.5 -13.9

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 * Chemical Reaction of Cycloalkane
• Cycloalkane gives two reaction:-
(i) Substitution Reaction

(ii) Addition reaction (open ring reaction)

(i) Substitution Reaction:- In this reaction ,one hydrogen atom replaced, but ring does
not affected.
—#substitute with or

UV light, it gives substitute products.

(a) When cyclopropane react with chlorine in the presence of uv light, it gives
chlorocyclopropane.
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Eg.

(b) when cyclohexane react with chlorine in the presence of UV light , it gives
chlorocyclohexene.

Eg.

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 (ii) Addition Reaction(ring opening reaction):- In this reaction, bond will break and the
ring will open.
-Higher cycloalkane does not give reaction.
-#addition of &
(a)When cyclopropane react with bromine( ) in the dark to give 1,3 dibromopropane
( used as a solvents ).

-#Addition of
(b)cyclopropane react with in the presence of Ni(Nickel) at 80⁰ C it give propane.

Cyclopropane Propane
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3.Method of Preparation of Cycloalkane

Types
1. From Dihalide
2. Dieckmann reaction
3. Simmons-smith reaction
4.From aromatic hydrocarbons
5. From calcium salt of dicarboxylic acid

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1. From Dihalide:-
-Terminal dihalide when treated with sodium(Na) or Zinc(Zc) from cycloalkanes.
Eg.1.

(1,3 dibromopropane) (Cyclopropane)

Eg.2.

2. Dieckmann reaction(from ester of dicarboxylic acid):-

-Ester of dicarboxylic acid, when heated with sodium,β-ketoester is formed,
which further on hydrolysis give cyclic ketones, which on dimension reduction
give cycloalkane. prayatna.kunj@gamil.com
Eg 1.

3. Simmons-smith reaction(from alkenes):-

-When alkene are treated with methylene iodine( ) in the presence of a
zinc-copper(Zn-Cu) couple, cyclopropane derivatives are formed.
Eg.1

Eg.2

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4. From aromatic hydrocarbons
-Six membered cycloalkane can be prepared by the catalyst reduction of
benzene and its derivatives.
Eg.1
Pressure

5. From calcium salts of dicarboxylic acids

-When the calcium barium salts of dicarboxylic acids are heated, cyclic
ketones are formed, then further on dimension reduction cyclic ketone
converts into cycloalkanes.
Eg.1

Cyclic ketone

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4. Baeyer’s Strain theory
Intro:-
• Adolf Baeyer proposed in 1885,and he get noble prize for this theory in1905.
• He explain the relative stability of starting few cycloalkane.
• His theory is based on the fact that, the normal angle between pair of carbon atom is 109⁰28’.
• Now , he assumed that all cycloalkane are planar.
• Stability of cycloalkane depends upon angle strain.

Angle strain = Stability

• In cycloalkane = more the angle strain , the more unstable.

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 Angle strain = It is angle difference between desired angle (109⁰28’) and actual angle

Angle strain = 1/2 [ desired angle - actual angle ]

= 1/2 [ 109⁰28’ - Actual angle ]

Eg.(i) Cyclopropane

Desired angle = 109°28'

Actual strain = 60°

Ange strain=24.75

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Eg.2 Cyclobutane
Desired angle strain=109°28'

Actual angle strain=90°

Angle strain= 1/2 [ 109°28'- 90° ]

= 9°44'

Eg.3 Cycle pentane

Desired angle strain=109°28'
Actual angle strain=108°
Angle strain=1/2[109°28'-108°]
= 0.44'

Eg.4 Cycle hexane

Desired angle strain=109°28'

Actual angle strain=120°
Angle strain=1/2[109°-120°]
=-5°16'

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 According to Baeyer’s strain theory:-
*Stability of cycloalkane are :-
— cyclopropane<cyclobutane<cyclohexane<cyclopentane
Stability
Limitation :—
- This theory only applies on the lower cycloalkane,bayers was not able to explain the effect of angle strain in layer ring system.
-According to baeyer cyclopentane should be much stable than cyclohexane ,

but practically it is reversed.(cyclohexane is more stable than cyclopentane)

-So, higher cycloalkane are not follow this rule(cyclohexane,cycloheptane are more stable)

-They do not give ring opening reaction like cyclopropane. prayatna.kunj@gamil.com

 5. Orbital Picture Of Angle Strain
—Bent Bond / - Banana bond theory

* Concept of maximum overlap of carbon orbitals.

* It is also called as banana bond theory , because bond look like as a banana shape.
* This theory also explain the stability of cycloalkanes( why cyclopropane most unstable).
* It is based on that , Greater the overlapping of atomic orbital stronger is the bond.
* Stronger is the bond = stability .
Eg.
Sigma bond = stronger(due to good overlapping)
Pi bond = weaker(due to bad overlapping)
* But in cyclopropane bent bond is formed, which is intermediate between sigma and pi bond.

(stronger from pi bond and weaker than sigma bond)

s=25% s=16%
Sp³
Hybridisation p=75% p=84%

*Cyclopropane:—
- due to formation of bent bond, the cyclopropane c-c bond is
weaker than normal c-c sigma bond.
- so, due to weaker bond cyclopropane is unstable and it can give
ring opening reaction easily.
- The cyclopropane , c-c-c bond angle is decreased slightly from
109°28' to 104°.
 - The decrease in overlap result in weakening of the bond and therefore
partially explain the instability of cyclopropane.
* Bent bond is formed in cyclopropane , due to their less angle(60°) than
109°28'
-Cyclobutane is more stable than cyclopropane but less than cyclopentane.

*Sachse-Mohr theory (theory of stainless rings):-

- Sachse and Mohr proposed this theory in 1918 to explain about the stability of
cyclohexane and higher cycloalkane .
- according to Baeyer’s member higher than cyclopentane should be increasingly
unstable ( limitation ).
- But according to Sachse-Mohr :-
*Cycloalkane are not in a plane ( co-planar ).
- Sachse Mohr’s theory proposed that higher membrane ring can free from strain if all
the ring carbon are not found into one plane. prayatna.kunj@gamil.com
 - They exhibit in two non-planar ‘folded’ or ‘puckered’ conformation both of which
are completely free from strain.
- These are stainless as the carbon atom lie in different planes and the normal angle
(109°28') is retained.

Example:- Cyclohexane

- chair form is more stable than boat form(chair form two types positions):—

(i) Axial position— perpendicular to the plane of the ring.

(ii) Equatorial position — around the plane of the ring

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