Cycloalkanes

• Alkanes with closed ring(s) of C atoms

• General formula: CnH2n (C3H6, C4H8, C5H10, etc.)
• Naming: use cyclo- prefix before alkane name

cyclopropane cyclobutane cyclopentane cyclohexane

n=3 n=4 n=5 n=6
C3H6 C4H8 C5H10 C6H12
Naming substituted cycloalkanes:
• 1 substituent: no numbering necessary
• 2 or more substituents: highest alpha priority on C #1
CH3
CH3
1-chloro-5-methylcyclohexane
Cl
methylcyclopentane 1-chloro-3-methylcyclohexane
 Fun Common Names

broken boxane
windowpane
windowpane

basketane
Teepee-ane
 Dashes and Wedges Bonds
Wedge
Indicates bond coming out
of the page toward you
Dashes
Indicates bond going into
the page away from you
Going into the page away from you

H3C H
Coming out at you (like 3-D movie)
H H
H CH3
 Stereoisomers
• Cycloalkane rings have two faces
• Stereoisomers: same connectivity, but different arrangement
of atoms in space
• Geometric Isomers: type of stereoisomer involving rings or
multiple bonds with substituents on two different carbons
– Designated as either cis or trans and must be included in the name
H Cl
Cl
cis isomer – substituents on C C
H Cl
same face of the ring H H
C C
Cl
cis-1,2-dichlorocyclobutane
H H
H Cl
Cl
trans isomer – substituents on H
C
H
C
H H
opposite faces of the ring C C
Cl
trans-1,2-dichlorocyclobutane H Cl
 Conformational Analysis
H3C H H3C CH3
180° rotation
Dash-wedge diagram H H H H
H CH3 H H

Conformational isomers: differ only by rotation about single bonds

• Also called conformers or rotamers
• Interconvert easily at room temperature
Newman projections: looking down a C-C bond
CH3
CH3 CH3
H3C H H H H3C CH3

H H  H H
H H 
H H
H CH3 H H H H
CH3

staggered is more stable than eclipsed

Steric strain: atoms/substituents “bumping into” each other
• More steric strain  higher in energy, less stable
 Strain in Cycloalkanes
What if cycloalkane rings were flat?

Bond angles: 60° 90° 108° 120°

Tetrahedral bond angle = 109.5°

Bond angle strain

Flat rings would require all C-H bonds to be eclipsed

Torsional (twisting) strain

Result: When possible, rings will compensate

to relieve both kinds of strain
 Cyclopropane and Cyclobutane

Cyclopropane Cyclobutane
Bond angles 60° Puckers to stagger C-H bonds
H H
All C-H bonds eclipsed
H
No way to relieve strain H
H
H

H
UNSTABLE H
Puckering decreases bond
angles to less than 90°
UNSTABLE
 Cyclopentane
H
H H
H
H
H H H
H H
“envelope”
conformation

Bond angles close to tetrahedral (108°)

Puckers to stagger C-H bonds

STABLE
 Cyclohexane
H H
H
H H
H
H
H H
“chair” H
H
H
conformation

Puckers to relieve bond angle strain and torsional strain

Result: All bond angles ~109°, all C-H bonds staggered
STABLE

H H H axial bonds: straight up or down

H H equatorial bonds: ~ in plane of ring
H
H
H H axial positions: crowded, only H can fit
H
H H equatorial positions: plenty of room
 Cyclohexane “ring flip”
• Axial and equatorial positions can be swapped by ring flipping
(Ea ~ 50 kJ/mol)

cis-1-bromo-4-chlorocyclohexane
Br Cl Cl
Br H H H
H H H
H H H H H
H H H
H H
H Cl H H HH Br H
H H
H H H H H
H
Br axial “boat” Br equatorial
Cl equatorial Cl axial

• Intermediate is a boat conformation, higher energy than chair

 Drawing chairs from flat pictures

CH3
CH3
H
CH3
CH3
H

cis-1,2-dimethylcyclohexane

Br
H
Br
CH3
CH3
H

trans-1-bromo-2-methylcyclohexane
 Optical Isomers
• Optical isomers are non-superimposable mirror images
– interact differently with polarized light
– type of stereoisomer
I I F F
Br * * Br Cl * * Cl
H H H H
Cl Cl H3C CH3
bromochloroiodomethane 1-chloro-1-fluoroethane

C* = stereocenter: C with 4 different substituents

hint that molecule may have optical isomers

mirror plane in molecule  no optical isomers

No optical  plane of symmetry:

isomers
Br
molecule halves are mirror images
 Chirality: Chiral vs. Achiral

right shoe left mit right-handed glass plate tennis

scissors racket

Chiral Achiral
 Chirality

mirror H H
H
H

Cl
Cl Br
Br Cl Br Cl
Br
I
I I I

Timberlake, Chemistry 7th Edition, page 484