❖ Introduction :-

➢ Cyclo alkanes are hydrocarbon with three or more carbon

atom in a ring.

➢ MF of cyclo alkanes is CnH2n

➢ First member of cyclo alkane is cyclo propane.

Name MF

Cyclo propane C3H6

Cyclo butane C4H8

Cyclo pentane C5H10

Cyclo hexane C6H12

Cyclo heptane C7H14

Cyclo octane C8H16

Cyclo Nonane C9H18

Cyclo Decane C10H20

❖ Classification and Nomenclature of cyclo alkanes:-

Cyclo alkanes

Simple Spiro Bicyclo Bridge

Prefix : Cyclo Spiro Bicyclo Bicyclo

=
=

1) Simple cyclo alkanes :-

Prefix :- Cyclo

Cyclo Propane

Cyclo Butane

Cyclo Pentane

Cyclo Hexane

Br

1-Bromo

Cyclo Propane Cl

Cl 1,1- dichloro

Cyclo Butane

OH

OH

OH
Cyclo Pentane-1,2,3-triol

Br

1-Bromo-3-methyl-

Cyclo Hexane

2) Spiro compounds :-

Prefix :- Spiro

➢ First give spiro prefix to compound.

➢ In square breakate write less carbon containing rings carbon

figure first and followed by more one.

➢ After breakate write alkane name by calculating total no. of

carbon. For eg. Spiro[2,2] Pentane

CH3

CH3

1-ethyl-2-propylcyclohexane Br

Bromo cyclo decane

Br Br

CH3
1,1-di Bromo-3-methyl-cyclo

decane

Spiro[2,3] hexane

Spiro[2,4] heptane

Spiro[2,5] octane

Spiro[3,3] heptane

Spiro[4,4] nonane

3) Bicyclo compounds(Fused) :-

Prefix :- Bicyclo

➢ First give prefix bicyclo.

➢ In square breakate, first write no. of carbon of highest ring no.

➢ Then write less carbon rings carbon nos. followed by total

carbon containing alkane name.

Bicyclo[1,1,0] butane Bicyclo[2,1,0] pentane

Bicyclo[2,2,0] hexane Bicyclo[3,2,0] heptane

Bicyclo[3,3,0] octane Bicyclo[4,3,0] nonane

Bicyclo[4,4,0] decane Bicyclo [4,2,0] octane

Bicyclo[6,1,0] nonane Bicyclo[5,1,0] octane

4) Bridge compounds :-

Prefix :- Bicyclo

➢ First give prefix bicylo

➢ In square breakate write long chain carbon nos. followed by

short chain carbon nos.

Bicyclo[2,2,1] heptane

Bicyclo[2,2,2] octane

Bicyclo[2,1,1] hexane

=
Bicyclo[1,1,1] pentane

❖ Physical properties of Cyclo alkanes :-

➢ C3

and C4

carbon containing cyclo alkanes are in gaseous

form.

➢ C5

to C8

carbon containing cyclo alkanes are in liquid form.

➢ C9

and more are in solid form.

➢ Cyclo propane is used as an anesthetics.

➢ MP increases with increasing in carbon.

➢ Density increases with increasing in carbon.

❖ Methods for the preparation of small ring cyclo alkanes :-

1) Diels-alder reaction :-

➢ Diels-alder reaction is 4+2 cyclo addition reaction.

➢ It is thermally allowed reaction(heat).

➢ In this reaction, Diene react with dienophile and gives cyclic

product(adduct).

➢ During the reaction two sigma bonds are formed and two Π-bonds

are lost.

For eg.

CH2

CH2

CH2

CH2

Reduction

Ni/H2

1,3-Butadiene Ethene Cyclo hexene Cyclo hexane

CH2

CH2

CH

CH
Reduction

Ni/H2

1,3-Butadiene Ethylene Cyclo hexene Cyclo hexane

1,3-diene

CH2

CH2

1,3-Butadiene Cyclobutene

Reduction

Ni/H2

Intermediate Bicyclo[4,2,0]

octane

CH2

CH2

+
1,3-Butadiene Cyclopropene

Reduction

Ni/H2

Intermediate Bicyclo[4,1,0]

heptane

CH2

CH2

1,3-Butadiene Cyclopentene

Reduction

Ni/H2

Intermediate Bicyclo[4,3,0]

nonane

CH2

CH2
H3C

2-Methyl- Ethene

1,3-Butadiene

H3C

Reduction

Ni/H2

H3C

Methyl Cyclohexene Methyl cyclo hexane

CH2

CH2

CH2

CH2

H3C

H3C
+

2,3-dimethyl- Ethene

1,3-Butadiene

H3C

H3C

Reduction

Ni/H2

H3C

H3C

Dimethyl Di methyl

Cyclohexene cyclo hexane

CH2

CH2

2) Simmon-smith carbene reaction :-

➢ Alkene on reaction with di iodo methane in the presence of

Cu-Zn and ether as solvent is known as Simmon-smith

carbene reaction.
CH3

H3

H3

C CH3

+ CH2

Cu-Zn

Ether

CH3

H3

H3

CH3
2,3-Dimethyl but-2-ene 1,1,2,2-tetra methyl

cyclo propabe

Mechanism :-

CH2

+ Zn CH2

Zn

Step-I

Step-II

CH2

Zn

I
CH3

H3C

H3C CH3

H3C CH3

H3C CH3

Zn

CH3

H3C

H3C

CH3

+ ZnI2

+ CH2
I2

Cu-Zn

Ether

Cyclo hexane Bicyclo[4,1,0]heptane

+ CH2

I2

Cu-Zn

Ether

Cyclo octene Bicyclo[6,1,0]nonane

H3C

CH3

+ CH2

I2

Cu-Zn

Ether

H3C

CH3

But-2-ene Trans-1,2-diimethyl

cyclo propane
R-C=C-R + CH2

I2

Cu-Zn

Ether R-C=C-R R R

2) Simmon-smith carbene reaction :-

➢ The reaction which is formed within the molecule.

a) Funds method/Wurtz method :-

➢ Dihalo alkanes treated with Na or Zn to formed cyclo alkanes.

Br

Br

+ Zn

1,3-dibromo

propane

Cyclo

propane

Cl

Cl

1,4-dichloro
butane

2 Na

Cyclo butane

b) Perkin’s method :-

➢ In this method, sodium salt of malonic ester treated with dihalo

alkane.

Br

Br

Di bromo

ethane

Na

Na

COOC2H5

COOC2H5

Di sodium salt of

di ethyl malonate
-NaBr

COOC2H5

COOC2H5

Hydrolysis

H2O

COOH

COOH

-CO2

Cyclo propane

c) Dieckmann’s method :-

➢ This method is used for 6 or more carbon containing compounds.

➢ It forms cyclic ketone which on hydrolysis followed by

decarboxylation and reduction formed cyclo alkane.

CH2

CH2
CH2

COOEt

CH2

COOEt

C2H5ONa O

COOEt

H2O O

COOH

Diethyl adipate Ethyl-2-oxo-cyclo

Pentane carboxylate

2-oxo-cyclopentane

carboxylic acid

-CO2

Cyclo pentanone

Reduction
Zn-Hg+ HCl

Cyclo pentane

-C2H5OH

❖ Chemical properties of Cyclo alkanes :-

1) Substitution reaction :-

➢ Cyclo alknaes gives substitution reactions likes alkanes

compounds.

➢ Generally, cyclo alkanes likes cyclo propane and cyclo butane

are unstable and open easily.

➢ Cyclo pentane & Cyclo hexane gives substitution reactions with

halogens.

Cl2

/ Br2 Br/Cl

Cyclo pentane Bromo/Chloro

Cyclo pentane

+ HBr/HCl

Cl2

/ Br2
Br/Cl

+ HBr/HCl

Cyclo hexane Bromo/Chloro

Cyclo hexane

2) Addition reaction :-

➢ Cyclo propane and cyclo butane gives addition reaction with

HBr/HCl, Br2

, Con. H2SO4

(H2O) and reduction reaction.

Br2

HBr

H2

H2

SO4

Ni/H2
CH2

CH2

CH2

Br Br

1,3-dibromo propane

H Br

CH2

CH2

CH2 1-bromo propane

CH3

CH2

CH3

Propane

Cyclo propane CH3

CH2

CH2

OH Propanol

3) Oxidation reaction :-

Oxidation of cyclo alkane gives dicarboxylic acid.

Br2

HBr

H2O

H2

SO4

Ni/H2

CH2

CH2

CH2

CH2

Br Br

1,4-dibromo butane

H Br

CH2

CH2

CH2

CH2 1-bromo butane

CH3
CH2

CH2

CH3

Butane

Cyclo butane CH3

CH2

CH2

CH2OH Butanol

KMnO4

[O]

COOH COOH

Cyclo pentane Glutaric acid

Cyclo hexane

KMnO4

[O]

COOH

COOH

Adipic acid

❖ Baeyer strain theory & it’s limitations :-

➢ Baeyer was the scientist who gave the theory for explaining

stability of cyclo alkanes which is known as Baeyer strain theory.

➢ According to the theory of labell and Vanthoff the four valency of

carbon are oriented towards carbon and valency angle is 109o28’.

➢ In cyclo propane, cyclo butane and cyclo pentane molecule, the

valency angle of carbon is less than 109o28’.

➢ While in cyclo hexane and other molecule, the valency angle is

greater than 109o28’.

➢ Thus, whenever the molecule of acyclic compound, the angle

between two valencies of carbon atoms chages from 109o28’, this

phenomena is called deviation.

➢ Because of deviation, strain occurs and stability of molecule is

decreases.

Deviatin α stain α 1

Stability

➢ If the angle between carbon atoms valency is less than 109o28’,

The deviation is positive and when the angle is greater than

109o28’, the deviation is negative.

➢ Angle deviation can be calculated by following formula.

D or μ = 1 [109o28’ – (2n - 4) * 90O]

2n
When, n = no. of carbon atom in a molecule

➢ For, cyclo propane n = 3

D or μ = 1 [109o28’ – (2(3) - 4) * 90O]

23

= 1 [109o28’ – 2 * 90O]

23

= 1 [109o28’ – 60O]

= 1 [49o 28’ ] (1O = 60’)

= 1 [48o 88’ ]

D or μ = 24o 44’

➢ For, cyclo Butane n = 4

D or μ = 1 [109o28’ – (2(4) - 4) * 90O]

24

= 1 [109o28’ – 90O]

2
= 1 [19o28’]

= 1 [18o 88’]

D or μ = 9o 44’

➢ For, cyclo Penane n = 5

D or μ = 1 [109o28’ – (2(5) - 4) * 90O]

25

= 1 [109o28’ – 6 * 90O]

25

= 1 [109o28’ - 1080

= 1 [1o 28’]

=1 [0o 88’]

D or μ = 0o 44’

➢ The angle deviation of cyclo propane, cyclo butane and cyclo

pentane are positive and it decreases so stability will increase.

➢ So Baeyer proposed that cyclo pentane is most stable while

other cyclo alkanes are unstable as compare to cyclo pentane.

Sr.

No.

Name Angle of

valency

Deviation in

angle

1 Cyclo propane 600 24044’

2 Cyclo butane 900 9404’

3 Cyclo pentane 1080 0

044’

4 Cyclo hexane 1200

-5

016’

Limitations of Baeyer stain theory :-

➢ According to Baeyer strain theory cyclo pentane is most stable but

at 3000C temperature, cyclo pentane get opened, while cyclo

hexane and other higher carbon containing cyclo alkanes can not

open at high temperature.

➢ Angle deviation in cyclo hexane and higher cyclo alkanes are

negative and in increasing order. So, stability should be decrease

but experiments proved that cyclo hexanes & higher cyclo alkanes

are very stable.

➢ So Baeyer strain theory is only applicable till cyclo pentane after

that this theory is not useful.

❖ Conformation and Conformational analysis :-

➢ Various shapes of a molecule can assume by rotation about the

single bonds are called conformations.

➢ The various conformations of the same molecule are referred as

conformers or rotamers.

➢ Conformations are different spatial arrangement of a molecule

around single bonds generated by rotation.

➢ The properties of a molecules are depends on conformation.

➢ Conformation analysis is the study of rotation motions in

molecules and how they affect molecules properties

i.e. energy change analysis.

❖ Conformation of ethane :-

➢ Ethane is the simplest hydrocarbon. It gives different

conformations.

➢ The two conformations are staggered and Eclipsed.

➢ In Eclipsed conformation each C-H bond is aligned

with C-H bond on neighbor carbon.

➢ In staggered conformations the C-H bond are

arranged so that each one bisect the angle defined by

two C-H bonds on adjcent carbon.

➢ The structural features that is eclipsed and staggered

conformation is described the relationship of atoms on adjcent

carbon atom.

➢ Each H-C-C-H unit is characterized by torsinal angle or

dihedral angle.

➢ Torsinal or dihedral angle is the angle between H-C-C plane

and C-C-H unit.

➢ Eclipsed bonds are characterized by 00 Torsinal angle.

➢ In Gauche, Torsinal angle is 600

➢ In anti, Torsinal angle 1800

➢ Staggered conformation have only two relation that is Gausch

or Anti.

➢ Due to rotation of 3600 in ethane potential energy of ethane is

change.
➢ The conformation which have least P.E. is most stable.

➢ The three staggered conformations shows minimum P.E. while

three shows (eclipsed) minimum P.E.

➢ When ethane is in eclipsed form, it is least stable due to

repulsion.

➢ When ethane is in staggered form, it is most stable due to less

repulsion.

❖ Conformation of propane :-

➢ The conformation of propane are similar to those of ethane

except that one of the H is replaced by CH3 group.

➢ The conformation of propane are shown in below figure.

❖ Conformational analysis of n-Butane :-

➢ The structural formula of n-Butane is as under.

HHHH

H-C-C-C-C-H

HHHH

➢ Let us consider C2

-C3 bond.
➢ Suppose the arrangement of two CH3 groups is as indicated in

structure-I, the fully eclipsed or cis conformation is obtained.

➢ Rotation around C2

-C3 bond gives different conformations.

➢ In butane, four different conformations are possible.

1) Fully eclipsed or Cis conformations (I) :-

2) Skew or Gauche conformations (II) & (VI) :-

3) Partially eclipsed conformation (III) & (V) :-

4) Staggered or Anti or Trans conformation (IV)

1) Fully eclipsed or Cis conformations (I) :-

➢ In this conformation, -CH3 groups are in eclipsed form. (behind)

➢ The methyl group is being bigger in size so it generates

repulsion.

➢ Hence, this state has more energy and it is most unstable.

2) Skew or Gauche conformations (II) & (VI) :-

➢ In skew or gauche (II) & (VI) structure, angle between two

methyl group is 600 & 3000

➢ Structure (II) & (VI) are enantiomers and are non-super

imposable.

➢ In this two structures both structures are far. Hence strain is

less. So torsinal or pitzer strain is also less, also energy is less

than fully & Partial eclipsed.

➢ So it is stable than partial & fully eclipsed.

3) Partially eclipsed conformation (III) & (V) :-

➢ In this conformation, the dihedral angle between the two methyl

groups is 1200 or 2400

➢ They are known as partial eclipsed because the groups are not

identical.

➢ Here, both methyl are eclipsed by smaller H atoms, so repulsion

takes place but less than methyl-methyl group repulsion.

➢ Hence, their energy is less than eclipsed structure but more than

of skew or Gauche.

➢ Also strain is less than eclipsed so it is stable than eclipsed and

less stable than Gauche or skew.

4) Staggered or Anti or Trans conformation (IV)

➢ In this conformation, the dihedral angle between both methyl

group is 1800

.
➢ Both methyl groups are far from each other so repulsion is

minimum hence torsinal strain does not exist.

➢ So it has least energy and more stability.

➢ The energy diagram for n-butane structure are as under.

➢ At 250C inter conversion can not be stopped completely.

Anti :- 69%,

Gauche 30.4%,

Partial eclipsed – 0.6% and

completely eclipsed 0.2%