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Cyclo alkanes Unit:- 5 PDF Download

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B.Pharmacy 3rd sem

BP301T.                    PHARMACEUTICAL ORGANIC CHEMISTRY –II (Theory)
PCI SYLLABUS:- UNIT V                                                                               07 Hours
Cyclo-alkanes*
Stabilities – Baeyer’s strain theory, limitation of Baeyer’s strain theory, Coulson and Moffitt’s modification,
Sachse Mohr’s theory (Theory of strain less rings), reactions of cyclopropane and cyclo-butane only.

                                                   CYCLO-ALKANES
What are cyclo-alkanes?
Cyclo-alkanes are also called cycloparaffins.
They are Alicyclic Compounds i.e. they are both aliphatic and cyclic compounds, and their properties are almost
similar to alkanes.
Cyclo-alkanes are saturated hydrocarbons, that means all the carbons present do not contain any pi bond, all their
valency are satisfied with sigma bonds.
Cyclo-alkanes have General Formula CnH2n with 1st member Cyclo-propane (Formula: C3H6).

        Isomerism: - Cycloalkanes have same molecular formula to that of corresponding Alkenes. So they are
functional isomers with alkenes of same carbon number.

Ex:-
All the above three structures have molecular formula C4H8 , But 1st two figures are functional isomer with the third
figure.
Nomenclature: It can be read in 3 sections
1. Naming of simple cycloalkanes: - It is done by attaching the prefix cyclo to the name of the corresponding normal
alkane having the same number of carbo atoms as in the ring. For example




2.Naming of substituted cycloalkanes: - Naming of substituents in cycloalkanes as shown in 1 st figure below are
similar to that of straight chain compounds. But in 2 nd compound which is a fused cycloalkane its typical.




Lets brake the name Bicyclo[2.2.1]heptane. Bicyclo implies the compound has two rings i.e. if we break two carbon
bonds, the compound will be an alkane of 7 carbon and can be a heptane. Now the most important part naming of
‘2.2.1’. It is so named because the number of carbons except bridgeheads and shared carbons is two (C-2 and C-3),
two (C-5 and C-6), and the bridge head made of one carbon i.e. C-7.
3.Example of typical cycloalkanes.: Some typical fused cyclo-alkanes are given below. In cubane each carbon
attached to three other carbon, in diamond each carbon attached to 4 other carbons.




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A note prepared for students of BPUT, Rourkela, Odisha
By:- Mr Satya Ranjan Mohanta, Asst. Prof. , Seemanta Institute of Pharmaceutical Sciences, Jharpokharia, Mayurbhanj
Methods of Preparation:
   1. From Di-halogen Compounds: - Suitable 1,3 or 1,4 like di- halogen alkanes on treatment with sodium or
      zinc give corresponding cycloalkanes. For example




    2. From Calcium or Barium salts of Dicarboxylic acids: - When the calcium or barium salt of adipic, pimelic,
       or suberic acid is heated, a cyclic ketone is formed. Cyclic ketones may be readily converted into the
       corresponding cycloalkanes by means of the Clemmensen Reduction.




    3. From Esters of Dicarboxylic acids (Dieckmann Reaction): - The diester of adipic, pimelic, or suberic acid
       when treated with sodium undergoes intramolecular acetoacetic ester condensation and a keto- ester is formed.
       The keto- ester on hydrolysis give corresponding cyclic ketones. Cyclic ketones on reduction yield the
       corresponding cyclo- ketones.




4. From Aromatic Compounds. Benzene may be catalytically hydrogenated at elevated temperature and pressure to
yield cyclohexane.




CHEMICAL REACTIONS
Cyclo-alkanes react mostly like their corresponding to their straight chain alkanes.
   1. Halogenation in presence of UV-light:- Produce mono substituted halogen without breaking the ring.




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A note prepared for students of BPUT, Rourkela, Odisha
By:- Mr Satya Ranjan Mohanta, Asst. Prof. , Seemanta Institute of Pharmaceutical Sciences, Jharpokharia, Mayurbhanj
     EX-




    2. Addition of Cl2/ Br2 in presence of CCl4 in dark:-Cyclopropane reacts with Cl2/ Br2 at room temperature
       and in the absence of diffused sunlight to produce I,3-dichlorocyclopropane and 1,3-dibromocyclopropane
       respectively. One of the carbon-carbon bonds of cyclopropane is broken and the two halogen atoms appear at
       the ends of the propane chain.




    3. Reaction with concentrated HBr and HI:- Produce1-bromopropane and 1-iodopropane respectively with
       ring braking.




4.Addition of Hydrogen / Catalytic Reduction:- Cyclo-propane and cyclo-butane react with hydrogen in the
presence of a nickel catalyst to produce n-propane and n-butane respectively. Cyclopentane and higher members of the
family do not give this reaction.




                                       STABILITY OF CYCLO-ALKANES
A stable organic compound means it is very less reactive. By the term stability we get an idea about chemical
reactivity of a compound. To describe stability of cycloalkanes some very famous theoretical concepts are there viz.
Bayer Strain Theory
Sachse Mohr Concept
Coulson and Moffitt’s modification
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A note prepared for students of BPUT, Rourkela, Odisha
By:- Mr Satya Ranjan Mohanta, Asst. Prof. , Seemanta Institute of Pharmaceutical Sciences, Jharpokharia, Mayurbhanj
                                                   Bayer Strain Theory

 Adolf von Baeyer, a German chemist and a Nobel prize winner from university of Munich, Germany in
 1885 proposed a theory to explain the relative stability of the first few cycloalkane. The theory based
 on following facts.
 . Cyclo-alkanes are saturated compounds. So all the carbons should have normal tetrahedral angle of
 109.50 .
 . Any deviation of bond angles from the normal tetrahedral value would, impose a condition of internal
 strain on the ring called angle strain.
 . More the value of angle strain less stable the compound is.                                                   A.V. Baeyer
 . He assumes that all the cyclo-alkanes are flat and coplanar that means they are two dimensional and
 present in one plane.

Case-Study:-
1.Cyclopropane:-




In cyclopropane, the three carbon atoms occupy the corners of an equilateral triangle. Thus cyclopropane has C—C—
C bond angles of 60°. This implies that the normal tetrahedral angle of 109.5° between any two bonds is compressed
to 60°, and that each of the two bonds involved is pulled in by 1/2(109°28'—60°)=24°44'.
The value 24°44' then represents the angle strain or the deviation through which each bond bends from the normal
tetrahedral direction.

2. Cyclo-butane:-




Here the four carbon atoms occupy the corners of a square. So it has C—C—C bond angles of 90° & angle strain on
each bond is 1/2(109°28'-90°) = 9°44'.

3.Cyclo-Pentane:-




Here the five carbon atoms lie at the corners of a regular pentagon. Thus cyclopentane has C—C—C bond angles of
108°. The angle strain which each bond fills is 1/2(109°28'— 108°) = 0044'.
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A note prepared for students of BPUT, Rourkela, Odisha
By:- Mr Satya Ranjan Mohanta, Asst. Prof. , Seemanta Institute of Pharmaceutical Sciences, Jharpokharia, Mayurbhanj
4.Cyclo-hexane:-




In cyclohexane the six carbon atoms occupy the corners of a regular hexagon. Thus cyclohexane has C—C—C bond

angles of 120°. The angle strain will be 1/2(109°28'— 1200)= -5°16'
Similarly, in the case of cyclo-heptane the deviation from the normal tetrahedral angle is -9033'. In the case of
cyclooctane it is - 12°46'.
Derivation:-

                                       Sl.No        Name                 Angle strain
                                       1            Cyclo-propane        +24°44'
                                       2            Cyclo-butane         +9°44'.
                                       3            Cyclo-pentane        +0044'.
                                       4            Cyclo-hexane         -5°16'
                                       5            Cyclo-heptane        -9033'
                                       6            Cyclo-octane         - 12°46'

    1.   The + sign indicates that the C—C bonds have to be compressed to satisfy the geometry of the ring. The - sign indicates
         that the C—C bonds have to be widened to satisfy the geometry of the ring. Whether the angle strain is positive or
         negative, its magnitude determines the extent of strain in the ring.
    2.   The deviation from the normal tetrahedral angle is maximum in the case of cyclopropane. So, it is most
      unstable and open up on the slightest provocation and thus releasing the strain within.
    3.The deviation from the normal tetrahedral angle is minimum in the ease of cyclopentane. This implies that
      cyclopentane is under least strain and should be most stable
   4. According to the Baeyer Strain Theory, cyclohexane and the higher cycloalkanes should become increasingly
      unstable and hence more reactive.
Drawbacks of Bayer-strain theory
   1. The limitation of Bayer strain theory is that he assumed that all cycloalkanes are planar.
   2. Baeyer was unable to explain the effect of angle strain in Larger Ring System.
   3. According to Baeyer Cyclopentane should be much stable than cyclohexane but practically it is reversed.
   4. Larger ring systems are not possible according to Baeyer as they have negative strain but they exist and much
      stable. - Larger ring systems are not planar but puckered to eliminate angle strain.


                               SACHSE MOHR’S CONCEPT OF STRAINLESS RINGS
In order to account for the stability of cycloalkanes beyond cyclopentane, Sachse and Mohr (1918) pointed out that
such rings can become absolutely free of strain if all the ring carbons are not forced into one plane as was supposed
by Baeyer.
If the ring assumes a such 3D condition the normal tetrahedral angles of 109°28 are retained and as a result, the
strain within the ring is relieved. Thus, cyclohexane can exist in two non-planar stainless forms, namely, the Boat
form and the Chair form.
In the Boat form, carbons 1, 2, 4 and 5 lie in the same plane and carbons 3 and 6 above the plane. In the chair form,
carbons I, 2, 4 and 5 lie in the same plane, but carbon 6 is above the plane and carbon 3 is below it.




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A note prepared for students of BPUT, Rourkela, Odisha
By:- Mr Satya Ranjan Mohanta, Asst. Prof. , Seemanta Institute of Pharmaceutical Sciences, Jharpokharia, Mayurbhanj
Actually, only one form of cyclohexane is known and not two forms as shown above. The failure to isolate the two
forms is due to rapid interconversions between them. Such non-planar strain less rings in which the ring carbon atoms
can have normal tetrahedral angles are also possible for larger ring compounds.

                          Coulson and Moffitt’s modification (Bent bond/Banana bond)
Coulson-Moffitt modify Baeyer strain theory to show the actual position of carbon-carbon bonds in cyclopropane,
which somewhat relieves the strain on C-C bonds.
So, to satisfy regular tetrahedral geometry (109028’) and equilateral triangle angle (600) they introduce a new type of
bond called banana bond/bent bond which is intermediate between sigma bond and pi-bond in case of overlapping.
What is this Bent bond:- Sigma bonds have head-on or end-to-end overlapping. The hybrid orbitals
including the intersection bonding region are present equally on both side of the molecular axis. But in case
of pi-bonds the lateral or sidewise overlapping of p-orbitals occur and here the bonding intersection area is
totally out of the molecular axis.




In Bent-bond (usually they are sigma bonds) the hybrid orbitals and intersection bonding area are not present
equally on the both side of molecular axis. The bonds are bent towards the direction of angle strain. So they
are somewhat more unstable than sigma bonds and less unstable than pi bonds.
                             Important Questions often asked from the unit
    1. Baeyer Strain theory. 10Marks
    2. Sachse-Mohr’s concept. 5 Marks
    3. Coulson and Moffitt’s modification. 5 Marks
    4. What is bent bond. 2 marks
    5. Method of preparation and chemical reactions for short questions.


REFERENCES

1.Organic Chemistry byMorrison and Boyd
2. Arun Bhal. A Text Book of Organic Chemistry, 22nd Edition Page no: 618
3. P L Soni. Text Book of Organic Chemistry, 29th Edition Page no: 2.58 & 2.477 .
4. https://profiles.uonbi.ac.ke/andakala/files/sch_102_lecture_week__8_2018-9.pdf
5.http://yengage.yenepoya.edu.in/idata/YenepoyaUniversity/ilFile/4/59/file_45980/001/Unit%20V%20POC%20II%2
0Cycloalkane.pdf




                                             www.remixeducation.in
A note prepared for students of BPUT, Rourkela, Odisha
By:- Mr Satya Ranjan Mohanta, Asst. Prof. , Seemanta Institute of Pharmaceutical Sciences, Jharpokharia, Mayurbhanj
Subject:
Pharmaceutical Organic chemistry 2
Semester:
3rd sem
Cource:
Bachelor of Pharmacy

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