1. Organic Chem I: lecture 9 by Doba Jackson, Ph.D.
Cycloalkanes
Organic Chem I: lecture 9 by
Doba Jackson, Ph.D.

2. Lecture Alkanes Cycloalkanes Naming alkanes con’t
Newman projections con’t
Cycloalkanes
Naming cycloalkanes
Cis-Trans isomerism
Cyclopropane
Cyclobutane

3. Introduction to Cycloalkanes

4. Cycloalkanes, common names

5. Naming Cycloalkanes Step 1: Find the Parent
If the ring has equal or more carbons, it is the parent.

6. Step 2: Number the substituents with the lowest numbers and write the name.

7. Substituents should have the lowest possible numbers

8. When two or more substituents can have the same number, they are numbered by alphabetical priority

9. When two or more substituents can have the same number, they are numbered by alphabetical priority

10. Some Examples

11. 4-bromo 2-methyl 1-tert-butyl
Problem 3.1- Give IUPAC names for the following
compounds
3-cyclobutyl pentane
1-methyl 3-propyl cyclopentane
1,4 dimethyl cyclohexane
1-isopropyl 2-methyl cyclohexane or
1-(1-methylethyl) 2-methyl cyclohexane
4-bromo 2-methyl 1-tert-butyl
cycloheptane
1-bromo 4-ethyl cyclodecane

12. Stability of Cycloalkanes: Ring Strain
Rings larger than 3 atoms are not flat
Cyclic molecules can assume nonplanar conformations to minimize strains by ring-puckering
Larger rings have many more possible conformations than smaller rings and are more difficult to analyze. 12

13. Summary: Types of Strain
Angle strain - expansion or compression of bond angles away from most stable
Torsional strain - eclipsing of bonds on neighboring atoms
Steric strain - repulsive interactions between nonbonded atoms in close proximity 13

14. Conformations of Cycloalkanes
Cyclopropane
3-membered ring must have planar structure
Symmetrical with C–C–C bond angles of 60°
Requires that sp3 based bonds are bent (and weakened)
All C-H bonds are eclipsed 14

15. Bent Bonds of Cyclopropane
In cyclopropane, the C-C bond is displaced outward from internuclear axis 15

16. Cyclobutane Cyclobutane has less angle strain than cyclopropane
Cyclobutane is slightly bent out of plane - one carbon atom is about 25° above
- The bend relieves the torsional strain 16

17. Cyclopentane
Planar cyclopentane would have no angle strain but very high torsional strain
Four carbon atoms are in a plane
The fifth carbon atom is above or below the plane – Puckered 17

18. Conformations of Cyclohexane
The cyclohexane ring is free of angle strain and torsional strain
Each carbon is in the staggered conformation
This is called a chair conformation 18

19. How to Draw Cyclohexane
Step 1: Draw two parallel lines slanted
downward
Step 2: Draw two lines starting from the
parallel lines slanting upward
and intersecting at a point.
Step 3: Draw two lines downward
starting from the other end of
the parallel lines and intersecting
at another point. 19

20. 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 20

21. Axial and Equatorial Positions
Each carbon atom in cyclohexane has one axial and one equatorial hydrogen
Each face of the ring has three axial and three equatorial hydrogens in an alternating arrangement 21

22. Drawing the Axial and Equatorial Hydrogens
Axial hydrogens are perpendicular to the ring
Equatorial hydrogens are paralell to the ring
Completed Cyclohexane 22

23. Conformational Mobility of Cyclohexane
Chair conformations readily interconvert, resulting in the exchange of axial and equatorial positions by a ring-flip 23

25. Conformations of Monosubstituted Cyclohexanes25

26. 26

27. Conformation of Butane27

28. Relationship to Gauche Butane Interactions
Gauche butane is less stable than anti butane by 3.8 kJ/mol because of steric interference between hydrogen atoms on the two methyl groups
The four-carbon fragment of axial methylcyclohexane and gauche butane have the same steric interaction
In general, equatorial positions give more stable isomer 28

29. Conformational Analysis of Disubstituted Cyclohexanes29

30. Conformational Analysis of Disubstituted Cyclohexanes
In disubstituted cyclohexanes the steric effects of both substituents must be taken into account.
We can denote cis and trans to disubstituted cyclohexanes.
In the cis isomer, both methyl groups are on the same face of the ring 30

31. Trans-1,2-Dimethylcyclohexane31

32. 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 interaction between methyls (3.8 kJ/mol).
Steric strain of 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 32

33. Conformations of Polycyclic Molecules
Decalin consists of two cyclohexane rings joined to share two carbon atoms and a common bond.
Two isomeric forms of decalin: trans fused or cis fused
In cis-decalin hydrogen atoms at the bridgehead carbons are on the same face of the rings
In trans-decalin, the bridgehead hydrogens are on opposite faces
Flips and rotations do not interconvert cis and trans 33

34. 34

35. Problem 4.13: Draw two conformations of trans 1,4 dimethylcyclohexane