Chapter 3

Functional Groups Alkanes

Hydrocarbons

Alkanes, alkenes, alkynes, benzene

cyclic

Functional Groups
Alkyl Halides, amines, alcohols,
ethers

Functional Groups
Carbonyl Compounds
Aldehydes and ketones
Carboxylic acids and derivatives

Functional Groups
Aromatics

Other Aromatics

Functional Groups

Alkanes and Cycloalkanes

Nomenclature/structure acyclic
alkanes with 1-3 carbons

Nomenclature/structure of acyclic
alkanes with 4-5 carbons

Alkyl Substituents

Replace ane of alkane with yl.

Common Names

Propyl and Isopropyl

Butyl, isobutyl, sec-butyl, tert-butyl

Primary, Secondary, and Tertiary Carbons

A primary carbon is bonded to one carbon.
A
. secondary carbon is bonded to two carbons.
A tertiary carbon is bonded to three carbons.
A quaternary carbon in bonded to four carbons

Alkanes Systematic Nomenclature

First identify the longest continuous chain

(the parent hydrocarbon).

Add the Name of the Substituent

Number the chain in the direction that gives the

substituent as low a number as possible.

List Substituents in Alphabetical Order

The correct name is the one that contains the

lowest of the possible numbers (5+3 < 4+6)

Multiple Substituents

Chain is numbered in the direction that puts the lowest number in the name.
Start numbering from the end that has the earliest branch point
Substituents are listed in alphabetical order (di- and tri- are not alphabetized).

Cycloalkanes

Skeletal structures do not show Cs and Hs bonded to Cs.

Bond angles in cyclic alkanes

Not 108o

Not 120o

We will revisit this when discussing bond rotations

and eclipssed vs staggered conformations

Angle Strain in cylcoalkanes

Angle strain results from poor orbitalorbital overlap because

bonds have to deviate from the ideal (109.5) bond angle.

Mono-Substituted Cycloalkanes

A number is not needed.

Di-Substituted Cycloalkanes

Substituents are stated in alphabetical order.

Lowest possible sum of substituent numbering
#1 goes to first-listed substituent.

Nomenclature of Alkyl Halides

Nomenclature of Ethers

Common
aprotic solvent
used in
chemical
synthesis

The substituents are listed in alphabetical order.

Nomenclature of Alcohols

1-propanol

2-propanol

2-butanol

Classification of Alcohols

Primary alcohol = OH is on a primary carbon.

Secondary alcohol = OH is on a secondary carbon.
Tertiary alcohol = OH is on a tertiary carbon.

Diols

Propylene diol used extensively

Systematic Names of Alcohols

Pay attention to the number of the substituent

only if you get the same number for the
functional group in both directions.
Begin numbering from the end of the chain with the earliest branch point

A Substituent is a Prefix
A Functional Group is a Suffix

Classification of Amines

The classification depends on how many groups are bonded to N.

Primary amine = one group bonded to N

Secondary amine

Tertiary amine

= two groups bonded N

= three groups bonded N

Common Names of Amines

Substituents are in alphabetical order followed

by amine.
They are all written as one word.

Dont forget acid/base properties

of amines

Some special amines

Summary of Nomenclature

The Structure of an Alkyl Halide

The CX bond of an alkyl halide becomes longer and weaker

as the size of the halogen increases.

The Structure of an Alcohol

Resembles the Structure of Water

An alcohol is structurally like water with one H replaced by an R.

The Structure of an Ether

Resembles the Structure of an Alcohol

An ether is structurally like water with both Hs replaced by Rs.

Boiling Points
The greater the attractive forces between molecules,
the higher the boiling point.

attractive forces
van der Waals forces
dipoledipole interactions
hydrogen bonds

Boiling Points

Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane

-167.7 C
-88.6 C
-42.1 C
-0.5 C
36.1 C
induced dipole-induced dipole
68.7 C
interactions
98.4 C
van der Waals forces
125.7 C

The greater the surface area of the molecule, the higher the bp.

Branching Lowers the Boiling Point

cigar

tennis ball

DipoleDipole Interactions

Dipoledipole interactions are

stronger than van der Waals forces.

Diethylether
35 = oC

Hydrogen Bonds in H2O and NH3

CH4 167.7 C

H2O 100 C

no hydrogen bonds

hydrogen bonds

Hydrogen bonds are stronger than

other dipoledipole interactions.

Compounds with Similar Shapes and Properties

Often Have Similar Physiological Activities

Drugs bind to their receptors by van der Waals interactions,

dipole-dipole interactions, and hydrogen bonding.

Solubility
like dissolves like

Polar compounds dissolve in polar solvents (H2O).

Nonpolar compounds dissolve in nonpolar solvents (hexane).

Solvation

Solvation is the interaction between solute molecules and solvent molecules.

Competing effects with increasing

carbon count

Competing effects with increasing

carbon count

Conformational Analysis of
alkane and cycloalkanes

Rotation Occurs About

Single ()Bonds

Staggered and Eclipsed Conformers

of Ethane

Rotation Can Occur About the

Three CarbonCarbon Bonds in Butane

Rotation About C-2C-3 in Butane

butane.mov

Steric strain is repulsion between the electron clouds of atoms or groups.

Cyclopropane

Cyclobutane

Molecules twist out of a planar arrangement

to minimize angle strain and the number of eclipsed hydrogens.

Cyclopentane

Molecules twist out of a planar arrangement to

minimize angle strain and the number of eclipsed hydrogens.

Chair Conformer of Cyclohexane

The chair conformer of cyclohexane is completely free of strain.

All bond angles are 111 and all adjacent bonds are staggered.

Axial and Equatorial Bonds

Ring Flip

Cyclohexane interconverts between two stable chair conformers.

Ring Flip

Cyclohexane interconverts between two stable chair conformers.

Conformers of Cyclohexane

Ring flip we will only talk about the two chair conformations

Conformers of Monosubstituted
Cyclohexanes

1,3-Diaxial Interactions

Cis and Trans Isomers

Conformers of Disubstituted
Cyclohexanes

1,4-dimethylcyclohexane

Each Isomer Has

Two Chair Conformers

1,2-dimethylcyclohexane

1,3-dimethylcyclohexane

cis-1-tert-butyl-3-methylcyclohexane

trans-1-tert-butyl-3-methylcyclohexane